JP2024046590A - Positive electrode composition for lithium ion batteries and method for producing positive electrode for lithium ion batteries - Google Patents
Positive electrode composition for lithium ion batteries and method for producing positive electrode for lithium ion batteries Download PDFInfo
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- JP2024046590A JP2024046590A JP2023083600A JP2023083600A JP2024046590A JP 2024046590 A JP2024046590 A JP 2024046590A JP 2023083600 A JP2023083600 A JP 2023083600A JP 2023083600 A JP2023083600 A JP 2023083600A JP 2024046590 A JP2024046590 A JP 2024046590A
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- positive electrode
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- lithium ion
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- electrode composition
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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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
【課題】集電体との接着性に優れ、電極の捲回時や繰り返し充放電に伴う活物質層の体積変化に追随できる柔軟性を有し、厳しい条件での圧延処理が不要であるリチウムイオン電池用正極組成物を提供すること。【解決手段】バインダー樹脂、導電助剤及び正極活物質を含むリチウムイオン電池用正極組成物であって、前記バインダー樹脂がビニル樹脂であり、前記ビニル樹脂が、カルボキシル基を有するビニルモノマー（ａ１）及び下記一般式（１）で表されるビニルモノマー（ａ２）を必須構成単量体とする重合体であり、前記バインダー樹脂のガラス転移温度が－４０～－５℃であり、前記バインダー樹脂の結晶化度が２０未満であるリチウムイオン電池用正極組成物。【選択図】 なし[Problem] To provide a positive electrode composition for lithium ion batteries which has excellent adhesion to a current collector, flexibility capable of following the volumetric changes in the active material layer that accompany the winding of the electrode or repeated charging and discharging, and does not require rolling treatment under severe conditions. [Solution] A positive electrode composition for lithium ion batteries comprising a binder resin, a conductive assistant, and a positive electrode active material, wherein the binder resin is a vinyl resin, which is a polymer having, as essential constituent monomers, a vinyl monomer (a1) having a carboxyl group and a vinyl monomer (a2) represented by the following general formula (1), the glass transition temperature of the binder resin is -40 to -5°C, and the crystallinity of the binder resin is less than 20. [Selected Figure] None
Description
本発明は、リチウムイオン電池用正極組成物及びリチウムイオン電池用正極の製造方法に関する。 The present invention relates to a positive electrode composition for lithium ion batteries and a method for producing a positive electrode for lithium ion batteries.
リチウムイオン電池は、高電圧、高エネルギー密度という特長を持つことから、携帯情報機器分野などにおいて広く利用され、携帯電話、ノート型パソコンを始めとする携帯端末用標準電池としての地位が確立されている。その用途は拡大する一方で、従来用途に加えてハイブリッド自動車や電気自動車などへの適用も検討されており一部では既に実用化されている。 Lithium-ion batteries, with their high voltage and high energy density characteristics, are widely used in the field of portable information devices and have established themselves as the standard battery for mobile terminals such as mobile phones and notebook computers. While their uses continue to expand, in addition to their traditional uses, they are also being considered for use in hybrid and electric vehicles, and some have already been put into practical use.
リチウムイオン電池用正極の製造方法としては、バインダー樹脂としてポリフッ化ビニリデン（ＰＶＤＦ）を導電助剤及び正極活物質と混合し、さらにＮ－メチルピロリドン等の有機溶剤を加えてペースト状にし、これを集電体上に塗布、乾燥する方法が知られている（特許文献１）。
しかし、これらの方法で得られる電極は結着力や柔軟性が十分とは言えず、電極の捲回時や繰り返し充放電に伴う活物質層の体積変化により活物質層が集電体から剥離して電池性能が低下するという問題があった。
バインダー樹脂として、ＰＶＤＦの代わりにスチレンーブタジエンゴム（ＳＢＲ）等を代替することも検討されているが、耐酸化性に乏しいため代替は困難であった。
A known method for manufacturing a positive electrode for a lithium-ion battery is to mix polyvinylidene fluoride (PVDF) as a binder resin with a conductive assistant and a positive electrode active material, add an organic solvent such as N-methylpyrrolidone to form a paste, and then apply the paste to a current collector and dry it (Patent Document 1).
However, the electrodes obtained by these methods do not have sufficient binding strength or flexibility, and there is a problem that the active material layer peels off from the current collector due to volume changes during winding of the electrode or due to repeated charging and discharging, resulting in a decrease in battery performance.
As a binder resin, the use of styrene-butadiene rubber (SBR) and the like as a substitute for PVDF has been considered, but substitution has been difficult due to poor oxidation resistance.
また、近年、電池の高容量化を目的として、電極の空隙率を下げるために、ロールプレス等の圧延処理条件が厳しくなっている。特に正極においては、諸々の制約からバインダー樹脂としてＰＶＤＦのような機械的変形性に乏しい結晶性樹脂を用いている場合がほとんどで、圧延処理の条件が大きな課題であった。バインダー樹脂を活物質や導電剤粒子表面に化学結合させることにより、圧延工程を省略もしくは簡略化したリチウムイオン電池電極板製造方法も提案されている（特許文献２）が、電池材料の選定に制約が大きく、対策として十分とは言えなかった。 In recent years, the conditions for rolling processes such as roll pressing have become stricter in order to reduce the porosity of electrodes in order to increase the capacity of batteries. In particular, for positive electrodes, due to various constraints, crystalline resins with poor mechanical deformability such as PVDF are almost always used as binder resins, and the conditions for rolling processes have been a major issue. A method for manufacturing lithium-ion battery electrode plates has been proposed in which the rolling process is omitted or simplified by chemically bonding the binder resin to the surface of the active material or conductive agent particles (Patent Document 2), but there are significant constraints on the selection of battery materials, and this is not a sufficient solution.
本発明は上記実情に鑑みて為されたものであり、集電体との接着性に優れ、電極の捲回時や繰り返し充放電に伴う活物質層の体積変化に追随できる柔軟性を有し、厳しい条件での圧延処理が不要であるリチウムイオン電池用正極組成物を提供することを目的としている。 The present invention was made in consideration of the above-mentioned circumstances, and aims to provide a positive electrode composition for lithium-ion batteries that has excellent adhesion to the current collector, flexibility that can follow the volumetric changes of the active material layer that occur when the electrode is wound or during repeated charging and discharging, and does not require rolling treatment under severe conditions.
本発明者らは、鋭意検討した結果、本発明に到達した。
本発明は、バインダー樹脂、導電助剤及び正極活物質を含むリチウムイオン電池用正極組成物であって、前記バインダー樹脂がビニル樹脂であり、前記ビニル樹脂が、カルボキシル基を有するビニルモノマー（ａ１）及び下記一般式（１）
ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２ （１）
［式（１）中、Ｒ１は水素原子又はメチル基であり、Ｒ２は炭素数４～３６の分岐アルキル基である。］
で表されるビニルモノマー（ａ２）を必須構成単量体とする重合体であり、前記バインダー樹脂のガラス転移温度が－４０～－５℃であり、前記バインダー樹脂の結晶化度が２０未満であることを特徴とするリチウムイオン電池用正極組成物、及び、バインダー樹脂、導電助剤、正極活物質及び水性溶媒を含むスラリーを作製する混合工程と、前記スラリーを集電体に塗布する塗布工程と、前記塗布工程後にスラリーを乾燥して前記集電体上に正極活物質層を形成する乾燥工程とを含むリチウムイオン電池用正極の製造方法、に関する。
The present inventors have arrived at the present invention as a result of intensive studies.
The present invention provides a positive electrode composition for a lithium ion battery comprising a binder resin, a conductive additive, and a positive electrode active material, wherein the binder resin is a vinyl resin, and the vinyl resin is a vinyl monomer (a1) having a carboxyl group. and the following general formula (1)
CH 2 =C(R 1 )COOR 2 (1)
[In formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a branched alkyl group having 4 to 36 carbon atoms. ]
It is a polymer having a vinyl monomer (a2) represented by as an essential constituent monomer, the glass transition temperature of the binder resin is -40 to -5°C, and the crystallinity of the binder resin is less than 20. A positive electrode composition for lithium ion batteries, a mixing step of preparing a slurry containing a binder resin, a conductive aid, a positive electrode active material, and an aqueous solvent, and a coating step of applying the slurry to a current collector. and a drying step of drying the slurry after the coating step to form a positive electrode active material layer on the current collector.
本発明によれば、集電体との接着性に優れ、電極の捲回時や繰り返し充放電に伴う活物質層の体積変化に追随できる柔軟性を有し、厳しい条件での圧延処理が不要であるリチウムイオン電池用正極組成物を提供することができる。 The present invention provides a positive electrode composition for lithium ion batteries that has excellent adhesion to the current collector, flexibility that allows it to follow the volumetric changes in the active material layer that occur when the electrode is wound or during repeated charging and discharging, and does not require rolling treatment under severe conditions.
［リチウムイオン電池用正極組成物］
本発明のリチウムイオン電池用正極組成物は、バインダー樹脂、導電助剤及び正極活物質を含むリチウムイオン電池用正極組成物である。
前記バインダー樹脂がビニル樹脂であり、前記ビニル樹脂が、カルボキシル基を有するビニルモノマー（ａ１）及び下記一般式（１）
ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２ （１）
［式（１）中、Ｒ１は水素原子又はメチル基であり、Ｒ２は炭素数４～３６の分岐アルキル基である。］
で表されるビニルモノマー（ａ２）を必須構成単量体とする重合体である。
[Positive electrode composition for lithium ion batteries]
The positive electrode composition for a lithium ion battery of the present invention is a positive electrode composition for a lithium ion battery containing a binder resin, a conductive support agent, and a positive electrode active material.
The binder resin is a vinyl resin, and the vinyl resin is a vinyl monomer (a1) having a carboxyl group and the following general formula (1).
CH 2 =C(R 1 )COOR 2 (1)
[In formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a branched alkyl group having 4 to 36 carbon atoms. ]
This is a polymer containing a vinyl monomer (a2) represented by the following as an essential constituent monomer.
