JP2011076916A - Binder for secondary battery electrode, secondary battery electrode, and secondary battery - Google Patents
Binder for secondary battery electrode, secondary battery electrode, and secondary battery Download PDFInfo
- Publication number
- JP2011076916A JP2011076916A JP2009228326A JP2009228326A JP2011076916A JP 2011076916 A JP2011076916 A JP 2011076916A JP 2009228326 A JP2009228326 A JP 2009228326A JP 2009228326 A JP2009228326 A JP 2009228326A JP 2011076916 A JP2011076916 A JP 2011076916A
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- Prior art keywords
- meth
- secondary battery
- binder
- component
- electrode
- Prior art date
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
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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
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は二次電池電極用バインダーならびにそれを用いる二次電池電極用スラリー、二次電池用電極および二次電池に関する。 The present invention relates to a binder for a secondary battery electrode, a slurry for a secondary battery electrode using the binder, an electrode for a secondary battery, and a secondary battery.
ノート型パソコン、携帯電話、PDAなどの携帯端末の普及が著しい。これら携帯端末の電源として、リチウムイオン二次電池が多く用いられている。携帯端末は、より利便性が求められて小型化、薄型化、軽量化と同時に高性能化が進められている。二次電池の高性能化に向けて、電極、電解液、その他の電池部材の改良が検討されており、特に重要な電極については、電極活物質や集電体そのものの検討の他、電極活物質などを集電体に結着するためのバインダーとなるポリマーの検討が鍵になっている。電極は、通常、水や有機溶媒等の液状媒体にバインダーとなるポリマーを分散または溶解させ、これに電極活物質および必要に応じて導電性カーボン等の導電付与剤を混合して二次電池電極用スラリー組成物を得、このスラリー組成物を集電体に塗布し、乾燥することにより、混合層を集電体に結着させて形成される。 The spread of portable terminals such as notebook personal computers, mobile phones and PDAs is remarkable. Lithium ion secondary batteries are often used as power sources for these portable terminals. Mobile terminals are required to be more convenient and are being made smaller, thinner, lighter, and higher in performance. To improve the performance of secondary batteries, improvements to electrodes, electrolytes, and other battery members are being studied. For particularly important electrodes, electrode active materials and current collectors are examined, as well as electrode active materials. The key is to study polymers that serve as binders for binding substances to current collectors. The electrode is usually a secondary battery electrode in which a polymer serving as a binder is dispersed or dissolved in a liquid medium such as water or an organic solvent, and an electrode active material and a conductive agent such as conductive carbon are mixed with the polymer. The slurry composition is obtained, and the slurry composition is applied to the current collector and dried to bind the mixed layer to the current collector.
二次電池の高性能化には、電池容量、寿命(サイクル特性)および高レートでの充放電容量の維持率(レート特性)の向上が必要である。電池容量は、電極活物質の充填量に強く影響される。また、レート特性は電子の移動の容易さに影響されるので、レート特性の向上には導電付与剤の増量が効果的である。限られた電池空間内で電極活物質と導電付与剤を増量するには、バインダー量を低減する必要がある。しかしながら、バインダーを減量すると電極活物質の結着性が損なわれ、繰り返し充放電によって集電体から電極活物質が剥離してサイクル特性が悪化する。このため、使用量が少なくても電極活物質を強く結着できるバインダーが求められている。 In order to improve the performance of the secondary battery, it is necessary to improve the battery capacity, life (cycle characteristics) and charge / discharge capacity maintenance rate (rate characteristics) at a high rate. The battery capacity is strongly influenced by the filling amount of the electrode active material. Further, since the rate characteristic is affected by the ease of electron movement, an increase in the conductivity-imparting agent is effective for improving the rate characteristic. In order to increase the electrode active material and the conductivity-imparting agent in a limited battery space, it is necessary to reduce the amount of binder. However, when the amount of the binder is reduced, the binding property of the electrode active material is impaired, and the electrode active material is peeled off from the current collector by repeated charge and discharge, thereby deteriorating cycle characteristics. For this reason, there is a demand for a binder that can strongly bind the electrode active material even if the amount used is small.
従来、リチウムイオン二次電池の正極用バインダーとしてはポリビニリデンフルオライドなどのフッ素含有ポリマーが汎用されている。フッ素含有ポリマーを用いると電極の製造が容易であるが、結着力や柔軟性が不足しているので電池の高容量化やレート特性の向上には困難がある。上記のフッ素含有ポリマーの欠点を改善する方法として、ゴム系高分子バインダーを用いることが提案された(特許文献1:特開平4−255670号公報)。しかし、ゴム系高分子を用いて電極を作成すると結着力や柔軟性は改善し得るものの、電極活物質がゴム系高分子に覆い隠されて電池反応が制限される問題がある。そこで、フッ素系ポリマーとゴム系高分子とを併用する試み、例えば、ブタジエン系ポリマーとの併用(特許文献2:特開平6−215761号公報)、アクリロニトリル−ブタジエン共重合体ゴム(NBR)との併用(特許文献3:特開平9−63590号公報)、アクリル系ポリマーとの併用(特許文献4:特開平9−199132号公報)、水素化NBRとアクリロニトリル・アクリル酸エステル共重合体との併用(特許文献5:特開2003−282061号公報)などが提案されている。 Conventionally, fluorine-containing polymers such as polyvinylidene fluoride have been widely used as positive electrode binders for lithium ion secondary batteries. When a fluorine-containing polymer is used, the production of the electrode is easy, but since the binding force and flexibility are insufficient, it is difficult to increase the capacity of the battery and improve the rate characteristics. As a method for improving the drawbacks of the fluorine-containing polymer, it has been proposed to use a rubber-based polymer binder (Patent Document 1: Japanese Patent Laid-Open No. 4-255670). However, when an electrode is formed using a rubber polymer, the binding force and flexibility can be improved, but there is a problem that the battery reaction is restricted because the electrode active material is covered with the rubber polymer. Therefore, an attempt to use a fluorine-based polymer and a rubber-based polymer together, for example, a combination with a butadiene-based polymer (Patent Document 2: JP-A-6-215761), an acrylonitrile-butadiene copolymer rubber (NBR) Combined use (Patent Document 3: JP-A-9-63590), combined use with acrylic polymer (Patent Document 4: JP-A-9-199132), combined use of hydrogenated NBR and acrylonitrile / acrylic ester copolymer (Patent Document 5: Japanese Patent Laid-Open No. 2003-282061) has been proposed.
また、特許文献6(WO2004/095613)には、N−メチルピロリドン(NMP)に可溶な重合体を与えるエチレン性不飽和単量体と、NMPに不溶な重合体を与えるエチレン性不飽和単量体とを多段重合して得られる重合体からなるリチウムイオン二次電池電極用バインダーが開示されている。NMPに可溶な単独重合体を与えるエチレン性不飽和単量体としては、アクリロニトリル、メタクリロニトリルおよび非カルボニル性酸素原子に結合するアルキル基の炭素数が6以下のエチレン性不飽和カルボン酸エステルなどが例示され、またNMPに不溶な単独重合体を与えるエチレン性不飽和単量体としては、非カルボニル性酸素原子に結合するアルキル基の炭素数が7以上のエチレン性不飽和カルボン酸エステルなどが例示されている。 Patent Document 6 (WO 2004/095613) describes an ethylenically unsaturated monomer that gives a polymer soluble in N-methylpyrrolidone (NMP) and an ethylenically unsaturated monomer that gives a polymer insoluble in NMP. A binder for a lithium ion secondary battery electrode comprising a polymer obtained by multistage polymerization of a monomer is disclosed. Examples of the ethylenically unsaturated monomer that gives a homopolymer soluble in NMP include acrylonitrile, methacrylonitrile, and an ethylenically unsaturated carboxylic acid ester having an alkyl group bonded to a non-carbonyl oxygen atom having 6 or less carbon atoms. Examples of the ethylenically unsaturated monomer that gives a homopolymer insoluble in NMP include ethylenically unsaturated carboxylic acid esters in which the alkyl group bonded to the non-carbonyl oxygen atom has 7 or more carbon atoms. Is illustrated.
しかしながら、発明者らの検討によれば、特許文献2〜5に記載のバインダーは、異なる2種のポリマーを機械的に混合して得られたものであるため、ポリマー同士の均一な分散性(相溶性)が必ずしも充分ではないことが分かった。そして、このようなバインダーを用いて得たスラリーは、経時安定性に劣り、約1日の静置で相分離し沈降物が発生し、スラリーの長期保管が困難であること、電池の製造工程の進行に合わせてスラリーを逐次調製する必要があり、工程の円滑化を妨げること、更に、バインダーを構成するポリマーの相溶性が充分ではないため、電極内でバインダーが相分離を起こし、ポリマーが偏析すること、が分かった。更にその結果、電極活物質層の柔軟性が損なわれ、このバインダーを使用した二次電池では、ポリマーの偏析により、レート特性、サイクル特性等の電池特性が経時的に低下するおそれがあることが明らかになった。 However, according to the studies by the inventors, the binders described in Patent Documents 2 to 5 are obtained by mechanically mixing two different types of polymers. It was found that (compatibility) is not always sufficient. And the slurry obtained using such a binder is inferior in stability over time, phase separation occurs by standing for about 1 day, precipitate is generated, and long-term storage of the slurry is difficult, battery manufacturing process It is necessary to prepare the slurry sequentially in accordance with the progress of the process, hindering the smoothing of the process, and furthermore, the compatibility of the polymer constituting the binder is not sufficient, so that the binder causes phase separation in the electrode, and the polymer I understood that it segregates. As a result, the flexibility of the electrode active material layer is impaired, and in secondary batteries using this binder, battery characteristics such as rate characteristics and cycle characteristics may deteriorate over time due to polymer segregation. It was revealed.
また、特許文献6に記載のバインダーでは、電解液に対する膨潤性を制御することができ長期サイクル特性は向上するものの、レート特性は十分に向上していない。また、バインダー中にNMP溶解成分と不溶成分とを有し、特性が大きく異なる2つの成分を多段重合していることから、ポリマー同士の均一な分散性(相溶性)が必ずしも充分ではなく、上記と同様な課題が生じることが分かった。 In addition, the binder described in Patent Document 6 can control the swellability with respect to the electrolytic solution and can improve the long-term cycle characteristics, but the rate characteristics are not sufficiently improved. In addition, since the binder has an NMP-soluble component and an insoluble component, and two components having greatly different characteristics are subjected to multistage polymerization, the uniform dispersibility (compatibility) between the polymers is not necessarily sufficient. It was found that the same problem occurs.
従って、本発明は、バインダーを含むスラリーが相分離を起こすことなく経時安定性に優れ、更に前記バインダーを有する二次電池において高いサイクル特性とレート特性を示す、二次電池電極用バインダーを提供することを目的としている。 Accordingly, the present invention provides a binder for a secondary battery electrode in which the slurry containing the binder is excellent in stability over time without causing phase separation, and further exhibits high cycle characteristics and rate characteristics in a secondary battery having the binder. The purpose is that.
本発明者らは、経時安定性に優れたバインダーを提供すべく鋭意検討したところ、多段重合により(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合を行うことで、組成の異なる2種以上の成分からなる、(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体であって、前記各成分が互いに相溶してなるバインダーが得られ、かつ共重合体の組成を適切な範囲に制御することで、スラリーの経時安定性が顕著に改善されることを見いだした。更に、前記共重合体が高含有量の(メタ)アクリロニトリルを含む成分を少なくとも有することにより、上記成分が導電剤の分散性に優れ、電極内において導電剤を均一に分布させることで、上記バインダーを含む二次電池において高いレート特性を有することを見出し、これらの知見に基づいて本発明を完成するに至った。 The present inventors diligently studied to provide a binder having excellent stability over time. As a result of copolymerization of (meth) acrylonitrile and (meth) acrylic acid ester by multistage polymerization, two types having different compositions were obtained. A copolymer of (meth) acrylonitrile and (meth) acrylic acid ester composed of the above components, wherein a binder in which the above components are compatible with each other is obtained, and the composition of the copolymer is set appropriately. It was found that the stability with time of the slurry was remarkably improved by controlling to the range. Furthermore, since the copolymer has at least a component containing a high content of (meth) acrylonitrile, the component is excellent in dispersibility of the conductive agent, and the conductive agent is uniformly distributed in the electrode. It has been found that the secondary battery including the battery has high rate characteristics, and the present invention has been completed based on these findings.
すなわち、上記課題を解決する本発明は、下記事項を要旨として含む。
(1)(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体からなる二次電池電極用バインダーであって、前記共重合体が、(メタ)アクリロニトリル単位の含有量が60重量%以上95重量%以下の成分(A)と、(メタ)アクリロニトリル単位の含有量が5重量%以上40重量%以下の成分(B)とからなり、前記成分(A)と成分(B)とが相溶してなる、二次電池電極用バインダー。
That is, this invention which solves the said subject contains the following matter as a summary.
(1) A binder for a secondary battery electrode comprising a copolymer of (meth) acrylonitrile and (meth) acrylic acid ester, wherein the copolymer has a (meth) acrylonitrile unit content of 60% by weight or more. 95% by weight or less of component (A) and (meth) acrylonitrile unit content of 5% by weight or more and 40% by weight or less of component (B), wherein component (A) and component (B) are in phase A binder for secondary battery electrodes formed by melting.
(2)前記共重合体における前記成分(A)と、前記成分(B)との比率が、20:80〜80:20(重量比)である(1)に記載の二次電池電極用バインダー。 (2) The binder for secondary battery electrodes according to (1), wherein the ratio of the component (A) and the component (B) in the copolymer is 20:80 to 80:20 (weight ratio). .
