TW201921787A - Electrode mixture for non-aqueous electrolyte secondary battery - Google Patents

Electrode mixture for non-aqueous electrolyte secondary battery

Info

Publication number
TW201921787A
TW201921787A TW107132080A TW107132080A TW201921787A TW 201921787 A TW201921787 A TW 201921787A TW 107132080 A TW107132080 A TW 107132080A TW 107132080 A TW107132080 A TW 107132080A TW 201921787 A TW201921787 A TW 201921787A
Authority
TW
Taiwan
Prior art keywords
mass
secondary battery
electrolyte secondary
aqueous electrolyte
copolymer
Prior art date
Application number
TW107132080A
Other languages
Chinese (zh)
Other versions
TWI770277B (en
Inventor
牛島靖仁
藤重隼一
藤田浩司
Original Assignee
日商住友精化股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商住友精化股份有限公司 filed Critical 日商住友精化股份有限公司
Publication of TW201921787A publication Critical patent/TW201921787A/en
Application granted granted Critical
Publication of TWI770277B publication Critical patent/TWI770277B/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Provided is an electrode mixture with a small resistance despite including a binding agent. Specifically provided is an electrode mixture for a non-aqueous electrolyte secondary battery, said electrode mixture including an electrode active material, a crosslinking agent, and a binding agent, wherein the binding agent includes a copolymer of a vinyl alcohol and an ethylenically unsaturated alkali metal carboxylate neutralization product, the crosslinking agent is a metal chelate complex compound, and the crosslinking agent is included at a rate of greater than or equal to 0.2 parts by mass and less than 10 parts by mass per 100 parts by mass of the total quantity of the binding agent and the crosslinking agent.

Description

非水電解質二次電池用電極合劑Electrode mixture for non-aqueous electrolyte secondary battery

本發明涉及一種非水電解質二次電池用電極合劑等。The present invention relates to an electrode mixture for a non-aqueous electrolyte secondary battery and the like.

發明背景
近年，隨著筆記型電腦、智慧型手機、可攜式遊戲機、PDA等攜帶式電子機器的普及，日益要求作為電源使用的二次電池能更小型化及高容量化，以使該等機器更為輕量且可長時間使用。此外，最近重視電池的攜帶性及處置性，大電流且可在短時間內充電的急速充電特性也逐漸成為重要的要求特性。BACKGROUND OF THE INVENTION In recent years, with the popularization of portable electronic devices such as notebook computers, smart phones, portable game consoles, and PDAs, secondary batteries used as power sources are increasingly required to be smaller and higher in capacity, so that The machine is lighter and can be used for a long time. In addition, recently, emphasis has been placed on the portability and disposal of batteries, and the rapid charging characteristics of large currents and charging in a short time have gradually become important required characteristics.

提升鋰二次電池之急速充電特性的手段，主要有改良電極構成構件。The means for improving the rapid charging characteristics of lithium secondary batteries mainly includes improving electrode constituent members.

屬於電極構成要素的黏合劑(黏結劑)也是左右二次電池性能的零件之一。黏合劑是為了牢固固定電極結構能而使用，藉由使用黏結力較高、較為強韌的黏合劑，可防止電池充放電時的電極損壞，使循環特性變佳(即壽命變長)。惟，一般而言，比起電極活性物質及導電助劑等，構成電極之構件之一的黏合劑的導電性較低，可能會成為充放電時的電阻成因。僅靠活性物質或導電助劑無法形成電極，黏合劑對接著構件而言不可欠缺。因此，為了提升電池性能，一直以來不斷追求開發含有黏合劑同時電阻又小的電極。A binder (binder), which is a constituent element of the electrode, is also one of the components that affects the performance of the secondary battery. The adhesive is used to firmly fix the structure of the electrode. By using a high-adhesive, strong adhesive, it can prevent the electrode from being damaged during charge and discharge of the battery, and improve the cycle characteristics (that is, longer life). However, in general, the adhesive constituting one of the members of the electrode has lower conductivity than an electrode active material, a conductive auxiliary agent, and the like, and may cause resistance during charging and discharging. An electrode cannot be formed only by an active material or a conductive auxiliary agent, and an adhesive is indispensable for a bonding member. Therefore, in order to improve the performance of batteries, there has been a continuous pursuit of the development of electrodes that contain a binder and have low resistance.

先前技術文獻
專利文獻
專利文獻1：日本特開2012-204203號公報
專利文獻2：日本特開2000-348730號公報Prior Art Literature Patent Literature Patent Literature 1: Japanese Patent Application Laid-Open No. 2012-204203 Patent Literature 2: Japanese Patent Application Laid-Open No. 2000-348730

發明概要
發明欲解決之課題
本發明係有鑑於上述習知技術之現狀所進行，其主要目的在於提供一種含有黏結劑同時電阻又小的電極合劑，進而從該電極合劑製造電極時可具備該電極的非水電解質二次電池用電極合劑。SUMMARY OF THE INVENTION Problems to be Solved by the Invention The present invention has been made in view of the current state of the conventional technology, and its main object is to provide an electrode mixture that contains a binder and has a low electrical resistance, and can further include the electrode when manufacturing an electrode from the electrode mixture. Electrode mixture for non-aqueous electrolyte secondary batteries.

用以解決課題之手段
本發明人等為了解決上述課題，經過鑽研的結果發現，藉由使用含有特定黏結劑、特定交聯劑及電極活性物質且尤以特定比率含有該黏結劑與該交聯劑之非水電解質二次電池用電極合劑，可製造電阻值低的電極，由此進一步反覆改良進而完成本發明。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have found that, by using a specific binder, a specific cross-linking agent, and an electrode active material, the binder and the cross-linking are contained in a specific ratio. The electrode mixture for a non-aqueous electrolyte secondary battery can be used to produce an electrode having a low resistance value, and the present invention has been further improved and improved.

本發明包含譬如下項載述之主題。
項1.
一種非水電解質二次電池用電極合劑，含有電極活性物質、交聯劑與黏結劑；
其中，前述黏結劑含有乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物；
前述交聯劑為金屬螯合錯合物；
並且，相對於前述黏結劑及前述交聯劑之合計量100質量份，含有0.2質量份以上且低於10質量份之前述交聯劑。
項2.
如項1記載之非水電解質二次電池用電極合劑，其中金屬螯合錯合物係選自於由鈦螯合錯合物及鋯螯合錯合物所構成群組中之至少1種。
項3.
如項1或2記載之非水電解質二次電池用電極合劑，其中前述交聯劑係具有2個以上可與羧基及/或羥基反應之官能基的交聯劑。
項4.
如項1或2記載之非水電解質二次電池用電極合劑，其中前述交聯劑係具有2個以上相同或不同之官能基的交聯劑，且前述官能基係選自於由烷氧基及醯化基所構成之群組。
項5.
如項1至4中任一項記載之非水電解質二次電池用電極合劑，其中前述乙烯性不飽和羧酸鹼金屬中和物為丙烯酸鹼金屬中和物及/或甲基丙烯酸鹼金屬中和物。
項6.
一種非水電解質二次電池用電極，使用有如項1~5中任一項記載之非水電解質二次電池用電極合劑。
項7.
一種非水電解質二次電池，具備如項6記載之非水電解質二次電池用電極。
項8.
一種電性機器，具備如項7記載之非水電解質二次電池。
項9.
一種非水電解質二次電池用電極合劑之製造方法，其包含將電極活性物質、交聯劑及黏結劑混合之步驟；
在此，前述交聯劑為金屬螯合錯合物，前述黏結劑為乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物，並且前述交聯劑係以相對於前述黏結劑及前述交聯劑之合計量100質量份為0.2質量份以上且低於10質量份的方式進行混合。The invention includes subject matter such as those set forth below.
Item 1.
An electrode mixture for a non-aqueous electrolyte secondary battery, comprising an electrode active material, a cross-linking agent, and a binder;
Wherein, the aforementioned binder contains a copolymer of vinyl alcohol and an alkali metal neutralizer of ethylenically unsaturated carboxylic acid;
The aforementioned cross-linking agent is a metal chelate complex;
In addition, the crosslinking agent is contained in an amount of 0.2 parts by mass or more and less than 10 parts by mass based on 100 parts by mass of the total amount of the binder and the crosslinking agent.
Item 2.
The electrode mixture for a non-aqueous electrolyte secondary battery according to item 1, wherein the metal chelate complex is at least one selected from the group consisting of a titanium chelate complex and a zirconium chelate complex.
Item 3.
The electrode mixture for a non-aqueous electrolyte secondary battery according to item 1 or 2, wherein the crosslinking agent is a crosslinking agent having two or more functional groups capable of reacting with a carboxyl group and / or a hydroxyl group.
Item 4.
The electrode mixture for a non-aqueous electrolyte secondary battery according to item 1 or 2, wherein the crosslinking agent is a crosslinking agent having two or more functional groups that are the same or different, and the functional group is selected from the group consisting of alkoxy groups. And the group formed by the base.
Item 5.
The electrode mixture for a non-aqueous electrolyte secondary battery according to any one of items 1 to 4, wherein the ethylenically unsaturated carboxylic acid alkali metal neutralizer is an acrylic acid alkali metal neutralizer and / or an methacrylic acid alkali metal neutralizer. And things.
Item 6.
An electrode for a non-aqueous electrolyte secondary battery using the electrode mixture for a non-aqueous electrolyte secondary battery according to any one of items 1 to 5.
Item 7.
A non-aqueous electrolyte secondary battery including the electrode for a non-aqueous electrolyte secondary battery according to item 6.
Item 8.
An electric device including the non-aqueous electrolyte secondary battery according to item 7.
Item 9.
A method for manufacturing an electrode mixture for a non-aqueous electrolyte secondary battery, comprising the steps of mixing an electrode active material, a cross-linking agent, and a binder;
Here, the aforementioned cross-linking agent is a metal chelate complex, the aforementioned bonding agent is a copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer, and the aforementioned cross-linking agent is relative to the aforementioned bonding agent and The total amount of the cross-linking agent is 0.2 parts by mass or more and less than 10 parts by mass.

發明效果
使用有本發明之非水電解質二次電池用電極合劑的電極循環性高，循環後的電阻值較低。亦即，藉由於電極使用本發明之黏結劑，可防止電池充放電時電極損壞，使循環特性變佳(即壽命變長)，因此充放電後電阻變低(即，提升速率特性而做到高輸出)。ADVANTAGE OF THE INVENTION The electrode using the electrode mixture for nonaqueous electrolyte secondary batteries of this invention has high cycleability, and the resistance value after cycling is low. That is, by using the adhesive of the present invention for the electrode, the electrode can be prevented from being damaged during charge and discharge of the battery, and the cycle characteristics are improved (that is, the life is longer), so the resistance after charge and discharge is lowered (that is, the rate characteristic is improved to achieve High output).

用以實施發明之形態
以下進一步詳細說明本發明之各實施形態。Embodiments for Carrying Out the Invention Each embodiment of the present invention will be described in further detail below.

本發明中包含之非水電解質二次電池用電極合劑含有電極活性物質(正極或負極用活性物質)、交聯劑與黏結劑，前述黏結劑含有乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物，前述交聯劑為金屬螯合錯合物。又，前述黏結劑與前述交聯劑係以特定比率(相對於前述黏結劑100質量份，前述交聯劑為0.2質量份以上且低於10質量份)含有。該合劑為含有前述各成分之組成物(合劑組成物)。又，該合劑宜為漿料之形態。The electrode mixture for a non-aqueous electrolyte secondary battery included in the present invention contains an electrode active material (active material for a positive electrode or a negative electrode), a cross-linking agent, and a binder, and the binder contains vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal. The copolymer of the compound, and the cross-linking agent is a metal chelate complex. The binder and the cross-linking agent are contained at a specific ratio (the mass of the cross-linking agent is 0.2 part by mass or more and less than 10 parts by mass relative to 100 parts by mass of the binder). This mixture is a composition (mixture composition) containing each of the aforementioned components. The mixture is preferably in the form of a slurry.

另，該電極合劑中除了電極活性物質、交聯劑及黏結劑以外，亦可含有例如液體介質(宜為水)。並且可進一步含有導電助劑、分散助劑等。The electrode mixture may contain, for example, a liquid medium (preferably water) in addition to an electrode active material, a cross-linking agent, and a binder. Further, it may further contain a conductive auxiliary agent, a dispersing auxiliary agent, and the like.

(黏結劑)
本發明中所用黏結劑含有乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物。該共聚物譬如可在含鹼金屬之鹼存在下，使令乙烯酯與乙烯性不飽和羧酸酯共聚而製得之共聚物，在水性有機溶劑與水之混合溶劑中皂化而製得。即，乙烯醇本身不穩定，故而無法直接作為單體使用，但藉由將使用乙烯酯作為單體而製得之聚合物進行皂化，則所生成之聚合物最後會成為以乙烯醇為單體聚合而成的態樣。(Binder)
The binder used in the present invention contains a copolymer of vinyl alcohol and an alkali metal neutralizer of ethylenically unsaturated carboxylic acid. For example, the copolymer can be obtained by copolymerizing a vinyl ester and an ethylenically unsaturated carboxylic acid ester in the presence of an alkali metal-containing base, and saponifying the copolymer in a mixed solvent of an aqueous organic solvent and water. That is, vinyl alcohol itself is unstable and cannot be used directly as a monomer. However, by saponifying a polymer prepared using vinyl ester as a monomer, the resulting polymer will eventually use vinyl alcohol as a monomer. Aggregated appearance.

前述乙烯酯可舉如乙酸乙烯酯、丙酸乙烯酯、三甲基乙酸乙烯酯等，因皂化反應容易進行，故以乙酸乙烯酯為宜。該等乙烯酯可單獨使用1種，亦可將2種以上組合使用。Examples of the vinyl ester include vinyl acetate, vinyl propionate, and trimethyl vinyl acetate. Since the saponification reaction easily proceeds, vinyl acetate is preferred. These vinyl esters may be used individually by 1 type, and may be used in combination of 2 or more type.

前述乙烯性不飽和羧酸酯可舉如丙烯酸或甲基丙烯酸之甲酯、乙酯、正丙酯、異丙酯、正丁酯及三級丁酯等，因皂化反應容易進行，故以丙烯酸甲酯及甲基丙烯酸甲酯為宜。該等乙烯性不飽和羧酸酯可單獨使用1種，亦可將2種以上組合使用。Examples of the aforementioned ethylenically unsaturated carboxylic acid esters include methyl, ethyl, n-propyl, isopropyl, n-butyl, and tertiary butyl esters of acrylic acid or methacrylic acid. Since the saponification reaction easily proceeds, acrylic acid is used. Methyl esters and methyl methacrylate are preferred. These ethylenically unsaturated carboxylic acid esters may be used individually by 1 type, and may be used in combination of 2 or more type.

