JP2010129369A - Binder for energy device electrode and method for producing the same - Google Patents
Binder for energy device electrode and method for producing the same Download PDFInfo
- Publication number
- JP2010129369A JP2010129369A JP2008302705A JP2008302705A JP2010129369A JP 2010129369 A JP2010129369 A JP 2010129369A JP 2008302705 A JP2008302705 A JP 2008302705A JP 2008302705 A JP2008302705 A JP 2008302705A JP 2010129369 A JP2010129369 A JP 2010129369A
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- JP
- Japan
- Prior art keywords
- emulsion polymerization
- binder
- meth
- monomer mixture
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- HKTGZPQHFCONFD-UHFFFAOYSA-N n-[(dimethylamino)methyl]-2-methylprop-2-enamide Chemical compound CN(C)CNC(=O)C(C)=C HKTGZPQHFCONFD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000652 nickel hydride Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Graft Or Block Polymers (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、二次電池、電気二重層キャパシタ、リチウムイオンキャパシタなどのエネルギーデバイスの電極を得るためのバインダーおよびその製造方法に関する。 The present invention relates to a binder for obtaining an electrode of an energy device such as a secondary battery, an electric double layer capacitor, or a lithium ion capacitor, and a method for producing the same.
近年、電子機器の小型化・軽量化の進歩は目覚しく、それに伴い、当該電子機器の駆動用電源として用いられる電池に対しても小型化・軽量化の要求が一層高まっている。このような小型化・軽量化の要求を満足するために、従来種々の二次電池が開発されており、例えばニッケル水素二次電池、リチウムイオン二次電池等のエネルギーデバイスが実用化されている。
而して、これらのエネルギーデバイスを構成する電極を製造する方法としては、水素吸蔵合金や黒鉛等よりなる活物質と、カルボキシメチルセルロース等よりなる増粘剤と、ラテックスよりなるバインダーとが含有されてなるペーストまたはスラリーを、集電体の表面に塗布して乾燥し、得られる塗膜に対して、加圧ロールなどによってプレス加工を施すことにより、電極層を形成する方法等が知られている（例えば特許文献１および特許文献２等参照。）。
ここで、バインダーは、活物質を結着する機能の他に、活物質を含む電極層と集電体との密着性を向上させる機能を有するものであり、かかるバインダーとしては、共役ジエンおよびエチレン性不飽和カルボン酸を含む単量体を乳化重合して得られるラテックス（特許文献３参照。）、芳香族ビルル、共役ジエン、（メタ）アクリル酸エステルおよびエチレン性不飽和カルボン酸を含む単量体を乳化重合して得られるラテックス（特許文献４参照。）などが知られている。
2. Description of the Related Art In recent years, progress in downsizing and weight reduction of electronic devices has been remarkable, and accordingly, demands for downsizing and weight reduction of batteries used as power sources for driving the electronic devices have further increased. In order to satisfy such demands for reduction in size and weight, various secondary batteries have been developed in the past, and energy devices such as nickel hydride secondary batteries and lithium ion secondary batteries have been put into practical use. .
Thus, as a method of manufacturing the electrodes constituting these energy devices, an active material made of a hydrogen storage alloy or graphite, a thickener made of carboxymethyl cellulose, and a binder made of latex are contained. There is known a method of forming an electrode layer by applying a paste or slurry to the surface of a current collector and drying the resulting coating film, and applying a press process to the resulting coating film with a pressure roll or the like. (See, for example, Patent Document 1 and Patent Document 2).
Here, in addition to the function of binding the active material, the binder has a function of improving the adhesion between the electrode layer containing the active material and the current collector. Examples of the binder include conjugated dienes and ethylene. Monomer containing a latex obtained by emulsion polymerization of a monomer containing an unsaturated carboxylic acid (see Patent Document 3), an aromatic bilyl, a conjugated diene, a (meth) acrylic acid ester and an ethylenically unsaturated carboxylic acid A latex obtained by emulsion polymerization of a body (see Patent Document 4) is known.
而して、近年、エネルギーデバイスの高容量化が求められており、このようなエネルギーデバイスを得るための手段の一つとして、高い圧力でプレス加工を行うことによって、高密度の電極層を形成することが検討されている。
しかしながら、高い圧力でプレス加工を行った場合には、得られる電極層が破壊されたり、集電体から剥離したりする、という問題がある。
また、電極層の破壊や剥離を防止または抑制するために、接着性の高いバインダーを用いた場合には、プレス加工時に電極層が加圧ロールに接着するため、結局、良好なプレス加工性を得ることが困難である。
Thus, in recent years, there has been a demand for higher capacity of energy devices, and as one means for obtaining such energy devices, a high-density electrode layer is formed by pressing at a high pressure. To be considered.