(3)(メタ)アクリロニトリルの含有量が60重量%以上95重量%である単量体組成物(A)と、(メタ)アクリロニトリルの含有量が5重量%以上40重量%である単量体組成物(B)とを多段重合することを特徴とする(1)に記載の二次電池電極用バインダーの製造方法。 (3) A monomer composition (A) having a (meth) acrylonitrile content of 60 wt% or more and 95 wt%, and a monomer having a (meth) acrylonitrile content of 5 wt% or more and 40 wt% The method for producing a binder for a secondary battery electrode according to (1), wherein the composition (B) is subjected to multistage polymerization.
(4)前記多段重合が、前記成分(A)を主たる生成物とする重合工程と、前記成分(B)を主たる生成物とする重合工程とを含むものである(3)に記載の二次電池電極用バインダーの製造方法。 (4) The secondary battery electrode according to (3), wherein the multistage polymerization includes a polymerization step in which the component (A) is a main product and a polymerization step in which the component (B) is a main product. Method for manufacturing binder.
(5)(1)又は(2)に記載の二次電池電極用バインダー、電極活物質、および溶媒を有する二次電池電極用スラリー。 (5) A secondary battery electrode slurry comprising the secondary battery electrode binder according to (1) or (2), an electrode active material, and a solvent.
(6)(1)又は(2)に記載の二次電池電極用バインダー及び電極活物質とからなる電極活物質層が、集電体に積層されてなる二次電池電極。 (6) A secondary battery electrode in which an electrode active material layer comprising the secondary battery electrode binder and electrode active material according to (1) or (2) is laminated on a current collector.
(7)正極、電解液、セパレーター及び負極を有する二次電池であって、
前記正極又は負極が、(6)記載の二次電池電極である二次電池。
(7) A secondary battery having a positive electrode, an electrolytic solution, a separator and a negative electrode,
The secondary battery whose said positive electrode or negative electrode is a secondary battery electrode of (6) description.
本発明のバインダーは、組成の異なる2種以上の成分からなる、(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体であって、前記各成分が互いに相溶してなり、かつ該共重合体の各成分の組成が特定範囲に制御されてなるため、バインダーを含むスラリーの経時安定性に優れる。 The binder of the present invention is a copolymer of (meth) acrylonitrile and (meth) acrylic acid ester composed of two or more components having different compositions, wherein the respective components are compatible with each other, and Since the composition of each component of the copolymer is controlled within a specific range, the slurry containing the binder is excellent in stability over time.
したがって、かかるバインダーを用いて製造した電極用スラリーは、長期間保管しても相分離を起こしにくいため、大量生産及び長期保管が可能であり、電池の製造工程の進行が円滑になり、また得られる電池の品質も一定化する。また製造された電極内においてもバインダーの相溶状態が安定して維持されるため、電極活物質層の柔軟性、結着性や、レート特性、サイクル特性等の電池特性が経時的に劣化することもない。 Therefore, an electrode slurry produced using such a binder is less likely to cause phase separation even when stored for a long period of time, and thus can be mass-produced and stored for a long period of time. The quality of the battery produced is also constant. In addition, since the compatibility state of the binder is stably maintained in the manufactured electrode, battery characteristics such as flexibility, binding property, rate characteristics, cycle characteristics, etc. of the electrode active material layer deteriorate with time. There is nothing.
更に、前記共重合体が、高含有量の(メタ)アクリロニトリルを含む成分を少なくとも有することにより、上記成分が導電剤の分散性に優れ、電極内において導電剤を均一に分布させることで、上記バインダーを含む二次電池において高いレート特性を有する。 Furthermore, when the copolymer has at least a component containing a high content of (meth) acrylonitrile, the component is excellent in dispersibility of the conductive agent, and the conductive agent is uniformly distributed in the electrode. A secondary battery containing a binder has high rate characteristics.
以下に本発明を詳述する。
1.バインダー
本発明の二次電池電極用バインダーは、組成の異なる2種以上の成分からなる、(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体であって、前記各成分が互いに相溶してなる。
The present invention is described in detail below.
1. Binder The binder for secondary battery electrodes of the present invention is a copolymer of (meth) acrylonitrile and (meth) acrylic acid ester comprising two or more components having different compositions, and the respective components are compatible with each other. Do it.
ここで、(メタ)アクリロニトリルとは、アクリロニトリルおよびメタアクリロニトリルの両者を含む意味で用いられる。すなわち、(メタ)アクリロニトリルは、アクリロニトリルあるいはメタアクリロニトリルのいずれか一方であってもよく、また両者を同時に含むものであってもよい。同様に、(メタ)アクリル酸エステルとは、アクリル酸エステルおよびメタアクリル酸エステルの両者を含む意味で用いられる。(メタ)アクリル酸エステルも同様に、アクリル酸エステルまたはメタアクリル酸エステル共重合体のいずれか一方であってもよく、また両者を同時に含むものであってもよい。 Here, (meth) acrylonitrile is used in the meaning including both acrylonitrile and methacrylonitrile. That is, (meth) acrylonitrile may be either acrylonitrile or methacrylonitrile, or may contain both at the same time. Similarly, (meth) acrylic acid ester is used in the meaning including both acrylic acid ester and methacrylic acid ester. Similarly, the (meth) acrylic acid ester may be either an acrylic acid ester or a methacrylic acid ester copolymer, or may contain both at the same time.
(メタ)アクリル酸エステルとしては、(メタ)アクリル酸アルキルエステル、および側鎖に官能基を有する(メタ)アクリル酸エステルが挙げられる。中でも、(メタ)アクリル酸アルキルエステルが好ましく、非カルボニル性酸素原子に結合するアルキル基の炭素数が1〜18である(メタ)アクリル酸アルキルエステルが好ましい。アルキル基の炭素数が上記範囲内であることにより、導電剤の分散性に優れ、高いレート特性を示す。 (Meth) acrylic acid ester includes (meth) acrylic acid alkyl ester and (meth) acrylic acid ester having a functional group in the side chain. Among them, (meth) acrylic acid alkyl ester is preferable, and (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms of the alkyl group bonded to the non-carbonyl oxygen atom is preferable. When the carbon number of the alkyl group is within the above range, the conductive agent is excellent in dispersibility and exhibits high rate characteristics.
非カルボニル性酸素原子に結合するアルキル基の炭素数が1〜18である(メタ)アクリル酸アルキルエステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸n−プロピル、アクリル酸イソプロピル、アクリル酸n−ブチル、アクリル酸t−ブチル、アクリル酸n−ヘキシル、アクリル酸2−エチルヘキシル、アクリル酸ノニル、アクリル酸ラウリル、アクリル酸ステアリル、アクリル酸シクロヘキシル、およびアクリル酸イソボルニルなどのアクリル酸アルキルエステル;
メタアクリル酸メチル、メタアクリル酸エチル、メタアクリル酸n−プロピル、メタアクリル酸イソプロピル、メタアクリル酸n−ブチル、メタアクリル酸t−ブチル、メタアクリル酸n−ヘキシル、メタアクリル酸2−エチルヘキシル、メタアクリル酸オクチル、メタアクリル酸イソデシル、メタアクリル酸ラウリル、メタアクリル酸トリデシル、メタアクリル酸ステアリル、およびメタアクリル酸シクロヘキシルなどのメタアクリル酸アルキルエステルが挙げられる。
Examples of the alkyl (meth) acrylate alkyl ester having 1 to 18 carbon atoms bonded to a non-carbonyl oxygen atom include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and acrylic acid n. Alkyl acrylate esters such as butyl, t-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, and isobornyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, Examples include methacrylic acid alkyl esters such as octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, and cyclohexyl methacrylate.
これらの中では、炭素数1〜18である(メタ)アクリル酸アルキルエステルがより好ましく、より好ましくは炭素数2〜12の(メタ)アクリル酸アルキルエステルであり、特に好ましくは(メタ)アクリル酸n−ブチル、(メタ)アクリル酸2−エチルヘキシルである。これらの(メタ)アクリル酸アルキルエステルを用いることにより、スラリー安定性、電極の柔軟性に優れ、かつ高いレート特性を示す。 Among these, (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms is more preferable, (meth) acrylic acid alkyl ester having 2 to 12 carbon atoms is more preferable, and (meth) acrylic acid is particularly preferable. n-butyl, 2-ethylhexyl (meth) acrylate. By using these alkyl (meth) acrylates, the slurry stability and electrode flexibility are excellent, and high rate characteristics are exhibited.
側鎖に官能基を有する(メタ)アクリル酸エステルとしては、アクリル酸2−メトキシエチルおよびメタアクリル酸2−メトキシエチルなどのアルコキシル基を有する(メタ)アクリル酸エステル;アクリル酸−2−ヒドロキシエチルおよびメタアクリル酸−2−ヒドロキシエチルなどのヒドロキシル基を有する(メタ)アクリル酸エステル;アクリル酸グリシジルおよびメタアクリル酸グリシジルなどのエポキシ基を有する(メタ)アクリル酸エステル;などが挙げられる。 As the (meth) acrylic acid ester having a functional group in the side chain, (meth) acrylic acid ester having an alkoxyl group such as 2-methoxyethyl acrylate and 2-methoxyethyl methacrylate; 2-hydroxyethyl acrylate And (meth) acrylic acid ester having a hydroxyl group such as 2-hydroxyethyl methacrylate; (meth) acrylic acid ester having an epoxy group such as glycidyl acrylate and glycidyl methacrylate;
本発明のバインダーを構成する上記(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体は、組成の異なる2種以上の成分からなる。すなわち、(メタ)アクリロニトリル・(メタ)アクリル酸エステル共重合体は、(メタ)アクリロニトリル単位の含有量が60重量%以上95重量%以下の成分(A)と、(メタ)アクリロニトリル単位の含有量が5重量%以上40重量%以下の成分(B)とからなる。 The copolymer of (meth) acrylonitrile and (meth) acrylic acid ester constituting the binder of the present invention comprises two or more components having different compositions. That is, the (meth) acrylonitrile / (meth) acrylic acid ester copolymer has a (meth) acrylonitrile unit content of 60% by weight to 95% by weight of component (A) and a (meth) acrylonitrile unit content. Is 5% by weight or more and 40% by weight or less of the component (B).
本発明において成分(A)は、(メタ)アクリロニトリル単位を60重量%以上95重量%以下含有する。成分(A)における(メタ)アクリロニトリル単位の含有量が、上記範囲であることにより、導電剤の分散性に優れ、電極内において導電剤を均一に分布させることができ、さらに本発明のバインダーを含む二次電池において高いレート特性を示すことができる。成分(A)における(メタ)アクリロニトリル単位の含有量は、好ましくは65重量%以上90重量%以下であり、更に好ましくは70重量%以上85重量%以下である。成分(A)における(メタ)アクリロニトリル単位の含有量が、上記範囲であることにより、高いレート特性を示しながらもスラリーの経時安定性に優れる。 In the present invention, the component (A) contains 60% by weight or more and 95% by weight or less of (meth) acrylonitrile units. When the content of the (meth) acrylonitrile unit in the component (A) is in the above range, the conductive agent is excellent in dispersibility, and the conductive agent can be uniformly distributed in the electrode. High rate characteristics can be exhibited in the secondary battery including the same. The content of the (meth) acrylonitrile unit in the component (A) is preferably 65% by weight or more and 90% by weight or less, more preferably 70% by weight or more and 85% by weight or less. When the content of the (meth) acrylonitrile unit in the component (A) is in the above range, the slurry has excellent stability over time while exhibiting high rate characteristics.
成分(A)は、(メタ)アクリロニトリル単位以外にも前述の(メタ)アクリル酸エステル単位や後述の(メタ)アクリロニトリル及び(メタ)アクリル酸エステルと共重合可能な単量体単位を含んでいてもよい。中でも、(メタ)アクリル酸エステル単位を含んでなることが好ましい。 In addition to the (meth) acrylonitrile unit, the component (A) includes a monomer unit copolymerizable with the above-mentioned (meth) acrylic acid ester unit and the (meth) acrylonitrile and (meth) acrylic acid ester described later. Also good. Among these, it is preferable to comprise a (meth) acrylic acid ester unit.
成分(A)中の(メタ)アクリル酸エステル単位の含有量は、成分(A)全量に対して5重量%以上40重量%以下が好ましく、更に好ましくは10重量%以上35重量%以下であり、特に好ましくは15重量%以上30重量%以下である。成分(A)中の(メタ)アクリル酸エステル単位の含有量が、上記範囲に含まれることにより、高いレート特性を示しながらもスラリーの経時安定性に優れる。 The content of the (meth) acrylic acid ester unit in the component (A) is preferably 5% by weight or more and 40% by weight or less, more preferably 10% by weight or more and 35% by weight or less with respect to the total amount of the component (A). Particularly preferably, it is 15% by weight or more and 30% by weight or less. When the content of the (meth) acrylic acid ester unit in the component (A) is included in the above range, the slurry has excellent stability over time while exhibiting high rate characteristics.
成分(A)中の(メタ)アクリル酸エステル以外のその他の共重合可能な単量体単位の含有量は、成分(A)全量に対して好ましくは20重量%以下、さらに好ましくは1〜10重量%である。成分(A)中の(メタ)アクリル酸エステル以外のその他の共重合可能な単量体単位の含有量が、上記範囲に含まれることにより、各単量体単位が示す上述の効果を発揮できると共に、本発明の効果であるバインダー及びスラリーの経時安定性に優れ、得られるバインダーのサイクル特性・レート特性共に優れる。 The content of other copolymerizable monomer units other than (meth) acrylic acid ester in component (A) is preferably 20% by weight or less, more preferably 1 to 10%, based on the total amount of component (A). % By weight. When the content of other copolymerizable monomer units other than the (meth) acrylic acid ester in the component (A) is included in the above range, the above-described effects of each monomer unit can be exhibited. In addition, the stability of the binder and the slurry, which is the effect of the present invention, is excellent, and the cycle characteristics and rate characteristics of the obtained binder are excellent.