另，亦可視需求將可與乙烯酯及乙烯性不飽和羧酸酯共聚之其他乙烯性不飽和單體加入乙烯酯及乙烯性不飽和羧酸酯中使用，使該等共聚。以如此方法製得之共聚物皂化而得的以乙烯醇為單體聚合而成之態樣的共聚物，亦可在本發明中作為黏結劑使用。In addition, other ethylenically unsaturated monomers that can be copolymerized with vinyl esters and ethylenically unsaturated carboxylic acid esters may be added to the vinyl esters and ethylenically unsaturated carboxylic acid esters for use in copolymerization, as required. The copolymer obtained by saponifying the copolymer prepared in this way and using vinyl alcohol as a monomer may also be used as a binder in the present invention.

此外，使乙烯酯及乙烯性不飽和羧酸酯(以及視需求之前述其他乙烯性不飽和單體)共聚時，亦可組合交聯劑來進行共聚。以此方式製得之共聚物進行皂化而得的共聚物，在本發明中同樣包含在乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物之內，適合當作黏結劑使用。亦即，乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物可為未交聯樹脂，亦可為交聯型樹脂。In addition, when copolymerizing a vinyl ester and an ethylenically unsaturated carboxylic acid ester (and other aforementioned ethylenically unsaturated monomers as required), a cross-linking agent may be combined to perform copolymerization. The copolymer obtained by saponification of the copolymer prepared in this way is also included in the copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer in the present invention, and is suitable for use as a binder. That is, the copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer may be an uncrosslinked resin or a crosslinked resin.

另，可用來調製以此方式製得之交聯型樹脂的交聯劑，在本說明書中係表記為「樹脂內交聯單體」以與本發明之非水電解質二次電池用電極合劑所含「交聯劑」做概念上之區分。即，本發明之非水電解質二次電池用電極合劑含有電極活性物質、「交聯劑」與黏結劑時，該黏結劑亦可含有交聯型樹脂，而調製該交聯型樹脂時則可使用「樹脂內交聯單體」。惟，以上僅為概念上之區別，無礙作為該「交聯劑」使用的物質和作為該「樹脂內交聯單體」使用的物質為相同物質。In addition, a cross-linking agent that can be used to prepare the cross-linked resin prepared in this way is referred to as "in-resin cross-linking monomer" in the present specification to be used with the electrode mixture for a non-aqueous electrolyte secondary battery Contains "crosslinking agent" to make a conceptual distinction. That is, when the electrode mixture for a non-aqueous electrolyte secondary battery of the present invention contains an electrode active material, a "crosslinking agent" and a binder, the binder may also contain a crosslinked resin, and when the crosslinked resin is prepared, Use "in-resin cross-linking monomer". However, the above are only conceptual differences, and the substances used as the "crosslinking agent" and the substances used as the "crosslinking monomer in the resin" are not the same.

樹脂內交聯單體可舉如具有2個或2個以上可共聚之反應性官能基者。該反應性官能基係可和乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物的原料單體共聚的反應性官能基。2個或2個以上之反應性官能基的各官能基係分別被***(鍵結至)其他共聚物之骨架中而進行交聯。可共聚之反應性官能基，理想上宜舉乙烯基。樹脂內交聯單體理想上宜舉具有2個乙烯基之單體。更具體而言，該樹脂內交聯單體理想上宜舉如二乙烯苯。又例如，理想上宜舉2官能性丙烯酸酯、2官能性甲基丙烯酸酯等(例如2-羥基-3-丙烯醯氧基丙基甲基丙烯酸酯、聚乙二醇二丙烯酸酯等)。此外，具有2個或2個以上乙烯碸基之交聯劑亦可作為樹脂內交聯單體使用，譬如宜舉以CH2 =CH-SO2 -CH2 -CO-NH-(CH2 )n -NH-CO-CH2 -SO2 -CH=CH2 (在此，n表示1~6之自然數且以2或3尤佳)表示之化合物。這類化合物之市售物可舉如FUJIFILM Co.製造之VS-B、VS-C。The resin cross-linking monomer may be, for example, one having two or more copolymerizable reactive functional groups. This reactive functional group is a reactive functional group copolymerizable with a raw material monomer of a copolymer of vinyl alcohol and an alkali metal neutralizer of an ethylenically unsaturated carboxylic acid. Each functional group of two or more reactive functional groups is respectively inserted (bonded to) the backbone of another copolymer to perform cross-linking. The copolymerizable reactive functional group is preferably a vinyl group. The resin cross-linking monomer is preferably a monomer having two vinyl groups. More specifically, the resin cross-linking monomer is desirably divinylbenzene. As another example, a bifunctional acrylate, a bifunctional methacrylate, etc. (for example, 2-hydroxy-3-propenyloxypropyl methacrylate, polyethylene glycol diacrylate, etc.) are preferable. In addition, a cross-linking agent having two or more vinyl fluorenyl groups can also be used as a cross-linking monomer in the resin. For example, CH 2 = CH-SO 2 -CH 2 -CO-NH- (CH 2 ) n -NH-CO-CH 2 -SO 2 -CH = CH 2 (herein, n represents a natural number of 1 to 6 and particularly preferably 2 or 3). Commercially available products of such compounds include VS-B and VS-C manufactured by FUJIFILM Co.

如同上述，本發明中包含之非水電解質二次電池用電極合劑含有電極活性物質、交聯劑與黏結劑。在此，該非水電解質二次電池用電極合劑和含有前述交聯型樹脂之黏結劑及含有電極活性物質之電極合劑為不同之物，有所區別。亦即，前述交聯型樹脂中所含源自「樹脂內交聯單體」的部分並非「交聯劑」。因為，樹脂內交聯單體在調製交聯型樹脂時早已被用於交聯而不具交聯能力(換言之，樹脂內交聯單體既已構成有交聯型樹脂之交聯部分)。As described above, the electrode mixture for a non-aqueous electrolyte secondary battery included in the present invention contains an electrode active material, a cross-linking agent, and a binder. Here, the electrode mixture for a non-aqueous electrolyte secondary battery is different from the binder containing the aforementioned crosslinked resin and the electrode mixture containing an electrode active material. That is, the portion derived from the "cross-linking monomer in the resin" contained in the aforementioned cross-linked resin is not a "cross-linking agent". Because the cross-linking monomer in the resin has already been used for cross-linking without cross-linking ability when preparing the cross-linking resin (in other words, the cross-linking monomer in the resin has already formed the cross-linking part of the cross-linking resin).

另，將本發明中包含之非水電解質二次電池用電極合劑進行熱處理並以交聯劑進行交聯後的組成物(譬如，具備將該合劑塗佈於金屬版或金屬箔上且進行熱處理所調製之非水電解質二次電池用電極的電極組成物)，和含有含前述交聯型樹脂之黏結劑與電極活性物質的電極合劑一樣是不同之物，兩者有所區別。因為在該組成物中，交聯劑不僅將黏結劑中所含共聚物彼此交聯，更可將黏結劑中所含共聚物與電極活性物質交聯，還可將電極活性物質彼此交聯。此外，將本發明中包含之非水電解質二次電池用電極合劑塗佈至金屬板或金屬箔後予以熱處理而獲得該組成物時(譬如，為電極組成物時)，交聯劑亦能使該金屬板或金屬箔與黏結劑中所含共聚物或電極活性物質結合。在含有含前述交聯型樹脂之黏結劑與電極活性物質的電極合劑中，交聯型樹脂內雖存在源自樹脂內交聯單體之交聯部分，但交聯型樹脂和電極活性物質並未交聯。In addition, a composition obtained by subjecting the electrode mixture for a non-aqueous electrolyte secondary battery included in the present invention to a heat treatment and cross-linking with a cross-linking agent (for example, comprising applying the mixture to a metal plate or metal foil and heat-treating the composition) The electrode composition of the prepared non-aqueous electrolyte secondary battery electrode) is different from the electrode mixture containing the binder containing the aforementioned crosslinked resin and the electrode active material, and the two are different. Because in this composition, the cross-linking agent not only cross-links the copolymer contained in the binder with each other, but also cross-links the copolymer contained in the binder with the electrode active material, and also cross-links the electrode active material with each other. In addition, when the electrode mixture for a non-aqueous electrolyte secondary battery included in the present invention is applied to a metal plate or metal foil and then heat-treated to obtain the composition (for example, when it is an electrode composition), the cross-linking agent can also be used. The metal plate or metal foil is combined with a copolymer or an electrode active material contained in a binder. In an electrode mixture containing a binder containing the aforementioned crosslinked resin and an electrode active material, although a crosslinked portion derived from a crosslinked monomer in the resin exists in the crosslinked resin, the crosslinked resin and the electrode active material are combined. Not cross-linked.

於圖1針對本發明中包含之非水電解質二次電池用電極合劑一態樣，顯示其概要。又，於圖2顯示將該電極合劑塗敷於金屬箔後，使其乾燥、加壓、加熱而調製出電極時之一態樣概要。另，僅含有含交聯型樹脂之黏結劑及電極活性物質的電極合劑，雖然和本發明之非水電解質二次電池用電極合劑不同，但於其中進一步添加交聯劑時，可成為本發明之非水電解質二次電池用電極合劑，於圖3將顯示其概要。FIG. 1 shows an outline of an electrode mixture for a non-aqueous electrolyte secondary battery included in the present invention. In addition, FIG. 2 shows an outline of an aspect when the electrode mixture is applied to a metal foil, and then dried, pressed, and heated to prepare an electrode. In addition, an electrode mixture containing only a binder containing a cross-linking resin and an electrode active material is different from the electrode mixture for a non-aqueous electrolyte secondary battery of the present invention, but when a cross-linking agent is further added thereto, the present invention can be obtained An electrode mixture for a non-aqueous electrolyte secondary battery will be summarized in FIG. 3.

作為本實施形態之皂化反應一例，於以下顯示乙酸乙烯酯/丙烯酸甲酯共聚物藉由氫氧化鉀(KOH)而被100%皂化時的皂化反應。As an example of the saponification reaction of this embodiment, a saponification reaction when the vinyl acetate / methyl acrylate copolymer is 100% saponified with potassium hydroxide (KOH) is shown below.

[化學式1]
[Chemical Formula 1]

另，如以上所示，本實施形態之乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物，係將乙烯酯與乙烯性不飽和羧酸酯無規共聚而使源自單體之酯部分皂化的物質，單體彼此之鍵結為C-C共價鍵。(以下，有時會表記為乙烯酯/乙烯性不飽和羧酸酯共聚物皂化物；又，如從前述說明可知，此處的符號「/」表示無規共聚)。In addition, as described above, the copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer in this embodiment is obtained by random copolymerization of a vinyl ester and an ethylenically unsaturated carboxylic acid ester to obtain a monomer. The ester part is saponified, and the monomers are bonded to each other by a CC covalent bond. (Hereinafter, it may be expressed as a saponified product of a vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer; as can be understood from the foregoing description, the symbol "/" herein indicates random copolymerization).

在本實施形態之共聚物中，乙烯酯與乙烯性不飽和羧酸酯之莫耳比(乙烯醇/乙烯性不飽和羧酸鹼金屬中和物)宜為95/5~5/95，且95/5~50/50較佳，90/10~60/40更佳。若在95/5~5/95之範圍內，皂化後所得聚合物特別能適當提升作為黏結劑的保持力。In the copolymer of this embodiment, the molar ratio of vinyl ester to ethylenically unsaturated carboxylic acid ester (vinyl alcohol / ethylenically unsaturated carboxylic acid alkali metal neutralized product) is preferably 95/5 to 5/95, and 95/5 ~ 50/50 is better, 90/10 ~ 60/40 is better. If it is in the range of 95/5 to 5/95, the polymer obtained after saponification can particularly appropriately improve the holding power as a binder.

因此，在製得之乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之前述共聚物中，共聚組成比以莫耳比計宜為95/5~5/95，且95/5~50/50較佳，90/10~60/40更佳。Therefore, in the aforementioned copolymer of the obtained vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer, the copolymerization composition ratio is preferably 95/5 to 5/95 in terms of molar ratio, and 95/5 to 50 / 50 is better, 90/10 ~ 60/40 is better.

就乙烯性不飽和羧酸鹼金屬中和物而言，宜為選自於由丙烯酸鹼金屬中和物及甲基丙烯酸鹼金屬中和物所構成群組中之至少1種。又，乙烯性不飽和羧酸鹼金屬中和物之鹼金屬，可舉鋰、鈉、鉀、銣、銫等，且以鉀及鈉為宜。尤其適當之乙烯性不飽和羧酸鹼金屬中和物，係選自於由丙烯酸鈉中和物、丙烯酸鉀中和物、甲基丙烯酸鈉中和物及甲基丙烯酸鉀中和物所構成群組中之至少1種。The ethylenically unsaturated carboxylic acid alkali metal neutralizer is preferably at least one selected from the group consisting of an acrylic acid alkali metal neutralizer and an alkali metal methacrylate neutralizer. Examples of the alkali metal of the ethylenically unsaturated carboxylic acid alkali metal neutralizer include lithium, sodium, potassium, rubidium, and cesium, and potassium and sodium are preferred. Particularly suitable alkali metal neutralizers of ethylenically unsaturated carboxylic acids are selected from the group consisting of sodium acrylate neutralizers, potassium acrylate neutralizers, sodium methacrylate neutralizers, and potassium methacrylate neutralizers. At least one of the group.

乙烯酯/乙烯性不飽和羧酸酯共聚物為乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物的前驅物，若從能以粉末狀製得共聚物的觀點來看，宜以懸浮聚合法來製得；換言之，宜在以乙烯酯及乙烯性不飽和羧酸酯為主體之單體已懸浮在含聚合觸媒之分散劑水溶液中的狀態下進行聚合，來做成聚合物粒子。The vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer is a precursor of a copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralized substance. It is preferable from the viewpoint that the copolymer can be obtained in powder form. It is prepared by suspension polymerization; in other words, it is suitable to polymerize in a state where monomers mainly composed of vinyl esters and ethylenically unsaturated carboxylic acid esters have been suspended in a dispersant aqueous solution containing a polymerization catalyst.物 粒。 Object particles.

前述聚合觸媒可舉如過氧化苯甲醯基、過氧化月桂基等有機過氧化物，偶氮雙異丁腈、偶氮雙二甲基戊腈等偶氮化合物，且以過氧化月桂基尤佳。Examples of the aforementioned polymerization catalyst include organic peroxides such as benzamyl peroxide and lauryl peroxide; azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile; and lauryl peroxide. It's better.

聚合觸媒之添加量相對於單體之總質量宜為0.01~5質量%，且0.05~3質量%較佳，0.1~3質量%更佳。若少於0.01質量%，會有聚合反應未完成之情況；若超過5質量%，則最後製得的乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物的黏結效果可能會不足。The addition amount of the polymerization catalyst with respect to the total mass of the monomer should preferably be 0.01 to 5 mass%, more preferably 0.05 to 3 mass%, and more preferably 0.1 to 3 mass%. If it is less than 0.01% by mass, the polymerization reaction may not be completed. If it exceeds 5% by mass, the adhesion effect of the copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralized product may be insufficient. .