However, when pressing is performed at a high pressure, there is a problem that the obtained electrode layer is broken or peeled off from the current collector.
In addition, in order to prevent or suppress the electrode layer from being broken or peeled off, when a binder with high adhesiveness is used, the electrode layer adheres to the pressure roll during press processing, so that good press workability is achieved. It is difficult to obtain.
本発明は以上のような事情に基づいてなされたものであって、その目的は、プレス加工における剥離または破壊が生じることがなくて良好なプレス加工性が得られ、しかも、集電体に対する密着性が高い電極層を形成することができるエネルギーデバイス電極用バインダーおよびその製造方法を提供することにある。 The present invention has been made based on the circumstances as described above, and the object thereof is to obtain good press workability without causing peeling or breakage in press work, and to adhere to the current collector. It is in providing the binder for energy device electrodes which can form an electrode layer with high property, and its manufacturing method.
本発明のエネルギーデバイス電極用バインダーは、多段階の乳化重合によって得られるラテックスよりなり、
第１段階の乳化重合による重合体成分が、芳香族ビニル化合物、共役ジエン化合物、（メタ）アクリル酸エステルおよびシアン化ビニル化合物を含有する単量体混合物から得られるものであり、
他の段階の乳化重合による重合体成分が、芳香族ビニル化合物、共役ジエン化合物および（メタ）アクリル酸エステルを含有する単量体混合物から得られるものである
ことを特徴とする。
The binder for an energy device electrode of the present invention comprises a latex obtained by multi-stage emulsion polymerization,
The polymer component by emulsion polymerization in the first stage is obtained from a monomer mixture containing an aromatic vinyl compound, a conjugated diene compound, a (meth) acrylic acid ester and a vinyl cyanide compound,
The polymer component obtained by emulsion polymerization in another stage is obtained from a monomer mixture containing an aromatic vinyl compound, a conjugated diene compound and a (meth) acrylic acid ester.
また、本発明のエネルギーデバイス電極用バインダーは、３段階の乳化重合によって得られるラテックスよりなり、
第１段階の乳化重合による重合体成分が、芳香族ビニル化合物、共役ジエン化合物、（メタ）アクリル酸エステルおよびシアン化ビニル化合物を含有する単量体混合物（Ｘ）から得られるものであり、
第２段階の乳化重合による重合体成分が、芳香族ビニル化合物、共役ジエン化合物および（メタ）アクリル酸エステルを含有する単量体混合物（Ｙ）から得られるものであり、 第３段階の乳化重合による重合体成分が、芳香族ビニル化合物、共役ジエン化合物および（メタ）アクリル酸エステルを含有する単量体混合物（Ｚ）から得られるものであることを特徴とする。
The binder for an energy device electrode of the present invention comprises a latex obtained by three-stage emulsion polymerization,
The polymer component by the first stage emulsion polymerization is obtained from a monomer mixture (X) containing an aromatic vinyl compound, a conjugated diene compound, a (meth) acrylic acid ester and a vinyl cyanide compound,
The polymer component by the second stage emulsion polymerization is obtained from a monomer mixture (Y) containing an aromatic vinyl compound, a conjugated diene compound and a (meth) acrylic acid ester, and the third stage emulsion polymerization. The polymer component is obtained from a monomer mixture (Z) containing an aromatic vinyl compound, a conjugated diene compound and a (meth) acrylic acid ester.
本発明のエネルギーデバイス電極用バインダーの製造方法は、芳香族ビニル化合物、共役ジエン化合物、（メタ）アクリル酸エステルおよびシアン化ビニル化合物を含有する単量体混合物を乳化重合する工程（１）と、
この工程（１）に続き、反応系中に、芳香族ビニル化合物、共役ジエン化合物および（メタ）アクリル酸エステルを含有する単量体混合物を連続的にまたは断続的に添加しながら乳化重合する工程（２）と
を有することを特徴とする。
The method for producing a binder for an energy device electrode of the present invention includes a step (1) of emulsion polymerization of a monomer mixture containing an aromatic vinyl compound, a conjugated diene compound, a (meth) acrylic acid ester and a vinyl cyanide compound,
Following this step (1), a step of emulsion polymerization while continuously or intermittently adding a monomer mixture containing an aromatic vinyl compound, a conjugated diene compound and a (meth) acrylic acid ester to the reaction system. (2).
本発明のエネルギーデバイス電極用バインダーの製造方法においては、工程（１）を４０〜６０℃の温度で行うことが好ましい。
また、工程（２）を５０〜７０℃の温度で行うことが好ましい。
In the manufacturing method of the binder for energy device electrodes of this invention, it is preferable to perform a process (1) at the temperature of 40-60 degreeC.