本発明において成分(B)は、(メタ)アクリロニトリル単位を5重量%以上40重量%以下含有する。成分(B)における(メタ)アクリロニトリル単位の含有量が、上記範囲であることにより、成分(A)との相溶性に優れ、また本発明のバインダーを含む二次電池用電極の柔軟性に優れる。成分(B)における(メタ)アクリロニトリル単位の含有量は、好ましくは10重量%以上30重量%以下であり、更に好ましくは15重量%以上25重量%以下である。成分(B)における(メタ)アクリロニトリル単位の含有量が上記範囲であることにより、高いバインダーの相溶性とスラリーの経時安定性を示しながらも電池内において耐電解液性に優れる。 In this invention, a component (B) contains 5 to 40 weight% of (meth) acrylonitrile units. When the content of the (meth) acrylonitrile unit in the component (B) is in the above range, the compatibility with the component (A) is excellent, and the flexibility of the secondary battery electrode containing the binder of the present invention is excellent. . The content of the (meth) acrylonitrile unit in the component (B) is preferably 10% by weight to 30% by weight, and more preferably 15% by weight to 25% by weight. When the content of the (meth) acrylonitrile unit in the component (B) is in the above range, the electrolytic solution resistance is excellent in the battery while exhibiting high compatibility of the binder and stability with time of the slurry.
成分(B)は、(メタ)アクリロニトリル単位以外にも前述の(メタ)アクリル酸エステル単位や後述の(メタ)アクリロニトリル及び(メタ)アクリル酸エステルと共重合可能な単量体単位を含んでいてもよい。中でも、(メタ)アクリル酸エステル単位を含んでなることが好ましい。 In addition to the (meth) acrylonitrile unit, the component (B) contains a monomer unit that can be copolymerized with the above-mentioned (meth) acrylic acid ester unit or the (meth) acrylonitrile and (meth) acrylic acid ester described later. Also good. Among these, it is preferable to comprise a (meth) acrylic acid ester unit.
成分(B)中の(メタ)アクリル酸エステル単位の含有量は、成分(B)全量に対して60重量%以上95重量%以下が好ましく、更に好ましくは70重量%以上90重量%以下であり、もっとも好ましく75重量%以上85重量%以下である。成分(B)中の(メタ)アクリル酸エステル単位の含有量が、上記範囲に含まれることにより高いレート特性を示しながらもスラリーの経時安定性に優れる。 The content of the (meth) acrylic acid ester unit in the component (B) is preferably 60% to 95% by weight, more preferably 70% to 90% by weight, based on the total amount of the component (B). Most preferably, it is 75 wt% or more and 85 wt% or less. When the content of the (meth) acrylic acid ester unit in the component (B) is within the above range, the slurry has excellent stability over time while exhibiting high rate characteristics.
成分(B)中の(メタ)アクリル酸エステル単位以外のその他の共重合可能な単量体単位の含有量は、成分(B)全量に対して好ましくは20重量%以下、さらに好ましくは1重量%以上10重量%以下である。(メタ)アクリル酸エステル以外のその他の共重合可能な単量体単位の含有量が、上記範囲に含まれることにより、各単量体単位が示す上述の効果を発揮できると共に、本発明の効果であるバインダー及びスラリーの経時安定性に優れ、得られるバインダーのサイクル特性・レート特性共に優れる。 The content of other copolymerizable monomer units other than the (meth) acrylic acid ester unit in the component (B) is preferably 20% by weight or less, more preferably 1% by weight based on the total amount of the component (B). % To 10% by weight. When the content of other copolymerizable monomer units other than (meth) acrylic acid ester is included in the above range, the above-described effects of each monomer unit can be exhibited and the effect of the present invention. The binder and the slurry are excellent in stability over time, and the obtained binder has excellent cycle characteristics and rate characteristics.
本発明の二次電池電極用バインダーにおいて、前記共重合体における成分(A)と、前記成分(B)との比率は、重量比で、20:80〜80:20であることが好ましく、更に好ましくは30:70〜70:30、特に好ましくは40:60〜60:40である。前記共重合体における成分(A)と、成分(B)との比率が上記範囲であることにより、成分(A)と成分(B)とが高い相溶性を示し、スラリーの経時安定性にも優れ、得られた二次電池のサイクル特性・レート特性共に優れる。 In the binder for a secondary battery electrode of the present invention, the ratio of the component (A) and the component (B) in the copolymer is preferably 20:80 to 80:20 by weight, Preferably it is 30: 70-70: 30, Most preferably, it is 40: 60-60: 40. When the ratio of the component (A) and the component (B) in the copolymer is within the above range, the component (A) and the component (B) exhibit high compatibility, and the aging stability of the slurry is also improved. Excellent and excellent in both cycle characteristics and rate characteristics of the obtained secondary battery.
バインダーを構成する(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体全量に対する(メタ)アクリロニトリル由来の単量体単位の含有量は、好ましくは30〜70重量%、さらに好ましくは40〜60重量%であり、また(メタ)アクリル酸エステル由来の単量体単位の含有量は、好ましくは70〜30重量%、さらに好ましくは60〜40重量%である。本発明のバインダー中の(メタ)アクリロニトリル由来の単量体単位及び(メタ)アクリル酸エステル由来の単量体単位の含有量が上記範囲であることにより、耐電解液性に優れ、かつバインダーを含む二次電池の出力特性に優れる。 The content of monomer units derived from (meth) acrylonitrile with respect to the total amount of copolymer of (meth) acrylonitrile and (meth) acrylic acid ester constituting the binder is preferably 30 to 70% by weight, more preferably 40 to 40%. The content of the monomer unit derived from (meth) acrylic acid ester is preferably 70 to 30% by weight, and more preferably 60 to 40% by weight. When the content of the monomer unit derived from (meth) acrylonitrile and the monomer unit derived from (meth) acrylic acid ester in the binder of the present invention is in the above range, the electrolyte solution resistance is excellent, and the binder Excellent output characteristics of secondary batteries.
また前記(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体には、(メタ)アクリロニトリル単位および(メタ)アクリル酸エステル単位に加えて、その他の単量体単位が含まれていてもよい。 The copolymer of (meth) acrylonitrile and (meth) acrylic acid ester may contain other monomer units in addition to the (meth) acrylonitrile unit and (meth) acrylic acid ester unit. Good.
その他の共重合可能な単量体単位としては、共役ジエン由来の単量体単位、多官能不飽和カルボン酸エステル由来の単量体単位、不飽和カルボン酸由来の単量体単位および芳香族ビニル化合物由来の単量体単位が挙げられる。 Other copolymerizable monomer units include monomer units derived from conjugated dienes, monomer units derived from polyfunctional unsaturated carboxylic acid esters, monomer units derived from unsaturated carboxylic acids, and aromatic vinyl. The monomer unit derived from a compound is mentioned.
共役ジエン由来の単量体単位を構成するために用いられる共役ジエンとしては、1,3−ブタジエン、2−メチル−1,3−ブタジエン、2,3−ジメチル−1,3−ブタジエン、2−エチル−1,3−ブタジエン、2−クロル−1,3−ブタジエン、1,3−ペンタジエン、1,3−ヘキサジエン、および2,4−ヘキサジエンなどが挙げられる。これらの共役ジエンの中でも1,3−ブタジエンが好ましい。共役ジエン単位を含有させることで、バインダーの柔軟性を制御できる。 Conjugated dienes used for constituting monomer units derived from conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2- Examples include ethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and 2,4-hexadiene. Of these conjugated dienes, 1,3-butadiene is preferred. By containing a conjugated diene unit, the flexibility of the binder can be controlled.
多官能不飽和カルボン酸エステル由来の単量体単位を構成するために用いられる多官能不飽和カルボン酸エステルとは、2以上の炭素−炭素二重結合を有するカルボン酸エステルである。多官能不飽和カルボン酸エステルの具体例としては、ジエチレングリコールジアクリレート、1,3−ブチレングリコールジアクリレート、トリプロピレングリコールアクリレート、1,4−ブタンジオールアクリレート、ネオペンチルグリコールジアクリレート、1,6−ヘキサンジオールアクリレート、1,9−ノナンジオールアクリレート、およびポリエチレングリコールジアクリレートなどジアクリル酸エステル類;トリメチロールプロパントリアクリレートなどのトリアクリル酸エステル類;エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、1,3−ブチレングリコールジメタクリレート、およびポリエチレングリコールジメタクリレートなどのジメタアクリル酸エステル類;トリメチロールプロパントリメタクリレートなどのトリメタアクリル酸エステル類;が挙げられる。かかる単量体単位を含有させることで、バインダーの電解液に対する膨潤が抑制され、得られる電池の長期保存特性が改善されることがある。 The polyfunctional unsaturated carboxylic acid ester used for constituting the monomer unit derived from the polyfunctional unsaturated carboxylic acid ester is a carboxylic acid ester having two or more carbon-carbon double bonds. Specific examples of the polyfunctional unsaturated carboxylic acid ester include diethylene glycol diacrylate, 1,3-butylene glycol diacrylate, tripropylene glycol acrylate, 1,4-butanediol acrylate, neopentyl glycol diacrylate, and 1,6-hexane. Diacrylates such as diol acrylate, 1,9-nonanediol acrylate, and polyethylene glycol diacrylate; Triacrylates such as trimethylolpropane triacrylate; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,3-butylene glycol Dimethacrylates such as dimethacrylate and polyethylene glycol dimethacrylate; trimethylolpro Tri methacrylates such as emissions trimethacrylate; and the like. By containing such a monomer unit, swelling of the binder with respect to the electrolytic solution may be suppressed, and the long-term storage characteristics of the obtained battery may be improved.
不飽和カルボン酸由来の単量体単位を構成するために用いられる不飽和カルボン酸としては、アクリル酸、メタアクリル酸、クロトン酸およびイソクロトン酸などの不飽和モノカルボン酸;マレイン酸、フマル酸、シトラコン酸、メサコン酸、グルタコン酸、およびイタコン酸などの不飽和ジカルボン酸;が挙げられる。中でも、不飽和モノカルボン酸が好ましい。不飽和カルボン酸単位を含有させることで、バインダーの結着性が向上することがある。 The unsaturated carboxylic acid used to constitute the monomer unit derived from the unsaturated carboxylic acid includes unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and isocrotonic acid; maleic acid, fumaric acid, And unsaturated dicarboxylic acids such as citraconic acid, mesaconic acid, glutaconic acid, and itaconic acid. Of these, unsaturated monocarboxylic acids are preferred. By containing an unsaturated carboxylic acid unit, the binding property of the binder may be improved.
芳香族ビニル化合物由来の単量体単位を構成するために用いられる芳香族ビニル化合物としては、スチレン、α−メチルスチレン、およびβ−メチルスチレンなどが挙げられ、スチレンが好ましい。芳香族ビニル単位を含有させることで、バインダーの結着性が向上することがある。 Examples of the aromatic vinyl compound used for constituting the monomer unit derived from the aromatic vinyl compound include styrene, α-methylstyrene, and β-methylstyrene, and styrene is preferable. By including an aromatic vinyl unit, the binding property of the binder may be improved.
バインダーを構成する(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体全量に対するその他の共重合可能な単量体単位の含有量は、好ましくは20重量%以下、さらに好ましくは1〜10重量%である。(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体中のその他の共重合可能な単量体単位の含有量が、上記範囲に含まれることにより、各単量体単位が示す上述の効果を発揮できると共に、本発明の効果であるバインダー及びスラリーの経時安定性に優れ、得られる二次電池のサイクル特性・レート特性共に優れる。 The content of other copolymerizable monomer units with respect to the total amount of the copolymer of (meth) acrylonitrile and (meth) acrylic acid ester constituting the binder is preferably 20% by weight or less, more preferably 1 to 10%. % By weight. When the content of other copolymerizable monomer units in the copolymer of (meth) acrylonitrile and (meth) acrylic acid ester is included in the above range, each monomer unit exhibits the above-described content. In addition to exhibiting the effects, the binder and slurry, which are the effects of the present invention, are excellent in stability over time, and the cycle characteristics and rate characteristics of the obtained secondary battery are excellent.
本発明においては、(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体中にガラス転移温度が25℃以下の成分が含まれることが好ましい。具体的には、成分(A)と成分(B)の少なくとも一方のガラス転移温度が、25℃以下であることが、高い柔軟性を有する電極が得られる為に好ましい。前記ガラス転移温度は、25℃以下であることが好ましく、更に好ましくは15℃以下、特に好ましくは−5℃以下である。 In the present invention, it is preferable that a component having a glass transition temperature of 25 ° C. or less is contained in the copolymer of (meth) acrylonitrile and (meth) acrylic acid ester. Specifically, it is preferable that the glass transition temperature of at least one of the component (A) and the component (B) is 25 ° C. or lower because an electrode having high flexibility can be obtained. The glass transition temperature is preferably 25 ° C. or lower, more preferably 15 ° C. or lower, and particularly preferably −5 ° C. or lower.
なお、(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体中の成分(A)及び成分(B)のガラス転移温度は、(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体のガラス転移温度を測定することで求めることができる。2つの成分のガラス転移温度が大きく異なる場合は、2つの異なるガラス転移温度を測定することができる。2つの成分のガラス転移温度が近い場合は、1つのガラス転移温度として測定され、成分(A)、成分(B)共にほぼ同じガラス転移温度であることを示している。 In addition, the glass transition temperature of the component (A) and the component (B) in the copolymer of (meth) acrylonitrile and (meth) acrylic acid ester is the copolymer weight of (meth) acrylonitrile and (meth) acrylic acid ester. It can be determined by measuring the glass transition temperature of the coalescence. When the glass transition temperatures of the two components are significantly different, two different glass transition temperatures can be measured. When the glass transition temperatures of the two components are close, it is measured as one glass transition temperature, indicating that both the component (A) and the component (B) have substantially the same glass transition temperature.