進行聚合時，前述分散劑按使用之單體種類、用量等來選擇適當物質即可，具體上可舉聚乙烯醇(部分皂化聚乙烯醇、完全皂化聚乙烯醇)、聚(甲基)丙烯酸及其鹽、聚乙烯吡咯啶酮、甲基纖維素、羧甲基纖維素、羥乙基纖維素、羥丙基纖維素等水溶性高分子；磷酸鈣、矽酸鎂等水不溶性無機化合物等。該等分散劑可單獨使用，亦可將2種以上組合使用。During the polymerization, the dispersant may be appropriately selected according to the type and amount of monomers used, and specifically, polyvinyl alcohol (partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol), and poly (meth) acrylic acid may be used. And its salts, polyvinyl pyrrolidone, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and other water-soluble polymers; water-insoluble inorganic compounds such as calcium phosphate and magnesium silicate, etc. . These dispersants may be used alone or in combination of two or more.

分散劑的使用量亦隨使用單體之種類等而定，惟相對於單體之總質量，宜為0.01~10質量%，且0.05~5質量%較佳。The amount of dispersant used also depends on the type of monomer used, but it is preferably 0.01 to 10% by mass, and preferably 0.05 to 5% by mass, relative to the total mass of the monomer.

此外，亦可添加鹼金屬、鹼土類金屬等水溶性鹽，以調整前述分散劑之界面活性效果等。可舉如氯化鈉、氯化鉀、氯化鈣、氯化鋰、無水硫酸鈉、硫酸鉀、磷酸氫二鈉、磷酸氫二鉀、磷酸三鈉及磷酸三鉀等，該等水溶性鹽可單獨使用1種，亦可將2種以上組合使用。In addition, water-soluble salts such as alkali metals and alkaline earth metals may be added to adjust the interfacial activity effect of the dispersant. Examples include sodium chloride, potassium chloride, calcium chloride, lithium chloride, anhydrous sodium sulfate, potassium sulfate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, trisodium phosphate and tripotassium phosphate, etc. One type may be used alone, or two or more types may be used in combination.

水溶性鹽之使用量依使用之分散劑的種類、用量等而定，惟相對於分散劑水溶液之質量，通常為0.01~10質量%。The amount of the water-soluble salt used depends on the type and amount of the dispersant used, but it is usually 0.01 to 10% by mass relative to the mass of the dispersant aqueous solution.

使單體聚合之溫度相對於聚合觸媒之10小時半衰期溫度宜為-20~20℃，且-10~10℃較佳。舉例而言，過氧化月桂基之10小時半衰期溫度約62℃。The temperature for polymerizing the monomer relative to the 10-hour half-life temperature of the polymerization catalyst should preferably be -20 to 20 ° C, and more preferably -10 to 10 ° C. For example, the 10-hour half-life temperature of lauryl peroxide is about 62 ° C.

相對於10小時半衰期溫度若低於-20℃，會有聚合反應未完成之情況；若超過20℃，則製得之乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物的黏結效果可能會不足。If the half-life temperature is lower than -20 ° C with respect to 10 hours, the polymerization may not be completed. If it exceeds 20 ° C, the copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralized product will stick together. The effect may be insufficient.

使單體聚合之時間依使用之聚合觸媒的種類、用量、聚合溫度等而定，不過通常為數小時~數十個鐘頭。The time for polymerizing the monomer depends on the type, amount, and polymerization temperature of the polymerization catalyst used, but it is usually several hours to dozens of hours.

聚合反應結束後，利用離心分離、過濾等方法使共聚物分離，製得呈含水餅狀之共聚物。所得含水餅狀之共聚物可直接利用或視需求進行乾燥後再用於皂化反應。After the polymerization reaction is completed, the copolymer is separated by a method such as centrifugal separation, filtration, and the like to obtain a copolymer in the form of a water cake. The obtained water-containing cake-like copolymer can be directly used or dried as required before being used in the saponification reaction.

本說明書中之聚合物的數量平均分子量係以具備使用DMF作為溶劑之GFC管柱(譬如Shodex公司製造之OHpak)的分子量測定裝置所求得之值。所述分子量測定裝置，可舉如Nihon Waters K.K.製造之2695、RI偵測器2414。The number average molecular weight of the polymer in the present specification is a value obtained by a molecular weight measuring device including a GFC column (for example, OHpak manufactured by Shodex Corporation) using DMF as a solvent. Examples of the molecular weight measuring device include 2695 and RI detector 2414 manufactured by Nihon Waters K.K.

皂化前之共聚物的數量平均分子量宜為10,000~1,000,000，且50,000~800,000較佳。藉由將皂化前之數量平均分子量設定在10,000~1,000,000之範圍內，作為黏結劑之黏結力有進一步提升之趨勢。因此，即使電極用合劑(尤其是負極合劑)為水系漿料，仍可輕易將漿料塗厚。The number average molecular weight of the copolymer before saponification is preferably 10,000 to 1,000,000, and more preferably 50,000 to 800,000. By setting the number-average molecular weight before saponification in the range of 10,000 to 1,000,000, the adhesive force as a binder has a tendency to further increase. Therefore, even if the electrode mixture (especially the negative electrode mixture) is an aqueous slurry, the slurry can be easily thickened.

皂化反應譬如可在含鹼金屬之鹼存在下，於只有水性有機溶劑或水性有機溶劑與水之混合溶劑中實施。用於前述皂化反應之含鹼金屬之鹼可使用既有公知物，惟以鹼金屬氫氧化物為宜；若從反應性高的觀點則以氫氧化鈉及氫氧化鉀尤佳。The saponification reaction can be carried out, for example, in the presence of an alkali containing an alkali metal in an aqueous organic solvent or a mixed solvent of an aqueous organic solvent and water. As the alkali metal-containing base used in the aforementioned saponification reaction, a conventionally known substance may be used, but an alkali metal hydroxide is preferred; from the viewpoint of high reactivity, sodium hydroxide and potassium hydroxide are particularly preferred.

前述鹼之用量相對於單體之莫耳數宜為60~140莫耳%，且80~120莫耳%較佳。在少於60莫耳%之鹼量，皂化可能會不足，而即使用超過140莫耳%也無法取得更多的效果，不符經濟效應。The amount of the aforementioned base relative to the mole number of the monomer is preferably 60 to 140 mole%, and more preferably 80 to 120 mole%. At an alkali level of less than 60 mol%, saponification may be insufficient, and even using more than 140 mol% will not achieve more results, which is not consistent with economic effects.

前述皂化反應宜僅用水性有機溶劑，或使用水性有機溶劑與水之混合溶劑。該水性有機溶劑可舉甲醇、乙醇、正丙醇、異丙醇、正丁醇、三級丁醇等低級醇類；丙酮、甲基乙基酮等酮類；及該等之混合物等，其中又以低級醇類為宜；若從可製得具優異黏結效果以及對機械剪切具優異耐性之乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物的觀點來看，則以甲醇及乙醇尤佳。The aforementioned saponification reaction is preferably an aqueous organic solvent or a mixed solvent of an aqueous organic solvent and water. Examples of the aqueous organic solvent include lower alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tertiary butanol; ketones such as acetone and methyl ethyl ketone; and mixtures thereof, etc., among which It is also preferable to use lower alcohols; if a copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer having excellent adhesion effect and excellent resistance to mechanical shear can be obtained, it is based on Methanol and ethanol are particularly preferred.

前述水性有機溶劑與水之混合溶劑中的水性有機溶劑/水之質量比宜為30/70~85/15，且40/60~85/15較佳，40/60~80/20更佳。落在30/70~85/15之範圍以外時，皂化前之共聚物的溶劑親和性或皂化後之共聚物的溶劑親和性恐不足而無法使皂化反應充分進行。水性有機溶劑少於30/70之比率時，不僅作為黏結劑之黏結力會下降，皂化反應時還會明顯增黏而難以於工業上製得乙烯酯/乙烯性不飽和羧酸酯共聚物皂化物；水性有機溶劑超出85/15之比率時，則製得之乙烯酯/乙烯性不飽和羧酸酯共聚物皂化物的水溶性會降低，一旦用於電極，可能會發生乾燥後之黏結力受損的情形。另，將含水餅狀之共聚物直接用於皂化反應時，前述水性有機溶劑/水之質量比亦包含含水餅狀之共聚物中之水。The mass ratio of the aqueous organic solvent / water in the aforementioned mixed solvent of aqueous organic solvent and water is preferably 30/70 ~ 85/15, more preferably 40/60 ~ 85/15, and more preferably 40/60 ~ 80/20. When it falls outside the range of 30/70 to 85/15, the solvent affinity of the copolymer before saponification or the solvent affinity of the copolymer after saponification may be insufficient, and the saponification reaction may not proceed sufficiently. When the ratio of the water-based organic solvent is less than 30/70, not only the adhesive force of the binder will decrease, but also the viscosity will increase significantly during the saponification reaction. ; When the water-based organic solvent exceeds the ratio of 85/15, the water solubility of the saponified vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer prepared will decrease. Once used in the electrode, the adhesion force after drying may occur. Damage. In addition, when the water-containing cake-like copolymer is directly used in the saponification reaction, the aforementioned mass ratio of the aqueous organic solvent / water also includes water in the water-containing cake-like copolymer.

能使乙烯酯/乙烯性不飽和羧酸酯共聚物皂化之溫度依單體之莫耳比而定，惟譬如以20~60℃為宜，且20~50℃較佳。在低於20℃之溫度下進行皂化時，有皂化反應未完成之虞；超過60℃之溫度則有反應系統內增黏而無法攪拌之情形。The temperature at which the vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer can be saponified depends on the molar ratio of the monomer, but for example, it is preferably 20 to 60 ° C, and more preferably 20 to 50 ° C. When saponification is performed at a temperature lower than 20 ° C, there is a possibility that the saponification reaction is not completed; when the temperature exceeds 60 ° C, the reaction system may increase viscosity and cannot be stirred.

皂化反應時間依使用之鹼的種類、用量等而有所不同，但反應通常會在數小時左右結束。The saponification reaction time varies depending on the type and amount of alkali used, but the reaction usually ends in a few hours.

在皂化反應結束之時間點，通常會形成糊狀或漿料狀之共聚物皂化物的分散體。利用離心分離、過濾等既有的公知方法進行固液分離後，以甲醇等低級醇等仔細洗淨而製得含液共聚物皂化物，再將其乾燥，可製得作為球狀單一粒子或球狀粒子凝集而成之凝集粒子的共聚物皂化物，亦即乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物。At the end of the saponification reaction, a dispersion of a saponified copolymer in the form of a paste or slurry is usually formed. After the solid-liquid separation is performed by a known method such as centrifugation and filtration, a liquid-containing copolymer saponified product is carefully washed with a lower alcohol such as methanol, and then dried to obtain a spherical single particle or Copolymer saponified of aggregated particles formed by agglomeration of spherical particles, that is, a copolymer of vinyl alcohol and an alkali metal neutralizer of ethylenically unsaturated carboxylic acid.

亦可在前述皂化反應以後，使用鹽酸、硫酸、磷酸、硝酸等無機酸；甲酸、乙酸、草酸、檸檬酸等有機酸等酸類，對共聚物皂化物進行酸處理，然後使用氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化銣、氫氧化銫、氫氧化鍅等任意鹼金屬，製得異種(即不同鹼金屬)的乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物。After the aforementioned saponification reaction, the copolymer saponification may be acid-treated with an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid; an organic acid such as formic acid, acetic acid, oxalic acid, or citric acid; and then lithium hydroxide or hydrogen Copolymers of vinyl alcohol and ethylenically unsaturated carboxylic acid alkali metal neutralizers made of any alkali metal such as sodium oxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, rubidium hydroxide, etc. .

將含液共聚物皂化物乾燥之條件並無特別限定，通常宜在常壓或減壓下，以30~120℃之溫度進行乾燥。The conditions for drying the saponified liquid-containing copolymer are not particularly limited, and it is generally suitable to dry at a temperature of 30 to 120 ° C under normal pressure or reduced pressure.

乾燥時間亦依乾燥時之壓力、溫度而定，不過通常為數小時~數十個鐘頭。The drying time also depends on the pressure and temperature during drying, but usually it is several hours to dozens of hours.

乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物的體積平均粒徑宜為1~200μm，且10~100μm較佳。1μm以上可以獲得較佳的黏結效果；200μm以下則可使水系增黏液較為均勻而獲得理想的黏結效果。另，共聚物之體積平均粒徑係於雷射繞射式粒度分布測定裝置(譬如島津製作所公司製造之SALD-7100)設置批次槽(batch cell；譬如同公司所製SALD-BC)，並使用2-丙醇或甲醇為分散溶劑所測定之值。The volume average particle diameter of the copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer is preferably 1 to 200 μm, and more preferably 10 to 100 μm. More than 1 μm can get better adhesion effect; below 200 μm can make the water-based thickening fluid more uniform and obtain the ideal adhesion effect. In addition, the volume average particle diameter of the copolymer is set in a laser diffraction particle size distribution measuring device (such as SALD-7100 manufactured by Shimadzu Corporation), and a batch cell (such as SALD-BC manufactured by the company) is provided, and The value measured using 2-propanol or methanol as a dispersion solvent.

將含液共聚物皂化物乾燥而製得之共聚物皂化物的體積平均粒徑超過100μm時，可藉由以機械式研磨處理等既有的公知粉碎方法進行粉碎，而將體積平均粒徑調整成譬如10~100μm。When the volume average particle diameter of the copolymer saponified product obtained by drying the liquid-containing copolymer saponified product exceeds 100 μm, the volume average particle diameter can be adjusted by pulverization by a conventionally known pulverization method such as mechanical grinding treatment. For example, 10 ~ 100μm.

機械式研磨處理係將撞擊、拉伸、摩擦、壓縮、剪切等外力施加在所得共聚物皂化物上之方法，所用裝置可舉滾磨機、振動磨機、行星式磨機、搖擺式磨機、臥式磨機、磨碎機、噴射磨機、研磨機、均質機、流化器、塗料搖動器(paint shaker)、混合器等等。舉例而言，行星式磨機係將共聚物皂化物和球珠一起放入容器內，使其自轉及公轉，並利用從而產生之力學能量將共聚物皂化物粉末予以粉碎或混合。已知，利用該方法可粉碎至奈米等級。Mechanical grinding treatment is a method of applying external forces such as impact, stretching, friction, compression, and shear to the obtained copolymer saponification. The equipment used can be a roller mill, a vibration mill, a planetary mill, or a swing mill. Machine, horizontal mill, attritor, jet mill, grinder, homogenizer, fluidizer, paint shaker, mixer, etc. For example, the planetary mill puts the copolymer saponified together with the balls into a container, makes it rotate and revolve, and uses the generated mechanical energy to pulverize or mix the copolymer saponified powder. It is known that this method can be pulverized to a nanometer grade.

乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物的黏結劑增黏效果，以含有1質量%之乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物的水溶液黏度為30mPa・s~10000mPa・s為佳，且40~5000mPa・s較佳。前述黏度只要為30mPa・s以上，所做出之漿料狀電極用合劑即可獲得適宜的黏度，塗敷於集電體時，合劑不會過度擴散而可輕易地進行塗敷，而且合劑中之活性物質及導電助劑的分散性亦佳。前述黏度若為10000mPa・s以下，所做出之合劑的黏度就不會過高，在集電體上輕薄又均勻的塗敷變得更為簡單。另，前述1質量%水溶液之黏度係以BROOKFIELD製造之旋轉黏度計(型式DV-I+)，在轉子No.5及50rpm(液溫25℃)下測得之值。Tackifying effect of the binder of a copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer, with an aqueous solution viscosity of 1% by mass of a copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer It is preferably 30 mPa · s to 10000 mPa · s, and more preferably 40 to 5000 mPa · s. As long as the aforementioned viscosity is 30 mPa · s or more, the prepared slurry-like electrode mixture can obtain an appropriate viscosity. When applied to a current collector, the mixture can be easily applied without excessive diffusion, and in the mixture. The dispersibility of active materials and conductive additives is also good. If the aforementioned viscosity is 10000 mPa · s or less, the viscosity of the mixture prepared will not be too high, and it becomes easier to apply a thin, uniform coating on the current collector. In addition, the viscosity of the aforementioned 1% by mass aqueous solution is a value measured at a rotor No. 5 and 50 rpm (liquid temperature 25 ° C.) using a rotary viscometer (type DV-I +) manufactured by BROOKFIELD.

乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物，可作為黏結力與黏結持續性優異的鋰離子二次電池電極用黏結劑發揮功能。關於其理由，吾等認為乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物可使集電體與活性物質及活性物質彼此牢固地黏結，不會有因反覆充放電所產生的活性物質體積變化使電極用合劑自集電體剝離或使活性物質脫落的情況，具有黏結持續性，故而不會使活性物質之容量下降；但不作限定性解釋。The copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer can function as a binder for lithium ion secondary battery electrodes with excellent adhesion and adhesion persistence. Regarding the reason, we believe that the copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer can make the current collector and the active material and the active material firmly adhere to each other without causing the repeated charge and discharge. Changes in the volume of the active material that cause the electrode mixture to peel off from the current collector or the active material to fall off have persistent adhesion, so the capacity of the active material does not decrease; however, it is not to be construed as a limitation.

本實施形態鋰離子二次電池電極用合劑(宜為電極漿料)中，可在不損及本發明效果之範圍內，於作為黏結劑之乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物中進一步添加其他水系黏結劑。此時，相對於乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物和其他水系黏結劑之合計質量，其他水系黏結劑之添加量宜少於80質量%。更宜少於70質量%。即換言之，黏結劑中之乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物的含有比率宜為20質量%以上且100質量%以下，且較宜為30質量%以上且100質量%以下。此外，該下限舉例來說可以在40質量%以上、50質量%以上、60質量%以上、70質量%以上、80質量%以上、90質量%以上或95質量%以上。The lithium ion secondary battery electrode mixture (preferably an electrode paste) of this embodiment can neutralize vinyl alcohol and ethylenically unsaturated carboxylic acid alkali metal as a binder within a range that does not impair the effect of the present invention. Other water-based binders are added to the copolymers of polymers. At this time, the addition amount of other water-based binders should be less than 80% by mass relative to the total mass of the copolymer of vinyl alcohol and the ethylenically unsaturated carboxylic acid alkali metal neutralizer and other water-based binders. More preferably, it is less than 70% by mass. In other words, the content ratio of the copolymer of vinyl alcohol and the alkali metal neutralizer of ethylenically unsaturated carboxylic acid in the binder is preferably 20% by mass or more and 100% by mass or less, and more preferably 30% by mass or more and 100% by mass %the following. The lower limit may be, for example, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more.

其他水系黏結劑之材料可舉如羧甲基纖維素(CMC)、聚丙烯酸、聚丙烯酸鈉、聚丙烯酸鹽等丙烯酸樹脂、褐藻酸鈉、聚醯亞胺(PI)、聚四氟乙烯(PTFE)、聚醯胺、聚醯胺醯亞胺、苯乙烯丁二烯橡膠(SBR)、聚乙烯醇(PVA)、乙烯乙酸共聚物(EVA)等材料。該等可單獨使用一種亦可將二種以上併用。其他水系黏結劑中，適合使用以聚丙烯酸鈉為代表之丙烯酸樹脂、褐藻酸鈉、聚醯亞胺等，且由宜使用丙烯酸樹脂。The materials of other water-based adhesives include acrylic resins such as carboxymethyl cellulose (CMC), polyacrylic acid, sodium polyacrylate, polyacrylate, sodium alginate, polyimide (PI), and polytetrafluoroethylene (PTFE). ), Polyamidoamine, polyamidoimide, styrene butadiene rubber (SBR), polyvinyl alcohol (PVA), ethylene acetate copolymer (EVA) and other materials. These may be used alone or in combination of two or more. Among other water-based adhesives, acrylic resins represented by sodium polyacrylate, sodium alginate, and polyimide are suitable, and acrylic resins are preferably used.

(交聯劑)
本發明使用之交聯劑係具有交聯能之金屬螯合錯合物。該金屬螯合錯合物可舉如鈦螯合錯合物、鋯螯合錯合物及鋁螯合錯合物等，其中又以鈦螯合錯合物及鋯螯合錯合物為宜，且鈦螯合錯合物較佳。(Crosslinking agent)
The cross-linking agent used in the present invention is a metal chelate complex having cross-linking energy. Examples of the metal chelate complex include titanium chelate complex, zirconium chelate complex, and aluminum chelate complex. Among them, titanium chelate complex and zirconium chelate complex are preferred. And titanium chelate complexes are preferred.

該交聯劑(金屬螯合錯合物)宜為具有2個以上(宜為2、3或4個且較宜為2個)可與羧基及/或羥基反應之官能基的交聯劑。而且交聯劑宜為水系交聯劑(水溶***聯劑)。可與羧基及/或羥基反應之官能基，係指能與羧基及/或羥基反應形成化學鍵之官能基。以烷氧基為例，即使自行起反應而脫離但就結果而言只要有形成鍵結，亦包含在內。觸媒之必要性或加熱之必要性並無特別限定。所述官能基之具體例，可適當列舉烷氧基及醯化基等。烷氧基可舉如碳數1~18(1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17或18)之直鏈或支鏈狀之烷氧基。醯化基可舉如乳酸酯基、硬脂酸酯基、異硬脂酸酯基等。The cross-linking agent (metal chelate complex) is preferably a cross-linking agent having two or more (preferably 2, 3 or 4 and more preferably 2) functional groups capable of reacting with a carboxyl group and / or a hydroxyl group. The crosslinking agent is preferably an aqueous crosslinking agent (water-soluble crosslinking agent). A functional group capable of reacting with a carboxyl group and / or a hydroxyl group means a functional group capable of reacting with a carboxyl group and / or a hydroxyl group to form a chemical bond. Taking an alkoxy group as an example, even if it reacts and detaches by itself, as long as a bond is formed, it is included. The necessity of the catalyst or the necessity of heating is not particularly limited. Specific examples of the functional group include an alkoxy group and a halogenated group as appropriate. Alkoxy can be as straight as 1 to 18 carbons (1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17 or 18) Chain or branched alkoxy. Examples of the halogenated group include a lactate group, a stearate group, and an isostearate group.

藉由該等官能基和乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物分子鏈的羧基及/或羥基反應，乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物可獲得交聯而提升機械強度。由於可與羧基及/或羥基反應之官能基是作為交聯劑起作用，因此在交聯劑分子中必須存在2個以上(宜為2、3或4個，且較宜為2個)。存在於交聯劑一分子內之該官能基可相同亦可互異。官能基數愈多，交聯點就會隨之增加，因此能提升機械強度，但太多時在電極塗敷液之狀態下會進展成凝膠化而可能難以進行塗敷，這時會相當不便。至於凝膠化的生成，除了乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物分子鏈中的羧基及/或羥基個數以外，也會受該共聚物與交聯劑之混合比影響，因此可藉由適當調整該等因素來避免凝膠化。By reacting these functional groups and vinyl alcohol with the carboxyl group and / or hydroxyl group of the molecular chain of the copolymer of the ethylenically unsaturated carboxylic acid alkali metal neutralizer, copolymerization of the vinyl alcohol and the ethylenically unsaturated carboxylic acid alkali metal neutralizer The material can be crosslinked to improve mechanical strength. Since the functional group capable of reacting with a carboxyl group and / or a hydroxyl group functions as a cross-linking agent, there must be more than two (preferably 2, 3 or 4 and more preferably 2) in the cross-linking agent molecule. The functional groups present in one molecule of the crosslinking agent may be the same or different from each other. As the number of functional groups increases, the cross-linking point will increase accordingly, which can improve the mechanical strength. However, when there are too many, it will progress to gelation in the state of the electrode coating solution and it may be difficult to apply, which will be quite inconvenient. As for the formation of gelation, in addition to the number of carboxyl groups and / or hydroxyl groups in the molecular chain of the copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer, it is also subject to the mixing of the copolymer and the crosslinking agent. Ratio, so gelation can be avoided by adjusting these factors appropriately.

具有烷氧基及/或醯化基之交聯劑(金屬螯合錯合物)可舉Matsumoto Fine Chemical Co. Ltd.製造之ORGATIX 系列等金屬螯合物。Examples of the cross-linking agent (metal chelate complex) having an alkoxy group and / or a halogenated group include metal chelate compounds such as the ORGATIX series manufactured by Matsumoto Fine Chemical Co. Ltd ..

鈦螯合錯合物具體上適合列舉如乳酸鈦銨鹽、乳酸鈦、三乙醇胺鈦、二乙醇胺鈦、胺基乙基胺基乙醇鈦、乙醯丙酮鈦、四乙醯丙酮鈦、乙基乙醯乙酸鈦、十二基苯磺酸鈦化合物、磷酸鈦化合物、辛二醇鈦、乙基乙醯乙酸鈦等，其中又以乳酸鈦銨鹽、乳酸鈦、三乙醇胺鈦、二乙醇胺鈦、胺基乙基胺基乙醇鈦較佳。更具體而言，可舉如(i-C3 H7 O)2 Ti(C6 H14 NO3 )2 、(HO)2 Ti[OCH(CH3 )COO- ]2 (NH4 + )2 、(HO)2 Ti[OCH(CH3 )COOH]2 、(i-C3 H7 O)Ti(OC2 H4 NHC2 H4 NH2 )3 、(i-C3 H7 O)2 Ti(C6 H7 O2 )2 、Ti(C5 H7 O2 )4 、(i-C3 H7 O)2 Ti(C6 H9 O3 )2 、Ti(O-i-C3 H7 )4 、(C8 H17 O)2 Ti(O2 C8 H17 )2 、(i-C3 H7 O)2 Ti(C6 H9 O3 )2 等。Specific examples of the titanium chelate complex include titanium ammonium lactate, titanium lactate, titanium triethanolamine, titanium diethanolamine, titanium aminoethylaminoethanol, titanium ethylacetone, titanium tetraethylacetone, ethylethyl钛 Titanium acetate, titanium dodecylbenzenesulfonate compound, titanium phosphate compound, titanium octyl glycol, titanium ethyl acetate, etc. Among them, titanium lactate ammonium salt, titanium lactate, titanium triethanolamine, titanium diethanolamine, amine Titanylethylaminoethoxide is preferred. More specifically, may be cited as (iC 3 H 7 O) 2 Ti (C 6 H 14 NO 3) 2, (HO) 2 Ti [OCH (CH 3) COO -] 2 (NH 4 +) 2, ( HO) 2 Ti [OCH (CH 3 ) COOH] 2 , (iC 3 H 7 O) Ti (OC 2 H 4 NHC 2 H 4 NH 2 ) 3 , (iC 3 H 7 O) 2 Ti (C 6 H 7 O 2 ) 2 , Ti (C 5 H 7 O 2 ) 4 , (iC 3 H 7 O) 2 Ti (C 6 H 9 O 3 ) 2 , Ti (OiC 3 H 7 ) 4 , (C 8 H 17 O ) 2 Ti (O 2 C 8 H 17 ) 2 , (iC 3 H 7 O) 2 Ti (C 6 H 9 O 3 ) 2 and the like.

所述鈦螯合錯合物之市售物，可舉如Matsumoto Fine Chemical Co. Ltd.製造之ORGATIX TC系列，更具體則可舉如ORGATIX TC-300、TC-310、TC-400、TC-315、TC-335、TC-500、及TC-510等。Commercial products of the titanium chelate complex include, for example, ORGATIX TC series manufactured by Matsumoto Fine Chemical Co. Ltd., and more specifically, ORGATIX TC-300, TC-310, TC-400, TC- 315, TC-335, TC-500, and TC-510.

又，鋯螯合錯合物適合列舉如氯化氧鋯化合物、乳酸鋯銨鹽、碳酸鋯銨等。更具體可舉如(HO)Zr[OCH(CH3 )COO- ]3 (NH4 + )3 等。Examples of the zirconium chelate complex include a zirconyl chloride compound, a zirconium lactate ammonium salt, and a zirconium ammonium carbonate. More specifically, may be cited as (HO) Zr [OCH (CH 3) COO -] 3 (NH 4 +) 3 and the like.

所述鋯螯合錯合物之市售物可舉如Matsumoto Fine Chemical Co. Ltd.製造之ORGATIX ZA系列、ORGATIX ZC系列(譬如ORGATIX ZC-126、ZC-300等)及SAN NOPCO Ltd.製造之AZ Coat 5800MT等。Commercial products of the zirconium chelate complex include, for example, ORGATIX ZA series, ORGATIX ZC series (such as ORGATIX ZC-126, ZC-300, etc.) manufactured by Matsumoto Fine Chemical Co. Ltd., and products manufactured by SAN NOPCO Ltd. AZ Coat 5800MT and so on.

鋁螯合錯合物可舉如參乙醯丙酮鋁、雙乙基乙醯乙酸鹽單乙醯丙酮鋁、參乙基乙醯乙酸鋁等，更具體可舉如Al(C5 H7 O2 )3 、Al(C5 H7 O2 )(C6 H9 O3 )2 、Al(C6 H9 O3 )3 。Examples of aluminum chelate complexes include aluminum acetone acetone, aluminum acetoacetate monoethyl acetoacetone, aluminum acetone acetoacetate, and the like, and more specifically, Al (C 5 H 7 O 2 ) 3 , Al (C 5 H 7 O 2 ) (C 6 H 9 O 3 ) 2 , Al (C 6 H 9 O 3 ) 3 .

所述有機鋁化合物之市售物可舉如Matsumoto Fine Chemical Co. Ltd.製造之ORGATIX AL系列。The commercial product of the organoaluminum compound may be, for example, the ORGATIX AL series manufactured by Matsumoto Fine Chemical Co. Ltd.

交聯劑可單獨使用1種，或可將2種以上組合使用。The crosslinking agent may be used singly or in combination of two or more kinds.