カルボキシル基を有するビニルモノマー（ａ１）としては、（メタ）アクリル酸、クロトン酸、桂皮酸等の炭素数３～１５のモノカルボン酸；（無水）マレイン酸、フマル酸、（無水）イタコン酸、シトラコン酸、メサコン酸等の炭素数４～２４のジカルボン酸；アコニット酸等の炭素数６～２４の３価～４価又はそれ以上の価数のポリカルボン酸等が挙げられる。これらの中でも（メタ）アクリル酸が好ましく、メタクリル酸が特に好ましい。 Examples of vinyl monomers (a1) having a carboxyl group include monocarboxylic acids having 3 to 15 carbon atoms, such as (meth)acrylic acid, crotonic acid, and cinnamic acid; dicarboxylic acids having 4 to 24 carbon atoms, such as maleic acid (anhydride), fumaric acid, itaconic acid (anhydride), citraconic acid, and mesaconic acid; and polycarboxylic acids having 6 to 24 carbon atoms and a valence of 3 to 4 or more, such as aconitic acid. Among these, (meth)acrylic acid is preferred, and methacrylic acid is particularly preferred.
上記一般式（１）で表されるビニルモノマー（ａ２）において、Ｒ１は水素原子又はメチル基を表す。Ｒ１はメチル基であることが好ましい。
Ｒ２は炭素数４～３６の分岐アルキル基であり、Ｒ２の具体例としては、１－アルキルアルキル基（１－メチルプロピル基（ｓｅｃ－ブチル基）、１，１－ジメチルエチル基（ｔｅｒｔ－ブチル基）、１－メチルブチル基、１－エチルプロピル基、１，１－ジメチルプロピル基、１－メチルペンチル基、１－エチルブチル基、１－メチルヘキシル基、１－エチルペンチル基、１－メチルヘプチル基、１－エチルヘキシル基、１－メチルオクチル基、１－エチルヘプチル基、１－メチルノニル基、１－エチルオクチル基、１－メチルデシル基、１－エチルノニル基、１－ブチルエイコシル基、１－ヘキシルオクタデシル基、１－オクチルヘキサデシル基、１－デシルテトラデシル基、１－ウンデシルトリデシル基等）、２－アルキルアルキル基（２－メチルプロピル基（ｉｓｏ－ブチル基）、２－メチルブチル基、２－エチルプロピル基、２，２－ジメチルプロピル基、２－メチルペンチル基、２－エチルブチル基、２－メチルヘキシル基、２－エチルペンチル基、２－メチルヘプチル基、２－エチルヘキシル基、２－メチルオクチル基、２－エチルヘプチル基、２－メチルノニル基、２－エチルオクチル基、２－メチルデシル基、２－エチルノニル基、２－ヘキシルオクタデシル基、２－オクチルヘキサデシル基、２－デシルテトラデシル基、２－ウンデシルトリデシル基、２－ドデシルヘキサデシル基、２－トリデシルペンタデシル基、２－デシルオクタデシル基、２－テトラデシルオクタデシル基、２－ヘキサデシルオクタデシル基、２－テトラデシルエイコシル基、２－ヘキサデシルエイコシル基等）、３～３４－アルキルアルキル基（３－アルキルアルキル基、４－アルキルアルキル基、５－アルキルアルキル基、３２－アルキルアルキル基、３３－アルキルアルキル基及び３４－アルキルアルキル基等）、並びに、プロピレンオリゴマー（７～１１量体）、エチレン／プロピレン（モル比１６／１～１／１１）オリゴマー、イソブチレンオリゴマー（７～８量体）及びα－オレフィン（炭素数５～２０）オリゴマー（４～８量体）等に対応するオキソアルコールのアルキル残基のような１又はそれ以上の分岐アルキル基を含有する混合アルキル基等が挙げられる。
これらのうち、電解液の吸液の観点から好ましいのは２－アルキルアルキル基であり、更に好ましいのは２－エチルヘキシル基及び２－デシルテトラデシル基である。
In the vinyl monomer (a2) represented by the above general formula (1), R 1 represents a hydrogen atom or a methyl group, and R 1 is preferably a methyl group.
R2 is a branched alkyl group having 4 to 36 carbon atoms, and specific examples of R2 include 1-alkylalkyl groups (1-methylpropyl group (sec-butyl group), 1,1-dimethylethyl group (tert-butyl group), 1-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1-methylpentyl group, 1-ethylbutyl group, 1-methylhexyl group, 1-ethylpentyl group, 1-methylheptyl group, 1-ethylhexyl group, 1-methyloctyl group, 1-ethylheptyl group, 1-methylnonyl group, 1-ethyloctyl group, 1-methyldecyl group, 1-ethylnonyl group, 1-ethyloctyl group, 1-methyldecyl group, 1-ethylnonyl group, 1-ethyloctyl group, 1-ethylnonyl group, 1-ethyloctyl group, 1-methyldecyl group, 1-ethylnonyl group, 1-ethyloctyl group, 1-ethyloctyl group, 1-methyldecyl group, 1-ethyloct ... a 2-methylpropyl group, a 2-methylbutyl group, a 2-ethylpropyl group, a 2,2-dimethylpropyl group, a 2-methylpentyl group, a 2-ethylbutyl group, a 2-methylhexyl group, a 2-ethylpentyl group, a 2-methylheptyl group, a 2-ethylhexyl group, a 2-methyloctyl group, a 2-ethylhept ...methyloctyl group, a 2 -methylnonyl group, 2-ethyloctyl group, 2-methyldecyl group, 2-ethylnonyl group, 2-hexyloctadecyl group, 2-octylhexadecyl group, 2-decyltetradecyl group, 2-undecyltridecyl group, 2-dodecylhexadecyl group, 2-tridecylpentadecyl group, 2-decyloctadecyl group, 2-tetradecyloctadecyl group, 2-hexadecyloctadecyl group, 2-tetradecyleicosyl group, 2-hexadecyleicosyl group, etc.), 3 to 34-alkylalkyl group (3-alkylalkyl group , 4-alkylalkyl group, 5-alkylalkyl group, 32-alkylalkyl group, 33-alkylalkyl group and 34-alkylalkyl group, as well as mixed alkyl groups containing one or more branched alkyl groups such as alkyl residues of oxoalcohols corresponding to propylene oligomers (7-11 mer), ethylene/propylene (molar ratio 16/1 to 1/11) oligomers, isobutylene oligomers (7-8 mers) and α-olefin (carbon number 5-20) oligomers (4-8 mers).
Among these, from the viewpoint of electrolyte absorption, 2-alkylalkyl groups are preferred, and 2-ethylhexyl and 2-decyltetradecyl groups are more preferred.
また、前記バインダー樹脂を構成する単量体には、ビニルモノマー（ａ１）及び上記一般式（１）で表されるビニルモノマー（ａ２）の他に、活性水素を含有しない共重合性ビニルモノマー（ａ３）が含まれていてもよい。
活性水素を含有しない共重合性ビニルモノマー（ａ３）としては、下記（ａ３１）～（ａ３５）が挙げられる。
（ａ３１）炭素数１～２０のモノオールと（メタ）アクリル酸から形成されるカルビル（メタ）アクリレート
上記モノオールとしては、（ｉ）脂肪族モノオール［メタノール、エタノール、ｎ－又はｉ－プロピルアルコール、ｎ－ブチルアルコール、ｎ－ペンチルアルコール、ｎ－オクチルアルコール、ノニルアルコール、デシルアルコール、ラウリルアルコール、トリデシルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール等］、（ｉｉ）脂環式モノオール［シクロヘキシルアルコール等］、（ｉｉｉ）芳香脂肪族モノオール［ベンジルアルコール等］及びこれらの２種以上の混合物が挙げられる。
The monomers constituting the binder resin may further include a copolymerizable vinyl monomer (a3) that does not contain active hydrogen, in addition to the vinyl monomer (a1) and the vinyl monomer (a2) represented by the general formula (1).
Examples of the copolymerizable vinyl monomer (a3) containing no active hydrogen include the following (a31) to (a35).
(a31) Carbyl (meth)acrylate formed from a monol having 1 to 20 carbon atoms and (meth)acrylic acid. Examples of the monol include (i) aliphatic monols [methanol, ethanol, n- or i-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, n-octyl alcohol, nonyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.], (ii) alicyclic monols [cyclohexyl alcohol, etc.], (iii) aromatic aliphatic monols [benzyl alcohol, etc.], and mixtures of two or more of these.
（ａ３２）ポリ（ｎ＝２～３０）オキシアルキレン（炭素数２～４）アルキル（炭素数１～１８）エーテル（メタ）アクリレート［メタノールのエチレンオキシド（以下ＥＯと略記）１０モル付加物（メタ）アクリレート、メタノールのプロピレンオキシド（以下ＰＯと略記）１０モル付加物（メタ）アクリレートなど］ (a32) Poly(n=2-30) oxyalkylene (2-4 carbon atoms) alkyl (1-18 carbon atoms) ether (meth)acrylate [10 mole adduct of methanol with ethylene oxide (hereinafter abbreviated as EO) (meth) Acrylate, 10 mole adduct of methanol with propylene oxide (hereinafter abbreviated as PO) (meth)acrylate, etc.]
（ａ３３）窒素含有ビニル化合物
（ａ３３－１）アミド基含有ビニル化合物
（ｉ）炭素数３～３０の（メタ）アクリルアミド化合物、例えばＮ，Ｎ－ジアルキル（炭素数１～６）もしくはジアラルキル（炭素数７～１５）（メタ）アクリルアミド［Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジベンジルアクリルアミドなど］、ジアセトンアクリルアミド
（ｉｉ）上記（メタ）アクリルアミド化合物を除く、炭素数４～２０のアミド基含有ビニル化合物、例えばＮ－メチル－Ｎ－ビニルアセトアミド、環状アミド（ピロリドン化合物（炭素数６～１３、例えば、Ｎ－ビニルピロリドンなど））
(a33) Nitrogen-containing vinyl compound (a33-1) Amide group-containing vinyl compound (i) (meth)acrylamide compound having 3 to 30 carbon atoms, such as N,N-dialkyl (1 to 6 carbon atoms) or dialkyl (carbon number 7-15) (Meth)acrylamide [N,N-dimethylacrylamide, N,N-dibenzylacrylamide, etc.], diacetone acrylamide (ii) Containing an amide group having 4 to 20 carbon atoms, excluding the above (meth)acrylamide compounds Vinyl compounds, such as N-methyl-N-vinylacetamide, cyclic amides (pyrrolidone compounds (6 to 13 carbon atoms, such as N-vinylpyrrolidone))
（ａ３３－２）（メタ）アクリレート化合物
（ｉ）ジアルキル（炭素数１～４）アミノアルキル（炭素数１～４）（メタ）アクリレート［Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、ｔ－ブチルアミノエチル（メタ）アクリレート、モルホリノエチル（メタ）アクリレートなど］
（ｉｉ）４級アンモニウム基含有（メタ）アクリレート〔３級アミノ基含有（メタ）アクリレート［Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレートなど］の４級化物（前記の４級化剤を用いて４級化したもの）など〕
(a33-2) (meth)acrylate compound (i) dialkyl (having 1 to 4 carbon atoms) aminoalkyl (having 1 to 4 carbon atoms) (meth)acrylate [N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate, morpholinoethyl (meth)acrylate, etc.]