なお、(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体中の各成分のガラス転移温度は、前記に例示した単量体およびその含有量を適宜に組み合わせることによって調整可能である。 In addition, the glass transition temperature of each component in the copolymer of (meth) acrylonitrile and (meth) acrylic acid ester can be adjusted by appropriately combining the monomers exemplified above and their contents.
本発明において、バインダーを構成する成分(A)はテトラヒドロフランに不溶な成分であり、成分(B)はテトラヒドロフランに可溶な成分である。 In the present invention, the component (A) constituting the binder is a component insoluble in tetrahydrofuran, and the component (B) is a component soluble in tetrahydrofuran.
従って、本発明のバインダー中の各成分中の(メタ)アクリロニトリル単位の含有量は、上記特性を用いて測定することができる。具体的には、バインダーをTHFに溶解させて、THF可溶分とTHF不溶分とに分離し、THF不溶分、THF可溶分、それぞれを、1H−NMR、13C−NMR等で共重合組成を分析することにより求める。 Therefore, the content of (meth) acrylonitrile units in each component in the binder of the present invention can be measured using the above characteristics. Specifically, the binder is dissolved in THF and separated into a THF soluble part and a THF insoluble part, and each of the THF insoluble part and the THF soluble part is shared by 1 H-NMR, 13 C-NMR, etc. It is determined by analyzing the polymerization composition.
本発明の二次電池電極用バインダーを構成する(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体は、上記のような組成の異なる2種以上の成分からなり、前記各成分が相溶してなる。ここでいう相溶とは、上記のような組成の異なる2種以上の各成分からなる(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体がポリマー溶液状態では均一に混ざり合い、ポリマー溶液よりフィルムを作製した際にはミクロ相分離状態をとることをいう。ここで、(メタ)アクリロニトリル・(メタ)アクリル酸エステル共重合体における、ポリマー溶液での相溶状態は、後述の電極用スラリー中に用いられるN−メチルピロリドン(以下、「NMP」と記載することがある。)に溶解させた際のポリマー溶液のヘイズ値により確認できる。また、ポリマー溶液より作製したポリマーフィルムのミクロ相分離状態は、透過型電子顕微鏡(以下、「TEM」と記載することがある)などにより確認できる。本発明においては、(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体をNMPに溶解させたポリマー溶液のヘイズ値が5%以下、ポリマー溶液から作製したフィルムのTEM画像においてドメインが200nm以下である場合に、ポリマー成分が相溶していると判断する。 The copolymer of (meth) acrylonitrile and (meth) acrylic acid ester constituting the binder for a secondary battery electrode of the present invention comprises two or more components having different compositions as described above, and each of the components is a phase. It is melted. The term "compatible" as used herein means that a copolymer of (meth) acrylonitrile and (meth) acrylic acid ester composed of two or more components having different compositions as described above is uniformly mixed in a polymer solution state. When a film is produced from a solution, it means taking a microphase separation state. Here, the compatible state in the polymer solution in the (meth) acrylonitrile / (meth) acrylic acid ester copolymer is described as N-methylpyrrolidone (hereinafter referred to as “NMP”) used in the electrode slurry described later. It can be confirmed by the haze value of the polymer solution when it is dissolved. Further, the microphase separation state of the polymer film prepared from the polymer solution can be confirmed by a transmission electron microscope (hereinafter sometimes referred to as “TEM”). In the present invention, the haze value of a polymer solution prepared by dissolving a copolymer of (meth) acrylonitrile and (meth) acrylic acid ester in NMP is 5% or less, and the domain is 200 nm in the TEM image of the film prepared from the polymer solution. When it is below, it is judged that the polymer component is compatible.
本発明のバインダーは、上記のように、組成の異なる2種以上の(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体が相溶してなり、かつ該共重合体の組成が特定範囲に制御されてなるため、経時安定性に優れる。したがって、かかるバインダーを用いて製造した電極形成用スラリーは、長期間保管しても相分離を起こしにくいため、大量生産及び長期保管が可能であり、電池の製造工程の進行が円滑になり、また得られる電池の品質も一定化する。また製造された電極内においてもバインダーの相溶状態が安定して維持されるため、電極層の柔軟性、結着性や、レート特性、サイクル特性等の電池特性が経時的に劣化することもない。 As described above, the binder of the present invention comprises a copolymer of two or more types of (meth) acrylonitrile and (meth) acrylic acid ester having different compositions, and the composition of the copolymer is specified. Since it is controlled within the range, the stability over time is excellent. Therefore, the electrode-forming slurry produced using such a binder is unlikely to cause phase separation even when stored for a long period of time, so that mass production and long-term storage are possible, and the battery manufacturing process proceeds smoothly. The quality of the battery obtained is also constant. In addition, since the compatibility state of the binder is stably maintained in the manufactured electrode, battery characteristics such as flexibility, binding property, rate characteristics, cycle characteristics, etc. of the electrode layer may deteriorate over time. Absent.
本発明の二次電池電極用バインダーは、上記の組成、性状を有する限り、その製法は特に限定はされないが、ポリマー成分が均一に相溶してなるバインダーを得る上では、特に多段重合法を採用することが有利である。 As long as the binder for secondary battery electrodes of the present invention has the above composition and properties, its production method is not particularly limited, but in order to obtain a binder in which the polymer components are uniformly mixed, a multistage polymerization method is particularly used. It is advantageous to adopt.
具体的には、(メタ)アクリロニトリルの含有量が60重量%以上95重量%である単量体組成物(A)と、(メタ)アクリロニトリルの含有量が5重量%以上40重量%以下である単量体組成物(B)とを多段重合する。本発明において、多段重合とは、単量体組成物の一部をまず重合し、引き続いて種類および/または混合比の異なる単量体組成物を添加して重合することをいう。「引き続いて」重合するとは、前段の重合工程において単量体が残存した状態、すなわち重合転化率が100%にならない時点で次段の重合を行うことをいう。 Specifically, the monomer composition (A) having a (meth) acrylonitrile content of 60 wt% or more and 95 wt% and the (meth) acrylonitrile content of 5 wt% or more and 40 wt% or less. Multi-stage polymerization is performed with the monomer composition (B). In the present invention, the multistage polymerization means that a part of the monomer composition is polymerized first, and then monomer compositions having different types and / or mixing ratios are added and polymerized. “Subsequently” polymerization means that the monomer is left in the previous polymerization step, that is, the polymerization of the next stage is performed when the polymerization conversion rate does not reach 100%.
多段重合は、重合系内の単量体組成、重合条件などの異なる二段階以上の重合工程を含む。本発明では、二段階または三段階で行うことが好ましく、特に二段階で行うことがより好ましい。四段階以上で行うと、工程が煩雑になり生産性が低下するおそれがある。以下、多段重合を二段階で行いバインダーを調製する工程について説明する。 Multi-stage polymerization includes two or more stages of polymerization processes in which the monomer composition and polymerization conditions in the polymerization system are different. In the present invention, it is preferably performed in two or three stages, and more preferably in two stages. If it is carried out in four or more stages, the process becomes complicated and the productivity may be lowered. Hereinafter, a process for preparing a binder by performing multistage polymerization in two stages will be described.
二段階で重合を行う場合は、前記成分(A)を主たる生成物とする重合工程と、前記成分(B)を主たる生成物とする重合工程とを含む多段重合であることが好ましく、成分(A)を主たる生成物とする一段目の重合工程と、引き続いて成分(B)を主たる生成物とする二段目の重合工程とを有する多段重合であることが、最終的に得られる共重合体の反応率が高いためにより好ましい。以下の説明では、一段目の重合で主として成分(A)生成し、二段目の重合で主として成分(B)を生成する場合について述べる。 In the case of carrying out the polymerization in two stages, it is preferably a multistage polymerization including a polymerization step in which the component (A) is a main product and a polymerization step in which the component (B) is a main product. The co-polymer finally obtained is a multi-stage polymerization having a first-stage polymerization step with A) as the main product and a second-stage polymerization step with component (B) as the main product. It is more preferable because the reaction rate of coalescence is high. In the following description, a case where the component (A) is mainly produced by the first stage polymerization and the component (B) is mainly produced by the second stage polymerization will be described.
一段目における重合では、(メタ)アクリロニトリル、(メタ)アクリル酸エステルおよび必要に応じその他の単量体成分を重合系に供給し、主として成分(A)生成する。一段目の重合系に供給される単量体組成物(単量体組成物(A))は、上述の成分(A)に含まれる単量体組成物から選ばれる。同時に過硫酸カリウムなどの重合開始剤を供給し、60℃程度に加温して単量体組成物(A)を重合し、主として成分(A)を生成する。一段目の重合工程における単量体組成物(A)の重合転化率は、好ましくは60〜97重量%、より好ましくは65〜97重量%、さらに好ましくは70〜95重量%である。一段目の重合工程における重合転化率が所定値に到達した時点で、成分(B)の単量体組成にほぼ等しい単量体組成物(B)を重合系に供給し、重合を継続する。単量体組成物(B)は、上述の成分(A)に含まれる単量体組成物から選ばれる。二段目の重合工程における単量体組成物(B)の重合転化率は、好ましくは90重量%以上、より好ましくは95重量%以上である。 In the polymerization in the first stage, (meth) acrylonitrile, (meth) acrylic acid ester and other monomer components as required are supplied to the polymerization system to mainly produce component (A). The monomer composition (monomer composition (A)) supplied to the first stage polymerization system is selected from the monomer compositions contained in the component (A). At the same time, a polymerization initiator such as potassium persulfate is supplied and heated to about 60 ° C. to polymerize the monomer composition (A) to mainly produce the component (A). The polymerization conversion rate of the monomer composition (A) in the first polymerization step is preferably 60 to 97% by weight, more preferably 65 to 97% by weight, and further preferably 70 to 95% by weight. When the polymerization conversion rate in the first stage polymerization process reaches a predetermined value, the monomer composition (B) substantially equal to the monomer composition of the component (B) is supplied to the polymerization system, and the polymerization is continued. The monomer composition (B) is selected from the monomer compositions contained in the component (A) described above. The polymerization conversion rate of the monomer composition (B) in the second polymerization step is preferably 90% by weight or more, more preferably 95% by weight or more.
重合系内に供給される、単量体組成物(A)と単量体組成物(B)との重量比(A/B)は、前記成分(A)と成分(B)との重量比にほぼ等しく、単量体組成物(A)/単量体組成物(B)は、20/80重量%〜80/20重量%、好ましくは30/70重量%〜70/30重量%、さらに好ましくは40/60重量%〜60/40重量%、である。 The weight ratio (A / B) between the monomer composition (A) and the monomer composition (B) supplied into the polymerization system is the weight ratio between the component (A) and the component (B). The monomer composition (A) / monomer composition (B) is 20/80 wt% to 80/20 wt%, preferably 30/70 wt% to 70/30 wt%, Preferably, it is 40/60 wt% to 60/40 wt%.
重合開始剤としては、慣用の成分、例えば、アゾ系重合開始剤[例えば、アゾビスニトリル(例えば、2,2’−アゾビスイソブチロニトリル(AIBN)などの2,2’−アゾビスブチロニトリル類;2,2’−アゾビス(2,4−ジメチルバレロニトリル)などの2,2’−アゾビスバレロニトリル類;2,2’−アゾビス(2−ヒドロキシメチルプロピオニトリル)などの2,2’−アゾビスプロピオニトリル類;1,1’−アゾビスシクロヘキサン−1−カルボニトリルなどの1,1’−アゾビス−1−シクロアルカンニトリル類;4,4’−アゾビス(4−シアノ吉草酸)などのアゾビスシアノカルボン酸など)、アゾニトリル(例えば、2−(カルバモイルアゾ)イソブチロニトリルなどのアゾブチロニトリル類;2−フェニルアゾ−4−メトキシ−2,4−ジメチルバレロニトリルなどのアゾバレロニトリル類など)など];パーオキサイド系重合開始剤[例えば、シクロヘキサノンパーオキサイド、3,3,5−トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイドなどのケトンパーオキサイド類、1,1−ビス(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、1,1−ビス(t−ブチルパーオキシ)シクロヘキサン、n−ブチル−4,4−ビス(t−ブチルパーオキシ)バレートなどのパーオキシケタール類、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、2,5−ジメチルヘキサン−2,5−ジハイドロパーオキサイドなどのハイドロパーオキサイド類、ジ−t−ブチルパーオキサイド、ジクミルパーオキサイド、t−ブチルクミルパーオキサイド、α,α’−ビス(t−ブチルパーオキシ−m−イソプロピル)ベンゼン、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキシン−3などのジアルキルパーオキサイド類、ベンゾイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、2,4−ジクロロベンゾイルパーオキサイドなどのジアシルパーオキサイド類、ビス(t−ブチルシクロヘキシル)パーオキシジカーボネートなどのパーオキシカーボネート類、t−ブチルパーオキシベンゾエート、2,5−ジメチル−2,5−ジ(ベンゾイルパーオキシ)ヘキサンなどのパーオキシエステル類など有機過酸化物;過酸化水素、過硫酸塩(過硫酸カリウム、過硫酸アンモニウムなど)などの無機過酸化物など]が例示できる。このような重合開始剤は、一種又は二種以上組み合わせて使用できる。 Examples of the polymerization initiator include conventional components such as an azo polymerization initiator [for example, 2,2′-azobisbutyric acid such as azobisnitrile (for example, 2,2′-azobisisobutyronitrile (AIBN)). Ronitriles; 2,2′-azobisvaleronitriles such as 2,2′-azobis (2,4-dimethylvaleronitrile); 2 such as 2,2′-azobis (2-hydroxymethylpropionitrile) 2,1'-azobispropionitriles; 1,1'-azobis-1-cycloalkanenitriles such as 1,1'-azobiscyclohexane-1-carbonitrile; 4,4'-azobis (4-cyano Azobiscyanocarboxylic acids such as valeric acid), azobutyronitriles such as azonitrile (eg 2- (carbamoylazo) isobutyronitrile; 2-phenyl Azovaleronitriles such as zo-4-methoxy-2,4-dimethylvaleronitrile)]; peroxide-based polymerization initiators [for example, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone Ketone peroxides such as peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, n-butyl-4 , 4-bis (t-butylperoxy) valate and other peroxyketals, cumene hydroperoxide, diisopropylbenzene hydroperoxide, hydroperoxide such as 2,5-dimethylhexane-2,5-dihydroperoxide Ji-t-B Ruperoxide, dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxide) Dialkyl peroxides such as oxy) hexyne-3, diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, bis (t-butylcyclohexyl) peroxydi Peroxycarbonates such as carbonates, organic peroxides such as peroxyesters such as t-butylperoxybenzoate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane; hydrogen peroxide, persulfuric acid Salt (potassium persulfate, ammonium persulfate) Beam, etc.) inorganic peroxides etc.] can be exemplified. Such polymerization initiators can be used alone or in combination.