令交聯劑及黏結劑合計質量為100質量份時，交聯劑含量為0.2質量份以上且低於10質量份。且0.3、0.4或0.5質量份以上較佳，0.6、0.7、0.8、0.9或1質量份以上更佳。又，9、8、或7或6質量份以下較佳，5或4質量份以下更佳，3質量%以下尤為適宜。藉由該交聯劑之含有比率低於10質量份，在電極塗敷液狀態下之凝膠化較不易進展，可輕鬆進行塗敷。而且，活性物質之比率變得相對較高，尤其是製得之電極的電阻值能適度降低。又，藉由該交聯劑之含有比率為0.2質量份以上，可適當獲得充分顯現交聯效果且黏結劑樹脂之機械強度高的理想電池性能。When the total mass of the crosslinking agent and the binder is 100 parts by mass, the content of the crosslinking agent is 0.2 parts by mass or more and less than 10 parts by mass. In addition, 0.3, 0.4, or 0.5 parts by mass or more is preferable, and 0.6, 0.7, 0.8, 0.9, or 1 part by mass or more is more preferable. In addition, 9, 8, or 7 or 6 parts by mass is preferable, 5 or 4 parts by mass is more preferable, and 3% by mass or less is particularly suitable. When the content ratio of the cross-linking agent is less than 10 parts by mass, gelation in the state of the electrode coating solution is less likely to progress, and coating can be easily performed. Moreover, the ratio of the active material becomes relatively high, and in particular, the resistance value of the prepared electrode can be reduced moderately. In addition, when the content ratio of the cross-linking agent is 0.2 parts by mass or more, it is possible to appropriately obtain ideal battery performance in which the cross-linking effect is sufficiently developed and the mechanical strength of the binder resin is high.

(正極活性物質)
正極活性物質可採用本技術領域中使用之正極活性物質。譬如，可適當使用：磷酸鐵鋰(LiFePO4 )、磷酸錳鋰(LiMnPO4 )、磷酸鈷鋰(LiCoPO4 )、焦磷酸鐵(Li2 FeP2 O7 )、鈷酸鋰複合氧化物(LiCoO2 )、尖晶石型錳酸鋰複合氧化物(LiMn2 O4 )、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(LiNi0.8 Co0.15 Al0.05 O2 )、鋰-鎳-鈷-錳複合氧化物(LiNix Coy Mn1-x-y O2 ，在此0＜x＜1、0＜y＜1、x+y＜1)、Li過剩系鎳-鈷-錳複合氧化物、氧化錳鎳(LiNi0.5 Mn1.5 O4 )、氧化錳(MnO2 )、釩系氧化物、硫系氧化物、聚矽氧系氧化物等。該等可單獨使用1種，或可將2種以上組合使用。(Positive electrode active material)
The positive electrode active material may be a positive electrode active material used in the technical field. For example, lithium iron phosphate (LiFePO 4 ), lithium manganese phosphate (LiMnPO 4 ), lithium cobalt phosphate (LiCoPO 4 ), iron pyrophosphate (Li 2 FeP 2 O 7 ), and lithium cobaltate composite oxide (LiCoO) can be suitably used. 2 ), spinel type lithium manganate composite oxide (LiMn 2 O 4 ), lithium manganate composite oxide (LiMnO 2 ), lithium nickelate composite oxide (LiNiO 2 ), lithium niobate composite oxide (LiNbO 2), lithium iron composite oxides (LiFeO2 2), lithium, magnesium oxide composite (a LiMgO 2), calcium, lithium composite oxide (LiCaO 2), copper lithium 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 was (LiNi 0.8 Co 0.15 Al 0.05 O 2), lithium - Ni - Co - manganese composite oxide (LiNi x Co y Mn 1- xy O 2, here 0 <x <1,0 <y < 1, x + y <1), Li excess nickel-cobalt-manganese composite oxide, manganese nickel oxide (LiNi 0.5 Mn 1.5 O 4 ), manganese oxide (MnO 2 ), vanadium-based oxide, sulfur-based oxide, polysiloxane Oxides, etc. These can be used individually by 1 type or in combination of 2 or more types.

(負極活性物質)
負極活性物質無特別限定，譬如可使用矽(Si)、錫(Sn)或含有該等之材料、碳(尤其是碳材料(譬如石墨、硬碳、軟碳))、鈦酸鋰等可大量吸留(occlusion)及釋放鋰離子的材料等。若為所述材料，不論是單體、合金、化合物、固溶物及含有含矽材料或含錫材料之複合活性物質中之任一者，皆可發揮本實施形態效果。含矽材料除了Si(矽)以外還可使用氧化矽(宜為SiOx(0.05＜x＜1.95)且更具體如SiO)或是於該等任一者中以選自於由B、Mg、Ni、Ti、Mo、Co、Ca、Cr、Cu、Fe、Mn、Nb、Ta、V、W、Zn、C、N、Sn所構成群組中之至少1種以上元素取代部分Si之合金或化合物、或固溶物等。該等可統稱為矽化合物。含錫材料可舉Ni2 Sn4 、Mg2 Sn、SnOx(0＜x＜2)、SnO2 、SnSiO3 、LiSnO等。碳材料可用結晶碳、非晶碳或將該等一起做使用。該等材料可分別單獨使用1種或可將2種以上組合使用。尤以選自於由矽、矽化合物及碳材料所構成群組中之至少1種為佳。又特別是在將矽及/或矽化合物和碳材料組合使用時，碳材料與矽及/或矽化合物之比率(碳材料/矽或矽化合物)以質量比計宜為5/95~50/50。該質量比之上限可為10/90或15/85。又，該質量比之下限可為40/60、35/65、30/70或25/75。(Negative electrode active material)
The negative electrode active material is not particularly limited. For example, silicon (Si), tin (Sn) or a material containing these, carbon (especially carbon materials (such as graphite, hard carbon, soft carbon)), lithium titanate, etc. Materials that occlude and release lithium ions. If it is the material, any one of a monomer, an alloy, a compound, a solid solution, and a composite active material containing a silicon-containing material or a tin-containing material can exert the effects of this embodiment. In addition to Si (silicon), silicon-containing materials may use silicon oxide (preferably SiOx (0.05 <x <1.95) and more specifically SiO) or in any of these selected from B, Mg, Ni , Ti, Mo, Co, Ca, Cr, Cu, Fe, Mn, Nb, Ta, V, W, Zn, C, N and Sn , Or solid solution. These may be collectively referred to as silicon compounds. Examples of the tin-containing material include Ni 2 Sn 4 , Mg 2 Sn, SnOx (0 <x <2), SnO 2 , SnSiO 3 , LiSnO, and the like. As the carbon material, crystalline carbon, amorphous carbon, or the like can be used together. These materials can be used individually by 1 type or in combination of 2 or more types. Particularly, it is preferably at least one selected from the group consisting of silicon, silicon compounds, and carbon materials. Especially when silicon and / or silicon compounds are used in combination with carbon materials, the ratio of carbon materials to silicon and / or silicon compounds (carbon materials / silicon or silicon compounds) should preferably be 5/95 ~ 50 / 50. The upper limit of the mass ratio may be 10/90 or 15/85. The lower limit of the mass ratio may be 40/60, 35/65, 30/70, or 25/75.

(導電助劑)
使用導電助劑時，導電助劑只要具有導電性，即無特別限定。可舉如金屬、碳、導電性高分子、導電性玻璃等之粉末，舉例來說：乙炔黑(AB)、科琴碳黑(KB)、碳黑(譬如SuperP(SP))、黑鉛、熱碳黑、爐黑、燈黑、槽製碳黑、滾筒黑(roller black)、盤黑(disc black)、軟碳、硬碳、石墨烯、非晶碳奈米碳管(CNT)、碳奈米纖維(譬如以名稱VGCF作為註冊商標之氣相成長碳纖維)等。該等可單獨使用一種亦可將二種以上併用。雖無特別限制，不過傳導助劑在電極合劑中宜含有譬如0.01~5質量%左右，且含有0.02~3質量%或0.05~2質量%左右較佳。(Conductive Auxiliary)
When a conductive additive is used, the conductive additive is not particularly limited as long as it has conductivity. Examples include powders of metals, carbon, conductive polymers, and conductive glass. For example: acetylene black (AB), Ketjen carbon black (KB), carbon black (such as SuperP (SP)), black lead, Thermal carbon black, furnace black, lamp black, grooved carbon black, roller black, disc black, soft carbon, hard carbon, graphene, amorphous carbon nano carbon tube (CNT), carbon Nanofibers (for example, vapor-grown carbon fibers with the name VGCF as a registered trademark). These may be used alone or in combination of two or more. Although there is no particular limitation, it is preferable that the conductive auxiliary agent is contained in the electrode mixture, for example, about 0.01 to 5% by mass, and more preferably about 0.02 to 3% by mass or 0.05 to 2% by mass.

(分散助劑)
使用分散助劑時，分散助劑可舉如葡萄糖醛酸、腐植酸、甘胺酸、聚甘胺酸、天冬胺酸、麩胺酸等。(Dispersion aid)
When a dispersing aid is used, examples of the dispersing aid include glucuronic acid, humic acid, glycine, polyglycine, aspartic acid, and glutamic acid.

(電極合劑)
於電極活性物質(正極活性物質或負極活性物質)中添加交聯劑、黏結劑及視需求之液體介質(宜為水)做成糊狀漿料，可製得電極合劑(正極合劑或負極合劑)。黏結劑可預先溶於水來做使用，亦可將活性物質、黏結劑之粉末預先混合後再加水混合。又，要添加其他成分時，同樣可混合至該漿料中。(Electrode mixture)
Adding a cross-linking agent, a binder and an optional liquid medium (preferably water) to the electrode active material (positive electrode active material or negative electrode active material) to make a paste slurry, and an electrode mixture (positive electrode mixture or negative electrode mixture) can be prepared ). The binder can be dissolved in water for use in advance, or the active substance and the powder of the binder can be mixed in advance and then mixed with water. When other components are to be added, they can be mixed into the slurry in the same manner.

液體介質(宜為水)之用量並無特別限定，舉例而言，令活性物質、交聯劑、黏結劑合計為100質量%時，用量宜為40質量%以上且2000質量%以下，且50質量%以上且1000質量%以下較佳，60質量%以上且500質量%以下更佳。
黏結劑的使用目的係將活性物質彼此及該等與集電體接著。即，其係為了在兩極之集電體上塗佈漿料並使該等乾燥時形成良好的活性物質層而使用。The amount of the liquid medium (preferably water) is not particularly limited. For example, when the total amount of the active substance, the cross-linking agent, and the binder is 100% by mass, the amount should be 40% by mass or more and 2000% by mass or less, and 50%. More preferably, it is more than 1000% by mass and more preferably more than 60% by mass and less than 500% by mass.
The purpose of using the binder is to attach the active materials to each other and to the current collector. That is, it is used in order to apply a slurry to the current collector of both electrodes, and to form a favorable active material layer at the time of drying.

黏結劑之用量亦無特別限定，舉例而言，相對於電極活性物質、交聯劑及黏結劑之合計質量，宜為0.5質量%以上，且1質量%以上較佳，2質量%以上更佳。而且宜為40質量%以下，且30質量%以下較佳，20質量%以下更佳，10質量%以下尤為適宜。黏結劑若為該上限以下，活性物質之比例相對下不會太少，電池充放電時能獲得較高容量。又，若為該下限以上，可獲得更佳的黏結力，取得更佳的循環壽命特性，而且因漿料黏性不足而產生凝集之傾向也會隨之減少。The amount of the binder is also not particularly limited. For example, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 2% by mass or more relative to the total mass of the electrode active material, the cross-linking agent, and the binder. . Moreover, it is preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. If the binder is below this upper limit, the proportion of the active material will not be too small, and a higher capacity can be obtained when the battery is charged and discharged. Moreover, if it is more than this lower limit, a better adhesive force can be obtained and a better cycle-life characteristic can be obtained, and the tendency for aggregation to occur due to insufficient viscosity of the slurry will also decrease accordingly.

該電極合劑可為正極用合劑或負極用合劑，尤以負極用合劑為宜。The electrode mixture may be a mixture for a positive electrode or a mixture for a negative electrode, and particularly preferably a mixture for a negative electrode.

另，雖不特別限制，惟在電極合劑中，電極活性物質含量宜為80質量%以上，且85質量%以上較佳，90質量%以上更佳。In addition, although not particularly limited, the content of the electrode active material in the electrode mixture is preferably 80% by mass or more, more preferably 85% by mass or more, and more preferably 90% by mass or more.

又，雖不特別限制，不過電極合劑中之交聯劑及黏結劑合計含量宜低於20質量%，且低於15質量%較佳，低於10質量%更佳。Although not particularly limited, the total content of the cross-linking agent and the binder in the electrode mixture is preferably less than 20% by mass, more preferably less than 15% by mass, and even more preferably less than 10% by mass.

(正極)
正極可用本技術領域中使用之手法製作。(positive electrode)
The positive electrode can be produced by a method used in the technical field.

正極之集電體只要是具有電子傳導性且能使所保持之正極材料通電的材料即無特別限定。譬如，可使用C、Ti、Cr、Mo、Ru、Rh、Ta、W、Os、Ir、Pt、Au、Al等導電性物質、或含有二種以上該等導電性物質之合金(譬如不鏽鋼)。若從導電性高、電解液中之穩定性和耐氧化性優異的觀點來看，集電體以C、Al、不鏽鋼等為佳；若再從材料成本觀點來看，則以Al等為宜。The collector of the positive electrode is not particularly limited as long as it is a material having electron conductivity and capable of energizing the held positive electrode material. For example, conductive materials such as C, Ti, Cr, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, Al, or alloys containing two or more such conductive materials (such as stainless steel) can be used. . From the viewpoints of high electrical conductivity and excellent stability and oxidation resistance in the electrolyte, the current collector is preferably C, Al, stainless steel, etc .; from the viewpoint of material cost, Al is more suitable. .

關於集電體形狀並無特別限制，可使用箔狀基材、三維基材等。惟，若使用三維基材(發泡金屬(foam metal)、網狀物、織布、不織布、多孔體等)，即使是與集電體欠缺密著性之黏結劑，也能獲得具高容量密度之電極。而且高速率充放電特性也會變佳。The shape of the current collector is not particularly limited, and a foil-shaped substrate, a three-dimensional substrate, or the like can be used. However, if a three-dimensional substrate (foam metal, mesh, woven fabric, non-woven fabric, porous body, etc.) is used, a high capacity can be obtained even with a binder that lacks adhesion to the current collector. The electrode of density. In addition, the high-rate charge-discharge characteristics will also be improved.

(負極)
負極可用本技術領域中使用之手法製作。(negative electrode)
The negative electrode can be produced by a method used in the technical field.

負極之集電體只要是具有電子傳導性且能使所保持之負極材料通電的材料即無特別限定。譬如，可使用C、Cu、Ni、Fe、V、Nb、Ti、Cr、Mo、Ru、Rh、Ta、W、Os、Ir、Pt、Au、Al等導電性物質、或含有二種以上該等導電性物質之合金(譬如不鏽鋼)。或者，亦可為於Fe鍍上Cu之物。若從導電性高、電解液中之穩定性和耐氧化性優異的觀點來看，集電體以C、Ni、不鏽鋼等為佳；若從材料成本的觀點來看，則以Cu、Ni為宜。The collector of the negative electrode is not particularly limited as long as it is a material having electron conductivity and capable of energizing the held negative electrode material. For example, C, Cu, Ni, Fe, V, Nb, Ti, Cr, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, Al, or two or more of them can be used Alloys such as conductive materials (such as stainless steel). Alternatively, it is also possible to plate Cu with Fe. From the viewpoint of high conductivity and excellent stability and oxidation resistance in the electrolyte, the current collector is preferably C, Ni, stainless steel, etc .; from the viewpoint of material cost, Cu and Ni are preferred. should.