Moreover, it is preferable to perform a process (2) at the temperature of 50-70 degreeC.
また、本発明のエネルギーデバイス電極用バインダーの製造方法においては、工程（２）に続き、反応系中に、芳香族ビニル化合物、共役ジエン化合物および（メタ）アクリル酸エステルを含有する単量体混合物を連続的にまたは断続的に添加しながら乳化重合する工程（３）
を有することが好ましい。
このような製造方法においては、工程（３）を５０〜７０℃の温度で行うことが好ましい。
Moreover, in the manufacturing method of the binder for energy device electrodes of this invention, the monomer mixture which contains an aromatic vinyl compound, a conjugated diene compound, and (meth) acrylic acid ester in a reaction system following a process (2). (3) emulsion polymerization while continuously or intermittently adding
It is preferable to have.
In such a manufacturing method, it is preferable to perform a process (3) at the temperature of 50-70 degreeC.
本発明のエネルギーデバイス電極用バインダーによれば、プレス加工における剥離または破壊が生じることがなくて良好なプレス加工性が得られ、しかも、集電体に対する密着性が高い電極層を形成することができる。
本発明の製造方法によれば、上記のエネルギーデバイス電極用バインダーを確実に製造することができる。
According to the binder for an energy device electrode of the present invention, it is possible to form an electrode layer having good press workability without causing peeling or breaking in press work and having high adhesion to a current collector. it can.
According to the manufacturing method of this invention, said energy device electrode binder can be manufactured reliably.
以下、本発明の実施の形態について詳細に説明する。
本発明のエネルギーデバイス電極用バインダー（以下、「電極用バインダー」という。）は、多段階の乳化重合工程、好ましくは３段階の乳化重合工程によって得られるラテックスよりなるものである。
Hereinafter, embodiments of the present invention will be described in detail.
The energy device electrode binder of the present invention (hereinafter referred to as “electrode binder”) is made of a latex obtained by a multi-stage emulsion polymerization process, preferably a three-stage emulsion polymerization process.
〔単量体成分〕
本発明においては、芳香族ビニル化合物、共役ジエン化合物、（メタ）アクリル酸エステル、およびシアン化ビニル化合物が必須の単量体成分として用いられる。
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、ｐ−メチルスチレン、ビニルトルエン、クロルスチレン、ジビニルベンゼンなどを例示することができ、これらの中では、スチレンが好ましい。
共役ジエン化合物としては、１，３−ブタジエン、イソプレン、２−クロロ−１，３−ブタジエン、クロロプレンなどを例示することができ、これらの中では、ブタジエンが好ましい。
（メタ）アクリル酸エステルとしては、（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ｉ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸ｉ−ブチル、（メタ）アクリル酸ｎ−アミル、（メタ）アクリル酸ｉ−アミル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２−ヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸ｉ−ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ヒドロキシメチル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸エチレングリコールジなどを例示することができ、これらの中では、（メタ）アクリル酸メチル、（メタ）アクリル酸ブチルが好ましく、特に好ましいものは（メタ）アクリル酸メチルである。
シアン化ビニル化合物としては、アクリロニトリル、メタクリロニトリル、α−クロルアクリロニトリル、α−エチルアクリロニトリルなどを例示することができ、これらの中では、アクリロニトリル、メタクリロニトリルが好ましい。
(Monomer component)
In the present invention, an aromatic vinyl compound, a conjugated diene compound, a (meth) acrylic acid ester, and a vinyl cyanide compound are used as essential monomer components.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, and the like. Among these, styrene is preferable.
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, and chloroprene. Among these, butadiene is preferable.
(Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, I-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-hexyl (meth) acrylate, octyl (meth) acrylate, Examples include (meth) acrylic acid i-nonyl, (meth) acrylic acid decyl, (meth) acrylic acid hydroxymethyl, (meth) acrylic acid hydroxyethyl, (meth) acrylic acid ethylene glycol di, and the like. Among them, methyl (meth) acrylate and butyl (meth) acrylate are preferable, and (meth) acrylic acid is particularly preferable. A chill.
Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like. Among these, acrylonitrile and methacrylonitrile are preferable.
