JP2012059488A - Negative electrode plate for nonaqueous secondary battery and nonaqueous secondary battery using the same - Google Patents

Negative electrode plate for nonaqueous secondary battery and nonaqueous secondary battery using the same Download PDF

Info

Publication number
JP2012059488A
JP2012059488A JP2010200658A JP2010200658A JP2012059488A JP 2012059488 A JP2012059488 A JP 2012059488A JP 2010200658 A JP2010200658 A JP 2010200658A JP 2010200658 A JP2010200658 A JP 2010200658A JP 2012059488 A JP2012059488 A JP 2012059488A
Authority
JP
Japan
Prior art keywords
negative electrode
weight
electrode mixture
rpm
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2010200658A
Other languages
Japanese (ja)
Inventor
Takuya Hirobe
卓也 廣部
Toshitaka Moriyama
利孝 森山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Corp
Original Assignee
Panasonic Corp
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 Panasonic Corp filed Critical Panasonic Corp
Priority to JP2010200658A priority Critical patent/JP2012059488A/en
Publication of JP2012059488A publication Critical patent/JP2012059488A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a negative electrode plate having excellent peel strength between a negative electrode mixture layer and a negative electrode collector, few aggregates, and few defects in the negative electrode mixture layer with the use of a thickener comprising two kinds of carboxymethyl cellulose having different viscosity and degrees of etherification for the negative electrode plate.SOLUTION: A negative electrode plate 7 for a nonaqueous secondary battery contains a negative electrode mixture layer 6 formed by applying a negative electrode mixture paint in which a negative electrode active material composed of a material capable of retaining at least lithium, a binder and a thickener are kneaded and dispersed by a dispersion medium on a negative electrode collector 5. The thickener is configured by combining a first carboxymethyl cellulose with low viscosity and a high degree of etherification, and a second carboxymethyl cellulose with high viscosity and a low degree of etherification.

Description

本発明はリチウムイオン二次電池に代表される非水系二次電池に関し、特に非水系二次電池用負極板およびこれを用いた非水系二次電池に関するものである。   The present invention relates to a non-aqueous secondary battery represented by a lithium ion secondary battery, and more particularly to a negative electrode plate for a non-aqueous secondary battery and a non-aqueous secondary battery using the same.

近年、電子機器や通信機器の小型化および軽量化が急速に進んでおり、これらの駆動用電源として用いられる二次電池に対しても小型化および軽量化が要求されている。このため、従来のアルカリ蓄電池に代わり、高エネルギー密度で高電圧を有する非水系二次電池、代表的なものとしてリチウムイオン二次電池が実用化されている。   In recent years, electronic devices and communication devices are rapidly becoming smaller and lighter, and secondary batteries used as power sources for driving these devices are also required to be smaller and lighter. For this reason, in place of the conventional alkaline storage battery, a non-aqueous secondary battery having a high energy density and a high voltage, and a lithium ion secondary battery as a representative one has been put into practical use.

このリチウムイオン二次電池用正極板の正極活物質としては、Ｌｉ−Ｍｎ系複合酸化物、Ｌｉ−Ｃｏ系複合酸化物、Ｌｉ−Ｎｉ系複合酸化物などが提案され、それらの一部が実用化に至っている。また、これらの複合酸化物の特性を改良すべく、さらに種々の元素置換を試みたＬｉ−Ｍｎ−Ｎｉ系複合酸化物、Ｌｉ−Ｃｏ−Ａｌ系複合酸化物、Ｌｉ−Ｍｇ−Ｃｏ系複合酸化物なども提案されている。   As the positive electrode active material of the positive electrode plate for a lithium ion secondary battery, Li-Mn composite oxide, Li-Co composite oxide, Li-Ni composite oxide, etc. have been proposed, and some of them are practically used. Has led to In addition, in order to improve the properties of these composite oxides, Li-Mn-Ni based composite oxides, Li-Co-Al based composite oxides, Li-Mg-Co based composite oxides were further tried for substitution of various elements. Things have also been proposed.

これらの複合酸化物を正極活物質として用い、そのような正極活物質と結着材とを分散媒に分散または溶解させてスラリー状の正極合剤塗料を調整し、この正極合剤塗料を金属箔からなる正極集電体の上に塗布して正極合剤層を形成することにより非水系二次電池用正極板は作製される。   These composite oxides are used as a positive electrode active material, and such a positive electrode active material and a binder are dispersed or dissolved in a dispersion medium to prepare a slurry-like positive electrode mixture paint. A positive electrode plate for a non-aqueous secondary battery is produced by coating on a positive electrode current collector made of foil to form a positive electrode mixture layer.

一方、非水系二次電池用負極板は、充電時に正極合剤層から放出されるリチウムイオン等の陽イオンを吸蔵できるカーボン等の炭素材料を負極活物質として用い、そのような負極活物質と増粘剤および結着材とを適当な分散媒に分散または溶解させてスラリー状の負極合剤塗料を調整し、この負極合剤塗料を金属箔からなる負極集電体の上に付着させて負極合剤層を形成することにより作製される。   On the other hand, a negative electrode plate for a non-aqueous secondary battery uses, as a negative electrode active material, a carbon material such as carbon that can occlude cations such as lithium ions released from the positive electrode mixture layer during charging. A slurry-like negative electrode mixture paint is prepared by dispersing or dissolving a thickener and a binder in an appropriate dispersion medium, and this negative electrode mixture paint is adhered onto a negative electrode current collector made of a metal foil. It is produced by forming a negative electrode mixture layer.

この負極合剤層は、欠陥が存在したり製造工程にて負極合剤層が脱落したりすると安全性に大きな影響を及ぼす。具体的には負極合剤層の脱落部にＬｉが析出して多孔質絶縁体としてのセパレータを突き破ることで短絡し発熱などの不具合を生じる場合がある。   This negative electrode mixture layer has a great influence on safety if there is a defect or the negative electrode mixture layer falls off during the production process. Specifically, Li may precipitate on the falling part of the negative electrode mixture layer and break through the separator as a porous insulator, thereby causing a short circuit and causing problems such as heat generation.

そこで、負極合剤層に発生するピンホールやクレーターなどの不良を改良するために、１重量％の水溶液の粘度が異なる２種類の増粘剤を使用し、２段階に分けて分散させる方法が提案されている（例えば、特許文献１参照）。   Therefore, in order to improve defects such as pinholes and craters generated in the negative electrode mixture layer, a method of dispersing in two stages using two types of thickeners having different viscosities of a 1% by weight aqueous solution. It has been proposed (see, for example, Patent Document 1).

また、乾燥時に生ずる負極合剤層の面質の悪化を抑制するために、増粘剤として親水性が高いエーテル化度が１．１５〜１．４５のカルボキシメチルセルロースナトリウム塩を使用する方法が提案されている（例えば、特許文献２参照）。   In addition, a method of using a carboxymethyl cellulose sodium salt having a high degree of etherification of 1.15 to 1.45 as a thickener is proposed in order to suppress deterioration of the surface quality of the negative electrode mixture layer that occurs during drying. (For example, refer to Patent Document 2).

また、負極活物質をイオン透過性のカルボキシメチルセルロース（ＣＭＣ）とスチレンブタジエンラバー（ＳＢＲ）で被覆することで初充電時のガス発生量を低減し初充電効率を向上することができ、さらにはサイクル試験におけるガス発生を抑制し容量維持率を改善することができる。このような目的でエーテル化度が０．５〜１．５で、かつ重量平均分子量が５０００〜５０００００のカルボキシメチルセルロースを使用する方法が提案されている（例えば、特許文献３参照）。   In addition, by covering the negative electrode active material with ion-permeable carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR), the amount of gas generated during the initial charge can be reduced and the initial charge efficiency can be improved. It is possible to suppress the gas generation in the test and improve the capacity maintenance rate. For this purpose, a method of using carboxymethylcellulose having a degree of etherification of 0.5 to 1.5 and a weight average molecular weight of 5,000 to 500,000 has been proposed (for example, see Patent Document 3).

特開２００９−９９４４１号公報JP 2009-99441 A 特開２００９−１４０６３７号公報JP 2009-140637 A 特開２００５−５１１３号公報JP 2005-5113 A

しかしながら、上述した特許文献１の従来技術では増粘剤の１重量％の水溶液の粘度を規定しているが、増粘剤として使用されるカルボキシメチルセルロースはエーテル化度によっても接着性が変化するため、１重量％の水溶液の粘度を規定するだけでは剥離強度が高くピンホールやクレーターなどの不良が少ない非水系二次電池用負極板を提供するには不十分である。   However, in the above-described prior art of Patent Document 1, the viscosity of a 1% by weight aqueous solution of a thickener is specified, but the adhesiveness of carboxymethyl cellulose used as a thickener changes depending on the degree of etherification. It is insufficient to provide a negative electrode plate for a non-aqueous secondary battery that has high peel strength and few defects such as pinholes and craters simply by defining the viscosity of a 1% by weight aqueous solution.

また、上述した特許文献２の従来技術では増粘剤として使用するカルボキシメチルセルロースのエーテル化度を１．１５〜１．４５の範囲で規定しているが、このような高エーテル化度のカルボキシメチルセルロースは結着力が低いため、負極合剤層が負極集電体から脱落する不具合や脱落に伴う電池特性の劣化および安全性の低下を引き起こす場合がある。また、負極合剤層が負極集電体から脱落するのを防ぐために増粘剤を多く使用した場合には、負極合剤層に含まれる負極活物質の比率が低下し電池の容量が低下する。   Further, in the above-described prior art of Patent Document 2, the degree of etherification of carboxymethyl cellulose used as a thickener is defined in the range of 1.15 to 1.45. Has a low binding force, the negative electrode mixture layer may drop off from the negative electrode current collector, or may cause deterioration of battery characteristics and drop in safety. In addition, when a large amount of thickener is used to prevent the negative electrode mixture layer from falling off the negative electrode current collector, the ratio of the negative electrode active material contained in the negative electrode mixture layer is reduced and the capacity of the battery is reduced. .

さらに上述した特許文献３の従来技術ではエーテル化度が０．５〜１．５で、かつ重量平均分子量が５０００〜５０００００のカルボキシメチルセルロースを使用する方法が提案されているが、この範囲の規定では負極活物質に対するカルボキシメチルセルロースの被覆状態がばらつくためガス発生の抑制やサイクル特性の改善に対して十分な効果が得られない。   Furthermore, in the above-described prior art of Patent Document 3, a method using carboxymethylcellulose having a degree of etherification of 0.5 to 1.5 and a weight average molecular weight of 5,000 to 500,000 is proposed. Since the coating state of carboxymethyl cellulose on the negative electrode active material varies, a sufficient effect for suppressing gas generation and improving cycle characteristics cannot be obtained.

本発明は上記従来の課題を鑑みてなされたもので、低粘度で高エーテル化度の第一のカルボキシメチルセルロースと、高粘度で低エーテル化度の第二のカルボキシメチルセルロースを組み合わせて構成した増粘剤を用いて非水系二次電池用負極板とすることで、少量の添加で適度の増粘作用および負極合剤層と負極集電体の間における剥離強度の増大作用を得ること、また合剤脱落などの不良の少ない非水系二次電池用負極板を提供すること、さらに負極活物質をカルボキシメチルセルロースで被覆することでガス発生を抑制しサイクル特性を向上することを目的とする。   The present invention has been made in view of the above-described conventional problems, and is a thickening agent composed of a combination of a first carboxymethyl cellulose having a low viscosity and a high degree of etherification and a second carboxymethyl cellulose having a high viscosity and a low degree of etherification. By using a negative electrode plate for a non-aqueous secondary battery using an agent, it is possible to obtain an appropriate thickening effect and an increase in peel strength between the negative electrode mixture layer and the negative electrode current collector with a small amount of addition. An object of the present invention is to provide a negative electrode plate for a non-aqueous secondary battery with few defects such as agent dropping, and to further improve the cycle characteristics by suppressing gas generation by coating the negative electrode active material with carboxymethyl cellulose.

上記従来の目的を達成するために本発明の非水系二次電池用負極板は、少なくともリチウムを保持しうる材料よりなる負極活物質と結着材および増粘剤を分散媒にて混練分散した負極合剤塗料を負極集電体の上に付着させて負極合剤層を形成した非水系二次電池用負極板であって、増粘剤を低粘度で高エーテル化度の第一のカルボキシメチルセルロースと、高粘度で低エーテル化度の第二のカルボキシメチルセルロースを組み合わせて構成したことを特徴とするものである。   In order to achieve the above-mentioned conventional object, the negative electrode plate for a non-aqueous secondary battery of the present invention is prepared by kneading and dispersing a negative electrode active material made of a material capable of holding at least lithium, a binder and a thickener in a dispersion medium. A negative electrode plate for a non-aqueous secondary battery in which a negative electrode mixture paint is deposited on a negative electrode current collector to form a negative electrode mixture layer, wherein the thickener has a low viscosity and a high degree of etherification. It is composed of a combination of methylcellulose and a second carboxymethylcellulose having a high viscosity and a low degree of etherification.

本発明の非水系二次電池用負極板によると、少量の添加で適度の増粘作用および負極合剤層と負極集電体の間における剥離強度の増大作用を得ることで負極合剤層の脱落による欠陥の発生を抑制し、安全性の高い非水系二次電池用負極板を提供することが可能となる。   According to the negative electrode plate for a non-aqueous secondary battery of the present invention, by adding a small amount, an appropriate thickening action and an increase in peel strength between the negative electrode mixture layer and the negative electrode current collector can be obtained. It is possible to provide a negative electrode plate for a non-aqueous secondary battery that suppresses the occurrence of defects due to dropping and has high safety.

本発明の一実施の形態の非水系二次電池における電極群の構成を示した断面模式図。The cross-sectional schematic diagram which showed the structure of the electrode group in the non-aqueous secondary battery of one embodiment of this invention. 本発明の一実施の形態の非水系二次電池の一例としての円筒形リチウムイオン二次電池の一部切欠斜視図。1 is a partially cutaway perspective view of a cylindrical lithium ion secondary battery as an example of a non-aqueous secondary battery according to an embodiment of the present invention.