(ii) Quaternary ammonium group-containing (meth)acrylates (quaternized products of tertiary amino group-containing (meth)acrylates [N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, etc.] (those quaternized using the above-mentioned quaternizing agents), etc.)
（ａ３３－３）複素環含有ビニル化合物
ピリジン化合物（炭素数７～１４、例えば２－又は４－ビニルピリジン）、イミダゾール化合物（炭素数５～１２、例えばＮ－ビニルイミダゾール）、ピロール化合物（炭素数６～１３、例えばＮ－ビニルピロール）、ピロリドン化合物（炭素数６～１３、例えばＮ－ビニル－２－ピロリドン）
(a33-3) Heterocycle-containing vinyl compounds Pyridine compounds (7 to 14 carbon atoms, e.g. 2- or 4-vinylpyridine), imidazole compounds (5 to 12 carbon atoms, e.g. N-vinylimidazole), pyrrole compounds (carbon atoms 6-13 carbon atoms, e.g. N-vinylpyrrole), pyrrolidone compounds (6-13 carbon atoms, e.g. N-vinyl-2-pyrrolidone)
（ａ３３－４）ニトリル基含有ビニル化合物
炭素数３～１５のニトリル基含有ビニル化合物、例えば（メタ）アクリロニトリル、シアノスチレン、シアノアルキル（炭素数１～４）アクリレート
(a33-4) Nitrile group-containing vinyl compounds Nitrile group-containing vinyl compounds having 3 to 15 carbon atoms, such as (meth)acrylonitrile, cyanostyrene, and cyanoalkyl (C1 to C4)acrylates.
（ａ３３－５）その他ビニル化合物
ニトロ基含有ビニル化合物（炭素数８～１６、例えばニトロスチレン）など
(a33-5) Other vinyl compounds Nitro group-containing vinyl compounds (having 8 to 16 carbon atoms, for example, nitrostyrene), etc.
（ａ３４）ビニル炭化水素
（ａ３４－１）脂肪族ビニル炭化水素
炭素数２～１８又はそれ以上のオレフィン［エチレン、プロピレン、ブテン、イソブチレン、ペンテン、ヘプテン、ジイソブチレン、オクテン、ドデセン、オクタデセンなど］、炭素数４～１０又はそれ以上のジエン［ブタジエン、イソプレン、１，４－ペンタジエン、１，５－ヘキサジエン、１，７－オクタジエンなど］など
(a34) Vinyl hydrocarbons (a34-1) Aliphatic vinyl hydrocarbons Olefins having 2 to 18 or more carbon atoms [ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.], dienes having 4 to 10 or more carbon atoms [butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, etc.], etc.
（ａ３４－２）脂環式ビニル炭化水素
炭素数４～１８又はそれ以上の環状不飽和化合物、例えばシクロアルケン（例えばシクロヘキセン）、（ジ）シクロアルカジエン［例えば（ジ）シクロペンタジエン］、テルペン（例えばピネン、リモネン及びインデン）
(a34-2) Alicyclic vinyl hydrocarbons Cyclic unsaturated compounds having 4 to 18 or more carbon atoms, such as cycloalkenes (e.g., cyclohexene), (di)cycloalkadienes [e.g., (di)cyclopentadiene], terpenes (e.g., pinene, limonene, and indene).
（ａ３４－３）芳香族ビニル炭化水素
炭素数８～２０またはそれ以上の芳香族不飽和化合物及びそれらの誘導体、例えばスチレン、α－メチルスチレン、ビニルトルエン、２，４－ジメチルスチレン、エチルスチレン、イソプロピルスチレン、ブチルスチレン、フェニルスチレン、シクロヘキシルスチレン、ベンジルスチレン、スチレンスルホン酸リチウム
(a34-3) Aromatic vinyl hydrocarbon Aromatic unsaturated compounds having 8 to 20 or more carbon atoms and derivatives thereof, such as styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, Isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, lithium styrene sulfonate
（ａ３５）ビニルエステル、ビニルエーテル、ビニルケトン、不飽和ジカルボン酸ジエステル
（ａ３５－１）ビニルエステル
脂肪族ビニルエステル［炭素数４～１５、例えば脂肪族カルボン酸（モノ－又はジカルボン酸）のアルケニルエステル（例えば酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ジアリルアジペート、イソプロペニルアセテート、ビニルメトキシアセテート）］
芳香族ビニルエステル［炭素数９～２０、例えば芳香族カルボン酸（モノ－又はジカルボン酸）のアルケニルエステル（例えばビニルベンゾエート、ジアリルフタレート、メチル－４－ビニルベンゾエート）、脂肪族カルボン酸の芳香環含有エステル（例えばアセトキシスチレン）］
(a35) Vinyl ester, vinyl ether, vinyl ketone, unsaturated dicarboxylic acid diester (a35-1) Vinyl ester Aliphatic vinyl ester [4 to 15 carbon atoms, e.g. alkenyl ester of aliphatic carboxylic acid (mono- or dicarboxylic acid) (e.g. vinyl acetate, vinyl propionate, vinyl butyrate, diallyl adipate, isopropenyl acetate, vinyl methoxy acetate)]
Aromatic vinyl esters [9 to 20 carbon atoms, such as alkenyl esters of aromatic carboxylic acids (mono- or dicarboxylic acids) (such as vinyl benzoate, diallyl phthalate, methyl-4-vinyl benzoate), aromatic ring-containing aliphatic carboxylic acids ester (e.g. acetoxystyrene)]
（ａ３５－２）ビニルエーテル
脂肪族ビニルエーテル〔炭素数３～１５、例えばビニルアルキル（炭素数１～１０）エーテル［ビニルメチルエーテル、ビニルブチルエーテル、ビニル２－エチルヘキシルエーテルなど］、ビニルアルコキシ（炭素数１～６）アルキル（炭素数１～４）エーテル［ビニル－２－メトキシエチルエーテル、メトキシブタジエン、３，４－ジヒドロ－１，２－ピラン、２－ブトキシ－２’－ビニロキシジエチルエーテル、ビニル－２－エチルメルカプトエチルエーテルなど］、ポリ（２～４）（メタ）アリロキシアルカン（炭素数２～６）［ジアリロキシエタン、トリアリロキシエタン、テトラアリロキシブタン、テトラメタアリロキシエタンなど］〕
芳香族ビニルエーテル（炭素数８～２０、例えばビニルフェニルエーテル、フェノキシスチレン）
(a35-2) Vinyl ethers Aliphatic vinyl ethers (having 3 to 15 carbon atoms, for example, vinyl alkyl (having 1 to 10 carbon atoms) ethers [vinyl methyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, etc.], vinyl alkoxy (having 1 to 6 carbon atoms) alkyl (having 1 to 4 carbon atoms) ethers [vinyl-2-methoxyethyl ether, methoxybutadiene, 3,4-dihydro-1,2-pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, etc.], poly(2-4)(meth)allyloxyalkanes (having 2 to 6 carbon atoms) [diallyloxyethane, triallyloxyethane, tetraallyloxybutane, tetramethallyloxyethane, etc.]]
Aromatic vinyl ethers (having 8 to 20 carbon atoms, e.g., vinyl phenyl ether, phenoxystyrene)
（ａ３５－３）ビニルケトン
脂肪族ビニルケトン（炭素数４～２５、例えばビニルメチルケトン、ビニルエチルケトン）
芳香族ビニルケトン（炭素数９～２１、例えばビニルフェニルケトン）
(a35-3) Vinyl ketone Aliphatic vinyl ketone (4 to 25 carbon atoms, e.g. vinyl methyl ketone, vinyl ethyl ketone)
Aromatic vinyl ketone (9 to 21 carbon atoms, e.g. vinyl phenyl ketone)
（ａ３５－４）不飽和ジカルボン酸ジエステル
炭素数４～３４の不飽和ジカルボン酸ジエステル、例えばジアルキルフマレート（２個のアルキル基は、炭素数１～２２の、直鎖、分枝鎖もしくは脂環式の基）、ジアルキルマレエート（２個のアルキル基は、炭素数１～２２の、直鎖、分枝鎖もしくは脂環式の基）
(a35-4) Unsaturated dicarboxylic acid diester Unsaturated dicarboxylic acid diester having 4 to 34 carbon atoms, such as dialkyl fumarate (two alkyl groups are linear, branched, or alicyclic, having 1 to 22 carbon atoms) (group of the formula), dialkyl maleate (the two alkyl groups are straight chain, branched chain, or alicyclic groups having 1 to 22 carbon atoms)
上記（ａ３）として例示したもののうち電解液の吸液および耐電圧の観点から好ましいのは、（ａ３１）、（ａ３２）、（ａ３３）および（ａ３４）であり、更に好ましいのは、（ａ３１）のうちのメチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、（ａ３４）のうちのスチレンスルホン酸リチウムである。 Of the above examples of (a3), from the viewpoint of electrolyte absorption and voltage resistance, (a31), (a32), (a33) and (a34) are preferred, and of (a31), methyl (meth)acrylate, ethyl (meth)acrylate and butyl (meth)acrylate, and of (a34), lithium styrenesulfonate are more preferred.