本発明においては、上記の単量体以外に、エチレン系不飽和カルボン酸およびその他の共重合可能な単量体を任意の単量体成分として必要に応じて用いることができる。
エチレン系不飽和カルボン酸としては、アクリル酸、イタコン酸、フマル酸、マレイン酸などを例示することができ、これらの中では、アクリル酸、イタコン酸が好ましい。
その他の共重合可能な単量体としては、（メタ）アクリルアミド、Ｎ−メチロールアクリルアミド等のエチレン性不飽和カルボン酸アミド類、酢酸ビニル、プロピオン酸ビニル等のカルボン酸ビニルエステル類、エチレン性不飽和カルボン酸アルキルエステル類、アミノエチルアクリレート、ジメチルアミノエチルアクリレート、ブチルアミノエチルアクリレート等のエチレン性不飽和カルボン酸アミノアルキルエステル類、アミノエチルアクリルアミド、ジメチルアミノメチルメタクリルアミド、メチルアミノプロピルメタクリルアミド等のエチレン性不飽和カルボン酸アミノアルキルアミド類、グリシジル（メタ）アクリレートなどの不飽和脂肪族グリシジルエステル類などを例示することができる。
In the present invention, in addition to the above monomers, an ethylenically unsaturated carboxylic acid and other copolymerizable monomers can be used as optional monomer components as required.
Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, itaconic acid, fumaric acid, maleic acid and the like. Among these, acrylic acid and itaconic acid are preferable.
Examples of other copolymerizable monomers include ethylenically unsaturated carboxylic acid amides such as (meth) acrylamide and N-methylol acrylamide, vinyl acetates such as vinyl acetate and vinyl propionate, and ethylenically unsaturated monomers. Ethylenically unsaturated carboxylic acid aminoalkyl esters such as carboxylic acid alkyl esters, aminoethyl acrylate, dimethylaminoethyl acrylate, butylaminoethyl acrylate, ethylene such as aminoethyl acrylamide, dimethylaminomethyl methacrylamide, methylaminopropyl methacrylamide And unsaturated aliphatic glycidyl esters such as carboxylic acid aminoalkylamides and glycidyl (meth) acrylate.
〔単量体混合物〕
第１段階の乳化重合工程においては、芳香族ビニル化合物、共役ジエン化合物、（メタ）アクリル酸エステルおよびシアン化ビニル化合物を含有する単量体混合物（Ｘ）が用いられる。
単量体混合物（Ｘ）において、各単量体成分の割合は、芳香族ビニル化合物が、好ましくは５〜７０質量％、より好ましくは１０〜６０質量％であり、共役ジエン化合物が、好ましくは１０〜６０質量％、より好ましくは２０〜５０質量％、（メタ）アクリル酸エステルが、好ましくは５〜４０質量％、より好ましくは１０〜３０質量％であり、シアン化ビニル化合物が、好ましくは１〜５０質量％、より好ましくは３〜４０質量％である。また、必要に応じて用いられるエチレン系不飽和カルボン酸およびその他の共重合可能な単量体の割合は、５質量％以下であることが好ましい。
芳香族ビニル化合物の割合が過小である場合には、得られるポリマーは、ガラス転移温度が低くなり過ぎて柔らかくなるため、剛度に乏しい電極になり易い傾向がある。一方、芳香族ビニル化合物の割合が過大である場合には、活物質との相互作用が不十分となり、活物質間および電極−銅箔間の密着性が低下する傾向がある。
共役ジエン化合物の割合が過小である場合には、得られるポリマーは、ガラス転移温度が高くなり過ぎて硬くなるため、柔軟性に乏しい電極になる傾向がある。一方、共役ジエン化合物の割合が過大である場合には、得られるポリマーは、ガラス転移温度が低くなり過ぎて柔らかくなるため、剛度に乏しい電極になる傾向がある。
（メタ）アクリル酸エステルの割合が過小である場合には、得られるポリマーは、使用する電解液との親和性に乏しいものとなるため、電池特性に悪影響を及ぼす傾向がある。一方、（メタ）アクリル酸エステルの割合が過大である場合には、得られるポリマーは、使用する電解液との親和性が大きくなり過ぎて膨潤が起き易くなるため、電池特性に悪影響を及ぼす傾向がある。
シアン化ビニル化合物の割合が過小である場合には、得られるポリマーは、使用する電解液との親和性に乏しいものとなるため、電池特性に悪影響を及ぼす傾向がある。一方、共役ジエン化合物の割合が過大である場合には、得られるポリマーは、使用する電解液との親和性が大きくなり過ぎて膨潤が起き易くなるため、電池特性に悪影響を及ぼす傾向がある。
(Monomer mixture)
In the first stage emulsion polymerization process, a monomer mixture (X) containing an aromatic vinyl compound, a conjugated diene compound, a (meth) acrylic acid ester and a vinyl cyanide compound is used.