本発明の第１の発明においては、少なくともリチウムを保持しうる材料よりなる負極活物質と結着材および増粘剤を分散媒にて混練分散した負極合剤塗料を負極集電体の上に付着させて負極合剤層を形成した非水系二次電池用負極板であって、増粘剤を低粘度で高エーテル化度の第一のカルボキシメチルセルロースと、高粘度で低エーテル化度の第二のカルボキシメチルセルロースを組み合わせて構成することで、負極活物質への吸着性が良好な第一のカルボキシメチルセルロースで負極活物質を被覆して接着作用の大きい第二のカルボキシメチルセルロースを負極活物質へ吸着しやすくすることで、負極集電体と負極合剤層との剥離強度を高めることができる。   In the first invention of the present invention, a negative electrode mixture paint obtained by kneading and dispersing a negative electrode active material made of a material capable of holding at least lithium, a binder, and a thickener in a dispersion medium is provided on a negative electrode current collector. A negative electrode plate for a non-aqueous secondary battery in which a negative electrode mixture layer is formed by attaching a thickener, a first carboxymethyl cellulose having a low viscosity and a high degree of etherification, and a high viscosity and a low degree of etherification. By combining two carboxymethylcelluloses, the first carboxymethylcellulose, which has good adsorptivity to the negative electrode active material, covers the negative electrode active material and adsorbs the second carboxymethylcellulose, which has a large adhesive action, to the negative electrode active material. By making it easy to do, the peeling strength of a negative electrode collector and a negative mix layer can be raised.

本発明の第２の発明においては、第一のカルボキシメチルセルロースのエーテル化度を１．０〜１．５とすることで、ミクロゲルを抑制しかつ少量で効率的に負極活物質を被覆することができる。   In the second invention of the present invention, by setting the degree of etherification of the first carboxymethyl cellulose to 1.0 to 1.5, it is possible to suppress the microgel and efficiently coat the negative electrode active material with a small amount. it can.

本発明の第３の発明においては、第一のカルボキシメチルセルロースの１重量％の水溶液の粘度を１０〜１，８００ｍＰａ・ｓとすることで、分散媒への溶解が容易となり負極合剤塗料中での凝集物の発生を抑制することができる。   In the third aspect of the present invention, by setting the viscosity of a 1% by weight aqueous solution of the first carboxymethyl cellulose to 10 to 1,800 mPa · s, dissolution in the dispersion medium is facilitated and in the negative electrode mixture paint The generation of aggregates can be suppressed.

本発明の第４の発明においては、第二のカルボキシメチルセルロースのエーテル化度を０．５〜０．８としたことで、少量でも高い剥離強度を得ることができる。   In 4th invention of this invention, high peel strength can be obtained even if it is a small quantity because the etherification degree of the 2nd carboxymethylcellulose was 0.5-0.8.

本発明の第５の発明においては、第二のカルボキシメチルセルロースの１重量％の水溶液の粘度を３，０００〜１０，０００ｍＰａ・ｓとしたことで、少量でも高い増粘作用を得ることができる。   In the fifth invention of the present invention, a high thickening effect can be obtained even in a small amount by setting the viscosity of the 1% by weight aqueous solution of the second carboxymethylcellulose to 3,000 to 10,000 mPa · s.

本発明の第６の発明においては、負極合剤塗料として負極活物質を１００重量部とした場合、前記第一のカルボキシメチルセルロースおよび第二のカルボキシメチルセルロースの総量を０．４重量部以上１．２重量部以下含有したことで、負極合剤層中の負極活物質の比率を高め電池の容量を高めることができる。   In the sixth aspect of the present invention, when the negative electrode active material is 100 parts by weight as the negative electrode mixture paint, the total amount of the first carboxymethyl cellulose and the second carboxymethyl cellulose is 0.4 parts by weight or more and 1.2. By containing the amount by weight or less, the ratio of the negative electrode active material in the negative electrode mixture layer can be increased and the capacity of the battery can be increased.

本発明の第７の発明においては、負極合剤塗料として負極活物質を１００重量部とした場合、第一のカルボキシメチルセルロースを０．１重量部以上０．４重量部以下含有し、第二のカルボキシメチルセルロースを０．３重量部以上０．８重量部以下含有したことで、第一のカルボキシメチルセルロースで活物質を適度に被覆して非水電解液の分解を抑制し、かつ第二のカルボキシメチルセルロースを負極活物質に効果的に吸着させることで、適度な増粘作用と剥離強度を得ることができる。   In the seventh aspect of the present invention, when the negative electrode active material is 100 parts by weight as the negative electrode mixture paint, the first carboxymethyl cellulose is contained in an amount of 0.1 parts by weight to 0.4 parts by weight, By containing 0.3 parts by weight or more and 0.8 parts by weight or less of carboxymethyl cellulose, the active material is appropriately coated with the first carboxymethyl cellulose to suppress decomposition of the non-aqueous electrolyte, and the second carboxymethyl cellulose By effectively adsorbing to the negative electrode active material, an appropriate thickening action and peel strength can be obtained.

本発明の第８の発明においては、前記負極合剤塗料として負極活物質の比表面積を３．０〜５．５ｍ２／ｇとしたことで、電池のサイクル特性と負極合剤層の剥離強度の向上を両立することができる。 In the eighth aspect of the present invention, the negative electrode active material has a specific surface area of 3.0 to 5.5 m 2 / g as the negative electrode mixture paint, so that the cycle characteristics of the battery and the peel strength of the negative electrode mixture layer can be obtained. Can be improved at the same time.

本発明の第９の発明においては、負極合剤塗料として結着材にスチレンブタジエンラバーを用いることで、非水系二次電池用負極板に適度の柔軟性を付与することができる。   In 9th invention of this invention, moderate softness | flexibility can be provided to the negative electrode plate for non-aqueous secondary batteries by using a styrene butadiene rubber for a binder as a negative mix paint.

本発明の第１０の発明においては、少なくともリチウム含有複合酸化物よりなる正極活物質と導電材および結着材を分散媒にて混練分散した正極合剤塗料を正極集電体の上に付着させて正極合剤層を形成した正極板と少なくともリチウムを保持しうる材料よりなる活物質と結着材および増粘剤を分散媒にて混練分散した負極合剤塗料を負極集電体の上に付着させて負極合剤層を形成し負極板との間に多孔質絶縁体を介在させて渦巻状に捲回または積層して構成した電極群を非水電解液とともに電池ケースに封入した非水系二次電池であって、負極板に上記第１〜９の発明に記載の非水系二次電池用負極板を用いることで、負極合剤層の脱落などの不具合を抑制し、負極合剤層の脱落による電池特性の劣化を抑制し、電池の容量を高めることができる。   In the tenth aspect of the present invention, a positive electrode mixture paint obtained by kneading and dispersing at least a positive electrode active material comprising a lithium-containing composite oxide, a conductive material, and a binder with a dispersion medium is adhered onto the positive electrode current collector. A negative electrode mixture coating material obtained by kneading and dispersing an active material, a binder, and a thickener in a dispersion medium with a positive electrode plate having a positive electrode mixture layer formed thereon and a material capable of holding at least lithium. A non-electrolytic solution encapsulated in a battery case together with a non-aqueous electrolyte solution is formed by adhering to form a negative electrode mixture layer and interposing a porous insulator between the negative electrode plate and winding or laminating it in a spiral shape An aqueous secondary battery that uses the negative electrode plate for a non-aqueous secondary battery according to any of the first to ninth inventions as a negative electrode plate, thereby suppressing problems such as dropping off of the negative electrode mixture layer. Suppressing deterioration of battery characteristics due to falling off of the layer and increasing battery capacity Kill.

以下、本発明の一実施の形態について図面を参照しながら説明する。   Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

まず、図１は本発明の一実施の形態の非水系二次電池における電極群１の構成を示した断面模式図である。同図１に示したように正極集電体２の両面に正極合剤層３を形成した正極板４および負極集電体５の両面に負極合剤層６を形成した負極板７により構成されており、これら正極板４と負極板７の間に多孔質絶縁体としてのセパレータ８を介してＡ方向に渦巻状に巻回して電極群１を構成している。   First, FIG. 1 is a schematic cross-sectional view showing a configuration of an electrode group 1 in a nonaqueous secondary battery according to an embodiment of the present invention. As shown in FIG. 1, a positive electrode plate 4 having a positive electrode mixture layer 3 formed on both surfaces of a positive electrode current collector 2 and a negative electrode plate 7 having a negative electrode mixture layer 6 formed on both surfaces of a negative electrode current collector 5. The electrode group 1 is configured by spirally winding the positive electrode plate 4 and the negative electrode plate 7 in the A direction via a separator 8 as a porous insulator.

次に、電極群１の構成要素について、さらに詳しく説明する。   Next, the components of the electrode group 1 will be described in more detail.

本発明のリチウムイオン二次電池用の負極板７は、負極集電体５の一面又は両面に形成される少なくとも炭素材料からなる負極活物質と結着材を含む負極合剤層６から構成される。負極板７の負極集電体５としては、電解銅箔や圧延銅箔等の銅箔が好ましく用いられる。   A negative electrode plate 7 for a lithium ion secondary battery of the present invention is composed of a negative electrode mixture layer 6 containing a negative electrode active material made of at least a carbon material and a binder formed on one surface or both surfaces of a negative electrode current collector 5. The As the negative electrode current collector 5 of the negative electrode plate 7, a copper foil such as an electrolytic copper foil or a rolled copper foil is preferably used.

このときの負極集電体５の厚さは通常、５〜５０μｍ程度とする。炭素材料は特に制限されるものではなく、例えば、天然黒鉛、球状あるいは繊維状の人造黒鉛、コークス等の易黒鉛化性炭素、フェノール樹脂焼成体等の難黒鉛化性炭素等を用いることができる。負極活物質は、塗工層中に均一に分散させるために１〜１００μｍの範囲の粒径を有し、且つ平均粒径が３〜３０μｍの粉体であることが好ましい。なお、これらの１種を単独であるいは２種以上を混合して用いてもよい。   At this time, the thickness of the negative electrode current collector 5 is usually about 5 to 50 μm. The carbon material is not particularly limited, and examples thereof include natural graphite, spherical or fibrous artificial graphite, graphitizable carbon such as coke, and non-graphitizable carbon such as a phenol resin fired body. . The negative electrode active material is preferably a powder having a particle size in the range of 1 to 100 μm and an average particle size of 3 to 30 μm in order to uniformly disperse it in the coating layer. In addition, you may use these 1 type individually or in mixture of 2 or more types.

また、人造黒鉛は、例えば、易黒鉛化性炭素を２８００℃以上の高温で熱処理して製造することができる。この場合の原料となる易黒鉛化性炭素には、コークス、ピッチ類を４００℃前後で加熱する過程で得られる光学異方性の小球体（メソカーボンマイクロビーズ：ＭＣＭＢ）等がある。   In addition, artificial graphite can be produced, for example, by heat-treating easily graphitizable carbon at a high temperature of 2800 ° C. or higher. The graphitizable carbon used as a raw material in this case includes optically anisotropic microspheres (mesocarbon microbeads: MCMB) obtained in the process of heating coke and pitch at around 400 ° C.

ここで、上述した負極活物質の比表面積は３．０ｍ２／ｇより小さいと第一のカルボキシメチルセルロースによる被覆が過剰となり初期効率が低下し、５．５ｍ２／ｇより大きいと第一のカルボキシメチルセルロースによる被覆が不足してサイクル特性が悪化するために３．０〜５．５ｍ２／ｇとすることが好ましい。 Here, the specific surface area of the negative electrode active material described above reduces the initial efficiency becomes excessive coating with 3.0 m 2 / g is less than a first carboxymethyl cellulose, 5.5 m 2 / g larger than the first carboxy Since the cycle characteristics are deteriorated due to insufficient coating with methylcellulose, it is preferably 3.0 to 5.5 m 2 / g.

このときの結着材は水に溶解し得る結着材であれば特に限定されるものではない。ペースト状の負極合剤塗料を負極集電体５に塗布、乾燥した後における負極活物質どうしおよび負極合剤層６と負極集電体５との結着を良好なものとしかつ水に容易に溶解または分散し得るという観点から、スチレンブタジエンラバーを採用することが望ましい。   The binding material at this time is not particularly limited as long as it can be dissolved in water. After the paste-like negative electrode mixture paint is applied to the negative electrode current collector 5 and dried, the negative electrode active materials and the binding between the negative electrode mixture layer 6 and the negative electrode current collector 5 are made favorable and easily in water. From the viewpoint of being able to be dissolved or dispersed, it is desirable to employ styrene butadiene rubber.

また、増粘剤は負極活物質である粉末状の炭素粒子に吸着し、その炭素粒子を負極合剤塗料中に分散させる役割を果たすとともに、負極活物質どうしおよび負極合剤層６と負極集電体５とを結着させる役割を果たすものである。   Further, the thickener is adsorbed on the powdered carbon particles as the negative electrode active material and plays a role of dispersing the carbon particles in the negative electrode mixture paint, and the negative electrode active materials and the negative electrode mixture layer 6 and the negative electrode collector. It plays a role of binding the electric body 5.

さらに、本発明の特徴である増粘剤は低粘度で高エーテル化度の第一のカルボキシメチルセルロースと高粘度で低エーテル化度の第二のカルボキシメチルセルロースを組み合わせて構成している。ここで、負極活物質への吸着性が良好な第一のカルボキシメチルセルロースで負極活物質を被覆して接着作用の大きい第二のカルボキシメチルセルロースで負極活物質へ吸着しやすくする役割を果たしている。   Furthermore, the thickener which is a feature of the present invention is composed of a combination of a first carboxymethyl cellulose having a low viscosity and a high degree of etherification and a second carboxymethyl cellulose having a high viscosity and a low degree of etherification. Here, the negative electrode active material is covered with the first carboxymethyl cellulose having good adsorptivity to the negative electrode active material, and the second carboxymethyl cellulose having a large adhesive action plays a role of facilitating adsorption to the negative electrode active material.