關於集電體形狀並無特別限制，可使用箔狀基材、三維基材等。在這之中，若採用三維基材(發泡金屬、網狀物、織布、不織布、多孔體基材等)，即使是與集電體欠缺密著性之黏結劑，也能獲得具高容量密度之電極。而且高速率充放電特性也會變佳。The shape of the current collector is not particularly limited, and a foil-shaped substrate, a three-dimensional substrate, or the like can be used. Among them, if a three-dimensional base material (foamed metal, mesh, woven fabric, non-woven fabric, porous base material, etc.) is used, even a binder with insufficient adhesion to the current collector can obtain a high degree of adhesion. Capacity density electrode. In addition, the high-rate charge-discharge characteristics will also be improved.

(電池)
使用本實施形態之非水電解質二次電池用電極，可做出本實施形態之非水電解質二次電池。非水電解質二次電池譬如宜為鋰離子二次電池。(battery)
By using the electrode for a non-aqueous electrolyte secondary battery of this embodiment, a non-aqueous electrolyte secondary battery of this embodiment can be manufactured. The non-aqueous electrolyte secondary battery is preferably a lithium ion secondary battery, for example.

在本實施形態之非水電解質二次電池中，鋰離子二次電池必須含有鋰離子，因此電解質鹽以鋰鹽為佳。該鋰鹽並無特別限制，具體例可舉六氟磷酸鋰、過氯酸鋰、四氟硼酸鋰、三氟甲磺酸鋰、三氟甲磺酸醯亞胺鋰等。該等鋰鹽可單獨使用1種或可將2種以上混合使用。上述鋰鹽的電負度高、容易離子化，因此充放電循環特性佳，可提升二次電池之充放電容量。In the non-aqueous electrolyte secondary battery of this embodiment, since the lithium ion secondary battery must contain lithium ions, the electrolyte salt is preferably a lithium salt. The lithium salt is not particularly limited, and specific examples thereof include lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, and lithium trifluoromethanesulfonate imine. These lithium salts may be used singly or in combination of two or more kinds. The lithium salt has a high electronegativity and is easily ionized, so it has good charge-discharge cycle characteristics and can improve the charge-discharge capacity of the secondary battery.

上述電解質之溶劑可使用例如碳酸伸丙酯、碳酸伸乙酯、碳酸二甲酯、碳酸二乙酯、γ-丁內酯等，且該等溶劑單獨使用一種或可將2種以上混合使用。尤其以碳酸伸丙酯單體、碳酸伸乙酯與碳酸二乙酯之混合物或γ-丁內酯單體為宜。另，上述碳酸伸乙酯與碳酸二乙酯之混合物的混合比可在其中一成分為10體積%以上且90體積%以下之範圍內任意調整。As the solvent of the electrolyte, for example, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, etc. can be used, and these solvents can be used alone or in combination of two or more. Particularly preferred are propylene carbonate monomer, a mixture of ethylene carbonate and diethyl carbonate, or γ-butyrolactone monomer. In addition, the mixing ratio of the above-mentioned mixture of ethylene carbonate and diethyl carbonate can be arbitrarily adjusted within a range in which one of the components is 10% by volume or more and 90% by volume or less.

又，本實施形態之鋰二次電池的電解質可為固體電解質或可為離子性液體。The electrolyte of the lithium secondary battery in this embodiment may be a solid electrolyte or an ionic liquid.

根據上述結構之鋰二次電池，可作為壽命特性優異之鋰二次電池發揮功能。The lithium secondary battery having the above structure can function as a lithium secondary battery having excellent life characteristics.

鋰二次電池之結構並無特別限定，可應用積層式電池、捲回式電池等既有的電池形態、結構。The structure of the lithium secondary battery is not particularly limited, and existing battery forms and structures such as a laminated battery and a roll-back battery can be applied.

(電性機器)
具備本實施形態之負極的非水電解質二次電池有優異的壽命特性，可作為各種電性機器(包含使用電氣之乘載工具在內)之電源利用。(Electric machine)
The non-aqueous electrolyte secondary battery provided with the negative electrode of this embodiment has excellent life characteristics, and can be used as a power source for various electric devices (including electric vehicles).

電性機器可舉如：攜帶型電視機、筆記型個人電腦、平板電腦、智慧型手機、個人電腦鍵盤、個人電腦用顯示器、桌上型個人電腦、CRT螢幕、個人電腦架、印表機、一體式個人電腦、穿戴式電腦、文字處理機、滑鼠、硬碟、個人電腦周邊設備、熨斗、冷氣機、冷藏庫、暖風加熱器、電毯、衣物乾燥機、棉被乾燥機、加濕器、除濕器、窗扇、送風機、換氣扇、附清洗功能的馬桶座、汽車導航裝置、手電筒、照明器具、攜帶式伴唱機、麥克風、空氣清淨機、血壓計、咖啡研磨機、咖啡機、日式暖桌、行動電話、遊戲機、音樂錄音機、音樂撥放器、光碟換片機(disc changer)、收音機、剃鬚刀、果汁機、碎紙機、淨水器、碗盤乾燥機、汽車音響、立體音響、揚聲器、耳機、收發報機、熨褲機、吸塵器、體脂肪計、體重計、健康測量計(health meter)、電影播放機、電鍋、電動刮鬍機、枱燈、電熱開水瓶、電子遊戲機、攜帶式遊戲機、電子辭典、電子記事簿、電磁調理器、電子計算機、電動推車、電動輪椅、電動工具、電動牙刷、腳爐、理髪器具、電話機、鐘錶、對講機、電撃殺蟲器、加熱板、烤麵包機、吹風機、電動鑽孔機、熱水器、平板加熱器、粉碎機、焊鐵、攝錄影機、傳真機、食物調理機、按摩機、燈泡、攪拌機、縫紉機、搗年糕機、遙控器、冷水器、冷風器、起泡器、電子樂器、機車、玩具類、除草機、浮標、腳踏車、汽車、混合動力車、插電式混合動力車、電動汽車、鐵路、船、飛機、緊急用蓄電池等。Examples of electrical equipment include: portable televisions, notebook personal computers, tablet computers, smartphones, personal computer keyboards, personal computer monitors, desktop personal computers, CRT monitors, personal computer shelves, printers, All-in-one personal computer, wearable computer, word processor, mouse, hard disk, personal computer peripherals, iron, air conditioner, refrigerator, heating heater, electric blanket, clothes dryer, quilt dryer, plus Humidifier, dehumidifier, window fan, blower, ventilation fan, toilet seat with cleaning function, car navigation device, flashlight, lighting equipment, portable record player, microphone, air cleaner, sphygmomanometer, coffee grinder, coffee machine, daily Table warmer, mobile phone, game console, music recorder, music player, disc changer, radio, shaver, juicer, shredder, water purifier, dish dryer, automobile Stereo, stereo, speaker, earphone, transceiver, trouser press, vacuum cleaner, body fat meter, weight scale, health meter, movie player, Electric pot, electric shaver, table lamp, electric boiling water bottle, electronic game machine, portable game machine, electronic dictionary, electronic memo pad, electromagnetic conditioner, electronic computer, electric cart, electric wheelchair, electric tool, electric toothbrush, Stoves, appliances, telephones, clocks, clocks, walkie-talkies, electric insecticides, heating plates, toasters, hair dryers, electric drills, water heaters, flat heaters, shredders, soldering irons, video cameras, fax machines , Food conditioner, massager, light bulb, mixer, sewing machine, rice cake machine, remote control, water cooler, air cooler, bubbler, electronic musical instrument, locomotive, toys, weeder, buoy, bicycle, automobile, hybrid Vehicles, plug-in hybrid vehicles, electric vehicles, railways, ships, airplanes, emergency batteries, etc.

另，本說明書中所謂的「含有」亦包含「本質上由其構成」及「由其構成」(The term "comprising" includes "consisting essentially of” and "consisting of.")。The term "comprising" as used in this specification also includes "consisting essentially of" and "consisting of."

又，針對上述本發明之各實施形態說明的各種特性(性質、結構、功能等)，在用於特定本發明包含之主題時，可任意組合。即，本發明包含所有由本說明書中記載之可組合的各特性之一切組合所構成的主題。
實施例In addition, various characteristics (property, structure, function, etc.) described with respect to the embodiments of the present invention described above can be arbitrarily combined when used to specify the subject matter included in the present invention. That is, this invention includes all the subject matter which consists of all the combinations of each characteristic which can be combined in this specification.
Examples

以下，以實施例進一步具體說明本實施形態，惟本發明不受該等實施例任何限定。另，Gr表示石墨。Hereinafter, this embodiment will be described in more detail by way of examples, but the present invention is not limited by these examples. In addition, Gr represents graphite.

(製作黏結劑)
(製造例1)合成乙烯酯/乙烯性不飽和羧酸酯共聚物
於具備攪拌機、溫度計、N2 氣導入管、回流冷卻機及滴下漏斗之容量2L反應槽中饋入水768g、無水硫酸鈉12g，噴吹N2 氣，使系內脫氧。接著饋入部分皂化聚乙烯醇(皂化度88%)1g、過氧化月桂基1g並使內溫升溫至60℃後，藉由滴下漏斗以4小時的時間滴下丙烯酸甲酯104g(1.209mol)及乙酸乙烯酯155g(1.802mol)之單體後，在內溫65℃下保存2小時，使反應完成。然後，將固體成分進行分濾而獲得乙烯酯/乙烯性不飽和羧酸酯共聚物288g(含水量10.4質量%)。使所得聚合物溶解於DMF後以濾器實施過濾，再以分子量測定裝置(Nihon Waters K.K.製造之2695、RI偵測器2414)求算數量平均分子量，得18.8萬。(Making adhesive)
(Production Example 1) Synthesis of a vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer In a capacity 2L reaction tank equipped with a stirrer, a thermometer, an N 2 gas introduction tube, a reflux cooler, and a dropping funnel, 768 g of water and 12 g of anhydrous sodium sulfate were fed. , Blowing N 2 gas to deoxidize the system. Next, 1 g of partially saponified polyvinyl alcohol (saponification degree of 88%) and 1 g of lauryl peroxide were fed and the internal temperature was raised to 60 ° C. Then, 104 g (1.209 mol) of methyl acrylate was dropped over a 4 hour period using a dropping funnel and After 155 g (1.802 mol) of vinyl acetate monomer, it was stored at an internal temperature of 65 ° C for 2 hours to complete the reaction. Then, the solid content was subjected to fractional filtration to obtain 288 g of a vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer (water content: 10.4% by mass). The obtained polymer was dissolved in DMF and filtered through a filter, and then the number average molecular weight was calculated with a molecular weight measuring device (Nihon Waters KK's 2695, RI detector 2414) to obtain 188,000.

(製造例2)調製乙烯酯/乙烯性不飽和羧酸酯共聚物皂化物
於與上述同樣之反應槽中饋入甲醇450g、水420g、氫氧化鈉132g(3.3mol)及製造例1中所得含水共聚物288g(含水量10.4質量%)，一邊攪拌一邊在30℃下進行3小時皂化反應。皂化反應結束後，將所得共聚物皂化物以甲醇洗淨、過濾並在70℃下使其乾燥6小時後，獲得乙烯酯/乙烯性不飽和羧酸酯共聚物皂化物(乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物，鹼金屬為鈉)193g。乙烯酯/乙烯性不飽和羧酸酯共聚物皂化物之體積平均粒徑為180μm。另，體積平均粒徑係以雷射繞射式粒度分布測定裝置((股)島津製作所公司製造之SALD-7100)進行測定。(Production Example 2) Preparation of a vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer saponified product Into the same reaction tank as described above, 450 g of methanol, 420 g of water, 132 g (3.3 mol) of sodium hydroxide, and Production Example 1 were fed. 288 g of water-containing copolymer (water content: 10.4% by mass) was subjected to a saponification reaction at 30 ° C. for 3 hours while stirring. After the saponification reaction was completed, the obtained copolymer saponified product was washed with methanol, filtered, and dried at 70 ° C. for 6 hours to obtain a vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer saponified product (vinyl alcohol and ethylenicity). Copolymer of unsaturated carboxylic acid alkali metal neutralizer (sodium metal is sodium) 193 g. The volume average particle diameter of the saponified product of the vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer was 180 μm. The volume average particle diameter was measured using a laser diffraction particle size distribution measuring device (SALD-7100 manufactured by Shimadzu Corporation).

(製造例3)粉碎乙烯酯/乙烯性不飽和羧酸酯共聚物皂化物
利用噴射磨機(Nippon Pneumatic Mfg.Co.,Ltd.製造之LJ)粉碎上述乙烯酯/乙烯性不飽和羧酸酯共聚物皂化物193g，獲得微粉末狀之乙烯酯/乙烯性不飽和羧酸酯共聚物皂化物173g。以雷射繞射式粒度分布測定裝置(島津製作所公司製造之SALD-7100)測定所得共聚物皂化物之粒徑，結果體積平均粒徑為39μm。以下，討論時以製造例3中所得乙烯酯/乙烯性不飽和羧酸酯共聚物皂化物作為共聚物[1]。(Production Example 3) The vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer saponified was pulverized using a jet mill (LJ manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to pulverize the vinyl ester / ethylenically unsaturated carboxylic acid ester. 193 g of copolymer saponified, and 173 g of saponified vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer was obtained in a fine powder form. The particle diameter of the obtained copolymer saponified product was measured by a laser diffraction particle size distribution measuring device (SALD-7100 manufactured by Shimadzu Corporation), and the volume average particle diameter was 39 μm. In the following discussion, the vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer saponified obtained in Production Example 3 is used as the copolymer [1].

另，共聚物[1]之1質量%水溶液的黏度為1,630mPa・s，乙烯酯與乙烯性不飽和羧酸酯之共聚組成比以莫耳比計為6/4。前述1質量%水溶液之黏度係使用BROOKFIELD製造之旋轉黏度計(型式DV-I+)，在轉子No.5及50rpm(液溫25℃)之條件下測得。In addition, the viscosity of the 1% by mass aqueous solution of the copolymer [1] was 1,630 mPa · s, and the copolymerization composition ratio of the vinyl ester and the ethylenically unsaturated carboxylic acid ester was 6/4 in molar ratio. The viscosity of the aforementioned 1% by mass aqueous solution was measured using a rotary viscometer (type DV-I +) manufactured by BROOKFIELD under conditions of a rotor No. 5 and 50 rpm (liquid temperature 25 ° C).