In the monomer mixture (X), the ratio of each monomer component is preferably an aromatic vinyl compound, preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and preferably a conjugated diene compound. 10 to 60% by mass, more preferably 20 to 50% by mass, (meth) acrylic acid ester is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and vinyl cyanide compound is preferably It is 1-50 mass%, More preferably, it is 3-40 mass%. Moreover, it is preferable that the ratio of the ethylenically unsaturated carboxylic acid and other copolymerizable monomer used as needed is 5 mass% or less.
When the ratio of the aromatic vinyl compound is too small, the obtained polymer tends to be an electrode with poor rigidity because the glass transition temperature becomes too low and becomes soft. On the other hand, when the ratio of the aromatic vinyl compound is excessive, the interaction with the active material becomes insufficient, and the adhesion between the active material and between the electrode and the copper foil tends to decrease.
When the proportion of the conjugated diene compound is too small, the obtained polymer tends to be an electrode with poor flexibility because the glass transition temperature becomes too high and becomes hard. On the other hand, when the proportion of the conjugated diene compound is excessive, the obtained polymer tends to be an electrode having poor rigidity because the glass transition temperature becomes too low and becomes soft.
When the ratio of (meth) acrylic acid ester is too small, the resulting polymer has poor affinity with the electrolyte used, and thus tends to adversely affect battery characteristics. On the other hand, when the proportion of (meth) acrylic acid ester is excessive, the resulting polymer tends to have a bad influence on the battery characteristics because the affinity with the electrolyte solution used becomes too large and the swelling tends to occur. There is.
When the proportion of the vinyl cyanide compound is too small, the resulting polymer has poor affinity with the electrolyte used, and thus tends to adversely affect battery characteristics. On the other hand, when the ratio of the conjugated diene compound is excessive, the resulting polymer has a tendency to adversely affect the battery characteristics because the affinity with the electrolytic solution to be used becomes too large and the swelling tends to occur.
第２段階の乳化重合工程においては、芳香族ビニル化合物、共役ジエン化合物および（メタ）アクリル酸エステルを含有する単量体混合物（Ｙ）が用いられる。
単量体混合物（Ｙ）において、各単量体成分の割合は、芳香族ビニル化合物が、好ましくは１０〜５０質量％、より好ましくは２０〜４０質量％であり、共役ジエン化合物が、好ましくは３０〜８０質量％、より好ましくは４０〜７０質量％、（メタ）アクリル酸エステルが、好ましくは３〜２０質量％、より好ましくは５〜１５質量％である。また、必要に応じて用いられるエチレン系不飽和カルボン酸の割合は、５質量％以下であることが好ましい。
芳香族ビニル化合物の割合が過小である場合には、得られるポリマーは、ガラス転移温度が低くなり過ぎて柔らかくなるため、剛度に乏しい電極になり易い傾向がある。一方、芳香族ビニル化合物の割合が過大である場合には、活物質との相互作用が不十分となり、活物質間および電極−銅箔間の密着性が低下する傾向がある。
共役ジエン化合物の割合が過小である場合には、得られるポリマーは、ガラス転移温度が高くなり過ぎて硬くなるため、柔軟性に乏しい電極になる傾向がある。一方、共役ジエン化合物の割合が過大である場合には、得られるポリマーは、ガラス転移温度が低くなり過ぎて柔らかくなるため、剛度に乏しい電極になる傾向がある。
（メタ）アクリル酸エステルの割合が過小である場合には、得られるポリマーは、使用する電解液との親和性に乏しいものとなるため、電池特性に悪影響を及ぼす傾向がある。一方、（メタ）アクリル酸エステルの割合が過大である場合には、得られるポリマーは、使用する電解液との親和性が大きくなり過ぎて膨潤が起き易くなるため、電池特性に悪影響を及ぼす傾向がある。
In the second stage emulsion polymerization process, a monomer mixture (Y) containing an aromatic vinyl compound, a conjugated diene compound and a (meth) acrylic acid ester is used.
In the monomer mixture (Y), the proportion of each monomer component is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, preferably a conjugated diene compound, for an aromatic vinyl compound. 30-80 mass%, More preferably, it is 40-70 mass%, (meth) acrylic acid ester becomes like this. Preferably it is 3-20 mass%, More preferably, it is 5-15 mass%. Moreover, it is preferable that the ratio of the ethylenically unsaturated carboxylic acid used as needed is 5 mass% or less.
When the ratio of the aromatic vinyl compound is too small, the obtained polymer tends to be an electrode with poor rigidity because the glass transition temperature becomes too low and becomes soft. On the other hand, when the ratio of the aromatic vinyl compound is excessive, the interaction with the active material becomes insufficient, and the adhesion between the active material and between the electrode and the copper foil tends to decrease.