また、この増粘剤は添加量も電池特性に影響を及ぼす。増粘剤が過剰な場合、それが炭素粒子の表面に吸着して過剰な被膜を形成する。その結果、リチウムイオンの移動が妨げられ、さらには炭素材料の電気絶縁性が大きくなるために、負極板７を構成した場合に電気抵抗が大きくなってしまうからである。 具体的には、負極合剤塗料中の増粘剤の含有割合を負極活物質を１００重量部とした場合０．４重量部以上で１．２重量部以下とすることが望ましい。   Further, the amount of the thickener added also affects the battery characteristics. If the thickener is excessive, it will adsorb on the surface of the carbon particles and form an excessive coating. As a result, the movement of lithium ions is hindered, and further, the electrical insulation of the carbon material is increased, so that the electrical resistance increases when the negative electrode plate 7 is configured. Specifically, the content of the thickener in the negative electrode mixture paint is desirably 0.4 parts by weight or more and 1.2 parts by weight or less when the negative electrode active material is 100 parts by weight.

一方、０．４重量部未満であると負極合剤層６と負極集電体５との密着性が悪く、極板製造工程で負極合剤層６が負極集電体５から脱落する不具合や脱落に伴う電池特性の劣化および安全性の低下を引き起こす場合がある。   On the other hand, when the amount is less than 0.4 parts by weight, the adhesion between the negative electrode mixture layer 6 and the negative electrode current collector 5 is poor, and the negative electrode mixture layer 6 falls off the negative electrode current collector 5 in the electrode plate manufacturing process. It may cause deterioration of battery characteristics and reduction of safety due to dropping.

ここで、増粘剤は、例えば、ポリエチレンオキサイド（ＰＯＥ）、ポリビニルアルコール（ＰＶＡ）、ポリアクリルアミド、ポリビニルピロリドン（ＰＶＰ）等の合成高分子や、セルロースエーテル系の樹脂を用いることができる。これらの中でもセルロースエーテル系樹脂は、人体に毒性を示すことはなく生体系に対しても無害であるという利点があることからこれを用いるのが望ましい。   Here, as the thickener, for example, synthetic polymers such as polyethylene oxide (POE), polyvinyl alcohol (PVA), polyacrylamide, polyvinyl pyrrolidone (PVP), and cellulose ether resins can be used. Among these, it is desirable to use a cellulose ether resin because it has an advantage that it is not toxic to the human body and is harmless to biological systems.

さらには、分散媒としての水に負極活物質を分散させるために親油性物質である黒鉛と分散媒である水をつなぐ材料であるため、親水性と疎水性（親油性）の両方の性質をもつ界面活性剤としての機能を有する必要があることからもセルロースエーテル系樹脂が望ましい。セルロースエーテル系樹脂は、エーテル化度、平均分子量、変性等が異なる種々のものがある。   Furthermore, since it is a material that connects graphite, which is a lipophilic substance, to water, which is a dispersion medium, in order to disperse the negative electrode active material in water as the dispersion medium, it has both hydrophilic and hydrophobic (lipophilic) properties. A cellulose ether resin is also desirable because it needs to have a function as a surfactant. There are various types of cellulose ether resins having different degrees of etherification, average molecular weight, modification and the like.

セルロースエーテル系樹脂は、セルロースが有する水酸基の一部をエーテル化したものである。セルロース単位には３つの水酸基が存在する。例えば、セルロースエーテルのすべてのセルロース単位において、水酸基の１つがエーテル化されている場合は、エーテル化度が１．０となる。つまり、エーテル化度は、セルロースに含まれる水酸基がどれだけエーテル化されているかを示す指標である。また、セルロースエーテル系樹脂は、付加する官能基によって種々のものを用いることができ、例えば、セルロースエーテルのナトリウム塩、アンモニウム塩等が挙げられる。   The cellulose ether resin is obtained by etherifying a part of the hydroxyl group of cellulose. There are three hydroxyl groups in the cellulose unit. For example, when one of the hydroxyl groups is etherified in all cellulose units of cellulose ether, the degree of etherification is 1.0. That is, the degree of etherification is an index indicating how much the hydroxyl group contained in cellulose is etherified. Various cellulose ether resins can be used depending on the functional group to be added, and examples thereof include sodium salt and ammonium salt of cellulose ether.

これらの塩のいずれか１種以上を用いればよい。セルロースエーテルとしては、例えば、メチルセルロース、エチルセルロース、ベンジルセルロース、トリエチルセルロース、シアノエチルセルロース、カルボキシメチルセルロース、カルボキシエチルセルロース、アミノエチルセルロース、およびオキシエチルセルロース等のグループから選ばれる１種または２種以上を用いることができる。   Any one or more of these salts may be used. As a cellulose ether, 1 type, or 2 or more types chosen from groups, such as methylcellulose, ethylcellulose, benzylcellulose, triethylcellulose, cyanoethylcellulose, carboxymethylcellulose, carboxyethylcellulose, aminoethylcellulose, and oxyethylcellulose, can be used, for example.

また、カルボキシメチルセルロースは分子量の異なる種類も市販されており、分子量が小さいと水に溶解したときの粘度が低くなり、結果として塗料の粘度が低くなり沈降する可能性が高くなる。しかしながら、分子量が小さいと負極活物質への吸着が容易となり分散もしやすくなる。一方、分子量が大きくなると水に溶解したときの粘度が高いため、沈降しにくく塗料は安定する。しかしながら、分子量が高いため負極活物質へ吸着しにくくなり、分散が悪くなるといった欠点を有する。このような粘度、分散の観点からも、分子量の異なるカルボキシメチルセルロースを使用することが望ましい。   In addition, carboxymethyl cellulose is also commercially available in different molecular weights. If the molecular weight is small, the viscosity when dissolved in water decreases, and as a result, the viscosity of the coating material decreases and the possibility of sedimentation increases. However, when the molecular weight is small, the adsorption to the negative electrode active material is facilitated and the dispersion becomes easy. On the other hand, when the molecular weight increases, the viscosity when dissolved in water is high, so that the paint is difficult to settle and the paint is stable. However, since the molecular weight is high, it is difficult to adsorb to the negative electrode active material, and there is a disadvantage that dispersion is deteriorated. From the viewpoints of such viscosity and dispersion, it is desirable to use carboxymethylcellulose having different molecular weights.

つまり、負極活物質への吸着が容易で、かつ分散媒である水への分散性が良好な分子量が小さいカルボキシメチルセルロースを第一の増粘剤として用い、増粘作用が得やすい分子量の大きいカルボキシメチルセルロースを第二の増粘剤として用いることで、凝集物が少なく沈降しにくい負極合剤塗料を得ることができる。   In other words, carboxymethylcellulose, which is easily adsorbed on the negative electrode active material and has good dispersibility in water as a dispersion medium and has a low molecular weight, is used as the first thickener, and a carboxymethyl cellulose having a high molecular weight that is easy to obtain a thickening action. By using methylcellulose as the second thickener, it is possible to obtain a negative electrode mixture coating material that has few aggregates and is difficult to settle.

ここで、第一のカルボキシメチルセルロースのエーテル化度が１．０より小さいと負極活物質への吸着性が悪くなり、１．５より大きいと負極活物質の被覆状態にむらが生じ均一な被覆が困難となるため、１．０以上１．５以下であることが好ましい。   Here, when the etherification degree of the first carboxymethyl cellulose is less than 1.0, the adsorptivity to the negative electrode active material is deteriorated, and when it is more than 1.5, the coating state of the negative electrode active material is uneven and uniform coating is obtained. Since it becomes difficult, it is preferable that it is 1.0 or more and 1.5 or less.

また、第一のカルボキシメチルセルロースの１重量％の水溶液の粘度が１０ｍＰａ・ｓより小さいと負極合剤塗料の粘度が不足し負極活物質を十分に被覆することが困難となり、１，８００ｍＰａ・ｓより大きいと負極活物質への吸着性が悪くなるため、１０ｍＰａ・ｓ以上１，８００ｍＰａ・ｓ以下であることが好ましい。   Further, if the viscosity of the 1% by weight aqueous solution of the first carboxymethyl cellulose is smaller than 10 mPa · s, the viscosity of the negative electrode mixture paint becomes insufficient, and it becomes difficult to sufficiently coat the negative electrode active material. If it is large, the adsorptivity to the negative electrode active material is deteriorated, and it is preferably 10 mPa · s or more and 1,800 mPa · s or less.

また、第二のカルボキシメチルセルロースのエーテル化度が０．５より小さいとカルボキシメチルセルロースに存在するミクロゲルが多くなり負極合剤層６に発生するスジなどの欠陥が増加し、エーテル化度が０．８より大きいと結着力が低くなり負極合剤層６と負極集電体５との密着性が低下するため、０．５以上０．８以下であることが好ましい。   On the other hand, if the degree of etherification of the second carboxymethyl cellulose is less than 0.5, the amount of microgels present in the carboxymethyl cellulose increases and defects such as streaks generated in the negative electrode mixture layer 6 increase, and the degree of etherification is 0.8. If it is larger, the binding force is lowered, and the adhesion between the negative electrode mixture layer 6 and the negative electrode current collector 5 is lowered. Therefore, it is preferably 0.5 or more and 0.8 or less.

また、第二のカルボキシメチルセルロースの１重量％の水溶液の粘度が３，０００ｍＰａ・ｓより小さいと負極合剤塗料の粘度が不足し均一に分散した負極合剤塗料を得ることが困難となり、１０，０００ｍＰａ・ｓより大きいと負極合剤塗料の粘度が高くなり負極合剤塗料を均一に塗布することが困難となるため、３，０００ｍＰａ・ｓ以上１０，０００ｍＰａ・ｓ以下であることが好ましい。   On the other hand, if the viscosity of the 1% by weight aqueous solution of the second carboxymethyl cellulose is less than 3,000 mPa · s, it becomes difficult to obtain a uniformly dispersed negative electrode mixture paint due to insufficient viscosity of the negative electrode mixture paint. If it is greater than 000 mPa · s, the viscosity of the negative electrode mixture paint becomes high and it becomes difficult to uniformly apply the negative electrode mixture paint. Therefore, it is preferably 3,000 mPa · s or more and 10,000 mPa · s or less.

また、第一のカルボキシメチルセルロースと第二のカルボキシメチルセルロースの総量が０．４重量部より少ないと負極合剤塗料の粘度が不足し均一に分散した負極合剤塗料を得ることが困難となり、１．２重量部より多いと非水系二次電池のサイクル特性が劣化するため、０．４重量部以上１．２重量部以下であることが好ましい。   On the other hand, if the total amount of the first carboxymethyl cellulose and the second carboxymethyl cellulose is less than 0.4 parts by weight, it becomes difficult to obtain a uniformly dispersed negative electrode mixture paint due to insufficient viscosity of the negative electrode mixture paint. If the amount is more than 2 parts by weight, the cycle characteristics of the non-aqueous secondary battery are deteriorated.

さらに、第一のカルボキシメチルセルロースが０．１重量部より少ないと負極活物質への被覆量が不足し、０．４重量部より多いと負極活物質の被覆状態にむらが生じ均一な被覆が困難となる。第二のカルボキシメチルセルロースが０．３重量部より少ないと負極合剤層６と負極集電体５との密着性が低くなり負極合剤層の脱落が生じ、０．８重量部より多くなると負極合剤塗料の粘度が高くなり負極合剤塗料を均一に塗布することが困難となる。よって、第一のカルボキシメチルセルロースは０．１重量部以上０．４重量部以下であることが好ましく、また第二のカルボキシメチルセルロースは０．３重量部以上０．８重量部以下であることが好ましい。   Furthermore, when the amount of the first carboxymethyl cellulose is less than 0.1 parts by weight, the amount of coating on the negative electrode active material is insufficient, and when the amount is more than 0.4 parts by weight, the coating state of the negative electrode active material becomes uneven and uniform coating is difficult. It becomes. When the amount of the second carboxymethyl cellulose is less than 0.3 parts by weight, the adhesion between the negative electrode mixture layer 6 and the negative electrode current collector 5 is lowered, and the negative electrode mixture layer falls off, and when the amount is more than 0.8 parts by weight, the negative electrode The viscosity of the mixture paint becomes high, and it becomes difficult to uniformly apply the negative electrode mixture paint. Therefore, the first carboxymethyl cellulose is preferably 0.1 parts by weight or more and 0.4 parts by weight or less, and the second carboxymethyl cellulose is preferably 0.3 parts by weight or more and 0.8 parts by weight or less. .

本発明のリチウムイオン二次電池用の負極板７は、上述した負極活物質と増粘剤及び結着材とを含む負極合剤層６から形成されるものであり、その形成方法は特に限定するものではない。負極活物質に増粘剤を分散した後に結着材を混合し分散媒として水を加えてペースト状にした負極合剤塗料を、銅等の金属箔からなる負極集電体５の表面に塗布、乾燥し、必要に応じて活物質密度を高めるべくプレスして形成することができる。   The negative electrode plate 7 for the lithium ion secondary battery of the present invention is formed from the negative electrode mixture layer 6 containing the negative electrode active material, the thickener and the binder described above, and the formation method thereof is particularly limited. Not what you want. After the thickener is dispersed in the negative electrode active material, the binder mixture is mixed and water is added as a dispersion medium to form a paste in the form of a paste and applied to the surface of the negative electrode current collector 5 made of a metal foil such as copper. It can be dried and pressed to increase the active material density as necessary.