(製造例4)
在製造例1中，除了將丙烯酸甲酯104g(1.209mol)及乙酸乙烯酯155g(1.802mol)改用丙烯酸甲酯25.9g(0.301mol)及乙酸乙烯酯232.8g(2.704mol)以外，進行與製造例1~3相同之操作而獲得乙烯酯/乙烯性不飽和羧酸酯共聚物皂化物。以該乙烯酯/乙烯性不飽和羧酸酯共聚物皂化物作為共聚物[2]。(Manufacturing example 4)
In Production Example 1, except that 104 g (1.209 mol) of methyl acrylate and 155 g (1.802 mol) of vinyl acetate were replaced with 25.9 g (0.301 mol) of methyl acrylate and 232.8 g (2.704 mol) of vinyl acetate, In the same manner as in Production Examples 1 to 3, a vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer saponified product was obtained. This vinyl ester / ethylenically unsaturated carboxylic acid ester copolymer saponified was used as a copolymer [2].

另，共聚物[2]之體積平均粒徑為34μm。又，共聚物[2]之1質量%水溶液的黏度為50mPa・s，乙烯酯與乙烯性不飽和羧酸酯之共聚組成比則為9/1。該體積平均粒徑及1質量%水溶液之黏度係以與共聚物[1]同樣方式進行測定。The volume average particle diameter of the copolymer [2] was 34 μm. The viscosity of the 1% by mass aqueous solution of the copolymer [2] was 50 mPa · s, and the copolymerization composition ratio of the vinyl ester and the ethylenically unsaturated carboxylic acid ester was 9/1. The volume average particle diameter and the viscosity of the 1% by mass aqueous solution were measured in the same manner as in the copolymer [1].

(交聯劑量之討論)
(實施例1)
將SiO(平均粒徑5-10μm：日立化成公司製)18.8質量份、Gr(G1：江西紫宸科技公司製)75.2質量份(SiO/Gr=2/8之質量比)、SP(SuperP：Timcal公司製碳黑)1.0質量份、製造例3中所得共聚物[1]4.95質量份、有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製、TC-400)0.05質量份及水100質量份混合，調製出漿料狀負極合劑。(Discussion of Crosslinking Dose)
(Example 1)
18.8 parts by mass of SiO (average particle diameter: 5-10 μm: manufactured by Hitachi Chemical Co., Ltd.), 75.2 parts by mass of Gr (G1: manufactured by Jiangxi Zijing Technology Co., Ltd.) (SiO / Gr = 2/8 mass ratio), SP (SuperP: 1.0 parts by mass of carbon black manufactured by Timcal Corporation, 4.95 parts by mass of copolymer [1] obtained in Production Example 3, 0.05 parts by mass of organic titanium compound cross-linking agent (manufactured by Matsumoto Fine Chemical Co. Ltd., TC-400), and water 100 The parts by mass were mixed to prepare a slurry-like negative electrode mixture.

將所得合劑塗佈於厚度10μm之電解銅箔上並使其乾燥後，以輥壓機(Ono-roll Co.製)加壓使電解銅箔與塗膜密接接合，接著進行加熱處理(減壓中在120℃下進行12小時)，製作負極。活性物質層(塗膜)之厚度為50μm，負極之基重為10mg/cm2 。The obtained mixture was applied to an electrolytic copper foil having a thickness of 10 μm and dried, and then pressed with a roll press (manufactured by Ono-Roll Co.) to closely bond the electrolytic copper foil to the coating film, followed by heat treatment (decompression). The reaction was performed at 120 ° C for 12 hours) to produce a negative electrode. The thickness of the active material layer (coating film) was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .

(實施例2)
將實施例1中之共聚物[1]4.95質量份換掉改用共聚物[1]4.9質量份，及換掉有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-400)0.05質量份改用有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-400)0.1質量份，除此以外以與實施例1同樣方式製作負極。活性物質層之厚度為50μm，負極之基重為10mg/cm2 。(Example 2)
4.95 parts by mass of the copolymer [1] in Example 1 was replaced with 4.9 parts by mass of the copolymer [1], and the organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co. Ltd.) was replaced. A negative electrode was produced in the same manner as in Example 1 except that 0.05 parts by mass was changed to 0.1 part by mass of an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co. Ltd.). The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .

(實施例3)
將實施例1中之共聚物[1]4.95質量份換掉改用共聚物[1]4.65質量份，及換掉有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-400)0.05質量份改用有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-400)0.35質量份，除此以外以與實施例1同樣方式製作負極。活性物質層之厚度為50μm，負極之基重為10mg/cm2 。(Example 3)
4.95 parts by mass of the copolymer [1] in Example 1 was replaced with 4.65 parts by mass of the copolymer [1], and the organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co. Ltd.) was replaced. An anode was produced in the same manner as in Example 1 except that 0.05 parts by mass was changed to 0.35 parts by mass of an organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co. Ltd.). The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .

(比較例A)
將實施例1中之共聚物[1] 4.95質量份換掉，不加交聯劑並僅混合共聚物[1]5.0質量份，除此以外以與實施例1同樣方式製作負極。活性物質層之厚度為50μm，負極之基重為10mg/cm2 。(Comparative Example A)
The negative electrode was produced in the same manner as in Example 1 except that 4.95 parts by mass of the copolymer [1] in Example 1 was replaced, and 5.0 parts by mass of the copolymer [1] was mixed without adding a crosslinking agent. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .

(比較例1)
將實施例1中之共聚物[1]4.95質量份換掉改用共聚物[1]4.995質量份，及換掉有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-400)0.05質量份改用有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-400)0.005質量份，除此以外以與實施例1同樣方式製作負極。活性物質層之厚度為50μm，負極之基重為10mg/cm2 。(Comparative example 1)
The copolymer [1] 4.95 parts by mass in Example 1 was replaced with a copolymer [1] 4.995 parts by mass, and the organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co. Ltd.) was replaced. An anode was produced in the same manner as in Example 1 except that 0.05 parts by mass was replaced with 0.005 parts by mass of an organic titanium compound cross-linking agent (TC-400 manufactured by Matsumoto Fine Chemical Co. Ltd.). The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .

(參考例1)
將實施例2中之共聚物[1]4.95質量份換掉改用共聚物[1]4.5質量份，以及換掉有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-400)0.05質量份改用有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-400)0.5質量份，除此以外以與實施例1同樣方式製作負極漿料，結果發生凝膠化而未製得漿料，因此很難塗敷至電解銅箔上。(Reference example 1)
4.95 parts by mass of the copolymer [1] in Example 2 was replaced by 4.5 parts by mass of the copolymer [1], and the organic titanium compound cross-linking agent (TC-400 manufactured by Matsumoto Fine Chemical Co. Ltd.) was replaced. An amount of 0.05 parts by mass was changed to 0.5 parts by mass of an organic titanium compound cross-linking agent (TC-400 manufactured by Matsumoto Fine Chemical Co. Ltd.). A negative electrode slurry was produced in the same manner as in Example 1 except that gelation occurred. No slurry was prepared, so it was difficult to apply to the electrolytic copper foil.

(交聯劑種類之討論)
(實施例4)
將實施例2中之有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-400)0.1質量份換掉，改用有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-300)0.1質量份，除此以外以與實施例2同樣方式製作負極。活性物質層之厚度為50μm，負極之基重為10mg/cm2 。(Discussion on the types of crosslinking agents)
(Example 4)
0.1 part by mass of the organic titanium compound cross-linking agent (TC-400 manufactured by Matsumoto Fine Chemical Co. Ltd.) in Example 2 was replaced with an organic titanium compound cross-linking agent (manufactured by Matsumoto Fine Chemical Co. Ltd.) TC-300) A negative electrode was produced in the same manner as in Example 2 except that it was 0.1 parts by mass. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .

(實施例5)
將實施例2中之有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-400)0.1質量份換掉，改用有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-315)0.1質量份，除此以外以與實施例2同樣方式製作負極。活性物質層之厚度為50μm，負極之基重為10mg/cm2 。(Example 5)
0.1 part by mass of the organic titanium compound cross-linking agent (TC-400 manufactured by Matsumoto Fine Chemical Co. Ltd.) in Example 2 was replaced with an organic titanium compound cross-linking agent (manufactured by Matsumoto Fine Chemical Co. Ltd.) TC-315) Except for 0.1 part by mass, a negative electrode was produced in the same manner as in Example 2. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .

(實施例6)
將實施例2中之有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-400)0.1質量份換掉，改用有機二氧化鋯化合物交聯劑(SAN NOPCO Ltd.製造之AZ-Coat 5800MT)0.1質量份，除此以外以與實施例2同樣方式製作負極。活性物質層之厚度為50μm，負極之基重為10mg/cm2 。(Example 6)
0.1 part by mass of the organic titanium compound crosslinking agent (TC-400 manufactured by Matsumoto Fine Chemical Co. Ltd.) in Example 2 was replaced with an organic zirconium dioxide compound crosslinking agent (AZ manufactured by SAN NOPCO Ltd.) -Coat 5800MT) 0.1 parts by mass, and a negative electrode was produced in the same manner as in Example 2. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .

(比較例2)
將實施例2中之有機鈦化合物交聯劑(Matsumoto Fine Chemical Co. Ltd.製造之TC-400)0.1質量份換掉，改用環氧系交聯劑(Nagase ChemteX Co.製、Denacol EX-810)0.1質量份，除此以外以與實施例2同樣方式製作負極。活性物質層之厚度為50μm，負極之基重為10mg/cm2 。(Comparative example 2)
0.1 part by mass of the organic titanium compound cross-linking agent (TC-400 manufactured by Matsumoto Fine Chemical Co. Ltd.) in Example 2 was replaced with an epoxy-based cross-linking agent (manufactured by Nagase ChemteX Co., Denacol EX- 810) Except for 0.1 part by mass, a negative electrode was produced in the same manner as in Example 2. The thickness of the active material layer was 50 μm, and the basis weight of the negative electrode was 10 mg / cm 2 .

另，關於上述各實施例中所用交聯劑，彙整列於表1。The cross-linking agents used in the above examples are summarized in Table 1.

[表1]
[Table 1]

於表2列出各負極之組成。The composition of each negative electrode is listed in Table 2.

[表2]
[Table 2]

(正極)
(實施例A)
將活性物質(Li(Ni0.8Co0.1Mn0.1)O2：北京當升科技公司製)95質量份、作為黏合劑之共聚物[1]3質量份、作為導電助劑之乙炔黑(DENKA BLACK：DENKA Co.Ltd.製)2質量份及水100質量份混合，調製出漿料狀正極合劑。(positive electrode)
(Example A)
95 parts by mass of active material (Li (Ni0.8Co0.1Mn0.1) O2: made by Beijing Dangsheng Technology Co., Ltd.), 3 parts by mass of copolymer [1] as a binder, and acetylene black (DENKA BLACK) as a conductive additive : Manufactured by DENKA Co. Ltd.) 2 parts by mass and 100 parts by mass of water were mixed to prepare a slurry-like positive electrode mixture.

將前述合劑塗佈於厚度10μm之鋁箔上並使其乾燥後，以輥壓機機(Ono-roll Co.製)使鋁箔與塗膜密接接合，接著進行加熱處理(減壓中在120℃下進行12小時以上)，製作正極。該正極之正極容量密度為1.6mAh/cm2 (活性物質物質層之平均厚度：50μm)。另，以下所示之所有討論中皆使用該正極作為正極電極。The mixture was applied to an aluminum foil having a thickness of 10 μm and dried, and then the aluminum foil and the coating film were tightly bonded with a roll press (manufactured by Ono-Roll Co.), followed by heat treatment (under reduced pressure at 120 ° C.). It was performed for 12 hours or more) to produce a positive electrode. The positive electrode has a positive electrode capacity density of 1.6 mAh / cm 2 (average thickness of an active material layer: 50 μm). The positive electrode is used as the positive electrode in all discussions shown below.

(組裝電池)
用實施例1~7、比較例A及比較例1~2中所得負極電極與實施例A中所得正極製作20mAh之小型袋式電池，該小型袋式電池具備作為分離件之PP(Celgard #2500：Celgard, LLC.製)，及作為電解液之裝有LiPF6 1mol/L電解質的EC/DEC(1/1 v/v%)+1質量%VC溶液(KISHIDA CHEMICAL Co.,Ltd.製)。(Assembled battery)
A 20 mAh small pouch battery was fabricated using the negative electrode obtained in Examples 1 to 7, Comparative Example A, and Comparative Examples 1 to 2 and the positive electrode obtained in Example A. The small pouch battery was equipped with PP (Celgard # 2500) as a separator. : Manufactured by Celgard, LLC.), And an EC / DEC (1/1 v / v%) + 1% by mass VC solution (manufactured by KISHIDA CHEMICAL Co., Ltd.) equipped with LiPF6 1 mol / L electrolyte as an electrolytic solution.

另，以下縮寫分別表示：PP為聚丙烯，LiPF6為六氟磷酸鋰，EC為碳酸伸乙酯，DEC為碳酸二乙酯，VC為碳酸伸乙烯酯。In addition, the following abbreviations indicate that PP is polypropylene, LiPF6 is lithium hexafluorophosphate, EC is ethylene carbonate, DEC is diethyl carbonate, and VC is ethylene carbonate.

＜老化後高速率放電試驗＞
用以上述方式製作之袋式電池，按以下(1)~(10)所示步驟，進行老化後之高速率放電試驗，算出DC-IR電阻值。
試驗溫度：30℃
截止電位：2.5-4.3V(vs.Li+/Li)
(1)在CC(CV)充電/CC放電中，於0.2C(0.05C)/0.2C之條件下實施10循環老化。此時記錄老化最後的平均放電電壓值。
※按充電/放電順序記載。括號內為CV的終端電流。
(2)在0.2C(0.05C)/0.5C之條件下實施3循環，並記錄第3循環之平均放電電壓值。
(3)在0.2C(0.05C)/0.2C下實施2循環。
(4)將(2)之放電率改為0.7C，實施3循環，並記錄第3循環之平均放電電壓值。
(5)在0.2C(0.05C)/0.2C下實施2循環。
(6)將(2)之放電率改為1.0C，實施3循環，並記錄第3循環之平均放電電壓值。
(7)在0.2C(0.05C)/0.2C下實施2循環。
(8)將(2)之放電率改為2.0C，實施3循環，並記錄第3循環之平均放電電壓值。
(9)製作橫軸為放電電流(速率)、縱軸為平均放電電壓之圖表。屆時，輸入0.2、0.5、0.7、1.0、2.0C時之平均電壓值。
(10)圖表斜率表示DC-IR之值(Ω)。
另，用製得之所有袋式電池，依本條件進行試驗。
經由試驗所算出之DC-IR值列於表3。＜ High-rate discharge test after aging ＞
According to the steps shown in (1) to (10) of the pouch battery manufactured in the above manner, a high-rate discharge test after aging is performed to calculate the DC-IR resistance value.
Test temperature: 30 ℃
Cut-off potential: 2.5-4.3V (vs. Li + / Li)
(1) In CC (CV) charge / CC discharge, 10-cycle aging is performed under the conditions of 0.2C (0.05C) /0.2C. At this time, record the average discharge voltage value at the end of aging.
※ Listed in order of charge / discharge. CV terminal current is in parentheses.
(2) Perform 3 cycles under the condition of 0.2C (0.05C) /0.5C, and record the average discharge voltage value of the 3rd cycle.
(3) Two cycles were performed at 0.2C (0.05C) /0.2C.
(4) Change the discharge rate of (2) to 0.7C, perform 3 cycles, and record the average discharge voltage value in the 3rd cycle.
(5) Perform 2 cycles at 0.2C (0.05C) /0.2C.
(6) Change the discharge rate of (2) to 1.0C, perform 3 cycles, and record the average discharge voltage value in the 3rd cycle.
(7) Two cycles were performed at 0.2C (0.05C) /0.2C.
(8) Change the discharge rate of (2) to 2.0C, implement 3 cycles, and record the average discharge voltage value in the 3rd cycle.
(9) Make a graph with discharge current (rate) on the horizontal axis and average discharge voltage on the vertical axis. At that time, input the average voltage value at 0.2, 0.5, 0.7, 1.0, and 2.0C.
(10) The slope of the graph indicates the value of DC-IR (Ω).
In addition, all the pouch batteries produced were tested under these conditions.
The DC-IR values calculated by the tests are shown in Table 3.