When the proportion of the conjugated diene compound is too small, the obtained polymer tends to be an electrode with poor flexibility because the glass transition temperature becomes too high and becomes hard. On the other hand, when the proportion of the conjugated diene compound is excessive, the obtained polymer tends to be an electrode having poor rigidity because the glass transition temperature becomes too low and becomes soft.
When the ratio of (meth) acrylic acid ester is too small, the resulting polymer has poor affinity with the electrolyte used, and thus tends to adversely affect battery characteristics. On the other hand, when the proportion of (meth) acrylic acid ester is excessive, the resulting polymer tends to have a bad influence on the battery characteristics because the affinity with the electrolyte solution used becomes too large and the swelling tends to occur. There is.
第３段階の乳化重合工程を行う場合においては、芳香族ビニル化合物、共役ジエン化合物および（メタ）アクリル酸エステルを含有する単量体混合物（Ｚ）が用いられる。
単量体混合物（Ｚ）において、各単量体成分の割合は、上記の単量体混合物（Ｙ）における各単量体成分の割合と同様の範囲から選択することができるが、実際に用いられる各単量体の種類およびそれらの割合は、単量体混合物（Ｙ）と同一のものであっても異なるものであってもよい。
In the case of performing the third stage emulsion polymerization step, a monomer mixture (Z) containing an aromatic vinyl compound, a conjugated diene compound and a (meth) acrylic acid ester is used.
In the monomer mixture (Z), the ratio of each monomer component can be selected from the same range as the ratio of each monomer component in the monomer mixture (Y). The kind of each monomer and the ratio thereof may be the same as or different from the monomer mixture (Y).
以上において、第１段階の乳化重合工程に供される単量体混合物（Ｘ）の量は、全ての段階の乳化重合工程に供される単量体全体（３段階の乳化重合工程であれば、単量体混合物（Ｘ）、単量体混合物（Ｙ）および単量体混合物（Ｚ）の合計）の３０〜７０質量％であることが好ましく、より好ましくは４０〜６０質量％である。単量体混合物（Ｘ）の量が過小である場合には、安定した乳化重合が困難であり、また、得られるポリマーは、電解液との親和性が低いものとなる傾向にある。一方、単量体混合物（Ｘ）の量が過大である場合には、電極の密着性およびプレス加工性に悪影響を及ぼす傾向にある。
また、３段階の乳化重合工程を行う場合には、第２段階の乳化重合工程に供される単量体混合物（Ｙ）の量は、全ての段階の乳化重合工程に供される単量体全体の３０〜７０質量％であることが好ましく、より好ましくは４０〜６０質量％である。
In the above, the amount of the monomer mixture (X) used for the first stage emulsion polymerization step is the whole monomer used for the emulsion polymerization step of all stages (if it is a three stage emulsion polymerization process) , Monomer mixture (X), monomer mixture (Y) and monomer mixture (Z)) is preferably 30 to 70% by mass, more preferably 40 to 60% by mass. When the amount of the monomer mixture (X) is too small, stable emulsion polymerization is difficult, and the resulting polymer tends to have a low affinity with the electrolytic solution. On the other hand, when the amount of the monomer mixture (X) is excessive, it tends to adversely affect the adhesion and press workability of the electrode.
Moreover, when performing a three-stage emulsion polymerization process, the quantity of the monomer mixture (Y) provided to a 2nd-stage emulsion polymerization process is the monomer provided to the emulsion polymerization process of all the stages. It is preferable that it is 30-70 mass% of the whole, More preferably, it is 40-60 mass%.
〔乳化重合〕
乳化重合工程は、多段階好ましくは３段階で行われ、各段階の乳化重合工程は、水性媒体中において、乳化剤、重合開始剤および分子量調節剤の存在下に行われる。
[Emulsion polymerization]
The emulsion polymerization process is performed in multiple stages, preferably in three stages, and each stage of the emulsion polymerization process is performed in an aqueous medium in the presence of an emulsifier, a polymerization initiator, and a molecular weight regulator.