分散媒として加える水の配合割合は特に制限されるものではない。水の配合割合によりペースト状の負極合剤塗料の粘度を調整することができるため、負極集電体５の表面への塗布方法によってその割合を適宜調整すればよい。一般に、ある負極集電体５の表面に負極合剤塗料を塗布し負極合剤層６を形成した場合、その負極合剤層６と負極集電体５との密着性は、負極合剤塗料を塗布後の乾燥による負極合剤層６の収縮と関係がある。つまり、負極合剤層６の収縮が大きいほど密着性は低下する。また、負極合剤層６の収縮は、負極合剤塗料の固形分濃度と関係があり、負極合剤塗料の固形分濃度が低くなると負極合剤層６の収縮は大きくなる。   The mixing ratio of water added as a dispersion medium is not particularly limited. Since the viscosity of the paste-like negative electrode mixture paint can be adjusted by the mixing ratio of water, the ratio may be appropriately adjusted depending on the method of application to the surface of the negative electrode current collector 5. In general, when a negative electrode mixture paint is applied to the surface of a certain negative electrode current collector 5 to form a negative electrode mixture layer 6, the adhesion between the negative electrode mixture layer 6 and the negative electrode current collector 5 is determined by the negative electrode mixture paint. This is related to the shrinkage of the negative electrode mixture layer 6 due to drying after coating. That is, the greater the shrinkage of the negative electrode mixture layer 6, the lower the adhesion. The shrinkage of the negative electrode mixture layer 6 is related to the solid content concentration of the negative electrode mixture paint, and the shrinkage of the negative electrode mixture layer 6 increases as the solid content concentration of the negative electrode mixture paint decreases.

したがって、ペースト状の負極合剤塗料を負極集電体５に塗布、乾燥して負極板７を形成する場合、塗布する負極合剤塗料の固形分濃度を高くすることで、乾燥後の負極合剤層６の収縮を小さくすることができる。すなわち、負極合剤塗料の固形分濃度が高いほど負極合剤層６と負極集電体５との密着性が高くなる。このような観点から、分散媒として加える水の配合割合は、ペースト状とした負極合剤塗料の全体の重量を１００重量部とした場合の５０重量部以下（固形分濃度５０重量％以上）とすることが望ましい。   Therefore, when the negative electrode plate 7 is formed by applying and drying a paste-like negative electrode mixture paint on the negative electrode current collector 5, the negative electrode mixture after drying can be obtained by increasing the solid content concentration of the applied negative electrode mixture paint. Shrinkage of the agent layer 6 can be reduced. That is, the higher the solid content concentration of the negative electrode mixture paint, the higher the adhesion between the negative electrode mixture layer 6 and the negative electrode current collector 5. From such a viewpoint, the mixing ratio of water added as a dispersion medium is 50 parts by weight or less (solid content concentration of 50% by weight or more) when the total weight of the paste-like negative electrode mixture paint is 100 parts by weight. It is desirable to do.

塗工時の負極合剤塗料の粘度は、負極合剤塗料の経時変化を抑制するためには３，０００ｍＰａ・ｓ以上が望ましく、負極合剤塗料を塗布、乾燥して形成した負極板７の幅方向の重量ばらつきを抑制するためには１２，０００ｍＰａ・ｓ以下とすることが望ましい。   The viscosity of the negative electrode mixture paint at the time of coating is preferably 3,000 mPa · s or more in order to suppress the change over time of the negative electrode mixture paint, and the negative electrode plate 7 formed by applying and drying the negative electrode mixture paint. In order to suppress the weight variation in the width direction, it is desirable to set it to 12,000 mPa · s or less.

塗工後の剥離強度は、負極板７の加工をする上で重要な評価項目である。剥離強度が４Ｎ／ｍ以下では、塗工後のプレス工程で負極合剤層６が脱落する可能性がある。   The peel strength after coating is an important evaluation item in processing the negative electrode plate 7. When the peel strength is 4 N / m or less, the negative electrode mixture layer 6 may fall off in the pressing step after coating.

本発明のリチウムイオン二次電池用の正極板４は、正極集電体２の一面又は両面に少なくとも正極活物質、導電材及び通常は結着材を含有する正極合剤層３を形成して構成される。正極板４の正極集電体２としては通常、アルミニウム箔が好ましく用いられる。正極集電体２の厚さは通常、５〜５０μｍ程度とする。正極活物質としては、従来から非水電解液二次電池の正極活物質として用いられている材料を用いることができ、例えば、ＬｉＭｎ２Ｏ４（マンガン酸リチウム）、ＬｉＣｏＯ２（コバルト酸リチウム）若しくはＬｉＮｉＯ２（ニッケル酸リチウム）等のリチウム酸化物、またはＴｉＳ２、ＭｎＯ２、ＭｏＯ３もしくはＶ２Ｏ５等のカルコゲン化合物を例示することができる。 A positive electrode plate 4 for a lithium ion secondary battery of the present invention is formed by forming a positive electrode mixture layer 3 containing at least a positive electrode active material, a conductive material and usually a binder on one or both surfaces of a positive electrode current collector 2. Composed. In general, an aluminum foil is preferably used as the positive electrode current collector 2 of the positive electrode plate 4. The thickness of the positive electrode current collector 2 is usually about 5 to 50 μm. As a positive electrode active material, the material conventionally used as a positive electrode active material of a nonaqueous electrolyte secondary battery can be used, for example, LiMn 2 O 4 (lithium manganate), LiCoO 2 (lithium cobaltate) Alternatively, a lithium oxide such as LiNiO 2 (lithium nickelate) or a chalcogen compound such as TiS 2 , MnO 2 , MoO 3, or V 2 O 5 can be exemplified.

正極活物質は、正極合剤塗料中に均一に分散させるために、１〜１００μｍの範囲の粒径を有し、且つ平均粒径が３〜３０μｍの粉体であることが好ましい。これらの正極活物質は単独で用いてもよいし、２種以上を組み合わせて用いてもよい。   The positive electrode active material is preferably a powder having a particle size in the range of 1 to 100 μm and an average particle size of 3 to 30 μm in order to be uniformly dispersed in the positive electrode mixture paint. These positive electrode active materials may be used alone or in combination of two or more.

正極合剤塗料中の正極活物質の配合割合は、分散媒を除く配合成分を基準（固形分基準）とした時に、高い電池容量の実現とサイクル特性とのバランスの点から９０〜９８．５重量％とすることが好ましく、更に９６〜９８．５重量％とすることが好ましい。   The mixing ratio of the positive electrode active material in the positive electrode mixture paint is 90 to 98.5 in terms of the balance between realizing high battery capacity and cycle characteristics when the compounding component excluding the dispersion medium is used as a standard (solid content standard). It is preferable to set it as weight%, Furthermore, it is preferable to set it as 96-98.5 weight%.

また、正極合剤塗料には通常結着材が添加される。結着材としては従来から用いられているもの、例えば、熱可塑性樹脂、より具体的にはポリエステル樹脂、ポリアミド樹脂、ポリアクリル酸エステル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、セルロース樹脂、ポリオレフィン樹脂、ポリビニル樹脂、ＰＴＦＥやポリフッ化ビニリデン等のフッ素系樹脂、または、ポリイミド樹脂あるいはスチレンブタジエンラバー等のゴム系樹脂等を使用することができる。この際、反応性官能基を導入したアクリレートモノマーまたはオリゴマーを結着材中に混入させることも可能である。そのほかにも、ゴム系の樹脂や、アクリル樹脂、ウレタン樹脂等の熱硬化性樹脂、アクリレートモノマー、アクリレートオリゴマー或いはそれらの混合物からなる電離放射線硬化性樹脂、上記各種の樹脂の混合物を使用することもできる。   A binder is usually added to the positive electrode mixture paint. Conventionally used binders such as thermoplastic resins, more specifically polyester resins, polyamide resins, polyacrylate resins, polycarbonate resins, polyurethane resins, cellulose resins, polyolefin resins, polyvinyl resins Fluorine resin such as PTFE and polyvinylidene fluoride, or rubber resin such as polyimide resin or styrene butadiene rubber can be used. At this time, an acrylate monomer or oligomer into which a reactive functional group is introduced can be mixed in the binder. In addition, rubber-based resins, thermosetting resins such as acrylic resins and urethane resins, ionizing radiation curable resins composed of acrylate monomers, acrylate oligomers or mixtures thereof, and mixtures of the above various resins may be used. it can.

正極活物質、導電材、結着材、及び他の配合成分を適切な溶剤中に入れ、ホモジナイザー、ボールミル、サンドミル、ロールミルまたはプラネタリーミキサー等の分散機により混合分散してペースト状の正極合剤塗料を作製する。   A positive electrode active material, a conductive material, a binder, and other compounding ingredients are put in an appropriate solvent, and mixed and dispersed by a disperser such as a homogenizer, ball mill, sand mill, roll mill, or planetary mixer, to obtain a paste-like positive electrode mixture Make a paint.

正極合剤塗料の塗布方法は特に限定されないが、例えばダイコート、コンマダイレクトコート、コンマリバースコート等のように厚い正極合剤層３を形成できる方法が適している。ただし、正極合剤層３に求められる厚さが比較的薄い場合には、グラビアコートやグラビアリバースコート等により塗布してもよい。正極合剤層３は複数回塗布、乾燥を繰り返すことにより形成してもよい。   The method for applying the positive electrode mixture paint is not particularly limited, but a method capable of forming a thick positive electrode mixture layer 3 such as die coating, comma direct coating, comma reverse coating, or the like is suitable. However, when the thickness required for the positive electrode mixture layer 3 is relatively thin, it may be applied by gravure coating, gravure reverse coating, or the like. The positive electrode mixture layer 3 may be formed by repeating coating and drying a plurality of times.

乾燥工程における熱源としては、熱風、赤外線、遠赤外線、マイクロ波、高周波、或いはそれらを組み合わせて利用できる。乾燥工程において集電体をサポート又はプレスする金属ローラや金属シートを加熱して放出させた熱によって乾燥してもよい。また、乾燥後電子線または放射線を照射することにより結着材を架橋反応させて合剤層を得ることもできる。   As a heat source in the drying process, hot air, infrared rays, far infrared rays, microwaves, high frequencies, or a combination thereof can be used. You may dry with the heat which discharge | released the metal roller and metal sheet which support or press a collector in a drying process. Moreover, a binder layer can also be obtained by crosslinking reaction of the binder by irradiating an electron beam or radiation after drying.

さらに、得られた正極合剤層３及び負極合剤層６をプレス加工することにより、合剤層の密度、集電体に対する密着性、均質性を向上させることができる。   Furthermore, by pressing the obtained positive electrode mixture layer 3 and negative electrode mixture layer 6, the density of the mixture layer, the adhesion to the current collector, and the homogeneity can be improved.

プレス加工は、例えば、金属ローラ、弾性ローラ、加熱ローラまたはシートプレス機等を用いて行う。本発明においてプレス温度は、合剤層の塗工膜を乾燥させる温度よりも低い温度とする限り、室温で行っても良いし又は加温して行っても良いが、通常は室温（室温の目安としては１５〜３５℃である。）で行う。   The press working is performed using, for example, a metal roller, an elastic roller, a heating roller, a sheet press machine, or the like. In the present invention, the pressing temperature may be performed at room temperature or may be performed as long as the temperature is lower than the temperature at which the coating film of the mixture layer is dried. As a guide, it is 15 to 35 ° C.).

ロールプレスは、ロングシート状の電極板を連続的にプレス加工できるので好ましい。ロールプレスを行う場合には定位プレス、定圧プレスいずれを行っても良い。プレスのライン速度は通常、５〜７５ｍ／ｍｉｎ．とする。ロールプレスの圧力を線圧で管理する場合、加圧ローラの直径に応じて調節するが、通常は線圧を０．５ｋｇｆ／ｃｍ〜２ｔｆ／ｃｍとする。   The roll press is preferable because a long sheet electrode plate can be continuously pressed. When performing the roll press, either a stereotaxic press or a constant pressure press may be performed. The line speed of the press is usually 5 to 75 m / min. And When the pressure of the roll press is managed by linear pressure, the pressure is adjusted according to the diameter of the pressure roller, but the linear pressure is usually 0.5 kgf / cm to 2 tf / cm.

正極合剤層３及び負極合剤層６の塗工量は通常、２０〜３５０ｇ／ｍ2とし、その厚さは、乾燥、プレス後に通常１０〜２５０μｍ、好ましくは５０〜１９０μｍの範囲にする。 The coating amount of the positive electrode mixture layer 3 and the negative electrode mixture layer 6 is usually 20 to 350 g / m 2 , and the thickness is usually 10 to 250 μm, preferably 50 to 190 μm after drying and pressing.

以下、上述した正極板４および負極板７を使用した本発明の非水系二次電池について説明する。図２に、非水系二次電池の一例としての円筒形のリチウムイオン二次電池９を縦に切断した斜視図により示す。   Hereinafter, the nonaqueous secondary battery of the present invention using the positive electrode plate 4 and the negative electrode plate 7 described above will be described. FIG. 2 is a perspective view of a cylindrical lithium ion secondary battery 9 as an example of a non-aqueous secondary battery cut vertically.

同図２の円筒形のリチウムイオン二次電池９においては、複合リチウム酸化物を正極活物質とする正極板４とリチウムを保持しうる材料を負極活物質とする負極板７とを多孔質絶縁体としてのセパレータ８を介し渦巻状に巻回して電極群１が作製される。   In the cylindrical lithium ion secondary battery 9 of FIG. 2, a porous insulation is made between a positive electrode plate 4 using a composite lithium oxide as a positive electrode active material and a negative electrode plate 7 using a material capable of holding lithium as a negative electrode active material. The electrode group 1 is produced by spirally winding the separator 8 as a body.

電極群１は、有底円筒形の電池ケース１０の内部に絶縁板１１により電池ケース１０とは絶縁されて収容される一方で、電極群１の下部より導出した負極リード１２が電池ケース１０の底部に接続されるとともに、電極群１の上部より導出した正極リード１３が封口板１４に接続される。また、電池ケース１０は、所定量の非水電解液（図示せず）が注液された後、開口部に封口ガスケット１５を周縁に取り付けた封口板１４を挿入し、電池ケース１０の開口部を内方向に折り曲げてかしめ封口される。   The electrode group 1 is housed in the bottomed cylindrical battery case 10 while being insulated from the battery case 10 by the insulating plate 11, while the negative electrode lead 12 led out from the lower part of the electrode group 1 is the battery case 10. The positive electrode lead 13 led out from the upper part of the electrode group 1 is connected to the sealing plate 14 while being connected to the bottom. In addition, after a predetermined amount of non-aqueous electrolyte (not shown) is injected into the battery case 10, a sealing plate 14 with a sealing gasket 15 attached to the periphery is inserted into the opening, and the opening of the battery case 10 is inserted. Is folded inward and crimped.