前記バインダー樹脂において、カルボキシル基を有するビニルモノマー（ａ１）、上記一般式（１）で表されるビニルモノマー（ａ２）及び活性水素を含有しない共重合性ビニルモノマー（ａ３）の含有量は、前記バインダー樹脂の重量を基準として、（ａ１）が０．１～８０重量％、（ａ２）が０．１～９９．９重量％、（ａ３）が０～９９．８重量％であることが好ましい。
モノマーの含有量が上記範囲内であると、電解液への吸液性が良好となる。
より好ましい含有量は、（ａ１）が１～５０重量％、（ａ２）が５～７０重量％、（ａ３）が５～８０重量％であり、さらに好ましい含有量は、（ａ１）が１～３０重量％、（ａ２）が５０～９６重量％、（ａ３）が５～５０重量％である。
In the binder resin, the contents of the vinyl monomer (a1) having a carboxyl group, the vinyl monomer (a2) represented by the above general formula (1), and the copolymerizable vinyl monomer (a3) not containing active hydrogen are preferably, based on the weight of the binder resin, such that (a1) is 0.1 to 80% by weight, (a2) is 0.1 to 99.9% by weight, and (a3) is 0 to 99.8% by weight.
When the content of the monomer is within the above range, the absorbency of the electrolyte solution is good.
More preferably, the contents of (a1) are 1 to 50% by weight, (a2) are 5 to 70% by weight, and (a3) are 5 to 80% by weight, and even more preferably, the contents of (a1) are 1 to 30% by weight, (a2) are 50 to 96% by weight, and (a3) are 5 to 50% by weight.
前記バインダー樹脂のガラス転移温度（Ｔｇ）は、－４０～－５℃である。
前記バインダー樹脂のＴｇが－４０℃未満であると得られる電極の強度が弱くなり、－５℃を超えると得られる電極の柔軟性が悪化する。
得られる電極の強度の観点から、前記バインダー樹脂のＴｇは好ましくは－３５～－１５℃である。
前記バインダー樹脂のＴｇは、前記バインダー樹脂を構成するモノマーの種類と比率で調整することができる。
The binder resin has a glass transition temperature (Tg) of -40 to -5°C.
If the Tg of the binder resin is less than -40°C, the strength of the obtained electrode will be weak, and if it exceeds -5°C, the flexibility of the obtained electrode will deteriorate.
From the viewpoint of the strength of the electrode obtained, the binder resin preferably has a Tg of -35 to -15°C.
The Tg of the binder resin can be adjusted by the type and ratio of monomers constituting the binder resin.
前記バインダー樹脂のＴｇは、セイコー電子工業（株）製ＤＳＣ２０、ＳＳＣ／５８０を用いて、ＡＳＴＭＤ３４１８－８２に規定の方法（ＤＳＣ法）で測定する。
＜測定条件＞
（１）３０℃から２０℃／分で１５０℃まで昇温
（２）１５０℃で１０分間保持
（３）２０℃／分で－６０℃まで冷却
（４）－６０℃で１０分間保持
（５）２０℃／分で１５０℃まで昇温
（６）（５）の過程にて測定される示差走査熱量曲線を解析し、変曲点の位置をガラス転移温度とする。
The Tg of the binder resin is measured by the method specified in ASTM D3418-82 (DSC method) using DSC20 and SSC/580 manufactured by Seiko Electronics Co., Ltd.
<Measurement conditions>
(1) Raise temperature from 30℃ to 150℃ at 20℃/min (2) Hold at 150℃ for 10 minutes (3) Cool to -60℃ at 20℃/min (4) Hold at -60℃ for 10 minutes (5 ) Analyze the differential scanning calorimetry curve measured in the process of heating up to 150°C at 20°C/min (6) and (5), and define the position of the inflection point as the glass transition temperature.
前記バインダー樹脂の結晶化度は、２０未満である。
前記バインダー樹脂の結晶化度が２０以上であると得られる電極の柔軟性が悪化する。
得られる電極の柔軟性の観点から、前記バインダー樹脂の結晶化度は好ましくは１５以下であり、より好ましくは１０以下である。
前記バインダー樹脂の結晶化度は、前記バインダー樹脂を構成するモノマーで調整することができる。例えば、分子間相互作用の大きな官能基を持つモノマー（カルボン酸、アミン等）や分極率の大きなモノマーを使用すれば結晶化度は大きくなり、長鎖炭化水素を有するモノマーを使用すれば結晶化度は小さくなる。
The binder resin has a crystallinity of less than 20.
If the crystallinity of the binder resin is 20 or more, the flexibility of the resulting electrode deteriorates.
From the viewpoint of flexibility of the resulting electrode, the crystallinity of the binder resin is preferably 15 or less, and more preferably 10 or less.
The degree of crystallinity of the binder resin can be adjusted by the monomer that constitutes the binder resin. For example, the degree of crystallinity is increased by using a monomer having a functional group with large intermolecular interaction (such as a carboxylic acid or an amine) or a monomer having large polarizability, and the degree of crystallinity is decreased by using a monomer having a long-chain hydrocarbon.
前記バインダー樹脂の結晶化度は、「ＪＩＳ Ｋ７１２２－１９８７ プラスチックの転移熱測定方法」に準じて、示差走査熱量（ＤＳＣ）測定にて吸熱ピークの面積から測定融解熱量（Ｊ／ｇ）を求め、測定された測定融解熱量に基づき以下の式により結晶化度を算出することにより定める。
結晶化度＝（測定融解熱量／完全結晶体融解熱量）×１００
上式中、測定融解熱量は、Ａｌ容器に計量した１０ｍｇの試料を窒素雰囲気下、２５℃～２００℃まで昇温速度２０℃／ｍｉｎで加熱し、次に冷却速度２０℃／ｍｉｎで２５℃まで冷却後、同様の条件でセカンドスキャンを行った際の融解熱量（Ｊ／ｇ）から結晶化熱量（Ｊ／ｇ）を差し引いた値のことである。
上式中、完全結晶体融解熱量は、上式中、測定融解熱量は、Ａｌ容器に計量した１０ｍｇの試料を窒素雰囲気下、２５℃～２００℃まで昇温速度１０℃／ｍｉｎで加熱し、次に冷却速度５℃／ｍｉｎで２５℃まで冷却後、再び１０℃／ｍｉｎで昇温・冷却したときの融解熱量（Ｊ／ｇ）のことである。
The degree of crystallinity of the binder resin is determined by calculating the measured heat of fusion (J/g) from the area of the endothermic peak in differential scanning calorimetry (DSC) measurement according to "JIS K7122-1987 Method for measuring heat of transition of plastics". It is determined by calculating the degree of crystallinity using the following formula based on the measured heat of fusion.
Crystallinity = (measured heat of fusion/heat of fusion of perfect crystal) x 100
In the above formula, the measured heat of fusion is calculated by heating a 10 mg sample weighed in an Al container in a nitrogen atmosphere from 25°C to 200°C at a heating rate of 20°C/min, and then cooling to 25°C at a cooling rate of 20°C/min. It is the value obtained by subtracting the heat of crystallization (J/g) from the heat of fusion (J/g) obtained when a second scan is performed under the same conditions after cooling to .
In the above formula, the heat of fusion of a perfectly crystalline substance is determined by heating a 10 mg sample weighed in an Al container at a heating rate of 10 °C/min from 25 °C to 200 °C in a nitrogen atmosphere. Next, after cooling to 25°C at a cooling rate of 5°C/min, it is the heat of fusion (J/g) when the temperature is raised and cooled again at a rate of 10°C/min.
前記バインダー樹脂の重量平均分子量（Ｍｗ）は、５０，０００～２００，０００であることが好ましい。前記バインダー樹脂の重量平均分子量が５０，０００～２００，０００であると得られる電極の強度が優れる。前記バインダー樹脂の重量平均分子量は、より好ましくは８０，０００～１５０，０００である。 The weight average molecular weight (Mw) of the binder resin is preferably 50,000 to 200,000. When the weight average molecular weight of the binder resin is 50,000 to 200,000, the resulting electrode has excellent strength. The weight average molecular weight of the binder resin is more preferably 80,000 to 150,000.
前記バインダー樹脂の重量平均分子量は、以下の条件でＧＰＣ（ゲルパーミエーションクロマトグラフィー）測定により求めることができる。なお、試料となる重合体をオルトジクロロベンゼン、Ｎ’－ジメチルホルムアミド（ＤＭＦ）、テトラヒドロフラン（ＴＨＦ）等の溶媒に溶解して０．２５重量％の溶液を調製し、不溶解分を口径１μｍのＰＴＦＥフィルターで濾過したものを試料溶液とする。
装置：ＡｌｌｉａｎｃｅＧＰＣ Ｖ２０００（Ｗａｔｅｒｓ社製）
溶媒：オルトジクロロベンゼン、ＤＭＦ、ＴＨＦ
標準物質：ポリスチレンサンプル
濃度：３ｍｇ／ｍｌ
カラム固定相：ＰＬｇｅｌ １０ｕｍ，ＭＩＸＥＤ－Ｂ ２本直列（ポリマーラボラトリーズ社製）
カラム温度：１３５℃
The weight average molecular weight of the binder resin can be determined by GPC (gel permeation chromatography) measurement under the following conditions: A sample polymer is dissolved in a solvent such as orthodichlorobenzene, N'-dimethylformamide (DMF), or tetrahydrofuran (THF) to prepare a 0.25 wt % solution, and the insoluble portion is filtered through a PTFE filter having a diameter of 1 μm to obtain a sample solution.
Apparatus: Alliance GPC V2000 (Waters)
Solvent: orthodichlorobenzene, DMF, THF
Standard material: polystyrene Sample concentration: 3 mg/ml
Column stationary phase: PLgel 10 um, MIXED-B 2 columns in series (Polymer Laboratories)
Column temperature: 135 ° C.
前記バインダー樹脂の引張破断ひずみは、１０００％以上であることが好ましい。
前記バインダー樹脂の引張破断ひずみが１０００％以上であると電極の柔軟性が向上する。電極の柔軟性の観点から、前記バインダー樹脂の引張破断ひずみは１０００～２０００％であることがより好ましい。
なお、後述する引張破断ひずみ測定において、試験片の標線間距離が５０ｃｍになった時点で安全装置が働いて測定が中止されるため、引張破断ひずみ４０００％を超えては測定できない。
The binder resin preferably has a tensile strain at break of 1000% or more.
When the tensile breaking strain of the binder resin is 1000% or more, the flexibility of the electrode is improved. From the viewpoint of flexibility of the electrode, the tensile strain at break of the binder resin is more preferably 1000 to 2000%.
In addition, in the tensile breaking strain measurement described below, a safety device is activated and the measurement is stopped when the distance between the gauge lines of the test piece reaches 50 cm, so it is not possible to measure if the tensile breaking strain exceeds 4000%.