乳化剤としては、アニオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤などを単独でまたは２種以上組み合わせて用いることができる。
アニオン性界面活性剤としては、高級アルコールの硫酸エステル、アルキルベンゼンスルホン酸塩、脂肪族スルホン酸塩、ポリエチレングリコールアルキルエーテルの硫酸エステルなどを用いることができる。
ノニオン性界面活性剤としては、ポリエチレングリコールのアルキルエステル型のもの、アルキルエーテル型のもの、アルキルフェニルエーテル型のものなどを用いることができる。
両性界面活性剤の具体例としては、アニオン部分が、カルボン酸塩、硫酸エステル塩、スルホン酸塩、リン酸エステル塩で、カチオン部分が、アミン塩、第４級アンモニウム塩であるものを用いることができ、具体的には、ラウリルベタイン、ステアリルベタインなどのベンタイン類、ラウリル−β−アラニン、ウラリルジ（アミノエチル）グリシン、オクチルジ（アミノエチル）グリシンなどのアミノ酸タイプのものを例示することができる。
乳化剤の使用量は、用いられる単量体１００質量部に対して０．５〜５質量部であることが好ましい。
As the emulsifier, anionic surfactants, nonionic surfactants, amphoteric surfactants and the like can be used alone or in combination of two or more.
As the anionic surfactant, sulfates of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, sulfates of polyethylene glycol alkyl ethers, and the like can be used.
As the nonionic surfactant, an alkyl ester type of polyethylene glycol, an alkyl ether type, an alkylphenyl ether type, or the like can be used.
Specific examples of amphoteric surfactants include those in which the anion moiety is a carboxylate salt, sulfate ester salt, sulfonate salt, or phosphate ester salt, and the cation moiety is an amine salt or a quaternary ammonium salt. Specifically, amino acid types such as bentines such as lauryl betaine and stearyl betaine, lauryl-β-alanine, lauryl di (aminoethyl) glycine, and octyldi (aminoethyl) glycine can be exemplified.
It is preferable that the usage-amount of an emulsifier is 0.5-5 mass parts with respect to 100 mass parts of monomers used.
重合開始剤としては、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウムなどの水溶性重合開始剤、過酸化ベンゾイル、ラウリルパーオキサイド、２，２’−アゾビスイソブチロニトリル等の油溶性重合開始剤、重亜硫酸ナトリウム等の還元剤との組み合わせによるレドックス系重合開始剤などを、単独でまたは２種以上を組み合わせて用いることができる。
重合開始剤の使用量は、単量体１００質量部に対して０．３〜３質量部であることが好ましい。
Examples of the polymerization initiator include water-soluble polymerization initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate, and oil-soluble polymerization initiators such as benzoyl peroxide, lauryl peroxide, and 2,2′-azobisisobutyronitrile. Redox polymerization initiators in combination with a reducing agent such as sodium bisulfite can be used alone or in combination of two or more.
It is preferable that the usage-amount of a polymerization initiator is 0.3-3 mass parts with respect to 100 mass parts of monomers.
分子量調節剤としては、クロロホルム、四塩化炭素などのハロゲン化炭化水素類、ｎ−ヘキシルメルカプタン、ｎ−オクチルメルカプタン、ｎ−トデシルメルカプタン、ｔ−ドテジルメルカプタン、チオグリコール酸などのメルカプタン類、ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイドなどのキサントゲン類、ターピノーレン、α−メチルスチレンダイマーなどの通常の乳化重合に使用されるものを用いることができる。
分子量調節剤の使用量は、単量体１００質量部に対して通常５質量部以下である。
As molecular weight regulators, halogenated hydrocarbons such as chloroform and carbon tetrachloride, mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-todecyl mercaptan, t-dotezyl mercaptan, thioglycolic acid, dimethyl What is used for normal emulsion polymerization, such as xanthogens, such as xanthogen disulfide and diisopropyl xanthogen disulfide, terpinolene, and α-methylstyrene dimer, can be used.
The usage-amount of a molecular weight regulator is 5 mass parts or less normally with respect to 100 mass parts of monomers.
第１段階の乳化重合工程は、重合温度が４０〜６０℃の範囲で行われることが好ましい。重合温度が４０℃未満である場合には、重合反応が進行し難くなり、ポリマー粒子の成長が不十分なものになってしまう傾向がある。一方、重合温度が６０℃を超える場合には、重合反応が過剰に進行してしまい、直鎖高分子量化ができず、また三次元架橋抑制が困難になってしまう傾向がある。
また、第１段階の乳化重合工程の重合時間は、単量体の種類や組成比、重合温度、重合転化率などを考慮して設定されるが、例えば４〜１０時間である。
第１段階の乳化重合工程においては、重合転化率が５０％以上であることが好ましく、より好ましくは６０％以上である。重合転化率が５０％未満の状態で、第２段階の乳化重合工程を行った場合には、直鎖高分子量化が不十分なものになってしまう傾向がある。
The first stage emulsion polymerization step is preferably carried out at a polymerization temperature in the range of 40 to 60 ° C. When the polymerization temperature is lower than 40 ° C., the polymerization reaction does not proceed easily, and the polymer particles tend to be insufficiently grown. On the other hand, when the polymerization temperature exceeds 60 ° C., the polymerization reaction proceeds excessively, the linear high molecular weight cannot be achieved, and the three-dimensional cross-linking suppression tends to be difficult.