ここで、セパレータ８は、リチウムイオン二次電池９の使用範囲に耐えうる組成であればよいが、特にポリエチレン、ポリプロピレン等のオレフィン系樹脂の微多孔フィルムを単一あるいは複合して用いるのが好ましい。このセパレータ８の厚みは１０〜２５μｍとするのが良い。   Here, the separator 8 may have any composition that can withstand the use range of the lithium ion secondary battery 9, but it is particularly preferable to use a single or composite of microporous films of olefin-based resins such as polyethylene and polypropylene. . The thickness of the separator 8 is preferably 10 to 25 μm.

このときの非水電解液は、電解質塩としてＬｉＰＦ６およびＬｉＢＦ４などの各種リチウム化合物を用いることができる。また溶媒としてエチレンカーボネート（ＥＣ）、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、メチルエチルカーボネート（ＭＥＣ）、プロピレンカーボネート（ＰＣ）を単独および組み合わせて用いることができる。また、正極板４または負極板７の上に良好な被膜を形成させるためおよび過充電時の安定性を保証するために、ビニレンカーボネート（ＶＣ）およびシクロヘキシルベンゼン（ＣＨＢ）、並びにその変性体を用いるのが好ましい。 The non-aqueous electrolyte at this time can use various lithium compounds such as LiPF 6 and LiBF 4 as electrolyte salts. Further, ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), and propylene carbonate (PC) can be used alone or in combination as a solvent. Further, in order to form a good film on the positive electrode plate 4 or the negative electrode plate 7 and to ensure the stability at the time of overcharge, vinylene carbonate (VC) and cyclohexylbenzene (CHB), and modified products thereof are used. Is preferred.

以下、本発明の具体的な実施例について説明する。   Hereinafter, specific examples of the present invention will be described.

まず、実施例１として低粘度で高エーテル化度の第一のカルボキシメチルセルロースと高粘度で低エーテル化度の第二のカルボキシメチルセルロースを使用した場合を示し、高粘度で低エーテル化度の第二のカルボキシメチルセルロースを使用しない場合を比較例１として示す。   First, as Example 1, the case of using a first carboxymethyl cellulose having a low viscosity and a high degree of etherification and a second carboxymethyl cellulose having a high viscosity and a low degree of etherification are shown. The case where no carboxymethylcellulose is used is shown as Comparative Example 1.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.23 and a viscosity of 420% by weight in an aqueous solution of 1% by weight. 0.25 parts by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は８０００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 8000 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は８Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 8 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例１）
負極活物質と分散機械は実施例１で用いたものを用い、増粘剤はエーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩を負極活物質１００重量部に対し、０．８重量部を投入し実施例１に記載のミキサーでプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として０．６重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら、減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は１５０００ｍＰａ・ｓであった。 (Comparative Example 1)
The negative electrode active material and the dispersing machine used were those used in Example 1. The thickener was carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and a viscosity of an aqueous solution of 1% by weight of 7200 mPa · s. 0.8 parts by weight were added to parts by weight, and the planetary rotation speed was mixed at 10 rotations for 5 minutes with the mixer described in Example 1. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm. Thereafter, 0.6 parts by weight of ion exchange water as a dispersion medium and styrene butadiene rubber as a solid material as a solid content are added and dispersed at a planetary rotation speed of 40 rpm and a disper rotation speed of 3000 rpm for 20 minutes. The mixture was defoamed under reduced pressure while stirring at a rotational speed of 20 rpm, and obtained as a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 15000 mPa · s.

負極板７の作製手順は実施例１と同様の方法で行った。負極合剤層６の剥離強度は４Ｎ／ｍであった。   The production procedure of the negative electrode plate 7 was performed in the same manner as in Example 1. The peel strength of the negative electrode mixture layer 6 was 4 N / m.

以上、実施例１および比較例１の結果を（表１）に示す。   The results of Example 1 and Comparative Example 1 are shown in (Table 1).

Figure 2012059488
Figure 2012059488

（表１）から明らかなように、第二のカルボキシメチルセルロースを用いない比較例１の非水系二次電池は、合剤の脱落が多く、９０度剥離強度が低く、また５００サイクル後の容量維持率が低いことがわかる。   As is clear from (Table 1), the non-aqueous secondary battery of Comparative Example 1 that does not use the second carboxymethyl cellulose has a large amount of mixture dropping, low 90-degree peel strength, and capacity maintenance after 500 cycles. It can be seen that the rate is low.

次に、第一のカルボキシメチルセルロースのエーテル化度が１．０〜１．５の適正な範囲に入っている場合を実施例２と実施例３に示し、エーテル化度が適正な範囲である１．０〜１．５から外れる場合を比較例２と比較例３に示す。   Next, the case where the etherification degree of the first carboxymethyl cellulose is in the proper range of 1.0 to 1.5 is shown in Example 2 and Example 3, and the etherification degree is in the proper range 1 The case where it deviates from 0.0-1.5 is shown in Comparative Example 2 and Comparative Example 3.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．００、１重量％水溶液の粘度にて４６０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.00 and a viscosity of 460 mPa · s in an aqueous solution of 1% by weight. 0.25 parts by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は８２００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 8200 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は９Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 9 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．５０、１重量％水溶液の粘度にて４００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is put in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.50 and a viscosity of 400 wt. 0.25 parts by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は７８００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 7800 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は７．５Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 7.5 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例２）
比較例２として第一のカルボキシメチルセルロースのエーテル化度が下限の１．０よりも小さい場合を示す。 (Comparative Example 2)
As Comparative Example 2, the case where the etherification degree of the first carboxymethylcellulose is smaller than the lower limit of 1.0 is shown.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が０．９５、１重量％水溶液の粘度にて４８０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was placed in a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 0.95 as a first thickener, and the viscosity of an aqueous solution of 1 wt% was 480 mPa · s. 0.25 parts by weight of carboxymethylcellulose sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は９２００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 9200 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は１０Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 10 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例３）
比較例３として第一のカルボキシメチルセルロースのエーテル化度が上限の１．５よりも大きい場合を示す。 (Comparative Example 3)
As Comparative Example 3, the case where the etherification degree of the first carboxymethyl cellulose is larger than the upper limit of 1.5 is shown.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．５５、１重量％水溶液の粘度にて３５０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material is put into a triaxial planetary dispersion / mixing / kneading machine, and the first thickening agent has a degree of etherification of 1.55 and a viscosity of 350 wt. 0.25 parts by weight of carboxymethylcellulose sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は７８００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 7800 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は５Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 5 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

Figure 2012059488
Figure 2012059488

（表２）から明らかなように、第一のカルボキシメチルセルロースのエーテル化度が適正な範囲である１．０〜１．５の下限から外れて０．９５である比較例２の非水系二次電池は合剤の脱落が多く、５００サイクル後の容量維持率が低いことがわかる。またエーテル化度が適正な範囲である１．０〜１．５の上限から外れて１．５５である比較例３の非水系二次電池は９０度剥離強度が低く、５００サイクル後の容量維持率が低いことがわかる。   As apparent from (Table 2), the non-aqueous secondary of Comparative Example 2 in which the degree of etherification of the first carboxymethylcellulose is 0.95, which is outside the lower limit of 1.0 to 1.5, which is an appropriate range. It can be seen that the battery has a large amount of the mixture and the capacity retention rate after 500 cycles is low. In addition, the nonaqueous secondary battery of Comparative Example 3 in which the degree of etherification is 1.55 deviating from the upper limit of 1.0 to 1.5, which is an appropriate range, has a low 90 degree peel strength and maintains the capacity after 500 cycles. It can be seen that the rate is low.

次に、第一のカルボキシメチルセルロースの１重量％水溶液の粘度が１０〜１８００ｍＰａ・ｓの適正な範囲に入っている場合を実施例４と実施例５に示し、１重量％水溶液の粘度が適正な範囲である１０〜１８００ｍＰａ・ｓを外れる場合を比較例４と比較例５に示す。   Next, the cases where the viscosity of the 1% by weight aqueous solution of the first carboxymethyl cellulose is within the proper range of 10 to 1800 mPa · s are shown in Example 4 and Example 5, and the viscosity of the 1% by weight aqueous solution is appropriate. The case where it is outside the range of 10 to 1800 mPa · s is shown in Comparative Example 4 and Comparative Example 5.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２８、１重量％水溶液の粘度にて１０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is put in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having an etherification degree of 1.28 and a viscosity of 10% by weight in an aqueous solution of 1% by weight. 0.25 parts by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は７５００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 7500 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は７Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 7 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２６、１重量％水溶液の粘度にて１８００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material was placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener was carboxymethylcellulose having a degree of etherification of 1.26 and a viscosity of 1 wt% aqueous solution of 1800 mPa · s. 0.25 parts by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は１１，０００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 11,000 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は８．５Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 8.5 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例４）
比較例４として第一のカルボキシメチルセルロースの１重量％水溶液の粘度が下限の１０ｍＰａ・ｓよりも小さい比較例を以下に示す。 (Comparative Example 4)
As Comparative Example 4, a comparative example in which the viscosity of a 1% by weight aqueous solution of the first carboxymethyl cellulose is smaller than the lower limit of 10 mPa · s is shown below.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２５、１重量％水溶液の粘度にて９ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was put into a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 1.25 as a first thickener, and the viscosity of an aqueous solution of 1% by weight was 9 mPa · s. 0.25 parts by weight of carboxymethylcellulose sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は６２００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 6200 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は４Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 4 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例５）
比較例５として第一のカルボキシメチルセルロースの１重量％水溶液の粘度が上限の１８００ｍＰａ・ｓよりも大きい比較例を以下に示す。 (Comparative Example 5)
As Comparative Example 5, a comparative example in which the viscosity of the 1% by weight aqueous solution of the first carboxymethyl cellulose is larger than the upper limit of 1800 mPa · s is shown below.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて１８５０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was put into a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 1.23 and the viscosity of an aqueous solution of 1 wt% was 1850 mPa · s as a first thickener. 0.25 parts by weight of carboxymethylcellulose sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は１３５００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 13500 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は９Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 9 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

Figure 2012059488
Figure 2012059488

（表３）から明らかなように、第一のカルボキシメチルセルロースの１重量％水溶液の粘度が適正な範囲である１０〜１８００ｍＰａ・ｓの下限から外れて９ｍＰａ・ｓである比較例４の非水系二次電池は負極合剤塗料の粘度が低く、９０度剥離強度が低いことが分かる。また１重量％水溶液の粘度が適正な範囲である１０〜１８００ｍＰａ・ｓの上限から外れて１８５０ｍＰａ・ｓである比較例５の非水系二次電池は負極合剤塗料の粘度が高く、５００サイクル後の容量維持率が低いことが分かる。   As is clear from (Table 3), the non-aqueous two-based solution of Comparative Example 4 in which the viscosity of the 1% by weight aqueous solution of the first carboxymethylcellulose is 9 mPa · s that is outside the lower limit of 10 to 1800 mPa · s, which is an appropriate range. It can be seen that the secondary battery has a low viscosity of the negative electrode mixture paint and a low 90-degree peel strength. Further, the non-aqueous secondary battery of Comparative Example 5 in which the viscosity of the 1 wt% aqueous solution is outside the upper limit of 10 to 1800 mPa · s which is an appropriate range and is 1850 mPa · s has a high viscosity of the negative electrode mixture paint, and after 500 cycles It can be seen that the capacity maintenance rate is low.

次に、第一のカルボキシメチルセルロースの投入量が０．１〜０．４重量部の適正な範囲に入っている場合を実施例６と実施例７に示し、投入量が０．１〜０．４重量部の適正な範囲を外れる場合を比較例６と比較例７に示す。   Next, the case where the input amount of the first carboxymethyl cellulose is within an appropriate range of 0.1 to 0.4 parts by weight is shown in Example 6 and Example 7, and the input amount is 0.1 to 0. The case where it deviates from the suitable range of 4 weight part is shown in Comparative Example 6 and Comparative Example 7.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．１０重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.23 and a viscosity of 420% by weight in an aqueous solution of 1% by weight. 0.10 parts by weight of sodium salt was added in powder form and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は７８００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 7800 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は８Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 8 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．４０重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.23 and a viscosity of 420% by weight in an aqueous solution of 1% by weight. 0.40 part by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は８２００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 8200 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は８．５Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 8.5 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例６）
比較例６として第一のカルボキシメチルセルロースの含有量が下限の０．１重量部よりも小さい比較例を以下に示す。 (Comparative Example 6)
As Comparative Example 6, a comparative example in which the content of the first carboxymethyl cellulose is smaller than the lower limit of 0.1 part by weight is shown below.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．０９重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was placed in a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 1.23 and the viscosity of an aqueous solution of 1 wt% was 420 mPa · s as the first thickener. Carboxymethylcellulose sodium salt 0.09 part by weight was added as powder and mixed with planetary rotation at 10 rotations for 5 minutes. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は７５００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 7500 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は８Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 8 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例７）
比較例７として第一のカルボキシメチルセルロースの含有量が上限の０．４重量部よりも大きい比較例を以下に示す。 (Comparative Example 7)
As Comparative Example 7, a comparative example in which the content of the first carboxymethyl cellulose is larger than the upper limit of 0.4 part by weight is shown below.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．４１重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was placed in a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 1.23 and the viscosity of an aqueous solution of 1 wt% was 420 mPa · s as the first thickener. Carboxymethylcellulose sodium salt (0.41 part by weight) was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は８４００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 8400 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は８．５Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 8.5 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

Figure 2012059488
Figure 2012059488

（表４）から明らかなように、第一のカルボキシメチルセルロースの投入量が０．１〜０．４重量部の適正な範囲の下限から外れて０．０９重量部である比較例６の非水系二次電池は５００サイクル後の容量維持率が低いことが分かる。また投入量が０．１〜０．４重量部の適正な範囲の上限から外れて０．４１重量部である比較例７の非水系二次電池は５００サイクル後の容量維持率が低いことが分かる。   As is clear from (Table 4), the amount of the first carboxymethyl cellulose input is 0.09 parts by weight, which is outside the lower limit of the appropriate range of 0.1 to 0.4 parts by weight. It can be seen that the secondary battery has a low capacity retention rate after 500 cycles. The non-aqueous secondary battery of Comparative Example 7 in which the input amount is 0.41 parts by weight deviating from the upper limit of the appropriate range of 0.1 to 0.4 parts by weight has a low capacity maintenance rate after 500 cycles. I understand.