重合開始剤の使用量は、特に制限されず、例えば、モノマーの合計100重量部に対して、0.1〜10重量部、好ましくは1〜5重量部程度である。 The usage-amount of a polymerization initiator is not restrict | limited in particular, For example, it is 0.1-10 weight part with respect to a total of 100 weight part of monomers, Preferably it is about 1-5 weight part.
重合温度としては、通常、50℃〜120℃、好ましくは60℃〜90℃程度の範囲から選択できる。なお、重合反応は、不活性ガス(例えば、窒素ガス、ヘリウムガス)雰囲気中で行うことができる。 The polymerization temperature can usually be selected from the range of about 50 ° C to 120 ° C, preferably about 60 ° C to 90 ° C. The polymerization reaction can be performed in an inert gas (for example, nitrogen gas, helium gas) atmosphere.
重合溶媒は、水であってもよく、また有機溶媒であってもよい。有機溶媒は1種類とは限らず、複数種類の有機溶媒による混合溶媒としてもよい。具体的には、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素類、メタノール、エタノール、n−プロパノール、イソプロパノール、tert−ブチルアルコール等の炭化水素系アルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等の炭化水素系ケトン類、ジメチルエーテル、ジエチルエーテル、メチルエチルエーテル、メチルtert−ブチルエーテル、ジエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル等の炭化水素系エーテル類、テトラヒドロフラン、1,4−ジオキサン等の環状脂肪族炭化水素系エーテル類、アセトニトリル等のニトリル類、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸tert−ブチル、プロピオン酸メチル、プロピオン酸エチル等の炭化水素系エステル類、トルエン、キシレン等の芳香族炭化水素類、塩化メチレン、クロロホルム、四塩化炭素等の塩化炭化水素類、1,1,2−トリクロロ−1,2,2−トリフルオロエタン(R−113)、1,1,1−トリクロロ−2,2,2−トリフルオロエタン(R−113a)、1,1−ジクロロ−1−フルオロエタン(R−141b)、3,3−ジクロロ−1,1,1,2,2−ペンタフルオロプロパン(R−225ca)、1,3−ジクロロ−1,1,2,2,3−ペンタフルオロプロパン(R−225cb)等のフッ化塩化炭化水素類、1,1,1,2,2,3,3,4,4,5,5,6,6−トリデカフルオロヘキサン、1,1,1,2,2,3,3,4,4−ノナフルオロヘキサンなどのフッ化炭化水素類、メチル−2,2,3,3−テトラフルオロエチルエーテル等のフッ化炭化水素系エーテル類、2,2,2−トリフルオロエタノール、1,1,1,3,3,3−ヘキサフルオロイソプロパノール、2,2,3,3−テトラフルオロプロパノール、2,2,3,3,4,4,5,5−オクタフルオロペンタノール等のフッ化炭化水素系アルコール類が挙げられるが、これらに限定されるものではない。 The polymerization solvent may be water or an organic solvent. The organic solvent is not limited to one type, and may be a mixed solvent of a plurality of types of organic solvents. Specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, hydrocarbon alcohols such as methanol, ethanol, n-propanol, isopropanol, tert-butyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Hydrocarbon ketones such as dimethyl ether, diethyl ether, methyl ethyl ether, methyl tert-butyl ether, hydrocarbon ethers such as diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether, and cyclic aliphatic hydrocarbons such as tetrahydrofuran and 1,4-dioxane Ethers, nitriles such as acetonitrile, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, tert-butyl acetate, propio Hydrocarbon esters such as methyl acid and ethyl propionate, aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, 1,1,2-trichloro-1, 2,2-trifluoroethane (R-113), 1,1,1-trichloro-2,2,2-trifluoroethane (R-113a), 1,1-dichloro-1-fluoroethane (R-141b) ), 3,3-dichloro-1,1,1,2,2-pentafluoropropane (R-225ca), 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R-225cb) ), Etc., 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, 1,1,1,2,2 , 3,3,4,4-Nonafluorohexa Fluorinated hydrocarbons such as methyl-2,2,3,3-tetrafluoroethyl ether, fluorinated hydrocarbon ethers such as 2,2,2-trifluoroethanol, 1,1,1,3 Fluorinated hydrocarbon alcohols such as 3,3-hexafluoroisopropanol, 2,2,3,3-tetrafluoropropanol, 2,2,3,3,4,4,5,5-octafluoropentanol Although it is mentioned, it is not limited to these.
このような多段重合により、ポリマー成分が均一に相溶してなる本発明のバインダーが得られる。 By such multistage polymerization, the binder of the present invention in which the polymer components are uniformly mixed is obtained.
本発明のバインダーの重合方法は特に限定されず、乳化重合法、懸濁重合法、分散重合法、または溶液重合法などの公知の重合法が採用できる。中でも、乳化重合法が好ましい。 The polymerization method of the binder of the present invention is not particularly limited, and a known polymerization method such as an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, or a solution polymerization method can be employed. Of these, emulsion polymerization is preferred.
また、本発明のバインダーを形成する(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体は、有機溶媒に溶解しうる。ここで、有機溶媒とは溶液重合により得られた重合体液をそのまま使用する場合には、重合溶媒を意味し、また溶媒置換して使用する場合には、置換溶媒を意味する。
本発明の目的を阻害しない範囲であれば、本発明のバインダーに、PVDF、PTFEやゴム質重合体などの従来のバインダーを併用することは可能である。
Moreover, the copolymer of (meth) acrylonitrile and (meth) acrylic acid ester forming the binder of the present invention can be dissolved in an organic solvent. Here, the organic solvent means a polymerization solvent when the polymer liquid obtained by solution polymerization is used as it is, and a substitution solvent when used after solvent substitution.
It is possible to use a conventional binder such as PVDF, PTFE or rubbery polymer in combination with the binder of the present invention as long as the object of the present invention is not impaired.
2.二次電池電極用スラリー
本発明の二次電池電極用スラリーは、上記二次電池電極用バインダー、電極活物質、および溶媒を含んでなる。
2. Secondary Battery Electrode Slurry The secondary battery electrode slurry of the present invention comprises the above secondary battery electrode binder, an electrode active material, and a solvent.
リチウムイオン二次電池正極用の電極活物質(正極活物質)は、リチウムイオンの吸蔵放出可能な活物質が用いられ、無機化合物からなるものと有機化合物からなるものとに大別される。 An electrode active material (positive electrode active material) for a lithium ion secondary battery positive electrode uses an active material capable of occluding and releasing lithium ions, and is broadly classified into an inorganic compound and an organic compound.
無機化合物からなる正極活物質としては、遷移金属酸化物、遷移金属硫化物、リチウムと遷移金属とのリチウム含有複合金属酸化物などが挙げられる。上記の遷移金属としては、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Mo等が使用される。
遷移金属酸化物としては、MnO、MnO2、V2O5、V6O13、TiO2、Cu2V2O3、非晶質V2O−P2O5、MoO3、V2O5、V6O13等が挙げられ、中でもサイクル安定性と容量からMnO、V2O5、V6O13、TiO2が好ましい。
Examples of the positive electrode active material made of an inorganic compound include transition metal oxides, transition metal sulfides, lithium-containing composite metal oxides of lithium and transition metals, and the like. Examples of the transition metal include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Mo.
Examples of transition metal oxides include MnO, MnO 2 , V 2 O 5 , V 6 O 13 , TiO 2 , Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , MoO 3 , V 2 O. 5 , V 6 O 13 and the like. Among them, MnO, V 2 O 5 , V 6 O 13 and TiO 2 are preferable from the viewpoint of cycle stability and capacity.
遷移金属硫化物としては、TiS2、TiS3、非晶質MoS2、FeS等が挙げられる。 The transition metal sulfide, TiS 2, TiS 3, amorphous MoS 2, FeS, and the like.
リチウム含有複合金属酸化物としては、層状構造を有するリチウム含有複合金属酸化物、スピネル構造を有するリチウム含有複合金属酸化物、オリビン型構造を有するリチウム含有複合金属酸化物などが挙げられる。 Examples of the lithium-containing composite metal oxide include a lithium-containing composite metal oxide having a layered structure, a lithium-containing composite metal oxide having a spinel structure, and a lithium-containing composite metal oxide having an olivine structure.
層状構造を有するリチウム含有複合金属酸化物としてはリチウム含有コバルト酸化物(LiCoO2)、リチウム含有ニッケル酸化物(LiNiO2)、Co−Ni−Mnのリチウム複合酸化物、Ni−Mn−Alのリチウム複合酸化物、Ni−Co−Alのリチウム複合酸化物等が挙げられる。 Examples of the lithium-containing composite metal oxide having a layered structure include lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), Co—Ni—Mn lithium composite oxide, and Ni—Mn—Al lithium. Examples thereof include composite oxides and lithium composite oxides of Ni—Co—Al.
スピネル構造を有するリチウム含有複合金属酸化物としてはマンガン酸リチウム(LiMn2O4)やMnの一部を他の遷移金属で置換したLi[Mn3/2M1/2]O4(ここでMは、Cr、Fe、Co、Ni、Cu等)等が挙げられる。 Examples of lithium-containing composite metal oxides having a spinel structure include lithium manganate (LiMn 2 O 4 ) and Li [Mn 3/2 M 1/2 ] O 4 in which a part of Mn is substituted with another transition metal (here M may be Cr, Fe, Co, Ni, Cu or the like.
オリビン型構造を有するリチウム含有複合金属酸化物としてはLiXMPO4(式中、Mは、Mn,Fe,Co,Ni,Cu,Mg,Zn,V,Ca,Sr,Ba,Ti,Al,Si,B及びMoから選ばれる少なくとも1種、0≦X≦2)であらわされるオリビン型燐酸リチウム化合物が挙げられる。 LiXMPO 4 (wherein, M is Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, LiXMPO 4 as the lithium-containing composite metal oxide having an olivine structure) An olivine type lithium phosphate compound represented by at least one selected from B and Mo, 0 ≦ X ≦ 2).
上記活物質の中でも、リチウム含有ニッケル酸化物(LiNiO2)、Co−Ni−Mnのリチウム複合酸化物、Ni−Mn−Alのリチウム複合酸化物、Ni−Co−Alのリチウム複合酸化物等のニッケル含有の活物質を用いることが好ましい。前記ニッケル含有の活物質は、本バインダーとの結着性に特に優れ、高いレート特性が得られる。 Among the above active materials, lithium-containing nickel oxide (LiNiO 2 ), Co—Ni—Mn lithium composite oxide, Ni—Mn—Al lithium composite oxide, Ni—Co—Al lithium composite oxide, etc. It is preferable to use a nickel-containing active material. The nickel-containing active material is particularly excellent in binding properties with the binder, and high rate characteristics are obtained.
有機化合物からなる正極活物質としては、例えば、ポリアニリン、ポリピロール、ポリアセン、ジスルフィド系化合物、ポリスルフィド系化合物、N−フルオロピリジニウム塩などが挙げられる。正極活物質は、上記の無機化合物と有機化合物の混合物であってもよい。本発明で用いる正極活物質の粒子径は、電池の他の構成要件との兼ね合いで適宜選択されるが、負荷特性、サイクル特性などの電池特性の向上の観点から、50%体積累積径が、通常0.1〜50μm、好ましくは1〜20μmである。50%体積累積径がこの範囲であると、充放電容量が大きい二次電池を得ることができ、かつ電極用スラリーおよび電極を製造する際の取扱いが容易である。50%体積累積径は、レーザー回折で粒度分布を測定することにより求めることができる。 Examples of the positive electrode active material made of an organic compound include polyaniline, polypyrrole, polyacene, disulfide compounds, polysulfide compounds, and N-fluoropyridinium salts. The positive electrode active material may be a mixture of the above inorganic compound and organic compound. The particle diameter of the positive electrode active material used in the present invention is appropriately selected in consideration of other constituent elements of the battery. From the viewpoint of improving battery characteristics such as load characteristics and cycle characteristics, the 50% volume cumulative diameter is Usually, it is 0.1-50 micrometers, Preferably it is 1-20 micrometers. When the 50% volume cumulative diameter is within this range, a secondary battery having a large charge / discharge capacity can be obtained, and handling of the slurry for electrodes and the electrodes is easy. The 50% volume cumulative diameter can be determined by measuring the particle size distribution by laser diffraction.