引張破断ひずみ測定用試験片は以下の通り作製する。
樹脂濃度２５重量％のバインダー樹脂溶液（溶媒にはトルエンを使用）を１０ｃｍ×１０ｃｍ×２ｃｍの型に流し込み、１００℃、０．０１ＭＰで３時間の減圧乾燥（＞－９０ｋＰａ）を行い、樹脂シートを得た。この樹脂シートをダンベル状（ＡＳＴＭ Ｄ６８３：試験片形状ＴｙｐｅＩＩ）に打ち抜き、１０ｃｍ×１０ｃｍの離型紙に挟み、１２０℃に温調した加圧プレス機で３０秒間、圧１５ＭＰａでプレスして厚み１００μｍの樹脂シートを作製した。
A test piece for measuring tensile strain at break is prepared as follows.
A binder resin solution with a resin concentration of 25% by weight (toluene was used as the solvent) was poured into a 10 cm x 10 cm x 2 cm mold, and dried under reduced pressure (>-90 kPa) at 100°C and 0.01 MP for 3 hours to form a resin sheet. I got it. This resin sheet was punched into a dumbbell shape (ASTM D683: test piece shape Type II), sandwiched between 10 cm x 10 cm release paper, and pressed at a pressure of 15 MPa for 30 seconds with a pressure press controlled at 120°C to obtain a 100 μm thick sheet. A resin sheet was produced.
前記引張破断ひずみは、前記樹脂シートを試験片として、ＡＳＴＭ Ｄ６８３（試験片形状ＴｙｐｅＩＩ）に準拠した引張試験において試験片が破断するまでのひずみを下記式によって算出した値である。
引張破断ひずみ（％）＝［（破断時試験片長さ－試験前試験片長さ）／試験前試験片長さ］×１００
The tensile breaking strain is a value calculated by the following formula, using the resin sheet as a test piece, and the strain required to break the test piece in a tensile test based on ASTM D683 (test piece shape Type II).
Tensile strain at break (%) = [(Length of test piece at break - Length of test piece before test) / Length of test piece before test] x 100
前記バインダー樹脂の引張破断ひずみは、前記バインダー樹脂を構成する単量体に占める多官能単量体の量で調整することができる。また、前記バインダー樹脂における結晶性ビニル樹脂の含有量でも調節することができる。なお、「結晶性ビニル樹脂」とは、示差走査熱量測定（ＤＳＣ測定ともいう）により得られる示差走査熱量曲線の昇温過程において、ＤＳＣ曲線に極大があり、吸熱ピークを有するビニル樹脂のことをいう。 The tensile breaking strain of the binder resin can be adjusted by the amount of polyfunctional monomers in the monomers constituting the binder resin. It can also be adjusted by the content of crystalline vinyl resin in the binder resin. Note that "crystalline vinyl resin" refers to a vinyl resin that has a maximum and endothermic peak in the differential scanning calorimetry (DSC) curve during the heating process of the differential scanning calorimetry curve obtained by DSC measurement.
前記バインダー樹脂とアルミ箔との剥離強度は、４～１０Ｎ／２５ｍｍであることが好ましい。
前記バインダー樹脂とアルミ箔との剥離強度が４～１０Ｎ／２５ｍｍであると、正極活物質層と集電体との接着性が向上する。正極活物質層と集電体との接着性の観点から、前記バインダー樹脂とアルミ箔との剥離強度が５～８Ｎ／２５ｍｍであることがより好ましい。
The peel strength between the binder resin and the aluminum foil is preferably 4 to 10 N/25 mm.
When the peel strength between the binder resin and the aluminum foil is 4 to 10 N/25 mm, the adhesiveness between the positive electrode active material layer and the current collector is improved. From the viewpoint of adhesion between the positive electrode active material layer and the current collector, it is more preferable that the peel strength between the binder resin and the aluminum foil is 5 to 8 N/25 mm.
剥離強度測定用試験片は以下の通り作製する。
樹脂濃度２５重量％のバインダー樹脂溶液（溶媒にはトルエンを使用）を１０ｃｍ×１０ｃｍ×２ｃｍの型に流し込み、１００℃、０．０１ＭＰで３時間の減圧乾燥（＞－９０ｋＰａ）を行い、トルエンを留去して樹脂シートを得た。この樹脂シートを１０ｃｍ×１０ｃｍの離型紙に挟み、１２０℃に温調した加圧プレス機で３０秒間、圧１５ＭＰａでプレスして厚み１００μｍの樹脂シートを作製した。
A test piece for measuring peel strength is prepared as follows.
A binder resin solution with a resin concentration of 25% by weight (toluene was used as the solvent) was poured into a 10 cm x 10 cm x 2 cm mold, and dried under reduced pressure (>-90 kPa) at 100 ° C and 0.01 MPa for 3 hours to remove the toluene and obtain a resin sheet. This resin sheet was sandwiched between 10 cm x 10 cm release paper and pressed at a pressure of 15 MPa for 30 seconds with a pressure press machine adjusted to 120 ° C to produce a resin sheet with a thickness of 100 μm.
前記バインダー樹脂とアルミ箔との剥離強度は、前記樹脂シートを厚さ２０μｍのアルミ箔と重ね、１００℃、１０ＭＰａで３０秒プレスして得られる接着フィルムに対して、１８０℃剥離強度試験（ＪＩＳＫ６８５４－２：１９９９接着剤－はく離接着強さ試験方法に準拠）を行うことで測定する。 The peel strength between the binder resin and the aluminum foil is measured by overlapping the resin sheet with 20 μm thick aluminum foil and pressing at 100°C and 10 MPa for 30 seconds to obtain an adhesive film, and then conducting a 180°C peel strength test (based on JIS K6854-2:1999 Adhesives - Peel Adhesion Strength Test Method).
前記バインダー樹脂とアルミ箔との剥離強度は、前記バインダー樹脂のＴｇで調整できる。具体的には、前記バインダー樹脂のＴｇを－２５～－１５℃にすることで前記剥離強度の数値範囲となることが多い。 The peel strength between the binder resin and the aluminum foil can be adjusted by the Tg of the binder resin. Specifically, the peel strength is often within the above numerical range by setting the Tg of the binder resin to -25 to -15°C.
本発明のリチウムイオン電池用正極組成物は、導電助剤を含む。導電助剤としては、導電性を有する材料であれば特に制限はない。
導電助剤としては、金属［アルミニウム、ステンレス（ＳＵＳ）、銀、金、銅及びチタン等］、カーボン［グラファイト（薄片状黒鉛（ＵＰ））、カーボンブラック（アセチレンブラック、ケッチェンブラック、ファーネスブラック、チャンネルブラック及びサーマルランプブラック等）及びカーボンナノファイバー（ＣＮＦ）等］、及びこれらの混合物等が挙げられる。
これらの導電助剤は１種単独で用いられてもよいし、２種以上併用してもよい。また、これらの合金又は金属酸化物が用いられてもよい。電気的安定性の観点から、好ましくはアセチレンブラックが好ましい。
The positive electrode composition for a lithium ion battery of the present invention contains a conductive additive. There are no particular limitations on the conductive aid as long as it is a conductive material.
Examples of conductive aids include metals [aluminum, stainless steel (SUS), silver, gold, copper, titanium, etc.], carbon [graphite (flake graphite (UP)), carbon black (acetylene black, Ketjen black, furnace black, channel black, thermal lamp black, etc.), carbon nanofibers (CNF), etc.], and mixtures thereof.
These conductive aids may be used alone or in combination of two or more. Also, alloys or metal oxides of these may be used. From the viewpoint of electrical stability, acetylene black is preferred.
本発明のリチウムイオン電池用正極組成物は、正極活物質を含む。
正極活物質としては、リチウムと遷移金属との複合酸化物｛遷移金属が１種である複合酸化物（ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＡｌＭｎＯ４、ＬｉＭｎＯ２及びＬｉＭｎ２Ｏ４等）、遷移金属元素が２種である複合酸化物（例えばＬｉＦｅＭｎＯ４、ＬｉＮｉ１－ｘＣｏｘＯ２、ＬｉＭｎ１－ｙＣｏｙＯ２、ＬｉＮｉ１／３Ｃｏ１／３Ａｌ１／３Ｏ２及びＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２）及び金属元素が３種類以上である複合酸化物［例えばＬｉＭａＭ’ｂＭ’’ｃＯ２（Ｍ、Ｍ’及びＭ’’はそれぞれ異なる遷移金属元素であり、ａ＋ｂ＋ｃ＝１を満たす。例えばＬｉＮｉ１／３Ｍｎ１／３Ｃｏ１／３Ｏ２）等］等｝、リチウム含有遷移金属リン酸塩（例えばＬｉＦｅＰＯ４、ＬｉＣｏＰＯ４、ＬｉＭｎＰＯ４及びＬｉＮｉＰＯ４）、遷移金属酸化物（例えばＭｎＯ２及びＶ２Ｏ５）、遷移金属硫化物（例えばＭｏＳ２及びＴｉＳ２）及び導電性高分子（例えばポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン及びポリ－ｐ－フェニレン及びポリビニルカルバゾール）等が挙げられ、２種以上を併用してもよい。
なお、リチウム含有遷移金属リン酸塩は、遷移金属サイトの一部を他の遷移金属で置換したものであってもよい。
The positive electrode composition for a lithium ion battery of the present invention includes a positive electrode active material.
As the positive electrode active material, composite oxides of lithium and transition metals {complex oxides containing one type of transition metal (such as LiCoO 2 , LiNiO 2 , LiAlMnO 4 , LiMnO 2 and LiMn 2 O 4 ), transition metal elements Two types of composite oxides (for example, LiFeMnO 4 , LiNi 1-x Co x O 2 , LiMn 1-y Co y O 2 , LiNi 1/3 Co 1/3 Al 1/3 O 2 and LiNi 0.8 Co 0.15 Al 0.05 O 2 ) and a composite oxide containing three or more types of metal elements [for example, LiM a M' b M'' c O 2 (M, M', and M'' are each different transition metal elements) and satisfies a+b+c=1.For example, LiNi 1/3 Mn 1/3 Co 1/3 O 2 ), etc.}, lithium-containing transition metal phosphates (for example, LiFePO 4 , LiCoPO 4 , LiMnPO 4 and LiNiPO 4 ), transition metal oxides (e.g. MnO 2 and V 2 O 5 ), transition metal sulfides (e.g. MoS 2 and TiS 2 ) and conductive polymers (e.g. polyaniline, polypyrrole, polythiophene, polyacetylene and poly-p-phenylene and polyvinylcarbazole), etc., and two or more types may be used in combination.