次に、第二のカルボキシメチルセルロースのエーテル化度が０．５〜０．８の適正な範囲に入っている場合を実施例８と実施例９に示し、エーテル化度が適正な範囲である０．５〜０．８を外れる場合を比較例８と比較例９に示す。   Next, the case where the etherification degree of the second carboxymethyl cellulose is in an appropriate range of 0.5 to 0.8 is shown in Example 8 and Example 9, and the degree of etherification is 0 in the proper range. Comparative examples 8 and 9 show cases where the deviation of .5 to 0.8 is exceeded.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.23 and a viscosity of 420% by weight in an aqueous solution of 1% by weight. 0.25 parts by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．５０、１重量％水溶液の粘度にて７４００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethyl cellulose sodium salt having an etherification degree of 0.50 and a viscosity of 1 wt% aqueous solution of 7400 mPa · s was added as powder and at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は８０００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 8000 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は１０Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 10 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.23 and a viscosity of 420% by weight in an aqueous solution of 1% by weight. 0.25 parts by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．８０、１重量％水溶液の粘度にて７１００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of 7100 mPa · s carboxymethylcellulose sodium salt is added as powder with a viscosity of 0.80, 1 wt% aqueous solution, and at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は７８００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 7800 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は７Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 7 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例８）
比較例８として第二のカルボキシメチルセルロースのエーテル化度が下限の０．５よりも小さい比較例を以下に示す。 (Comparative Example 8)
As Comparative Example 8, a comparative example in which the degree of etherification of the second carboxymethyl cellulose is smaller than the lower limit of 0.5 is shown below.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was placed in a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 1.23 and the viscosity of an aqueous solution of 1 wt% was 420 mPa · s as the first thickener. 0.25 parts by weight of carboxymethylcellulose sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．４８、１重量％水溶液の粘度にて７６００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethyl cellulose sodium salt having an etherification degree of 0.48 and a viscosity of 1% by weight of 7600 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は８１００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 8100 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は１１Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 11 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例９）
比較例９として第二のカルボキシメチルセルロースのエーテル化度が上限の０．８よりも大きい比較例を以下に示す。 (Comparative Example 9)
As Comparative Example 9, a comparative example in which the degree of etherification of the second carboxymethyl cellulose is larger than the upper limit of 0.8 is shown below.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was placed in a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 1.23 and the viscosity of an aqueous solution of 1 wt% was 420 mPa · s as the first thickener. 0.25 parts by weight of carboxymethylcellulose sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．８２、１重量％水溶液の粘度にて７１００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as the second thickener, 0.55 parts by weight of carboxymethyl cellulose sodium salt having a degree of etherification of 0.82, 1% by weight aqueous solution with a viscosity of 7100 mPa · s was added in powder form at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は７６００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 7600 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は５．５Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 5.5 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

Figure 2012059488
Figure 2012059488

（表５）から明らかなように、第二のカルボキシメチルセルロースのエーテル化度が適正な範囲である０．５〜０．８の下限から外れて０．４８である比較例８の非水系二次電池は合剤の脱落が多く、９０度剥離強度が低く、５００サイクル後の容量維持率が低いことがわかる。またエーテル化度が適正な範囲である０．５〜０．８の上限から外れて０．８２である比較例９の非水系二次電池は９０度剥離強度が低いことがわかる。   As is clear from (Table 5), the non-aqueous secondary of Comparative Example 8 in which the degree of etherification of the second carboxymethyl cellulose is 0.48, which is outside the lower limit of 0.5 to 0.8, which is an appropriate range. It can be seen that the battery has a lot of dropping of the mixture, the 90-degree peel strength is low, and the capacity retention after 500 cycles is low. It can also be seen that the non-aqueous secondary battery of Comparative Example 9 having a degree of etherification of 0.82 that deviates from the upper limit of 0.5 to 0.8, which is an appropriate range, has a low 90 degree peel strength.

次に、第二のカルボキシメチルセルロースの１重量％水溶液の粘度が３０００〜１００００ｍＰａ・ｓの適正な範囲に入っている場合を実施例１０と実施例１１に示し、１重量％水溶液の粘度が適正な範囲である３０００〜１００００ｍＰａ・ｓを外れる場合を比較例１０と比較例１１に示す。   Next, the case where the viscosity of the 1% by weight aqueous solution of the second carboxymethyl cellulose is within an appropriate range of 3000 to 10000 mPa · s is shown in Example 10 and Example 11, and the viscosity of the 1% by weight aqueous solution is appropriate. The case where it is outside the range of 3000 to 10000 mPa · s is shown in Comparative Example 10 and Comparative Example 11.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.23 and a viscosity of 420% by weight in an aqueous solution of 1% by weight. 0.25 parts by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．７、１重量％水溶液の粘度にて３０００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having an etherification degree of 0.7 and a 1% by weight aqueous solution of 3000 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は３２００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 3200 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は６．５Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of the negative electrode mixture layer 6 was 6.5 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.23 and a viscosity of 420% by weight in an aqueous solution of 1% by weight. 0.25 parts by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．７、１重量％水溶液の粘度にて１００００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.7 and a 1% by weight aqueous solution of 10000 mPa · s was added as a powder at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は７８００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 7800 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は１１Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 11 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例１０）
比較例１０として第二のカルボキシメチルセルロースの１重量％水溶液の粘度が下限の３０００ｍＰａ・ｓよりも小さい比較例を以下に示す。 (Comparative Example 10)
As Comparative Example 10, a comparative example in which the viscosity of a 1% by weight aqueous solution of the second carboxymethyl cellulose is smaller than the lower limit of 3000 mPa · s is shown below.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was placed in a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 1.23 and the viscosity of an aqueous solution of 1 wt% was 420 mPa · s as the first thickener. 0.25 parts by weight of carboxymethylcellulose sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．７、１重量％水溶液の粘度にて２９００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethylcellulose sodium salt having an etherification degree of 0.7 and a viscosity of 1% by weight of 2900 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は２５００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 2500 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は４．５Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 4.5 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例１１）
比較例１１として第二のカルボキシメチルセルロースの１重量％水溶液の粘度が上限の１００００ｍＰａ・ｓよりも大きい比較例を以下に示す。 (Comparative Example 11)
As Comparative Example 11, a comparative example in which the viscosity of the 1% by weight aqueous solution of the second carboxymethyl cellulose is larger than the upper limit of 10,000 mPa · s is shown below.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was placed in a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 1.23 and the viscosity of an aqueous solution of 1 wt% was 420 mPa · s as the first thickener. 0.25 parts by weight of carboxymethylcellulose sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて１１０００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．５５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.55 parts by weight of carboxymethyl cellulose sodium salt having an etherification degree of 0.69 and a 1% by weight aqueous solution of 11000 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は１４０００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 14000 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は１２Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 12 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

Figure 2012059488
Figure 2012059488

（表６）から明らかなように、第二のカルボキシメチルセルロースの１重量％水溶液の粘度が適正な範囲である３０００〜１００００ｍＰａ・ｓの下限から外れて２９００ｍＰａ・ｓである比較例１０の非水系二次電池は負極合剤塗料の粘度が低く、９０度剥離強度が低いことが分かる。また１重量％水溶液の粘度が適正な範囲である３０００〜１００００ｍＰａ・ｓの上限から外れて１１０００ｍＰａ・ｓである比較例１１の非水系二次電池は負極合剤塗料の粘度が高いことが分かる。   As is clear from (Table 6), the non-aqueous two of Comparative Example 10 in which the viscosity of the 1% by weight aqueous solution of the second carboxymethyl cellulose is 2900 mPa · s that is outside the lower limit of 3000 to 10000 mPa · s, which is an appropriate range. It can be seen that the secondary battery has a low viscosity of the negative electrode mixture paint and a low 90-degree peel strength. Moreover, it turns out that the viscosity of the negative mix paint is high in the non-aqueous secondary battery of Comparative Example 11 in which the viscosity of the 1% by weight aqueous solution is 11000 mPa · s that is outside the upper limit of 3000 to 10000 mPa · s, which is an appropriate range.

次に、第二のカルボキシメチルセルロースの投入量が０．３〜０．８重量部の適正な範囲に入っている場合を実施例１２と実施例１３に示し、投入量が０．３〜０．８重量部の適正な範囲を外れる場合を比較例１２と比較例１３に示す。   Next, Example 12 and Example 13 show the case where the amount of the second carboxymethylcellulose charged is within an appropriate range of 0.3 to 0.8 parts by weight. The case where it deviates from the suitable range of 8 weight part is shown in comparative example 12 and comparative example 13.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.23 and a viscosity of 420% by weight in an aqueous solution of 1% by weight. 0.25 parts by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．３０重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.30 part by weight of 7200 mPa · s carboxymethylcellulose sodium salt with a viscosity of 0.69, 1% by weight aqueous solution is added as powder and at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は３２００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 3200 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は６．５Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of the negative electrode mixture layer 6 was 6.5 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.23 and a viscosity of 420% by weight in an aqueous solution of 1% by weight. 0.25 parts by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．８０重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.80 parts by weight of 7200 mPa · s carboxymethylcellulose sodium salt is added as powder at a viscosity of 0.69, 1 wt% aqueous solution, and at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は１００００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 10,000 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は１０Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 10 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例１２）
比較例１２として第二のカルボキシメチルセルロースの含有量が下限の０．３重量部よりも小さい比較例を以下に示す。 (Comparative Example 12)
As Comparative Example 12, a comparative example in which the content of the second carboxymethyl cellulose is smaller than the lower limit of 0.3 part by weight is shown below.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was placed in a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 1.23 and the viscosity of an aqueous solution of 1 wt% was 420 mPa · s as the first thickener. 0.25 parts by weight of carboxymethylcellulose sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２９重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.29 parts by weight of carboxymethylcellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は２８００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 2800 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は５Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 5 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例１３）
比較例１３として第二のカルボキシメチルセルロースの含有量が上限の０．８重量部よりも大きい比較例を以下に示す。 (Comparative Example 13)
As Comparative Example 13, a comparative example in which the content of the second carboxymethyl cellulose is larger than 0.8 parts by weight of the upper limit is shown below.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２５重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was placed in a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 1.23 and the viscosity of an aqueous solution of 1 wt% was 420 mPa · s as the first thickener. 0.25 parts by weight of carboxymethylcellulose sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．８２重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.82 parts by weight of carboxymethyl cellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は１３００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 1300 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は１２Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 12 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

Figure 2012059488
Figure 2012059488

（表７）から明らかなように、第二のカルボキシメチルセルロースの投入量が０．３〜０．８重量部の適正な範囲の下限から外れて０．２９重量部である比較例１２の非水系二次電池は９０度剥離強度が低いことが分かる。また投入量が０．３〜０．８重量部の適正な範囲の上限から外れて０．８２重量部である比較例１３の非水系二次電池は負極合剤塗料の粘度が高いことが分かる。   As is clear from (Table 7), the amount of the second carboxymethylcellulose input is 0.29 parts by weight, which is outside the lower limit of the appropriate range of 0.3 to 0.8 parts by weight. It can be seen that the secondary battery has a low 90 degree peel strength. Further, it can be seen that the nonaqueous secondary battery of Comparative Example 13 in which the input amount is outside the upper limit of the appropriate range of 0.3 to 0.8 parts by weight is 0.82 parts by weight, the viscosity of the negative electrode mixture paint is high. .

次に、第一のカルボキシメチルセルロースと第二のカルボキシメチルセルロースの合計が０．４〜１．２重量部の適正な範囲に入っている場合を実施例１４と実施例１５に示し、適正な範囲である０．４〜１．２重量部を外れる場合を比較例１４と比較例１５に示す。   Next, a case where the total of the first carboxymethyl cellulose and the second carboxymethyl cellulose is in an appropriate range of 0.4 to 1.2 parts by weight is shown in Example 14 and Example 15, The case where it deviates from 0.4 to 1.2 parts by weight is shown in Comparative Example 14 and Comparative Example 15.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２０重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.23 and a viscosity of 420% by weight in an aqueous solution of 1% by weight. 0.20 part by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．３０重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.30 part by weight of 7200 mPa · s carboxymethylcellulose sodium salt with a viscosity of 0.69, 1% by weight aqueous solution is added as powder and at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は３１００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 3100 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は６．５Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of the negative electrode mixture layer 6 was 6.5 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．４０重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   100 parts by weight of the negative electrode active material is placed in a triaxial planetary dispersion / mixing / kneading machine, and the first thickener is carboxymethylcellulose having a degree of etherification of 1.23 and a viscosity of 420% by weight in an aqueous solution of 1% by weight. 0.40 part by weight of sodium salt was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．８０重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, as a second thickener, 0.80 parts by weight of 7200 mPa · s carboxymethylcellulose sodium salt is added as powder at a viscosity of 0.69, 1 wt% aqueous solution, and at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は１００００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 10,000 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は１０Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 10 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例１４）
比較例１４として第一のカルボキシメチルセルロースと第二のカルボキシメチルセルロースの総量が下限の０．４重量部よりも小さい比較例を以下に示す。 (Comparative Example 14)
As Comparative Example 14, a comparative example in which the total amount of the first carboxymethyl cellulose and the second carboxymethyl cellulose is smaller than the lower limit of 0.4 part by weight is shown below.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．２重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was placed in a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 1.23 and the viscosity of an aqueous solution of 1 wt% was 420 mPa · s as the first thickener. Carboxymethylcellulose sodium salt 0.2 parts by weight was added as powder and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．１８重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, 0.18 parts by weight of carboxymethyl cellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as powder is added as a powder, at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は２２００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 2200 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は３Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 3 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

（比較例１５）
比較例１５として第一のカルボキシメチルセルロースと第二のカルボキシメチルセルロースの総量が上限の１．２重量部よりも大きい比較例を以下に示す。 (Comparative Example 15)
As Comparative Example 15, a comparative example in which the total amount of the first carboxymethyl cellulose and the second carboxymethyl cellulose is larger than 1.2 parts by weight of the upper limit is shown below.