負極用の電極活物質(負極活物質)としては、グラファイトやコークス等の炭素の同素体が挙げられる。前記炭素の同素体からなる活物質は、金属、金属塩、酸化物などとの混合体や被覆体の形態で利用することもできる。また、負極活物質としては、ケイ素、錫、亜鉛、マンガン、鉄、ニッケル等の酸化物や硫酸塩、金属リチウム、Li−Al、Li−Bi−Cd、Li−Sn−Cd等のリチウム合金、リチウム遷移金属窒化物、シリコン等を使用できる。負極活物質の粒径は、電池の他の構成要件との兼ね合いで適宜選択されるが、初期効率、負荷特性、サイクル特性などの電池特性の向上の観点から、50%体積累積径が、通常1〜50μm、好ましくは15〜30μmである。 Examples of the electrode active material for the negative electrode (negative electrode active material) include carbon allotropes such as graphite and coke. The active material composed of the allotrope of carbon can be used in the form of a mixture with a metal, a metal salt, an oxide, or the like or a cover. Moreover, as a negative electrode active material, lithium alloys, such as oxides and sulfates, such as silicon, tin, zinc, manganese, iron, nickel, lithium metal, Li-Al, Li-Bi-Cd, Li-Sn-Cd, Lithium transition metal nitride, silicon, etc. can be used. The particle diameter of the negative electrode active material is appropriately selected in consideration of other constituent elements of the battery. From the viewpoint of improving battery characteristics such as initial efficiency, load characteristics, and cycle characteristics, a 50% volume cumulative diameter is usually The thickness is 1 to 50 μm, preferably 15 to 30 μm.
電極活物質と上記バインダーの量の割合は、電極活物質100重量部に対し、バインダーが、通常0.1〜30重量部、好ましくは0.2〜20重量部、より好ましくは0.5〜10重量部である。バインダーの量がこの範囲であると、得られる電極は集電体と電極活物質層と、および活物質層内部での結着力に優れ、かつ、内部抵抗が小さくサイクル特性の優れる電池を得ることができる。 The ratio of the amount of the electrode active material and the binder is generally 0.1 to 30 parts by weight, preferably 0.2 to 20 parts by weight, more preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the electrode active material. 10 parts by weight. When the amount of the binder is within this range, the obtained electrode has a current collector, an electrode active material layer, and an excellent binding force inside the active material layer, and a battery with low internal resistance and excellent cycle characteristics can be obtained. Can do.
本発明の二次電池電極用スラリーは、電極活物質および上記バインダーの他に、必要に応じ、増粘剤、導電材、補強材、分散剤、レベリング剤、電解液添加剤などの各種の機能を発現する添加剤を含有させることができる。 In addition to the electrode active material and the binder, the slurry for the secondary battery electrode of the present invention has various functions such as a thickener, a conductive material, a reinforcing material, a dispersing agent, a leveling agent, and an electrolytic solution additive as necessary. The additive which expresses can be contained.
増粘剤としては、カルボキシメチルセルロース、メチルセルロース、ヒドロキシプロピルセルロースなどのセルロース系ポリマーおよびこれらのアンモニウム塩並びにアルカリ金属塩;(変性)ポリ(メタ)アクリル酸およびこれらのアンモニウム塩並びにアルカリ金属塩;(変性)ポリビニルアルコール、アクリル酸又はアクリル酸塩とビニルアルコールの共重合体、無水マレイン酸又はマレイン酸もしくはフマル酸とビニルアルコールの共重合体などのポリビニルアルコール類;ポリエチレングリコール、ポリエチレンオキシド、ポリビニルピロリドン、変性ポリアクリル酸、酸化スターチ、リン酸スターチ、カゼイン、各種変性デンプンなどが挙げられ、好ましくはカルボキシメチルセルロースのアンモニウム塩並びにアルカリ金属塩が用いられる。これは上記増粘剤がスラリー作製時に活物質の表面を均一に覆いやすいため、活物質間の接着を向上させる効果があるためである。増粘剤としては、上記以外に、アクリロニトリル−ブタジエン共重合体水素化物も用いることができる。 Examples of thickeners include cellulosic polymers such as carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, and ammonium salts and alkali metal salts thereof; (modified) poly (meth) acrylic acid and ammonium salts and alkali metal salts thereof; ) Polyvinyl alcohols such as polyvinyl alcohol, copolymers of acrylic acid or acrylate and vinyl alcohol, maleic anhydride or copolymers of maleic acid or fumaric acid and vinyl alcohol; polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, modified Examples include polyacrylic acid, oxidized starch, phosphoric acid starch, casein, various modified starches, and preferably ammonium salts and alkali metal salts of carboxymethyl cellulose. Used. This is because the thickener is easy to cover the surface of the active material uniformly during slurry preparation, and thus has an effect of improving the adhesion between the active materials. As the thickener, acrylonitrile-butadiene copolymer hydride can also be used in addition to the above.
増粘剤の配合量は、電極活物質100重量部に対して、0.5〜2.0重量部が好ましい。増粘剤の配合量がこの範囲であると、塗工性、集電体との密着性が良好である。 As for the compounding quantity of a thickener, 0.5-2.0 weight part is preferable with respect to 100 weight part of electrode active materials. When the blending amount of the thickener is within this range, the coating property and the adhesion with the current collector are good.
導電材としては、アセチレンブラック、ケッチェンブラック、カーボンブラック、グラファイト、気相成長カーボン繊維、およびカーボンナノチューブ等の導電性カーボンを使用することができる。導電材を用いることにより、活物質同士の電気的接触を向上させることができ、二次電池に用いる場合に放電レート特性を改善することができる。導電材の配合量は、電極活物質100重量部に対して通常0〜20重量部、好ましくは1〜10重量部である。 As the conductive material, conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor-grown carbon fiber, and carbon nanotube can be used. By using the conductive material, the electrical contact between the active materials can be improved, and the discharge rate characteristics can be improved when used for a secondary battery. The compounding amount of the conductive material is usually 0 to 20 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the electrode active material.
補強材としては、各種の無機および有機の球状、板状、棒状または繊維状のフィラーが使用できる。補強材を用いることにより強靭で柔軟な負極を得ることができ、優れた長期サイクル特性を示すことができる。補強剤の配合量は、電極活物質100重量部に対して通常0.01〜20重量部、好ましくは1〜10重量部である。前記範囲に含まれることにより、高い容量と高い負荷特性を示すことができる。 As the reinforcing material, various inorganic and organic spherical, plate-like, rod-like or fibrous fillers can be used. By using a reinforcing material, a tough and flexible negative electrode can be obtained, and excellent long-term cycle characteristics can be exhibited. The compounding quantity of a reinforcing agent is 0.01-20 weight part normally with respect to 100 weight part of electrode active materials, Preferably it is 1-10 weight part. By being included in the said range, a high capacity | capacitance and a high load characteristic can be shown.
分散剤としてはアニオン性化合物、カチオン性化合物、非イオン性化合物、高分子化合物が例示される。分散剤は用いる電極活物質や導電剤に応じて選択される。電極用スラリー中の分散剤の含有割合は、電極活物質の総量100重量部に対して0.01〜10重量部であることが好ましい。分散剤量が上記範囲であることによりスラリーの安定性に優れ、平滑な負極を得ることができ、高い電池容量を示すことができる。 Examples of the dispersant include an anionic compound, a cationic compound, a nonionic compound, and a polymer compound. A dispersing agent is selected according to the electrode active material and electrically conductive agent to be used. The content of the dispersing agent in the electrode slurry is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the electrode active material. When the amount of the dispersant is in the above range, the slurry has excellent stability, a smooth negative electrode can be obtained, and a high battery capacity can be exhibited.
レベリング剤としては、アルキル系界面活性剤、シリコン系界面活性剤、フッ素系界面活性剤、金属系界面活性剤などの界面活性剤が挙げられる。前記レベリング剤を混合することにより、塗工時に発生するはじきを防止したり、電極の平滑性を向上させることができる。電極用スラリー中のレベリング剤の含有割合は、電極活物質の総量100重量部に対して、好ましくは0.01〜10重量部である。レベリング剤が上記範囲であることにより電極作製時の生産性、平滑性及び電池特性に優れる。 Examples of the leveling agent include surfactants such as alkyl surfactants, silicon surfactants, fluorine surfactants, and metal surfactants. By mixing the leveling agent, the repelling that occurs during coating can be prevented, and the smoothness of the electrode can be improved. The content ratio of the leveling agent in the electrode slurry is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the electrode active material. When the leveling agent is within the above range, the productivity, smoothness, and battery characteristics during electrode production are excellent.
電解液添加剤としては、電極用スラリー中及び電解液中に使用されるビニレンカーボネートなどを用いることができる。電極用スラリー中の電解液添加剤の含有割合は、電極活物質100重量部に対して、好ましくは0.01〜10重量部である。電解液添加剤が、上記範囲であることによりサイクル特性及び高温特性に優れる。その他には、フュームドシリカやフュームドアルミナなどのナノ微粒子が挙げられる。前記ナノ微粒子を混合することにより電極用スラリーのチキソ性をコントロールすることができ、さらにそれにより得られる電極のレベリング性を向上させることができる。電極用スラリー中のナノ微粒子及の含有割合は、電極活物質100重量部に対して、好ましくは0.01〜10重量部である。ナノ微粒子が上記範囲であることによりスラリー安定性、生産性に優れ、高い電池特性を示す。 As the electrolytic solution additive, vinylene carbonate used in the electrode slurry and the electrolytic solution can be used. The content ratio of the electrolyte additive in the electrode slurry is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the electrode active material. When the electrolytic solution additive is in the above range, the cycle characteristics and the high temperature characteristics are excellent. Other examples include nanoparticles such as fumed silica and fumed alumina. By mixing the nanoparticles, the thixotropy of the electrode slurry can be controlled, and the leveling property of the resulting electrode can be improved. The content ratio of the nanoparticles and the like in the electrode slurry is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the electrode active material. When the nanoparticles are in the above range, the slurry stability and productivity are excellent, and high battery characteristics are exhibited.
さらに、本発明の二次電池電極用スラリーには、電池の安定性や寿命を高めるため、トリフルオロプロピレンカーボネート、ビニレンカーボネート、カテコールカーボネート、1,6−ジオキサスピロ[4,4]ノナン−2,7−ジオン、12−クラウン−4−エーテル等が使用できる。また、これらは後述する電解液に含有せしめて用いてもよい。 Furthermore, the secondary battery electrode slurry of the present invention includes trifluoropropylene carbonate, vinylene carbonate, catechol carbonate, 1,6-dioxaspiro [4,4] nonane-2,7 in order to increase the stability and life of the battery. -Dione, 12-crown-4-ether, etc. can be used. These may be used by being contained in an electrolyte solution described later.
二次電池電極用スラリーにおける有機溶媒の量は、電極活物質やバインダーなどの種類に応じ、塗工に好適な粘度になるように調整して用いる。具体的には、電極活物質、バインダーおよび他の添加剤を合わせた固形分の濃度が、好ましくは30〜90重量%、より好ましくは40〜80重量%となる量に調整して用いられる。 The amount of the organic solvent in the secondary battery electrode slurry is adjusted so as to have a viscosity suitable for coating depending on the type of electrode active material, binder, and the like. Specifically, the solid content concentration of the electrode active material, the binder, and other additives is preferably adjusted to 30 to 90% by weight, more preferably 40 to 80% by weight.
電極用スラリーは、二次電池電極用バインダー、電極活物質、必要に応じ添加される添加剤、およびその他の有機溶媒を、混合機を用いて混合して得られる。混合は、上記の各成分を一括して混合機に供給し、混合してもよいが、導電材および増粘剤を有機溶媒中で混合して導電材を微粒子状に分散させ、次いで二次電池電極用バインダー、電極活物質を添加して、さらに混合することがスラリーの分散性が向上するので好ましい。混合機としては、ボールミル、サンドミル、顔料分散機、擂潰機、超音波分散機、ホモジナイザー、プラネタリーミキサー、ホバートミキサーなどを用いることができるが、ボールミルを用いると導電材、電極活物質の凝集を抑制できるので好ましい。 The electrode slurry is obtained by mixing a secondary battery electrode binder, an electrode active material, an additive added as necessary, and other organic solvents using a mixer. Mixing may be performed by supplying the above components all at once to the mixer and mixing them. However, the conductive material and the thickener are mixed in an organic solvent to disperse the conductive material in the form of fine particles. It is preferable to add a battery electrode binder and an electrode active material and further mix them, because the dispersibility of the slurry is improved. As the mixer, a ball mill, sand mill, pigment disperser, crusher, ultrasonic disperser, homogenizer, planetary mixer, Hobart mixer, etc. can be used. Is preferable.
本発明の二次電池電極用スラリーの粒度は、好ましくは35μm以下であり、さらに好ましくは25μm以下である。スラリーの粒度が上記範囲にあると、導電材の分散性が高く、均質な電極が得られる。 The particle size of the slurry for secondary battery electrodes of the present invention is preferably 35 μm or less, more preferably 25 μm or less. When the particle size of the slurry is in the above range, the conductive material is highly dispersible and a homogeneous electrode can be obtained.
3.二次電池電極
本発明の二次電池電極は、金属箔などの集電体に本発明の二次電池電極用スラリーを付着させたものである。かかる二次電池電極の製造法としては、例えば、上記のスラリーを集電体に塗布し、乾燥する方法などがあげられる。電極には、電極活物質が集電体表面に形成されたバインダー中に分散して固定される。
3. Secondary battery electrode The secondary battery electrode of the present invention is obtained by attaching the slurry for the secondary battery electrode of the present invention to a current collector such as a metal foil. Examples of a method for producing such a secondary battery electrode include a method in which the slurry is applied to a current collector and dried. The electrode active material is dispersed and fixed to the electrode in a binder formed on the current collector surface.