＜循環試驗＞
用以上述方式完成高速率放電試驗後的各袋式電池，按以下所示步驟進行循環試驗。
試驗溫度：30℃
截止電位：2.5-4.3V(vs.Li+/Li)
循環速率：0.5C(0.05C)/0.5C
循環次數：100
循環後，用下式算出容量維持率。結果列於表3。
※容量維持率(%)=[100循環後之放電容量(mAh/g)]/[老化後之初始放電容量(mAh/g)]×100＜ Cycle test ＞
After completing the high-rate discharge test in the above manner, each pouch battery was subjected to a cycle test in accordance with the steps shown below.
Test temperature: 30 ℃
Cut-off potential: 2.5-4.3V (vs. Li + / Li)
Cycle rate: 0.5C (0.05C) /0.5C
Number of cycles: 100
After the cycle, the capacity retention rate was calculated using the following formula. The results are shown in Table 3.
※ Capacity maintenance rate (%) = [Discharge capacity after 100 cycles (mAh / g)] / [Initial discharge capacity after aging (mAh / g)] × 100

＜100循環後高速率放電試驗＞
用上述方式完成循環試驗後之各袋式電池，進行高速率放電試驗。另，試驗方法、條件與老化後高速率放電試驗相同。
經由試驗所算出之DC-IR值列於表3。<High-rate discharge test after 100 cycles>
After completing the cycle test in the above manner, each pouch battery was subjected to a high-rate discharge test. In addition, the test methods and conditions are the same as the high-rate discharge test after aging.
The DC-IR values calculated by the tests are shown in Table 3.

又，DC-IR電阻值(Ω)之值愈低，可稱電池性能(放電特性)愈佳；容量維持率(%)之值愈高，則可稱電池性能(循環特性)愈佳。In addition, the lower the value of the DC-IR resistance (Ω), the better the battery performance (discharge characteristics); the higher the value of the capacity retention rate (%), the better the battery performance (cycle characteristics).

[表3]
[table 3]

圖1係針對本發明中包含之非水電解質二次電池用電極合劑之一態樣，顯示其概要。FIG. 1 is a view showing an outline of an electrode mixture for a non-aqueous electrolyte secondary battery included in the present invention.

圖2係顯示將圖1所示非水電解質二次電池用電極合劑塗敷於金屬箔後，使其乾燥、加壓、加熱而調製出電極時之一態樣概要。 FIG. 2 is a schematic view showing a state when the electrode mixture for a non-aqueous electrolyte secondary battery shown in FIG. 1 is applied to a metal foil, and then dried, pressed, and heated to prepare an electrode.

圖3係針對在含有交聯型樹脂之黏結劑及含有電極活性物質之電極合劑以及進一步添加交聯劑時，可成為本發明之非水電解質二次電池用電極合劑的情況顯示其概要。 FIG. 3 shows the outline of the case where the binder for a non-aqueous electrolyte secondary battery of the present invention can be used when a binder containing a cross-linking resin, an electrode mixture containing an electrode active material, and a cross-linking agent are further added.

Claims (9)

一種非水電解質二次電池用電極合劑，含有電極活性物質、交聯劑與黏結劑； 其中，前述黏結劑含有乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物； 前述交聯劑為金屬螯合錯合物； 並且，相對於前述黏結劑及前述交聯劑之合計量100質量份，含有0.2質量份以上且低於10質量份之前述交聯劑。An electrode mixture for a non-aqueous electrolyte secondary battery, comprising an electrode active material, a cross-linking agent, and a binder; Wherein, the aforementioned binder contains a copolymer of vinyl alcohol and an alkali metal neutralizer of ethylenically unsaturated carboxylic acid; The aforementioned cross-linking agent is a metal chelate complex; In addition, the crosslinking agent is contained in an amount of 0.2 parts by mass or more and less than 10 parts by mass based on 100 parts by mass of the total amount of the binder and the crosslinking agent. 如請求項1之非水電解質二次電池用電極合劑，其中金屬螯合錯合物係選自於由鈦螯合錯合物及鋯螯合錯合物所構成群組中之至少1種。The electrode mixture for a non-aqueous electrolyte secondary battery according to claim 1, wherein the metal chelate complex is at least one selected from the group consisting of a titanium chelate complex and a zirconium chelate complex. 如請求項1或2之非水電解質二次電池用電極合劑，其中前述交聯劑係具有2個以上可與羧基及/或羥基反應之官能基的交聯劑。The electrode mixture for a non-aqueous electrolyte secondary battery according to claim 1 or 2, wherein the crosslinking agent is a crosslinking agent having two or more functional groups capable of reacting with a carboxyl group and / or a hydroxyl group. 如請求項1或2之非水電解質二次電池用電極合劑，其中前述交聯劑係具有2個以上相同或不同之官能基的交聯劑，且前述官能基係選自於由烷氧基及醯化基所構成之群組。The electrode mixture for a non-aqueous electrolyte secondary battery according to claim 1 or 2, wherein the crosslinking agent is a crosslinking agent having two or more functional groups that are the same or different, and the functional group is selected from the group consisting of alkoxy groups. And the group formed by the base. 如請求項1至4中任一項之非水電解質二次電池用電極合劑，其中前述乙烯性不飽和羧酸鹼金屬中和物為丙烯酸鹼金屬中和物及/或甲基丙烯酸鹼金屬中和物。The electrode mixture for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 4, wherein the aforementioned ethylenically unsaturated carboxylic acid alkali metal neutralizer is an acrylic acid alkali metal neutralizer and / or an methacrylic acid alkali metal neutralizer. And things. 一種非水電解質二次電池用電極，使用有如請求項1至5中任一項之非水電解質二次電池用電極合劑。An electrode for a non-aqueous electrolyte secondary battery using the electrode mixture for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 5. 一種非水電解質二次電池，具備如請求項6之非水電解質二次電池用電極。A non-aqueous electrolyte secondary battery includes the electrode for a non-aqueous electrolyte secondary battery according to claim 6. 一種電性機器，具備如請求項7之非水電解質二次電池。An electric device provided with a non-aqueous electrolyte secondary battery as claimed in claim 7. 一種非水電解質二次電池用電極合劑之製造方法，其包含將電極活性物質、交聯劑及黏結劑混合之步驟； 在此，前述交聯劑為金屬螯合錯合物，前述黏結劑為乙烯醇與乙烯性不飽和羧酸鹼金屬中和物之共聚物，並且前述交聯劑係以相對於前述黏結劑及前述交聯劑之合計量100質量份為0.2質量份以上且低於10質量份的方式進行混合。A method for manufacturing an electrode mixture for a non-aqueous electrolyte secondary battery, comprising the steps of mixing an electrode active material, a cross-linking agent, and a binder; Here, the aforementioned cross-linking agent is a metal chelate complex, the aforementioned bonding agent is a copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid alkali metal neutralizer, and the aforementioned cross-linking agent is relative to the aforementioned bonding agent and The total amount of the cross-linking agent is 0.2 parts by mass or more and less than 10 parts by mass.
TW107132080A 2017-09-12 2018-09-12 Electrode mixture for non-aqueous electrolyte secondary battery TWI770277B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017175158 2017-09-12
JP2017-175158 2017-09-12

Publications (2)

Publication Number Publication Date
TW201921787A true TW201921787A (en) 2019-06-01
TWI770277B TWI770277B (en) 2022-07-11

Family

ID=65723277

Family Applications (2)

Application Number Title Priority Date Filing Date
TW107132080A TWI770277B (en) 2017-09-12 2018-09-12 Electrode mixture for non-aqueous electrolyte secondary battery
TW107132078A TWI803520B (en) 2017-09-12 2018-09-12 Electrode mixture for non-aqueous electrolyte secondary battery

Family Applications After (1)

Application Number Title Priority Date Filing Date
TW107132078A TWI803520B (en) 2017-09-12 2018-09-12 Electrode mixture for non-aqueous electrolyte secondary battery

Country Status (5)

Country Link
JP (2) JP7139341B2 (en)
KR (1) KR20200051521A (en)
CN (2) CN110832679B (en)
TW (2) TWI770277B (en)
WO (2) WO2019054350A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019087258A1 (en) * 2017-10-30 2019-05-09 日立化成株式会社 Resin composition, cured product, molding and method for producing same, film capacitor and method or producing same
US20220336815A1 (en) 2019-09-30 2022-10-20 Zeon Corporation Binder composition for secondary battery, slurry composition for secondary battery electrode, electrode for secondary battery, and secondary battery
CN112164799A (en) * 2020-09-29 2021-01-01 浙江大学 Boron crosslinked binder, electrode slice and preparation method
CN112670506B (en) * 2020-12-22 2022-04-19 北京理工大学重庆创新中心 Nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by fast ion conductor and preparation method thereof
CN112952100B (en) * 2021-05-13 2021-07-30 蜂巢能源科技有限公司 Cobalt-free anode material slurry and preparation method and application thereof
CN114614017A (en) * 2022-03-24 2022-06-10 深圳市皓飞实业有限公司 Binder, negative pole piece and lithium ion battery

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3066682B2 (en) * 1992-09-10 2000-07-17 富士写真フイルム株式会社 Chemical battery
JP2000021408A (en) * 1998-06-30 2000-01-21 Shin Kobe Electric Mach Co Ltd Nonaqueous electrolyte secondary battery
JP2000348730A (en) 2000-01-01 2000-12-15 Seiko Instruments Inc Nonaqueous electrolyte secondary battery
JP2012069457A (en) * 2010-09-27 2012-04-05 Konica Minolta Holdings Inc Porous layer and lithium ion secondary battery
JP5684620B2 (en) 2011-03-25 2015-03-18 三井化学株式会社 Nonaqueous secondary battery binder resin composition, nonaqueous secondary battery negative electrode, and nonaqueous secondary battery
KR102369389B1 (en) * 2012-10-12 2022-03-02 내셔날 인스티튜트 오브 어드밴스드 인더스트리얼 사이언스 앤드 테크놀로지 Binder for use in positive electrode for lithium ion secondary battery, positive electrode for lithium ion secondary battery containing said binder, lithium ion secondary battery using said positive electrode, and electrical machinery and apparatus
CN105340110B (en) * 2013-06-28 2018-08-24 住友精化株式会社 Anode for nonaqueous electrolyte secondary battery mixture, the anode for nonaqueous electrolyte secondary battery containing the mixture, the non-aqueous electrolyte secondary battery and electrical equipment for having the cathode
WO2015151440A1 (en) * 2014-04-01 2015-10-08 住友精化株式会社 Binder for electric double-layer capacitor electrode, electric double-layer capacitor electrode comprising same binder, electric double-layer capacitor using same electrode, and electric apparatus
JP6278804B2 (en) * 2014-04-04 2018-02-14 住友精化株式会社 Lithium ion secondary battery electrode mixture, lithium ion secondary battery electrode containing this mixture, lithium ion secondary battery equipped with this electrode, and electrical equipment
KR102475886B1 (en) * 2015-06-25 2022-12-08 삼성전자주식회사 Negative electrode for lithium metal battery and lithium metal battery including the same
JP6844240B2 (en) * 2015-12-16 2021-03-17 三菱ケミカル株式会社 Binder composition for secondary battery negative electrode, secondary battery negative electrode and secondary battery
JP6647624B2 (en) * 2016-02-08 2020-02-14 住友精化株式会社 Non-aqueous electrolyte secondary battery electrode mixture, non-aqueous electrolyte secondary battery electrode containing the mixture, and non-aqueous electrolyte secondary battery and electric device provided with the electrode
JP2017152121A (en) * 2016-02-23 2017-08-31 Tdk株式会社 Negative electrode for lithium ion secondary battery and lithium ion secondary battery including the same

Also Published As

Publication number Publication date
TWI770277B (en) 2022-07-11
JPWO2019054350A1 (en) 2020-08-27
WO2019054350A1 (en) 2019-03-21
TW201921786A (en) 2019-06-01
TWI803520B (en) 2023-06-01
JPWO2019054348A1 (en) 2020-08-27
CN110832679B (en) 2023-04-28
CN110800141A (en) 2020-02-14
CN110832679A (en) 2020-02-21
CN110800141B (en) 2024-01-02
KR20200051521A (en) 2020-05-13
WO2019054348A1 (en) 2019-03-21
JP7139341B2 (en) 2022-09-20
JP7139342B2 (en) 2022-09-20
KR20200051520A (en) 2020-05-13

Similar Documents

Publication Publication Date Title
TWI743101B (en) Adhesives for non-aqueous electrolyte secondary battery electrodes, electrode mixtures for non-aqueous electrolyte secondary batteries, electrodes for non-aqueous electrolyte secondary batteries, non-aqueous electrolyte secondary batteries, and electrical equipment
JP5686332B2 (en) Binder for positive electrode of lithium ion secondary battery, positive electrode for lithium ion secondary battery containing this binder, lithium ion secondary battery and electric equipment using this positive electrode
TWI770277B (en) Electrode mixture for non-aqueous electrolyte secondary battery
JP6278804B2 (en) Lithium ion secondary battery electrode mixture, lithium ion secondary battery electrode containing this mixture, lithium ion secondary battery equipped with this electrode, and electrical equipment
KR20160024921A (en) Negative-electrode mixture for non-aqueous electrolyte secondary cell, negative electrode for non-aqueous electrolyte secondary cell containing said mixture, non-aqueous electrolyte secondary cell provided with said negative electrode, and electrical device
JP7223699B2 (en) Binder for non-aqueous electrolyte secondary battery electrode, electrode mixture for non-aqueous electrolyte secondary battery, electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and electrical equipment
TWI771498B (en) Binder for non-aqueous electrolyte secondary battery electrodes, electrode mixture for non-aqueous electrolyte secondary batteries, electrodes for non-aqueous electrolyte secondary batteries, non-aqueous electrolyte secondary batteries and electrical equipment
KR102659815B1 (en) Electrode mixture for non-aqueous electrolyte secondary batteries