Note that the lithium-containing transition metal phosphate may be one in which some of the transition metal sites are replaced with another transition metal.
本発明のリチウムイオン電池用正極組成物における前記バインダー樹脂の重量割合は、結着性能と電気特性の観点の観点から、前記リチウムイオン電池用正極組成物の重量を基準として１～５重量％であることが好ましい。
また、前記リチウムイオン電池用正極組成物における前記正極活物質の重量割合は、電池性能の観点から、前記リチウムイオン電池用正極組成物の重量を基準として９０～９８重量％であることが好ましい。
The weight ratio of the binder resin in the positive electrode composition for lithium ion batteries of the present invention is preferably 1 to 5% by weight based on the weight of the positive electrode composition for lithium ion batteries from the viewpoints of binding performance and electrical characteristics.
From the viewpoint of battery performance, the weight ratio of the positive electrode active material in the positive electrode composition for lithium ion batteries is preferably 90 to 98% by weight based on the weight of the positive electrode composition for lithium ion batteries.
［リチウムイオン電池用正極の製造方法］
本発明は、バインダー樹脂、導電助剤、正極活物質及び水性溶媒を含むスラリーを作製する混合工程と、前記スラリーを集電体に塗布する塗布工程と、前記塗布工程後にスラリーを乾燥して前記集電体上に正極活物質層を形成する乾燥工程とを含むリチウムイオン電池用正極の製造方法である。
バインダー樹脂、導電助剤及び正極活物質としては、それぞれ上述のバインダー樹脂、導電助剤及び正極活物質が使用できる。
[Method of manufacturing positive electrode for lithium ion battery]
The present invention provides a method for producing a positive electrode for a lithium ion battery, the method including: a mixing step of preparing a slurry containing a binder resin, a conductive assistant, a positive electrode active material, and an aqueous solvent; a coating step of coating the slurry onto a current collector; and a drying step of drying the slurry after the coating step to form a positive electrode active material layer on the current collector.
As the binder resin, the conductive assistant, and the positive electrode active material, the above-mentioned binder resin, conductive assistant, and positive electrode active material can be used, respectively.
（混合工程）
本発明は、前記バインダー樹脂、導電助剤、正極活物質及び水性溶媒を含むスラリーを作製する混合工程を含む。
混合工程では、前記バインダー樹脂、導電助剤、正極活物質及び水性溶媒を含むスラリーを作製する。前記リチウムイオン電池用正極組成物と水性溶媒とを混合する方法としては、特に限定されず、公知の方法を用いることができる。
また、混合する順序にも制限はなく、バインダー樹脂、導電助剤、正極活物質及び水性溶媒を、どの順序で混合してもよい。
(Mixing process)
The present invention includes a mixing step of preparing a slurry containing the binder resin, conductive aid, positive electrode active material, and aqueous solvent.
In the mixing step, a slurry containing the binder resin, conductive aid, positive electrode active material, and aqueous solvent is prepared. The method for mixing the positive electrode composition for lithium ion batteries and the aqueous solvent is not particularly limited, and any known method can be used.
Furthermore, there is no restriction on the order of mixing, and the binder resin, conductive aid, positive electrode active material, and aqueous solvent may be mixed in any order.
水性溶媒としては、水を必須構成成分とする液体であれば制限なく使用でき、後述する、水、有機溶剤の水溶液、界面活性剤の水溶液、水溶性ポリマーの水溶液及びこれらの２以上の混合物等が用いることができる。 As the aqueous solvent, any liquid containing water as an essential component can be used without restriction, and examples of the aqueous solvent that can be used include water, an aqueous solution of an organic solvent, an aqueous solution of a surfactant, an aqueous solution of a water-soluble polymer, and mixtures of two or more of these, as described below.
（塗布工程）
本発明は、前記混合工程で得た前記スラリーを集電体に塗布する塗布工程を含む。
塗布する方法としては、特に限定されず、公知の、バーコーター等の塗工装置を用いることができる。
(Coating process)
The present invention includes a coating step of coating the slurry obtained in the mixing step onto a current collector.
The method of application is not particularly limited, and a known application device such as a bar coater can be used.
集電体を構成する材料としては、銅、アルミニウム、チタン、ステンレス鋼、ニッケル及びこれらの合金等の金属材料、並びに、焼成炭素、導電性高分子材料、導電性ガラス等が挙げられる。
集電体の形状は特に限定されず、上記の材料からなるシート状の集電体、及び、上記の材料で構成された微粒子からなる堆積層であってもよい。
集電体の厚さは、特に限定されないが、５０～５００μｍであることが好ましい。
Examples of the material constituting the current collector include metal materials such as copper, aluminum, titanium, stainless steel, nickel, and alloys thereof, as well as fired carbon, conductive polymer materials, conductive glass, and the like.
The shape of the current collector is not particularly limited, and may be a sheet-like current collector made of the above-mentioned material or a deposited layer made of fine particles made of the above-mentioned material.
The thickness of the current collector is not particularly limited, but is preferably 50 to 500 μm.
（乾燥工程）
本発明は、前記塗布工程後にスラリーを乾燥して前記集電体上に正極活物質層を形成する乾燥工程を含む。
乾燥工程で前記スラリーに含まれる水性溶媒を除去することが好ましい。水性溶媒を除去する方法としては、オーブンや真空オーブンを用いた乾燥が好ましい。水性溶媒を除去する雰囲気としては、空気、不活性ガス、真空状態などが挙げられる。また、水性溶媒を除去する温度は、６０～２５０℃が好ましい。
(Drying process)
The present invention includes a drying step of drying the slurry after the coating step to form a positive electrode active material layer on the current collector.
It is preferable to remove the aqueous solvent contained in the slurry in a drying step. As a method for removing the aqueous solvent, drying using an oven or a vacuum oven is preferable. The atmosphere for removing the aqueous solvent may be air, an inert gas, or a vacuum state. In addition, the temperature for removing the aqueous solvent is preferably 60 to 250°C.
本明細書には、以下の事項が開示されている。 This specification discloses the following:
本開示（１）は、バインダー樹脂、導電助剤及び正極活物質を含むリチウムイオン電池用正極組成物であって、
前記バインダー樹脂がビニル樹脂であり、
前記ビニル樹脂が、カルボキシル基を有するビニルモノマー（ａ１）及び下記一般式（１）
ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２ （１）
［式（１）中、Ｒ１は水素原子又はメチル基であり、Ｒ２は炭素数４～３６の分岐アルキル基である。］
で表されるビニルモノマー（ａ２）を必須構成単量体とする重合体であり、
前記バインダー樹脂のガラス転移温度が－４０～－５℃であり、
前記バインダー樹脂の結晶化度が２０未満であることを特徴とするリチウムイオン電池用正極組成物である。
The present disclosure (1) provides a positive electrode composition for a lithium ion battery, comprising a binder resin, a conductive assistant, and a positive electrode active material,
The binder resin is a vinyl resin,
The vinyl resin is a vinyl monomer (a1) having a carboxyl group and a vinyl monomer represented by the following general formula (1):
CH2 =C( R1 ) COOR2 (1)
[In formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a branched alkyl group having 4 to 36 carbon atoms.]
It is a polymer having, as an essential constituent monomer, a vinyl monomer (a2) represented by the following formula:
The glass transition temperature of the binder resin is −40 to −5° C.,
The positive electrode composition for a lithium ion battery is characterized in that the crystallinity of the binder resin is less than 20.
本開示（２）は、前記バインダー樹脂の重量平均分子量が、５０，０００～２００，０００である本開示（１）に記載のリチウムイオン電池用正極組成物である。 The present disclosure (2) is a positive electrode composition for a lithium ion battery according to the present disclosure (1), in which the weight average molecular weight of the binder resin is 50,000 to 200,000.
本開示（３）は、前記バインダー樹脂の引張破断ひずみが１０００％以上であり、
前記引張破断ひずみは、前記バインダー樹脂をダンベル状に打ち抜き、ＡＳＴＭ Ｄ６８３（試験片形状ＴｙｐｅＩＩ）に準拠した引張試験において試験片が破断するまでのひずみを下記式によって算出した値である本開示（１）又は（２）に記載のリチウムイオン電池用正極組成物である。
引張破断ひずみ（％）＝［（破断時試験片長さ－試験前試験片長さ）／試験前試験片長さ］×１００
The present disclosure (3) provides that the binder resin has a tensile strain at break of 1000% or more,
The tensile breaking strain is a value obtained by punching out the binder resin into a dumbbell shape and calculating the strain until the test piece breaks in a tensile test based on ASTM D683 (test piece shape Type II) using the following formula. ) or the positive electrode composition for a lithium ion battery according to (2).
Tensile strain at break (%) = [(Length of test piece at break - Length of test piece before test) / Length of test piece before test] x 100
本開示（４）は、前記バインダー樹脂とアルミ箔との剥離強度が４～１０Ｎ／２５ｍｍである本開示（１）～（３）のいずれかに記載のリチウムイオン電池用正極組成物である。 The present disclosure (4) is a positive electrode composition for a lithium ion battery according to any one of the present disclosures (1) to (3), in which the peel strength between the binder resin and the aluminum foil is 4 to 10 N/25 mm.
本開示（５）は、前記リチウムイオン電池用正極組成物における前記バインダー樹脂の重量割合が、前記リチウムイオン電池用正極組成物の重量を基準として１～５重量％であり、
前記リチウムイオン電池用正極組成物における前記正極活物質の重量割合が、前記リチウムイオン電池用正極組成物の重量を基準として９０～９８重量％である本開示（１）～（４）のいずれに記載のリチウムイオン電池用正極組成物である。
The present disclosure (5) provides that the weight proportion of the binder resin in the positive electrode composition for lithium ion batteries is 1 to 5% by weight based on the weight of the positive electrode composition for lithium ion batteries,
In any of the present disclosure (1) to (4), the weight ratio of the positive electrode active material in the positive electrode composition for lithium ion batteries is 90 to 98% by weight based on the weight of the positive electrode composition for lithium ion batteries. This is a positive electrode composition for a lithium ion battery as described above.