集電体は、導電性を有するものであれば限定されないが、通常、アルミ箔や銅箔などの金属箔が使用される。金属箔の厚さは特に限定されないが、通常1〜50μm好ましくは1〜30μmである。集電体の厚さが薄過ぎる場合は、機械的強度が弱くなり、破断、皺よりが発生しやすいといった生産上の問題を生じる場合があり、厚過ぎる場合は、電池全体としての容量が低下する傾向となる。集電体は、電極活物質層との接着強度を高めるため、その表面が粗面化処理されたものが好ましい。粗面化方法としては、機械的研磨法、電解研磨法、化学研磨法などが挙げられる。機械的研磨法においては、研磨剤粒子を固着した研磨布紙、砥石、エメリバフ、鋼線などを備えたワイヤーブラシ等が使用される。また、電極活物質層との接着強度や導電性を高めるために、集電体表面に中間層を形成してもよい。 The current collector is not limited as long as it has conductivity, but metal foil such as aluminum foil and copper foil is usually used. Although the thickness of metal foil is not specifically limited, Usually, 1-50 micrometers, Preferably it is 1-30 micrometers. If the current collector is too thin, the mechanical strength will be weakened, which may cause production problems such as breakage and wrinkling, and if it is too thick, the capacity of the battery as a whole will decrease. Tend to. In order to increase the adhesive strength with the electrode active material layer, the current collector is preferably one whose surface is roughened. Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method. In the mechanical polishing method, an abrasive cloth paper with a fixed abrasive particle, a grindstone, an emery buff, a wire brush provided with a steel wire or the like is used. Further, an intermediate layer may be formed on the current collector surface in order to increase the adhesive strength and conductivity with the electrode active material layer.
スラリーの集電体への塗布方法は特に制限されない。例えば、ドクターブレード法、ディップ法、リバースロール法、ダイレクトロール法、グラビア法、エクストルージョン法、ハケ塗りなどによって塗布される。塗布する量も特に制限されないが、有機溶媒を除去した後に形成される電極活物質層の厚さが通常0.005〜5mm、好ましくは0.01〜2mmになる程度の量である。乾燥方法も特に制限されず、例えば温風、熱風、低湿風による乾燥、真空乾燥、(遠)赤外線や電子線などの照射による乾燥が挙げられる。乾燥条件は、通常は応力集中が起こって電極活物質層に亀裂が入ったり、電極活物質層が集電体から剥離しない程度の速度範囲の中で、できるだけ早く液状媒体が揮発するように調整する。 The method for applying the slurry to the current collector is not particularly limited. For example, it is applied by a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating, or the like. The amount to be applied is not particularly limited, but is an amount such that the thickness of the electrode active material layer formed after removing the organic solvent is usually 0.005 to 5 mm, preferably 0.01 to 2 mm. The drying method is not particularly limited, and examples thereof include drying with warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams. The drying conditions are adjusted so that the liquid medium volatilizes as soon as possible within a speed range that normally prevents stress concentration from causing cracks in the electrode active material layer or peeling of the electrode active material layer from the current collector. To do.
更に、乾燥後の集電体をプレスすることにより電極を安定させてもよい。プレス方法は、金型プレスやカレンダープレスなどの方法が挙げられる。 Further, the electrode may be stabilized by pressing the current collector after drying. Examples of the pressing method include a mold press and a calendar press.
本発明の二次電池電極は、高い密度であることが好ましい。高い密度であるほど本発明の効果が高く得られる。電極の密度は、用いる活物質材料とその混合比によって決まるが、例えば正極活物質であるLiCoO2を用いて、その混合比が90重量%以上である場合においては、3.7g/cc以上の密度であることが好ましい。電極密度が高くなるほどレート特性は悪化する傾向にあるが、本発明のバインダーを用いることにより高いレート特性を維持することができる。 The secondary battery electrode of the present invention preferably has a high density. The higher the density, the higher the effect of the present invention. The density of the electrode is determined by the active material used and the mixing ratio thereof. For example, when LiCoO 2 that is the positive electrode active material is used and the mixing ratio is 90 wt% or more, the density is 3.7 g / cc or more. A density is preferred. The rate characteristics tend to deteriorate as the electrode density increases, but high rate characteristics can be maintained by using the binder of the present invention.
4.二次電池
本発明の二次電池は、上記の本発明の二次電池電極を有する二次電池である。より詳細には、上記の二次電池電極および電解液と、従来公知のセパレータおよび電池容器等の部品とを組み合わせて得られる。具体的な製造方法としては、例えば、正極と負極とをセパレータを介して重ね合わせ、これを電池形状に応じて巻く、折るなどして電池容器に入れ、電池容器に電解液を注入して封口する方法が挙げられる。また必要に応じてエキスパンドメタルや、ヒューズ、PTC素子などの過電流防止素子、リード板などを入れ、電池内部の圧力上昇、過充放電の防止をする事もできる。電池の形状は、コイン型、ボタン型、シート型、円筒型、角形、扁平型など何れであってもよい。
4). Secondary battery The secondary battery of the present invention is a secondary battery having the above-described secondary battery electrode of the present invention. More specifically, it is obtained by combining the above-described secondary battery electrode and electrolytic solution with components such as conventionally known separators and battery containers. As a specific manufacturing method, for example, a positive electrode and a negative electrode are overlapped via a separator, and this is wound according to the shape of the battery, folded into a battery container, and an electrolyte is injected into the battery container to seal it. The method of doing is mentioned. If necessary, an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate, or the like can be inserted to prevent an increase in pressure inside the battery and overcharge / discharge. The shape of the battery may be any of a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like.
電解液としては、有機溶媒に支持電解質を溶解した有機電解液が用いられる。支持電解質としては、リチウム塩が用いられる。リチウム塩としては、特に制限はないが、LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLiなどが挙げられる。中でも、溶媒に溶けやすく高い解離度を示すLiPF6、LiClO4、CF3SO3Liが好ましい。これらは、二種以上を併用してもよい。解離度の高い支持電解質を用いるほどリチウムイオン伝導度が高くなるので、支持電解質の種類によりリチウムイオン伝導度を調節することができる。 As the electrolytic solution, an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is used. A lithium salt is used as the supporting electrolyte. The lithium salt is not particularly limited, LiPF 6, LiAsF 6, LiBF 4, LiSbF 6, LiAlCl 4, LiClO 4, CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi, (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like. Among these, LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferable. Two or more of these may be used in combination. Since the lithium ion conductivity increases as the supporting electrolyte having a higher degree of dissociation is used, the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
電解液に使用する有機溶媒としては、支持電解質を溶解できるものであれば特に限定されないが、ジメチルカーボネート(DMC)、エチレンカーボネート(EC)、ジエチルカーボネート(DEC)、プロピレンカーボネート(PC)、ブチレンカーボネート(BC)、メチルエチルカーボネート(MEC)などのカーボネート類;γ−ブチロラクトン、ギ酸メチルなどのエステル類;1,2−ジメトキシエタン、テトラヒドロフランなどのエーテル類;スルホラン、ジメチルスルホキシドなどの含硫黄化合物類;が好適に用いられる。またこれらの溶媒の混合液を用いてもよい。中でも、誘電率が高く、安定な電位領域が広いのでカーボネート類が好ましい。用いる溶媒の粘度が低いほどリチウムイオン伝導度が高くなるので、溶媒の種類によりリチウムイオン伝導度を調節することができる。 The organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte, but dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate. Carbonates such as (BC) and methyl ethyl carbonate (MEC); esters such as γ-butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide; Are preferably used. Moreover, you may use the liquid mixture of these solvents. Among these, carbonates are preferable because they have a high dielectric constant and a wide stable potential region. Since the lithium ion conductivity increases as the viscosity of the solvent used decreases, the lithium ion conductivity can be adjusted depending on the type of the solvent.
電解液中における支持電解質の濃度は、通常1〜30重量%、好ましくは5重量%〜20重量%である。また、支持電解質の種類に応じて、通常0.5〜2.5モル/Lの濃度で用いられる。支持電解質の濃度が低すぎても高すぎてもイオン導電度は低下する傾向にある。用いる電解液の濃度が低いほど重合体粒子の膨潤度が大きくなるので、電解液の濃度によりリチウムイオン伝導度を調節することができる。 The concentration of the supporting electrolyte in the electrolytic solution is usually 1 to 30% by weight, preferably 5% to 20% by weight. Further, it is usually used at a concentration of 0.5 to 2.5 mol / L depending on the type of the supporting electrolyte. If the concentration of the supporting electrolyte is too low or too high, the ionic conductivity tends to decrease. Since the degree of swelling of the polymer particles increases as the concentration of the electrolytic solution used decreases, the lithium ion conductivity can be adjusted by the concentration of the electrolytic solution.
(実施例)
以下に、実施例を挙げて本発明を説明するが、本発明はこれに限定されるものではない。尚、本実施例における部および%は、特記しない限り重量基準である。
実施例及び比較例中の評価は以下の条件にて行った。
(Example)
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. In the examples, parts and% are based on weight unless otherwise specified.
Evaluation in Examples and Comparative Examples was performed under the following conditions.
<バインダー特性:相溶性の評価>
得られた重合体のNMP溶液のヘイズ値をデジタルヘイズ計にて測定した。
また、得られた重合体のNMP溶液を120℃10時間窒素雰囲気下で乾燥し、重合体のポリマーフィルムを作製し、ミクロ相分離状態を透過型電子顕微鏡により観察した。重合体のNMP溶液のヘイズ値が5%以下かつTEM画像のドメインの大きさが200nm以下である場合に、重合体が相溶していると判断した。
<Binder properties: compatibility evaluation>
The haze value of the NMP solution of the obtained polymer was measured with a digital haze meter.
Further, the obtained NMP solution of the polymer was dried at 120 ° C. for 10 hours in a nitrogen atmosphere to produce a polymer film of the polymer, and the microphase separation state was observed with a transmission electron microscope. When the haze value of the NMP solution of the polymer was 5% or less and the domain size of the TEM image was 200 nm or less, it was judged that the polymer was compatible.
<スラリー特性:スラリー安定性>
直径1cmの試験管内に、得られた電極用スラリーを高さ5cmまで入れ、5本ずつ試験サンプルとする。前記試験サンプルを机上に垂直に設置する。設置した電極用スラリーの状態を10日間観測し、下記の基準により判定する。2相分離が見られないほどスラリー安定性に優れることを示す。
A:10日後にも2相分離がみられない。
B:6〜10日後に2相分離がみられる。
C:2〜5日後に2相分離がみられる。
D:1日後に2相分離がみられる。
E:3時間以内に2相分離がみられる。
<Slurry characteristics: slurry stability>
The obtained electrode slurry is put in a test tube having a diameter of 1 cm to a height of 5 cm, and five test samples are used. The test sample is placed vertically on a desk. The state of the installed electrode slurry is observed for 10 days and determined according to the following criteria. It shows that the slurry stability is so excellent that two-phase separation is not observed.
A: Two-phase separation is not observed even after 10 days.
B: Two-phase separation is observed after 6 to 10 days.
C: Two-phase separation is observed after 2 to 5 days.
D: Two-phase separation is observed after 1 day.
E: Two-phase separation is observed within 3 hours.
<電極特性:柔軟性>
電極を幅1cm×長さ5cmの矩形に切って試験片とする。試験片の集電体側の面を下にして机上に置き、長さ方向の中央(端部から2.5cmの位置)、集電体側の面に直径1mm のステンレス棒を短手方向に横たえて設置する。このステンレス棒を中心にして試験片を電極活物質層が外側になるように180度折り曲げる。径の異なるステンレス棒をそれぞれ用いて、試験片の電極活物質層の折り曲げた部分について、ひび割れまたは剥がれの有無を観察し、下記の基準により判定する。径が小さいステンレス棒への捲きつけにおいて、ひび割れがないほど、電極が柔軟性に優れることを示す。
A:1mmのステンレス棒への捲きつけで割れなし
B:1.5mmのステンレス棒への捲きつけで割れなし
1mmのステンレス棒への捲きつけで割れあり
C:2mmのステンレス棒への捲きつけで割れなし
1.5mmのステンレス棒への捲きつけで割れあり
D:2.5mmのステンレス棒への捲きつけで割れなし
2mmのステンレス棒への捲きつけで割れあり
E:3mm以上のステンレス棒への捲きつけで割れなし
2.5mmのステンレス棒への捲きつけで割れあり
<Electrode characteristics: flexibility>
The electrode is cut into a rectangle having a width of 1 cm and a length of 5 cm to form a test piece. Place the test specimen on the current collector side down and lay a stainless steel rod with a diameter of 1 mm on the current collector side in the center of the length (2.5 cm from the end). Install. The test piece is bent 180 degrees around the stainless bar so that the electrode active material layer is on the outside. Using stainless bars having different diameters, the bent portions of the electrode active material layer of the test piece are observed for cracking or peeling, and determined according to the following criteria. It shows that an electrode is excellent in flexibility so that there is no cracking when it is wound on a stainless steel rod having a small diameter.
A: No cracking by scratching to 1mm stainless steel rod B: No cracking by hammering to 1.5mm stainless steel rod C: Cracking by hammering to 1mm stainless steel rod C: By soldering to 2mm stainless steel rod No cracking by cracking to 1.5mm stainless steel rod D: No cracking by scratching to 2.5mm stainless steel rod E: Cracking by soldering to 2mm stainless steel rod E: To stainless steel rod of 3mm or more No cracks
Cracked by hammering on 2.5mm stainless steel rod
<電池特性:サイクル特性>
得られたリチウムイオン二次電池を用いて、それぞれ20℃で0.1Cの定電流で4.3Vまで充電し、0.1Cの定電流で3.0Vまで放電する充放電サイクルを行った。充放電サイクルは100サイクルまで行い、初期放電容量に対する100サイクル目の放電容量の比を容量維持率とし、下記の基準で判定した。この値が大きいほど繰り返し充放電による容量減が少ないことを示す。
A:80%以上
B:75%以上80%未満
C:70%以上75%未満
D:50%以上70%未満
E:50%未満
<Battery characteristics: cycle characteristics>
Using the obtained lithium ion secondary battery, a charge / discharge cycle in which the battery was charged to 4.3 V at a constant current of 0.1 C at 20 ° C. and discharged to 3.0 V at a constant current of 0.1 C was performed. The charge / discharge cycle was performed up to 100 cycles, and the ratio of the discharge capacity at the 100th cycle to the initial discharge capacity was defined as the capacity retention rate, and the following criteria were used. It shows that the capacity | capacitance reduction by repeated charging / discharging is so small that this value is large.