まず、負極活物質１００重量部を３軸遊星方式の分散・混合・混練機に入れ、第一の増粘剤としてエーテル化度が１．２３、１重量％水溶液の粘度にて４２０ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．３重量部を粉のまま加えプラネタリーの回転数を１０回転で５分間混ぜた。その後、分散媒としてのイオン交換水６５重量部を投入し、１０ｒｐｍの回転速度で５分間、その後４０ｒｐｍの回転速度で３０分間分散した。   First, 100 parts by weight of the negative electrode active material was placed in a triaxial planetary dispersion / mixing / kneading machine, and the etherification degree was 1.23 and the viscosity of an aqueous solution of 1 wt% was 420 mPa · s as the first thickener. Carboxymethylcellulose sodium salt (0.3 parts by weight) was added in powder form and mixed for 5 minutes at 10 rotations of the planetary. Thereafter, 65 parts by weight of ion-exchanged water as a dispersion medium was added and dispersed for 5 minutes at a rotation speed of 10 rpm, and then for 30 minutes at a rotation speed of 40 rpm.

次に、第二の増粘剤として、エーテル化度が０．６９、１重量％水溶液の粘度にて７２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩０．９５重量部を粉のまま加え４０ｒｐｍの回転速度で１０分間分散した。   Next, 0.95 parts by weight of carboxymethyl cellulose sodium salt having a degree of etherification of 0.69 and an aqueous solution of 1% by weight of 7200 mPa · s as a second thickener was added in powder form at a rotational speed of 40 rpm. Dispersed for 10 minutes.

その後、分散媒としてのイオン交換水と、結着材としてスチレンブタジエンラバーを固形分として１重量部加え、プラネタリーの回転数を４０ｒｐｍ、ディスパーの回転数３０００ｒｐｍで２０分間分散したのち、プラネタリーの回転数を２０ｒｐｍで攪拌しながら減圧下で脱泡し、５０重量％の固形分の負極合剤塗料として得た。得られた負極合剤塗料の粘度は１３０００ｍＰａ・ｓであった。   Then, 1 part by weight of styrene butadiene rubber as a solid content is added as a dispersion medium and 1 part by weight of styrene butadiene rubber as a binder, and the planetary rotation speed is 40 rpm and the disperser rotation speed is 3000 rpm for 20 minutes. While stirring at 20 rpm, defoaming was performed under reduced pressure to obtain a negative electrode mixture paint having a solid content of 50% by weight. The viscosity of the obtained negative electrode mixture paint was 13000 mPa · s.

得られた負極合剤塗料を銅箔（１０μｍの厚み）に一面当りの乾燥重量が１２０ｇ／ｍ2になるように両面にダイコーターを用いて負極合剤塗料を塗布した後６０℃で乾燥して負極合剤層６を形成した。この負極合剤層６の剥離強度は１２Ｎ／ｍであった。両面に塗工した後、負極板７の厚みが１５０μｍになるようにプレスを行い所定の幅にスリットして負極板７を得た。 The obtained negative electrode mixture paint was applied to a copper foil (thickness of 10 μm) so that the dry weight per side was 120 g / m 2 using a die coater on both sides, and then dried at 60 ° C. Thus, a negative electrode mixture layer 6 was formed. The peel strength of this negative electrode mixture layer 6 was 12 N / m. After coating on both surfaces, the negative electrode plate 7 was pressed so as to have a thickness of 150 μm and slit to a predetermined width to obtain the negative electrode plate 7.

Figure 2012059488
Figure 2012059488

（表８）から明らかなように、第一のカルボキシメチルセルロースと第二のカルボキシメチルセルロースの合計が０．４〜１．２重量部の適正な範囲の下限から外れて０．３８重量部である比較例１４の非水系二次電池は負極合剤塗料の粘度が低く、９０度剥離強度が低く、５００サイクル後の容量維持率が低いことが分かる。また第一のカルボキシメチルセルロースと第二のカルボキシメチルセルロースの合計が０．４〜１．２重量部の適正な範囲の上限から外れて１．２５重量部である比較例１５の非水系二次電池は負極合剤塗料の粘度が高く、５００サイクル後の容量維持率が低いことが分かる。   As is clear from (Table 8), the total of the first carboxymethyl cellulose and the second carboxymethyl cellulose is 0.38 parts by weight outside the lower limit of the appropriate range of 0.4 to 1.2 parts by weight. It can be seen that the non-aqueous secondary battery of Example 14 has a low viscosity of the negative electrode mixture paint, a low 90-degree peel strength, and a low capacity retention rate after 500 cycles. Moreover, the non-aqueous secondary battery of Comparative Example 15 in which the total of the first carboxymethyl cellulose and the second carboxymethyl cellulose is 1.25 parts by weight deviating from the upper limit of the appropriate range of 0.4 to 1.2 parts by weight. It can be seen that the viscosity of the negative electrode mixture paint is high and the capacity retention rate after 500 cycles is low.

なお実施例および比較例では比表面積が３．８ｍ２／ｇの負極活物質を使用したが、比表面積は３．０〜５．５ｍ２／ｇの範囲でも問題ない。 In Examples and Comparative Examples, a negative electrode active material having a specific surface area of 3.8 m 2 / g was used, but there is no problem even if the specific surface area is in the range of 3.0 to 5.5 m 2 / g.

またカルボキシメチルセルロースに関しては、アンモニウム塩、ナトリウム塩などあるが、ナトリウム塩が望ましい。   As for carboxymethylcellulose, there are ammonium salt, sodium salt, etc., but sodium salt is desirable.

以下に評価方法を示す。   The evaluation method is shown below.

塗料粘度はＢＨ型粘度計を用い、塗料温度を２５℃に調整してからローターを２０ｒｐｍで回転させて測定した。塗工時の条件に依存するが、負極合剤塗料の粘度は３，０００〜１２，０００ｍＰａ・ｓの範囲であることが望ましいため、得られた負極合剤塗料の粘度を測定した。   The paint viscosity was measured by adjusting the paint temperature to 25 ° C. using a BH viscometer and rotating the rotor at 20 rpm. Although it depends on the coating conditions, the viscosity of the negative electrode mixture paint is preferably in the range of 3,000 to 12,000 mPa · s. Therefore, the viscosity of the obtained negative electrode mixture paint was measured.

塗工面の評価は塗布乾燥後の負極合剤層６の１００ｃｍ２に存在するφ０．５ｍｍ以上の欠陥部を目視で観察し欠陥数を評価した。 Evaluation of the coated surface was performed by visually observing a defect portion of φ0.5 mm or more present in 100 cm 2 of the negative electrode mixture layer 6 after coating and drying to evaluate the number of defects.

密着力はＪＩＳ−Ｃ６４８１−１９９５に準拠した９０度剥離強度試験行った。負極集電体５への負極合剤層６の密着力は、片方の負極合剤層６を取り除いた後にもう片方の負極合剤層６を両面テープで固定し、負極集電体５を負極合剤層６に対して垂直になる方向に引張り、毎分５０ｍｍの速さで連続的に約３０ｍｍ剥がして、この間での荷重の平均値を剥離強度として負極集電体５への負極合剤層６の密着力の評価に用いた。本検討の負極合剤層６の剥離強度が低いと、負極板７の加工（例えば、スリット、プレス）で負極合剤層６が脱落する危険性がある。   The adhesion strength was a 90 degree peel strength test based on JIS-C6481-1995. The adhesion strength of the negative electrode mixture layer 6 to the negative electrode current collector 5 is determined by removing the negative electrode mixture layer 6 and fixing the other negative electrode mixture layer 6 with a double-sided tape. Pulling in the direction perpendicular to the mixture layer 6 and peeling off about 30 mm continuously at a speed of 50 mm per minute, and the negative electrode mixture to the negative electrode current collector 5 using the average value of the load during this period as the peel strength Used to evaluate the adhesion of the layer 6. If the peel strength of the negative electrode mixture layer 6 in this study is low, there is a risk that the negative electrode mixture layer 6 may fall off during processing of the negative electrode plate 7 (for example, slitting or pressing).

正極板４の作製方法は、正極活物質１００重量部に導電材としてアセチレンブラックを２重量部と、結着材としてポリフッ化ビニリデンを２重量部と、分散媒としてN−メチル−２−ピロリドンとを攪拌混合し、ペースト状の正極合剤塗料を得た。一面あたりの塗工量は約２６０．０ｇ／ｍ2とし、厚さ１５μｍのアルミニウム箔の両面にダイコーターを用いて正極合剤塗料を塗工した。その後、乾燥し、ロールプレスにより圧延、乾燥後、所定の寸法に切断して正極板４を得た。 The positive electrode plate 4 is produced by 100 parts by weight of the positive electrode active material, 2 parts by weight of acetylene black as a conductive material, 2 parts by weight of polyvinylidene fluoride as a binder, and N-methyl-2-pyrrolidone as a dispersion medium. Were mixed with stirring to obtain a paste-like positive electrode mixture paint. The coating amount per side was about 260.0 g / m 2, and the positive electrode mixture paint was applied to both sides of an aluminum foil having a thickness of 15 μm using a die coater. Thereafter, it was dried, rolled by a roll press, dried, and then cut into predetermined dimensions to obtain a positive electrode plate 4.

上記の正極板４と負極板７とをセパレータ８を介して、図２に示したようにＡ方向に渦巻状に巻回して電極群１を作製した。この電極群１を有底円筒形の電池ケース１０の内部に、絶縁板１１により電池ケース１０とは絶縁されて収容する一方で、電極群１の下部より導出した負極リード１２が電池ケース１０の底部に接続するとともに、電極群１の上部より導出した正極リード１３が封口板１４に接続した。また、電池ケース１０に所定量の非水電解液を注液した後、開口部に封口ガスケット１５を周縁に取り付けた封口板１４を挿入し、電池ケース１０の開口部を内方向に折り曲げてかしめ封口して円筒形リチウムイオン二次電池９を作製した。   The positive electrode plate 4 and the negative electrode plate 7 were wound spirally in the direction A as shown in FIG. The electrode group 1 is accommodated in the bottomed cylindrical battery case 10 while being insulated from the battery case 10 by the insulating plate 11, while the negative electrode lead 12 led out from the lower part of the electrode group 1 is provided in the battery case 10. The positive lead 13 led out from the top of the electrode group 1 was connected to the sealing plate 14 while being connected to the bottom. Further, after pouring a predetermined amount of non-aqueous electrolyte into the battery case 10, a sealing plate 14 with a sealing gasket 15 attached to the periphery is inserted into the opening, and the opening of the battery case 10 is bent inward and caulked. Sealed to produce a cylindrical lithium ion secondary battery 9.

サイクル特性の評価は２５℃の環境下で０．３Ｃレートでの４．２Ｖ定電流・定電圧の５時間充電と、１Ｃレートの２．５Ｖ放電のサイクルを繰り返し、５００サイクル後の容量維持率を測定した。   The evaluation of the cycle characteristics was conducted by repeating a cycle of 4.2V constant current / constant voltage for 5 hours at a 0.3C rate and a 2.5V discharge at a 1C rate in an environment of 25 ° C., and a capacity retention rate after 500 cycles Was measured.

これら実施例１〜１５および比較例１〜１５の結果より、本発明の方法により形成した非水系二次電池用負極板の不良が減少し、サイクル特性と安全性に優れた非水系二次電池を生産することが可能となることが確認できた。   From the results of Examples 1 to 15 and Comparative Examples 1 to 15, defects in the negative electrode for a non-aqueous secondary battery formed by the method of the present invention are reduced, and the non-aqueous secondary battery having excellent cycle characteristics and safety is obtained. It has been confirmed that it will be possible to produce.

本発明にかかる非水系二次電池用負極板を用いた非水系二次電池は電池特性に優れたポータブル機器の電源として有用である。   The non-aqueous secondary battery using the negative electrode plate for a non-aqueous secondary battery according to the present invention is useful as a power source for portable devices having excellent battery characteristics.