本開示（６）は、本開示（１）～（５）に記載の前記リチウムイオン電池用正極組成物における前記バインダー樹脂、導電助剤、正極活物質及び水性溶媒を含むスラリーを作製する混合工程と、前記スラリーを集電体に塗布する塗布工程と、前記塗布工程後にスラリーを乾燥して前記集電体上に正極活物質層を形成する乾燥工程とを含むリチウムイオン電池用正極の製造方法である。 The present disclosure (6) is a method for producing a positive electrode for a lithium ion battery, comprising a mixing step of preparing a slurry containing the binder resin, conductive assistant, positive electrode active material, and aqueous solvent in the positive electrode composition for a lithium ion battery described in the present disclosures (1) to (5), a coating step of coating the slurry on a current collector, and a drying step of drying the slurry after the coating step to form a positive electrode active material layer on the current collector.
次に本発明を実施例によって具体的に説明するが、本発明の主旨を逸脱しない限り本発明は実施例に限定されるものではない。 The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples as long as they do not deviate from the spirit of the present invention.
（製造例１：バインダー樹脂（Ａ－１）の製造）
攪拌機、温度計、還流冷却管、滴下ロート及び窒素ガス導入管を付した４つ口コルベンに、２－エチルヘキシルメタクリレート６５．０重量部、２－エチルヘキシルアクリレート３０．０重量部、アクリル酸４．６重量部、１，６－ヘキサンジオールジメタクリレート０．４重量部、トルエン７０重量部を仕込み６５℃に昇温した。さらに、トルエン１０重量部及び２，２’－アゾビス（２，４－ジメチルバレロニトリル）０．２００重量部を混合した。得られた単量体混合液について、コルベン内に窒素を吹き込みながら、重合開始剤混合液を滴下ロートで４時間かけて連続的に滴下してラジカル重合を行った。温度を７５℃に昇温し、重合を２時間継続し、トルエンを加えて樹脂濃度２５重量％のバインダー樹脂（Ａ－１）溶液を得た。
(Production Example 1: Production of Binder Resin (A-1))
In a four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, 65.0 parts by weight of 2-ethylhexyl methacrylate, 30.0 parts by weight of 2-ethylhexyl acrylate, 4.6 parts by weight of acrylic acid, 0.4 parts by weight of 1,6-hexanediol dimethacrylate and 70 parts by weight of toluene were charged and heated to 65°C. Furthermore, 10 parts by weight of toluene and 0.200 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed. The obtained monomer mixture was continuously dropped with a dropping funnel over 4 hours while blowing nitrogen into the flask, to carry out radical polymerization. The temperature was raised to 75°C, polymerization was continued for 2 hours, and toluene was added to obtain a binder resin (A-1) solution with a resin concentration of 25% by weight.
（製造例２～８：バインダー樹脂（Ａ－２）～（Ａ－６）及び（ＡＸ－２）、（ＡＸ－３）の製造）
モノマーの種類、仕込み重量部数を表１に示すように変更した他は製造例１と同様にしてバインダー樹脂（Ａ－２）～（Ａ－６）及び（ＡＸ－２）、（ＡＸ－３）を製造した。
(Production Examples 2 to 8: Production of Binder Resins (A-2) to (A-6), (AX-2), and (AX-3))
Binder resins (A-2) to (A-6), (AX-2) and (AX-3) were produced in the same manner as in Production Example 1, except that the types of monomers and the weight parts charged were changed as shown in Table 1.
（製造例９～１４：バインダー樹脂（Ａ－７）～（Ａ－１０）及び（ＡＸ－４）、（ＡＸ－５）の製造）
モノマーの種類、仕込み重量部数を表２に示すように変更し、またトルエンをイソプロピルアルコールに変更した他は製造例１と同様にしてバインダー樹脂（Ａ－７）～（Ａ－１０）及び（ＡＸ－４）、（ＡＸ－５）を製造した。
(Production Examples 9 to 14: Production of Binder Resins (A-7) to (A-10), (AX-4), and (AX-5))
The type of monomer and the number of parts by weight charged were changed as shown in Table 2, and binder resins (A-7) to (A-10), (AX-4) and (AX-5) were produced in the same manner as in Production Example 1, except that toluene was replaced with isopropyl alcohol.
（樹脂シートの作製）
製造例で得た樹脂濃度２５重量％のバインダー樹脂溶液を１０ｃｍ×１０ｃｍ×２ｃｍの型に流し込み、１００℃、０．０１ＭＰで３時間の減圧乾燥を行い、トルエン又はイソプロピルアルコールを留去してバインダー樹脂シートを得た。この樹脂シートを所定の大きさに切り取り、１０ｃｍ×１０ｃｍの離型紙に挟み、１２０℃に温調した加圧プレス機で３０秒間、圧１５ＭＰａでプレスして厚み１００μｍの樹脂シートを作製して、前記引張破断ひずみの測定及びアルミ箔との剥離強度の測定に供した。結果を表３及び４に示した。
なお、バインダー樹脂（ＡＸ－１）としては、ポリフッ化ビニリデン（以下 ＰＶＤＦ）［キシダ化学（株）、商標 ＃１１００］を使用した。
また、表４に記載の引張破断ひずみについて「測定不可」とあるのは、前記引張試験において標線間距離５０ｃｍまで試験片が破断しなかったことを示す。
(Preparation of resin sheet)
The binder resin solution with a resin concentration of 25% by weight obtained in the production example was poured into a mold of 10 cm x 10 cm x 2 cm, and dried under reduced pressure at 100°C and 0.01 MP for 3 hours to distill off toluene or isopropyl alcohol to form a binder. A resin sheet was obtained. This resin sheet was cut to a predetermined size, sandwiched between 10 cm x 10 cm release paper, and pressed at a pressure of 15 MPa for 30 seconds using a pressure press machine controlled at 120°C to produce a resin sheet with a thickness of 100 μm. The sample was used to measure the tensile strain at break and the peel strength from aluminum foil. The results are shown in Tables 3 and 4.
As the binder resin (AX-1), polyvinylidene fluoride (hereinafter referred to as PVDF) [manufactured by Kishida Kagaku Co., Ltd., trademark #1100] was used.
Further, regarding the tensile strain at break described in Table 4, "unmeasurable" indicates that the test piece did not break up to a distance between gauge lines of 50 cm in the tensile test.
（実施例１～１０、比較例１～５：リチウムイオン電池用正極組成物の作製及び正極の作製）
正極活物質粒子（ＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２粉末、体積平均粒子径４μｍ）９０重量部、アセチレンブラック（ＡＢ）［デンカ（株）ＤＥＮＫＡ ＢＬＡＣＫ Ｌｉ－１００］５重量部、前記バインダー樹脂溶液（２５重量％溶液）５重量部およびトルエン１００重量部を仕込み、あわとり練太郎による攪拌を２０００ｒｐｍで１分間行い、正極用スラリー組成物を調整した。この正極用スラリー組成物をアプリケーターで厚み２０μｍのアルミ箔に乾燥後の膜厚が１００μｍになるように塗布し、１００℃で２時間乾燥させ、正極シートを得た。この正極シートをΦ１５ｍｍに打ち抜いて、リチウムイオン電池用正極を作製した。
(Examples 1 to 10, Comparative Examples 1 to 5: Preparation of Positive Electrode Composition for Lithium Ion Batteries and Preparation of Positive Electrodes)
90 parts by weight of positive electrode active material particles (LiNi 0.8 Co 0.15 Al 0.05 O 2 powder, volume average particle diameter 4 μm), 5 parts by weight of acetylene black (AB) [Denka Co., Ltd. DENKA BLACK Li-100], 5 parts by weight of the binder resin solution (25 wt% solution) and 100 parts by weight of toluene were charged, and the mixture was stirred at 2000 rpm for 1 minute with a mixer to prepare a positive electrode slurry composition. This positive electrode slurry composition was applied to an aluminum foil having a thickness of 20 μm with an applicator so that the film thickness after drying was 100 μm, and the mixture was dried at 100 ° C. for 2 hours to obtain a positive electrode sheet. This positive electrode sheet was punched out to Φ15 mm to prepare a positive electrode for a lithium ion battery.
＜碁盤目試験＞
碁盤目試験は、以下の方法で測定した。
前記正極用スラリー組成物をアプリケーターで厚み０．５ｍｍのアルミ板に乾燥後の膜厚が１８０μｍになるように塗布し、１００℃で２時間乾燥させ、電極シートを得た。この電極シートをＪＩＳＫ５４００―５－６に準拠して測定した。結果を表５に示した。
［評価基準］
◎：全く剥がれない
〇：剥がれが１０％未満
△：剥がれが１０％以上、３０％未満
×：剥がれが３０％以上
<Grid test>
The cross-cut test was performed by the following method.
The slurry composition for the positive electrode was applied to an aluminum plate having a thickness of 0.5 mm with an applicator so that the film thickness after drying would be 180 μm, and then dried at 100° C. for 2 hours to obtain an electrode sheet. This electrode sheet was measured in accordance with JIS K5400-5-6. The results are shown in Table 5.
[Evaluation criteria]
◎: No peeling at all ◯: Less than 10% peeling △: 10% or more but less than 30% peeling ×: 30% or more peeling
＜折り曲げ試験＞
折り曲げ試験は、電極の柔軟性を示すものであり、下記方法によって観測した。
前記正極用スラリー組成物をアプリケーターで厚み２０μｍのアルミ箔に乾燥後の膜厚が１８０μｍになるように塗布し、１００℃で２時間乾燥させ、電極シートを得た。
両端が固定された所定Φ（ｍｍ）の棒に、得られた電極シートを巻き付け、さらに電極シートに１００ｇの重しを吊り下げた。Φ（ｍｍ）の大きさを小さくしていき、電極が割れ始めたΦ（ｍｍ）を観測した。結果を表５に示した。
<Bending test>
The bending test indicates the flexibility of the electrode and was observed by the following method.
The slurry composition for positive electrodes was applied to an aluminum foil having a thickness of 20 μm with an applicator so that the film thickness after drying would be 180 μm, and then dried at 100° C. for 2 hours to obtain an electrode sheet.
The obtained electrode sheet was wrapped around a rod of a given Φ (mm) with both ends fixed, and a weight of 100 g was hung from the electrode sheet. The size of Φ (mm) was gradually reduced, and the Φ (mm) at which the electrode began to crack was observed. The results are shown in Table 5.