A: 80% or more B: 75% or more and less than 80% C: 70% or more and less than 75% D: 50% or more and less than 70% E: Less than 50%
<電池特性:レート特性>
測定条件を、定電流量2.0Cに変更したほかは、前記サイクル特性の測定と同様にして、各定電流量における放電容量を測定した。0.1Cでの電池容量に対する2.0Cでの放電容量の割合を百分率で算出して充放電レート特性とし、下記の基準で判定した。この値が大きいほど、内部抵抗が小さく、高速充放電が可能であることを示す。
A:65%以上
B:60%以上65%未満
C:55%以上60%未満
D:50%以上55%未満
E:40%以上50%未満
F:40%未満
<Battery characteristics: Rate characteristics>
The discharge capacity at each constant current amount was measured in the same manner as the measurement of the cycle characteristics except that the measurement condition was changed to a constant current amount of 2.0C. The ratio of the discharge capacity at 2.0 C to the battery capacity at 0.1 C was calculated as a percentage to obtain charge / discharge rate characteristics, and the following criteria were used. It shows that internal resistance is so small that this value is large, and high-speed charge / discharge is possible.
A: 65% or more B: 60% or more and less than 65% C: 55% or more and less than 60% D: 50% or more and less than 55% E: 40% or more and less than 50% F: Less than 40%
(実施例1)
<重合体−1の作製>
攪拌機付きオートクレーブに、アクリロニトリルを70部、ブチルアクリレート27部およびグリシジルメタクリレート3部からなる成分(A)100部と、イオン交換水1200部、ドデシルベンゼンスルホン酸ナトリウム15部及び過硫酸カリウム0.9部を入れ、十分に攪拌した後、60℃に加温して一段目の重合を開始した。重合転化率が70%に到達した時点で、二段目の単量体としてアクリロニトリルを15部、ブチルアクリレート82部、グリシジルメタクリレート3部からなる成分(B)を、前記単量体組成物(A)の等量である100部添加して反応を継続した。二段目の重合転化率が95%以上になった時点で冷却して重合を停止した。ついで、総重量の3倍のN―メチルピロリドン(NMP)を加え、エバポレーターで水分を蒸発させ、固形分が6%の重合体−1のNMP溶液を得た。重合体−1の低温側のガラス転移温度と相溶状態を評価した。結果を表2に示す。
Example 1
<Preparation of polymer-1>
In an autoclave equipped with a stirrer, 70 parts of acrylonitrile, 100 parts of component (A) consisting of 27 parts of butyl acrylate and 3 parts of glycidyl methacrylate, 1200 parts of ion-exchanged water, 15 parts of sodium dodecylbenzenesulfonate and 0.9 parts of potassium persulfate The mixture was sufficiently stirred and heated to 60 ° C. to initiate the first stage polymerization. When the polymerization conversion rate reached 70%, the component (B) comprising 15 parts of acrylonitrile, 82 parts of butyl acrylate and 3 parts of glycidyl methacrylate as the second stage monomer was added to the monomer composition (A ) Was added in an amount equal to 100 parts, and the reaction was continued. When the second stage polymerization conversion reached 95% or more, the polymerization was stopped by cooling. Next, 3 times the total weight of N-methylpyrrolidone (NMP) was added, and the water was evaporated by an evaporator to obtain an NMP solution of polymer-1 having a solid content of 6%. The glass transition temperature and the compatible state on the low temperature side of polymer-1 were evaluated. The results are shown in Table 2.
<正極用スラリーの作成>
リチウム含有コバルト酸化物系の活物質(品名:セルシードC−10N、日本化学工業)100部に対し、バインダー1.2部(固形分相当)および導電剤としてアセチレンブラック2部を混合し、更にN−メチルピロリドンを固形分濃度が80%になるように混合させてプラネタリーミキサーで混合して正極用スラリーを調製した。
<Preparation of slurry for positive electrode>
To 100 parts of lithium-containing cobalt oxide active material (product name: Cellseed C-10N, Nippon Chemical Industry), 1.2 parts of binder (corresponding to solid content) and 2 parts of acetylene black as a conductive agent are mixed, and N -A slurry for positive electrode was prepared by mixing methylpyrrolidone so as to have a solid content of 80% and mixing with a planetary mixer.
<正極の製造>
上記正極用スラリーをコンマコーターで厚さ20μmのアルミ箔上に、乾燥後の膜厚が120μm程度になるように塗布し、60℃で20分間乾燥後、150℃で2時間加熱処理して電極原反を得た。この電極原反をロールプレスで圧延し、密度が3.7g/cm3、銅箔および正極活物質層の合計厚みが100μmに制御された正極極板を作製した。作製した正極極板の柔軟性を測定した。その結果を表2に示す。
<Production of positive electrode>
The positive electrode slurry is applied on a 20 μm thick aluminum foil with a comma coater so that the film thickness after drying is about 120 μm, dried at 60 ° C. for 20 minutes, and then heat-treated at 150 ° C. for 2 hours to form an electrode. I got the original fabric. This electrode original fabric was rolled with a roll press to produce a positive electrode plate in which the density was 3.7 g / cm 3 and the total thickness of the copper foil and the positive electrode active material layer was controlled to 100 μm. The flexibility of the produced positive electrode plate was measured. The results are shown in Table 2.
<電池の作製>
得られた正極極板を直径15mmの円形シートに切り抜いた。この正極の正極活物質層面側に直径18mm、厚さ25μmの円形ポリプロピレン製多孔膜からなるセパレーター、負極として用いる金属リチウム、エキスパンドメタルを順に積層し、これをポリプロピレン製パッキンを設置したステンレス鋼製のコイン型外装容器(直径20mm、高さ1.8mm、ステンレス鋼厚さ0.25mm)中に収納した。この容器中に電解液を空気が残らないように注入し、ポリプロピレン製パッキンを介して外装容器に厚さ0.2mmのステンレス鋼のキャップをかぶせて固定し、電池缶を封止して、直径20mm、厚さ約2mmのリチウムイオン二次電池を製造した。作製したリチウムイオン二次電池について、電池特性を評価した。その結果を表2に示す。
<Production of battery>
The obtained positive electrode plate was cut out into a circular sheet having a diameter of 15 mm. A separator made of a circular polypropylene porous film having a diameter of 18 mm and a thickness of 25 μm, a metallic lithium used as a negative electrode, and an expanded metal are sequentially laminated on the positive electrode active material layer surface side of this positive electrode, and this is made of stainless steel provided with a polypropylene packing. It was stored in a coin-type outer container (diameter 20 mm, height 1.8 mm, stainless steel thickness 0.25 mm). The electrolyte is poured into the container so that no air remains, and the outer container is fixed with a 0.2 mm thick stainless steel cap through a polypropylene packing, and the battery can is sealed, and the diameter is A lithium ion secondary battery having a thickness of 20 mm and a thickness of about 2 mm was produced. The battery characteristics of the produced lithium ion secondary battery were evaluated. The results are shown in Table 2.
(実施例2〜7および比較例1)
重合体溶液を調製する際、成分(A)及び成分(B)を構成する単量体、並びにこれらの重量比を表1に記載のように変更した以外は、実施例1と同様の操作を行った。評価結果を表2に示す。
(Examples 2-7 and Comparative Example 1)
When preparing the polymer solution, the same operations as in Example 1 were performed except that the monomers constituting the component (A) and the component (B), and the weight ratio thereof were changed as shown in Table 1. went. The evaluation results are shown in Table 2.
(実施例8)
正極用スラリーを作製する際に、正極活物質としてCo−Ni−Mnのリチウム複合酸化物系の活物質(品名:セルシードNMC613、日本化学工業社製)を用いたほかは、実施例1と同様の操作を行った。評価結果を表2に示す。
(Example 8)
When producing the slurry for the positive electrode, the same as Example 1 except that a Co—Ni—Mn lithium composite oxide based active material (product name: Cellseed NMC613, manufactured by Nippon Chemical Industry Co., Ltd.) was used as the positive electrode active material. Was performed. The evaluation results are shown in Table 2.
(比較例2)
ポリアクリル酸n−ブチル(ガラス転移点温度が−55℃)50部と、ポリフッ化ビニリデン(ガラス転移点温度が−40℃)50部とをNMPに溶解し、固形分濃度6%の重合体溶液を得た。実施例1において、重合体溶液として重合体−1のかわりにポリアクリル酸n−ブチルとポリフッ化ビニリデンの混合溶液を用いた他は、実施例1と同様の操作を行った。評価結果を表2に示す。
(Comparative Example 2)
A polymer having a solid content concentration of 6% obtained by dissolving 50 parts of poly (n-butyl acrylate) (glass transition temperature of −55 ° C.) and 50 parts of polyvinylidene fluoride (glass transition temperature of −40 ° C.) in NMP. A solution was obtained. In Example 1, the same operation as in Example 1 was performed, except that a mixed solution of n-butyl polyacrylate and polyvinylidene fluoride was used as the polymer solution instead of polymer-1. The evaluation results are shown in Table 2.
なお、表1中、「AN」はアクリロニトリル、「BA」はアクリル酸n−ブチル、「2EHA」はアクリル酸2−エチルヘキシル、「GMA」はグリシジルメタクリレート、を表す。 In Table 1, “AN” represents acrylonitrile, “BA” represents n-butyl acrylate, “2EHA” represents 2-ethylhexyl acrylate, and “GMA” represents glycidyl methacrylate.
本発明によれば、実施例1〜実施例8に示すように、バインダーを構成する(メタ)アクリロニトリルと(メタ)アクリル酸エステルとの共重合体の成分(A)及び成分(B)中に含まれるそれぞれの(メタ)アクリロニトリルの含有量が本願所定の範囲にあると、スラリーの安定性、電極の柔軟性が良好であり、レート特性、サイクル特性等の電池特性に優れた二次電池が得られることが分かる。また、実施例の中でも、成分(A)中の(メタ)アクリロニトリルの含有量が70〜85重量%にあり、成分(B)中の(メタ)アクリロニトリルの含有量が15〜25重量%の範囲にあり、かつ成分(A)と成分(B)の比率が重量比で40:60〜60:40にあるバインダーを用い、かつ電極活物質としてCo−Ni−Mnのリチウム複合酸化物系を用いた実施例8は、スラリー安定性、電極柔軟性及び電池特性の全てにおいて最も優れている。 According to the present invention, as shown in Examples 1 to 8, in the component (A) and the component (B) of the copolymer of (meth) acrylonitrile and (meth) acrylic acid ester constituting the binder. When the content of each (meth) acrylonitrile contained is within the predetermined range of the present application, the stability of the slurry and the flexibility of the electrode are good, and a secondary battery excellent in battery characteristics such as rate characteristics and cycle characteristics is obtained. You can see that Further, in the examples, the content of (meth) acrylonitrile in the component (A) is 70 to 85% by weight, and the content of (meth) acrylonitrile in the component (B) is in the range of 15 to 25% by weight. And a ratio of component (A) to component (B) in a weight ratio of 40:60 to 60:40 is used, and a Co—Ni—Mn lithium composite oxide system is used as an electrode active material. Example 8 was the most excellent in all of slurry stability, electrode flexibility, and battery characteristics.
一方、重合体成分の相溶性に劣るもの(比較例1)、2種のポリマーを混合したもの(比較例2)では、スラリー安定性、電極柔軟性及び電池特性の全てが著しく劣る。 On the other hand, in the case where the compatibility of the polymer components is inferior (Comparative Example 1) and in the case of mixing two kinds of polymers (Comparative Example 2), all of the slurry stability, electrode flexibility and battery characteristics are remarkably inferior.
Claims (7)
前記共重合体が、
(メタ)アクリロニトリル単位の含有量が60重量%以上95重量%以下の成分(A)と、
(メタ)アクリロニトリル単位の含有量が5重量%以上40重量%以下の成分(B)とからなり、
前記成分(A)と成分(B)とが相溶してなる、二次電池電極用バインダー。 A binder for a secondary battery electrode comprising a copolymer of (meth) acrylonitrile and (meth) acrylic acid ester,
The copolymer is
A component (A) having a (meth) acrylonitrile unit content of 60% by weight to 95% by weight;
The content of the (meth) acrylonitrile unit is 5% by weight or more and 40% by weight or less of the component (B),
A binder for a secondary battery electrode, wherein the component (A) and the component (B) are compatible.
(メタ)アクリロニトリルの含有量が5重量%以上40重量%である単量体組成物(B)とを多段重合することを特徴とする請求項1に記載の二次電池電極用バインダーの製造方法。 A monomer composition (A) having a (meth) acrylonitrile content of 60 wt% or more and 95 wt%,
2. The method for producing a binder for a secondary battery electrode according to claim 1, wherein the monomer composition (B) having a (meth) acrylonitrile content of 5 wt% to 40 wt% is subjected to multistage polymerization. .
前記正極又は負極が、請求項6記載の二次電池電極である二次電池。 A secondary battery having a positive electrode, an electrolyte, a separator and a negative electrode,
The secondary battery whose said positive electrode or negative electrode is the secondary battery electrode of Claim 6.
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