１ 電極群
２ 正極集電体
３ 正極合剤層
４ 正極板
５ 負極集電体
６ 負極合剤層
７ 負極板
８ セパレータ
９ リチウムイオン二次電池
１０ 電池ケース
１１ 絶縁板
１２ 負極リード
１３ 正極リード
１４ 封口板
１５ 封口ガスケット DESCRIPTION OF SYMBOLS 1 Electrode group 2 Positive electrode collector 3 Positive electrode mixture layer 4 Positive electrode plate 5 Negative electrode collector 6 Negative electrode mixture layer 7 Negative electrode plate 8 Separator 9 Lithium ion secondary battery 10 Battery case 11 Insulating plate 12 Negative electrode lead 13 Positive electrode lead 14 Sealing plate 15 Sealing gasket

Claims (10)

少なくともリチウムを保持しうる材料よりなる活物質と結着材および増粘剤を分散媒にて混練分散した負極合剤塗料を負極集電体の上に付着させて負極合剤層を形成した非水系二次電池用負極板であって、前記増粘剤を低粘度で高エーテル化度の第一のカルボキシメチルセルロースと、高粘度で低エーテル化度の第二のカルボキシメチルセルロースを組み合わせて構成したことを特徴とする非水系二次電池用負極板。 A negative electrode mixture layer is formed by adhering a negative electrode mixture paint obtained by kneading and dispersing an active material made of a material capable of holding at least lithium, a binder, and a thickener in a dispersion medium onto a negative electrode current collector. A negative electrode plate for an aqueous secondary battery, wherein the thickener is composed of a first carboxymethyl cellulose having a low viscosity and a high degree of etherification and a second carboxymethyl cellulose having a high viscosity and a low degree of etherification. A negative electrode plate for a non-aqueous secondary battery. 前記第一のカルボキシメチルセルロースのエーテル化度を１．０〜１．５としたことを特徴とする請求項１に記載の非水系二次電池用負極板。 2. The negative electrode plate for a non-aqueous secondary battery according to claim 1, wherein the degree of etherification of the first carboxymethyl cellulose is 1.0 to 1.5. 前記第一のカルボキシメチルセルロースの１重量％の水溶液の粘度が１０〜１，８００ｍＰａ・ｓとしたことを特徴とする請求項１に記載の非水系二次電池用負極板。 2. The negative electrode plate for a non-aqueous secondary battery according to claim 1, wherein the viscosity of a 1 wt% aqueous solution of the first carboxymethyl cellulose is 10 to 1,800 mPa · s. 前記第二のカルボキシメチルセルロースのエーテル化度を０．５〜０．８としたことを特徴とする請求項１に記載の非水系二次電池用負極板。 2. The negative electrode plate for a non-aqueous secondary battery according to claim 1, wherein the degree of etherification of the second carboxymethyl cellulose is 0.5 to 0.8. 前記第二のカルボキシメチルセルロースの１重量％の水溶液の粘度が３，０００〜１０，０００ｍＰａ・ｓとしたことを特徴とする請求項１に記載の非水系二次電池用負極板。 2. The negative electrode plate for a non-aqueous secondary battery according to claim 1, wherein a viscosity of a 1% by weight aqueous solution of the second carboxymethyl cellulose is 3,000 to 10,000 mPa · s. 前記負極合剤塗料として負極活物質を１００重量部とした場合前記第一のカルボキシメチルセルロースおよび第二のカルボキシメチルセルロースの総量が０．４重量部以上１．２重量部以下含有したことを特徴とする請求項１に記載の非水系二次電池用負極板。 When the negative electrode active material is 100 parts by weight as the negative electrode mixture paint, the total amount of the first carboxymethyl cellulose and the second carboxymethyl cellulose is 0.4 to 1.2 parts by weight. The negative electrode plate for non-aqueous secondary batteries according to claim 1. 前記負極合剤塗料として負極活物質を１００重量部とした場合、第一のカルボキシメチルセルロースを０．１重量部以上０．４重量部以下含有し、第二のカルボキシメチルセルロースを０．３重量部以上０．８重量部以下含有したことを特徴とする請求項１に記載の非水系二次電池用負極板。 When the negative electrode active material is 100 parts by weight as the negative electrode mixture paint, the first carboxymethyl cellulose is contained in an amount of 0.1 parts by weight or more and 0.4 parts by weight or less, and the second carboxymethyl cellulose is contained in an amount of 0.3 parts by weight or more. The negative electrode plate for a non-aqueous secondary battery according to claim 1, wherein the negative electrode plate is contained in an amount of 0.8 part by weight or less. 前記負極合剤塗料として負極活物質の比表面積を３．０〜５．５ｍ２／ｇとしたことを特徴とする請求項１に記載の非水系二次電池用負極板。 The negative electrode plate for a non-aqueous secondary battery according to claim 1, wherein the negative electrode active material has a specific surface area of 3.0 to 5.5 m 2 / g as the negative electrode mixture paint. 前記負極合剤塗料として結着材にスチレンブタジエンラバーを用いたことを特徴とする請求項１に記載の非水系二次電池用負極板。 The negative electrode plate for a non-aqueous secondary battery according to claim 1, wherein styrene butadiene rubber is used as a binder for the negative electrode mixture paint. 少なくともリチウム含有複合酸化物よりなる正極活物質と導電材および結着材を分散媒にて混練分散した正極合剤塗料を正極集電体の上に付着させて正極合剤層を形成した正極板と少なくともリチウムを保持しうる材料よりなる活物質と結着材および増粘剤を分散媒にて混練分散した負極合剤塗料を負極集電体の上に付着させて負極合剤層を形成し負極板との間に多孔質絶縁体を介在させて渦巻状に捲回または積層して構成した電極群を非水電解液とともに電池ケースに封入した非水系二次電池であって、前記負極板に請求項１〜９のいずれか一つに記載の非水系二次電池用負極板を用いたことを特徴とする非水系二次電池。 A positive electrode plate having a positive electrode mixture layer formed by adhering a positive electrode mixture coating material obtained by kneading and dispersing a positive electrode active material comprising at least a lithium-containing composite oxide, a conductive material, and a binder in a dispersion medium onto a positive electrode current collector And a negative electrode mixture paint obtained by kneading and dispersing an active material made of a material capable of holding at least lithium, a binder, and a thickener in a dispersion medium to form a negative electrode mixture layer on the negative electrode current collector. A non-aqueous secondary battery in which a porous insulator is interposed between a negative electrode plate and an electrode group wound or laminated in a spiral shape and enclosed in a battery case together with a non-aqueous electrolyte, the negative electrode A non-aqueous secondary battery using the negative electrode plate for a non-aqueous secondary battery according to claim 1 as a plate.
JP2010200658A 2010-09-08 2010-09-08 Negative electrode plate for nonaqueous secondary battery and nonaqueous secondary battery using the same Pending JP2012059488A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010200658A JP2012059488A (en) 2010-09-08 2010-09-08 Negative electrode plate for nonaqueous secondary battery and nonaqueous secondary battery using the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2010200658A JP2012059488A (en) 2010-09-08 2010-09-08 Negative electrode plate for nonaqueous secondary battery and nonaqueous secondary battery using the same

Publications (1)

Publication Number Publication Date
JP2012059488A true JP2012059488A (en) 2012-03-22

Family

ID=46056369

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2010200658A Pending JP2012059488A (en) 2010-09-08 2010-09-08 Negative electrode plate for nonaqueous secondary battery and nonaqueous secondary battery using the same

Country Status (1)

Country Link
JP (1) JP2012059488A (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013089422A (en) * 2011-10-17 2013-05-13 Toyota Motor Corp Lithium secondary battery manufacturing method
JP2013257978A (en) * 2012-06-11 2013-12-26 Toyota Motor Corp Negative electrode paste and method for producing negative electrode paste
JP2014011077A (en) * 2012-06-29 2014-01-20 Toyota Motor Corp Nonaqueous electrolyte secondary battery manufacturing method and nonaqueous electrolyte secondary battery
JP2014165038A (en) * 2013-02-26 2014-09-08 Murata Mfg Co Ltd Electrode material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same
JP2015138658A (en) * 2014-01-22 2015-07-30 トヨタ自動車株式会社 Method for manufacturing electrode for lithium secondary battery, and granulated material
WO2015118834A1 (en) * 2014-02-04 2015-08-13 三洋電機株式会社 Negative electrode for non-aqueous electrolyte secondary battery
JP2016076342A (en) * 2014-10-03 2016-05-12 株式会社豊田中央研究所 Electrode for nonaqueous secondary battery, and nonaqueous secondary battery
WO2016104315A1 (en) * 2014-12-24 2016-06-30 Ｎｅｃエナジーデバイス株式会社 Method for producing paste for production of negative electrodes, method for producing negative electrode for lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, and lithium ion secondary battery
KR20160112748A (en) * 2015-03-20 2016-09-28 주식회사 엘지화학 Method for preparing negative electrode composition of lithium secondary battery, and negative electrode and lithium secondary battery prepared by using the same
KR101863383B1 (en) 2013-12-18 2018-05-31 주식회사 엘지화학 An anode for a lithium ion secondary battery with high capacity properties
JP2020194681A (en) * 2019-05-27 2020-12-03 株式会社Ｇｓユアサ Power storage element
CN112072091A (en) * 2020-09-16 2020-12-11 远景动力技术(江苏)有限公司 Negative electrode, method for producing same, and lithium ion battery using same
CN112072112A (en) * 2020-09-16 2020-12-11 远景动力技术(江苏)有限公司 Electrode thickening agent and preparation method thereof
WO2024095759A1 (en) * 2022-10-31 2024-05-10 三菱鉛筆株式会社 Slurry composition for negative electrodes for secondary batteries

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013089422A (en) * 2011-10-17 2013-05-13 Toyota Motor Corp Lithium secondary battery manufacturing method
JP2013257978A (en) * 2012-06-11 2013-12-26 Toyota Motor Corp Negative electrode paste and method for producing negative electrode paste
JP2014011077A (en) * 2012-06-29 2014-01-20 Toyota Motor Corp Nonaqueous electrolyte secondary battery manufacturing method and nonaqueous electrolyte secondary battery
JP2014165038A (en) * 2013-02-26 2014-09-08 Murata Mfg Co Ltd Electrode material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same
KR101863383B1 (en) 2013-12-18 2018-05-31 주식회사 엘지화학 An anode for a lithium ion secondary battery with high capacity properties
JP2015138658A (en) * 2014-01-22 2015-07-30 トヨタ自動車株式会社 Method for manufacturing electrode for lithium secondary battery, and granulated material
JPWO2015118834A1 (en) * 2014-02-04 2017-03-23 三洋電機株式会社 Anode for non-aqueous electrolyte secondary battery
WO2015118834A1 (en) * 2014-02-04 2015-08-13 三洋電機株式会社 Negative electrode for non-aqueous electrolyte secondary battery
JP2016076342A (en) * 2014-10-03 2016-05-12 株式会社豊田中央研究所 Electrode for nonaqueous secondary battery, and nonaqueous secondary battery
CN107004838A (en) * 2014-12-24 2017-08-01 Nec 能源元器件株式会社 Preparation method for the paste for preparing negative pole, the preparation method of negative pole for lithium rechargeable battery, negative pole and lithium rechargeable battery for lithium rechargeable battery
JPWO2016104315A1 (en) * 2014-12-24 2017-10-05 Ｎｅｃエナジーデバイス株式会社 Method for producing paste for negative electrode production, method for producing negative electrode for lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery
WO2016104315A1 (en) * 2014-12-24 2016-06-30 Ｎｅｃエナジーデバイス株式会社 Method for producing paste for production of negative electrodes, method for producing negative electrode for lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, and lithium ion secondary battery
JP2020074292A (en) * 2014-12-24 2020-05-14 株式会社エンビジョンＡｅｓｃエナジーデバイス Manufacturing method of paste anode manufacturing precursor, manufacturing method of anode manufacturing paste, manufacturing method of anode for lithium ion secondary battery, and manufacturing method of lithium ion secondary battery
US10700356B2 (en) 2014-12-24 2020-06-30 Envision Aesc Energy Devices Ltd. Method for producing paste for production of negative electrodes, method for producing negative electrode for lithium ion secondary batteries, negative electrode for lithium secondary batteries, and lithium ion secondary battery
KR20160112748A (en) * 2015-03-20 2016-09-28 주식회사 엘지화학 Method for preparing negative electrode composition of lithium secondary battery, and negative electrode and lithium secondary battery prepared by using the same
KR102018854B1 (en) * 2015-03-20 2019-09-05 주식회사 엘지화학 Method for preparing negative electrode composition of lithium secondary battery, and negative electrode and lithium secondary battery prepared by using the same
JP2020194681A (en) * 2019-05-27 2020-12-03 株式会社Ｇｓユアサ Power storage element
JP7215329B2 (en) 2019-05-27 2023-01-31 株式会社Ｇｓユアサ Storage element
CN112072091A (en) * 2020-09-16 2020-12-11 远景动力技术(江苏)有限公司 Negative electrode, method for producing same, and lithium ion battery using same
CN112072112A (en) * 2020-09-16 2020-12-11 远景动力技术(江苏)有限公司 Electrode thickening agent and preparation method thereof
WO2024095759A1 (en) * 2022-10-31 2024-05-10 三菱鉛筆株式会社 Slurry composition for negative electrodes for secondary batteries

Similar Documents

Publication Publication Date Title
JP2012059488A (en) Negative electrode plate for nonaqueous secondary battery and nonaqueous secondary battery using the same
KR100781709B1 (en) Method of preparation of cathode coat-materials for lithium ion secondary battery and the same
JP4834030B2 (en) Positive electrode for lithium secondary battery and lithium secondary battery using the same
JP2011192539A (en) Electrode for nonaqueous electrolyte secondary battery and method for manufacturing the same, and nonaqueous electrolyte secondary battery
JP2014044895A (en) Electrolyte-negative electrode structure and lithium ion secondary battery including the same
JP2009099441A (en) Negative electrode plate for nonaqueous electrolyte solution secondary battery, its manufacturing method, and nonaqueous electrolyte solution secondary battery
JP6068237B2 (en) Electrolyte-negative electrode structure and lithium ion secondary battery comprising the same
JP3652769B2 (en) Electrode plate for non-aqueous electrolyte secondary battery
JP5029017B2 (en) Negative electrode plate for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery using the same
JP2008204886A (en) Negative electrode active material, its evaluation method, negative electrode plate for nonaqueous electrolyte secondary battery using it, and nonaqueous electrolyte secondary battery
JP2014133194A (en) Manufacturing method of film-coated object, film-coated object, nonaqueous secondary battery negative plate, nonaqueous secondary battery, and mobile body
JP6614439B2 (en) Negative electrode for power storage element and power storage element
JP5200329B2 (en) Electrode plate for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery
JP2011253684A (en) Battery manufacturing method
JP4357857B2 (en) Slurries for electrode mixture layers, electrode plates, and non-aqueous electrolyte batteries
JP2009224099A (en) Manufacturing method of negative electrode plate for nonaqueous electrolyte secondary battery
JP5557619B2 (en) Nonaqueous electrolyte secondary battery
JP4971646B2 (en) Method for producing positive electrode mixture-containing composition, method for producing negative electrode mixture-containing composition, method for producing positive electrode for battery, method for producing negative electrode for battery, non-aqueous secondary battery and method for producing the same
JP4834975B2 (en) Coating composition for active material layer, electrode plate for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
JP2013084399A (en) Lithium ion secondary battery anode manufacturing method and lithium ion secondary battery manufacturing method
JP5662746B2 (en) Lithium ion secondary battery
JP5072061B2 (en) Method for producing positive electrode for non-aqueous secondary battery and non-aqueous secondary battery
JP2013073867A (en) Positive electrode active material for nonaqueous electrolyte secondary battery and method for manufacturing the same, and nonaqueous electrolyte secondary battery
JP4527423B2 (en) Coating composition for active material layer, electrode plate for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
JP2003173780A (en) Coating composition for anode, anode plate, and nonaqueous electrolyte solution secondary battery