＜成型圧の測定＞
成型圧は、電極の成型性を示すものであり、下記方法によって測定した。
実施例１～６及び比較例１～３で作製した正極の空隙率を２０％にするのに必要なプレス圧（ｋＮ）を測定した。なお、一度のプレスで空隙率２０％にならない場合、電極を新しいものに取り換えて、プレス圧を上げて再度測定するものとする。
前記空隙率（％）は以下式で算出した。
空隙率［％］＝電極空隙体積［ｃｍ３］／（プレス後の電極の膜厚［μｍ］／１０４×電極面積［ｃｍ２］）
なお、電極空隙体積［ｃｍ３］は、電極重量と電極構成材料の重量を乗じたものを電極構成材料の密度で割って求めた。
<Measurement of molding pressure>
The molding pressure indicates the moldability of the electrode, and was measured by the following method.
The pressing pressure (kN) required to make the porosity of the positive electrodes produced in Examples 1 to 6 and Comparative Examples 1 to 3 20% was measured. If the porosity did not reach 20% in one pressing, the electrode was replaced with a new one, and the pressing pressure was increased to measure again.
The porosity (%) was calculated by the following formula.
Porosity [%]=electrode void volume [cm 3 ]/(film thickness of electrode after pressing [μm]/10 4 ×electrode area [cm 2 ])
The electrode void volume [cm 3 ] was calculated by multiplying the electrode weight by the weight of the electrode constituent material and dividing the product by the density of the electrode constituent material.
（リチウムイオン電池用負極の作製）
黒鉛９７重量部、カルボキシメチルセルロースナトリウム１．５重量部、ＳＢＲ［日本ゼオン（株）、ＢＭ－４００Ｂ，固形分４０重量％］１．５重量部及びイオン交換水１００重量部を仕込み、あわとり練太郎による攪拌を２０００ｒｐｍで１分間行い、負極用スラリー組成物を調整した。この負極用スラリー組成物をアプリケーターで厚み３０μｍの銅箔に乾燥後の膜厚が１００μｍ程度になるように塗布し、１００℃で２時間乾燥させ、電極シートを得た。この電極シートをΦ１６ｍｍに打ち抜いて、リチウムイオン電池用負極を作製した。
(Preparation of negative electrodes for lithium ion batteries)
97 parts by weight of graphite, 1.5 parts by weight of sodium carboxymethylcellulose, 1.5 parts by weight of SBR [Zeon Corporation, BM-400B, solid content 40% by weight], and 100 parts by weight of ion-exchanged water were charged, and the mixture was stirred at 2000 rpm for 1 minute using a mixer to prepare a slurry composition for the negative electrode. This slurry composition for the negative electrode was applied to a copper foil having a thickness of 30 μm with an applicator so that the film thickness after drying was about 100 μm, and the mixture was dried at 100° C. for 2 hours to obtain an electrode sheet. This electrode sheet was punched out to Φ16 mm to prepare a negative electrode for a lithium ion battery.
（電解液の作製）
エチレンカーボネート（ＥＣ）とジエチルカーボネート（ＤＥＣ）を体積割合でＥＣ：ＤＥＣ＝１：１で混合した混合溶媒に、電解質としてＬｉＰＦ６を１ｍｏｌ／Ｌの割合で溶解させて電解液を作製した。
(Preparation of Electrolyte)
An electrolyte solution was prepared by dissolving LiPF 6 as an electrolyte at a ratio of 1 mol/L in a mixed solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at a volume ratio of EC:DEC=1:1.
（性能評価用電池の作製）
作製したリチウムイオン電池用正極を、Φ１６ｍｍに打ち抜いた前記リチウムイオン電池用負極と共に２０３２型コインセル内の両端に配置した。
正極側の集電体としては、厚さ２０μｍのアルミ箔を用いた。
電極間にセパレータ（セルガード３５０１）を挿入し、評価用電池セルを作製した。
評価用電池セルに上記電解液を注液密封し、評価用電池を作製した。
(Preparation of batteries for performance evaluation)
The prepared positive electrode for a lithium ion battery was placed on both ends of a 2032-type coin cell together with the negative electrode for a lithium ion battery punched to a diameter of 16 mm.
As the current collector on the positive electrode side, an aluminum foil having a thickness of 20 μm was used.
A separator (Celgard 3501) was inserted between the electrodes to prepare a battery cell for evaluation.
The above electrolyte was poured into a battery cell for evaluation and sealed to prepare a battery for evaluation.
＜電池評価＞
室温下、充放電測定装置［ＨＪ０５０１ＳＭ８Ａ］［北斗電工（株）製］を用いて、０．１Ｃで４．２ＣまでＣＣ－ＣＶ（カットオフ電流０．０１Ｃ）で充電を行い、１時間休止した後、０．１Ｃで２．５Ｖまで放電を行った。この時の充電容量を初回充電容量Ｘ０とし、放電容量を初回容量Ｙ０とした。その後、充放電を繰り返し、５０サイクル目の放電容量Ｙ１を得た。
初回クーロン効率（％）＝初回放電容量（Ｙ０）／初回充電容量（Ｘ０）×１００とした。
<Battery evaluation>
At room temperature, the battery was charged at 0.1 C up to 4.2 C with CC-CV (cutoff current 0.01 C) using a charge/discharge measuring device [HJ0501SM8A] [manufactured by Hokuto Denko Corporation], and after resting for 1 hour, it was discharged at 0.1 C down to 2.5 V. The charge capacity at this time was designated as the initial charge capacity X0, and the discharge capacity was designated as the initial capacity Y0. Thereafter, the battery was repeatedly charged and discharged to obtain the discharge capacity Y1 at the 50th cycle.
Initial coulombic efficiency (%)=initial discharge capacity (Y0)/initial charge capacity (X0)×100.
５０サイクル放電容量維持率（％）＝Ｙ１ ／Ｙ０×１００として、下記の基準によりサイクル特性の評価を行った。結果を表５に示した。
［評価基準］
◎：放電容量維持率が９１％以上
○：放電容量維持率が８９％以上９１％未満
△：放電容量維持率が８９％未満
The cycle characteristics were evaluated according to the following criteria, with the 50th cycle discharge capacity retention rate (%) = Y1/Y0 x 100. The results are shown in Table 5.
[Evaluation criteria]
◎: Discharge capacity retention rate is 91% or more. ○: Discharge capacity retention rate is 89% or more and less than 91%. △: Discharge capacity retention rate is less than 89%.
表５から、各実施例の正極は、集電体との接着性に優れ、電極の捲回時や繰り返し充放電に伴う活物質層の体積変化に追随できる柔軟性を有し、厳しい条件での圧延処理が不要であることが分かる。 From Table 5, the positive electrode of each example has excellent adhesion to the current collector, has flexibility that can follow the volume change of the active material layer during electrode winding and repeated charging and discharging, and can be used under severe conditions. It can be seen that the rolling process is not necessary.
本発明のリチウムイオン電池用正極組成物から得られるリチウムイオン電池は、特に、携帯電話、パーソナルコンピューター及びハイブリッド自動車、電気自動車用に用いられるリチウムイオン電池として有用である。
The lithium ion batteries obtained from the lithium ion battery positive electrode composition of the present invention are particularly useful as lithium ion batteries for use in mobile phones, personal computers, hybrid automobiles, and electric automobiles.
Claims (6)
前記バインダー樹脂がビニル樹脂であり、
前記ビニル樹脂が、カルボキシル基を有するビニルモノマー（ａ１）及び下記一般式（１）
ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２ （１）
［式（１）中、Ｒ１は水素原子又はメチル基であり、Ｒ２は炭素数４～３６の分岐アルキル基である。］
で表されるビニルモノマー（ａ２）を必須構成単量体とする重合体であり、
前記バインダー樹脂のガラス転移温度が－４０～－５℃であり、
前記バインダー樹脂の結晶化度が２０未満であることを特徴とするリチウムイオン電池用正極組成物。 A positive electrode composition for a lithium ion battery comprising a binder resin, a conductive aid, and a positive electrode active material,
the binder resin is a vinyl resin,
The vinyl resin has a carboxyl group-containing vinyl monomer (a1) and the following general formula (1)
CH 2 =C(R 1 )COOR 2 (1)
[In formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a branched alkyl group having 4 to 36 carbon atoms. ]
A polymer having a vinyl monomer (a2) represented by as an essential constituent monomer,
The binder resin has a glass transition temperature of -40 to -5°C,
A positive electrode composition for a lithium ion battery, wherein the binder resin has a crystallinity of less than 20.
前記引張破断ひずみは、前記バインダー樹脂をダンベル状（ＡＳＴＭ Ｄ６８３記載の試験片形状ＴｙｐｅＩＩ）に打ち抜き、ＡＳＴＭ Ｄ６８３（試験片形状ＴｙｐｅＩＩ）に準拠した引張試験において試験片が破断するまでのひずみを下記式によって算出した値である請求項１に記載のリチウムイオン電池用正極組成物。
引張破断ひずみ（％）＝［（破断時試験片長さ－試験前試験片長さ）／試験前試験片長さ］×１００ The binder resin has a tensile breaking strain of 1000% or more;
2. The positive electrode composition for lithium ion batteries according to claim 1, wherein the tensile breaking strain is a value obtained by punching out the binder resin into a dumbbell shape (test piece shape Type II described in ASTM D683) and calculating the strain until a test piece breaks in a tensile test in accordance with ASTM D683 (test piece shape Type II) using the following formula:
Tensile breaking strain (%) = [(test piece length at break - test piece length before test) / test piece length before test] x 100
前記リチウムイオン電池用正極組成物における前記正極活物質の重量割合が、前記リチウムイオン電池用正極組成物の重量を基準として９０～９８重量％である請求項１に記載のリチウムイオン電池用正極組成物。 The weight ratio of the binder resin in the lithium ion battery positive electrode composition is 1 to 5% by weight based on the weight of the lithium ion battery positive electrode composition;
The weight ratio of the positive electrode active material in the positive electrode composition for lithium ion batteries is 90 to 98% by weight based on the weight of the positive electrode composition for lithium ion batteries.
A method for manufacturing a positive electrode for a lithium ion battery, comprising: a mixing step of preparing a slurry containing a binder resin, a conductive additive, a positive electrode active material, and an aqueous solvent; a coating step of coating the slurry onto a current collector; and a drying step of drying the slurry after the coating step to form a positive electrode active material layer on the current collector.
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