The polymerization time in the first stage emulsion polymerization step is set in consideration of the type and composition ratio of the monomer, the polymerization temperature, the polymerization conversion rate, etc., and is, for example, 4 to 10 hours.
In the first stage emulsion polymerization step, the polymerization conversion rate is preferably 50% or more, more preferably 60% or more. When the second stage emulsion polymerization step is performed in a state where the polymerization conversion rate is less than 50%, the straight chain high molecular weight tends to be insufficient.
第２段階の乳化重合工程は、第１段階の乳化重合工程に続いて、反応系に上記の単量体混合物（Ｙ）を連続的にまたは断続的に添加しながら行われる。ここで、反応系には、単量体混合物（Ｙ）と共に、分子量調節剤などを添加することができる。
このような第２段階の乳化重合工程は、重合温度が５０〜７０℃の範囲で行われることが好ましい。重合温度が５０℃未満である場合には、重合反応が進行し難くなり、ポリマー粒子の成長が不十分なものになってしまう傾向がある。一方、重合温度が７０℃を超える場合には、重合反応が過剰に進行してしまい、直鎖高分子量化ができず、また三次元架橋抑制が困難になってしまう傾向がある。
また、第２段階の乳化重合工程の重合時間は、単量体の種類や組成比、重合温度、重合転化率などを考慮して設定されるが、例えば１〜５時間である。
The second stage emulsion polymerization step is carried out following the first step emulsion polymerization step while continuously or intermittently adding the monomer mixture (Y) to the reaction system. Here, a molecular weight regulator etc. can be added to a reaction system with a monomer mixture (Y).
Such a second stage emulsion polymerization step is preferably carried out at a polymerization temperature in the range of 50 to 70 ° C. When the polymerization temperature is less than 50 ° C., the polymerization reaction does not proceed easily, and the polymer particles tend to be insufficiently grown. On the other hand, when the polymerization temperature exceeds 70 ° C., the polymerization reaction proceeds excessively, the linear high molecular weight cannot be achieved, and the three-dimensional cross-linking suppression tends to be difficult.
The polymerization time of the second stage emulsion polymerization step is set in consideration of the type and composition ratio of the monomer, the polymerization temperature, the polymerization conversion rate, etc., and is, for example, 1 to 5 hours.
第３段階の乳化重合工程は、第２段階の乳化重合工程に続いて、反応系に上記の単量体混合物（Ｚ）を連続的にまたは断続的に添加しながら行われる。ここで、反応系には、単量体混合物（Ｚ）と共に、分子量調節剤などを添加することができる。
このような第３段階の乳化重合工程は、第２段階の乳化重合工程と同様に、重合温度が５０〜７０℃の範囲で行われることが好ましい。
また、第３段階の乳化重合工程の重合時間は、単量体の種類や組成比、重合温度、重合転化率などを考慮して設定されるが、例えば５〜１５時間である。
第３段階の乳化重合工程においては、単量体全体の重合転化率が８０％以上であることが好ましく、より好ましくは８５％以上である。
The third stage emulsion polymerization process is performed while continuously or intermittently adding the monomer mixture (Z) to the reaction system following the second stage emulsion polymerization process. Here, a molecular weight regulator etc. can be added to a reaction system with a monomer mixture (Z).
Such a third stage emulsion polymerization process is preferably carried out at a polymerization temperature in the range of 50 to 70 ° C., as in the second stage emulsion polymerization process.
The polymerization time of the third stage emulsion polymerization step is set in consideration of the type and composition ratio of the monomer, the polymerization temperature, the polymerization conversion rate, etc., and is, for example, 5 to 15 hours.
In the third stage emulsion polymerization step, the polymerization conversion rate of the whole monomer is preferably 80% or more, more preferably 85% or more.
〔ラテックス〕
本発明の電極用バインダーを構成するラテックスは、分散粒子の平均粒子径が５０〜１５０ｎｍであることが好ましく、より好ましくは７０〜１４０ｎｍである。平均粒子径が５０ｎｍ未満である場合には、電極を形成する際の乾燥工程において、ポリマーのマイグレーションが生じやすくなるため、得られる電極は組成が不均一なものとなり易い傾向がある。一方、数平均粒子径が１５０ｎｍを超える場合には、得られる電極中の材料間で十分な有効接着点数を得難い傾向がある。
また、ラテックスを構成するポリマーのガラス転移点は−１００〜１００℃であることが好ましく、より好ましくは−５０〜７０℃である。ガラス転移点が−１００℃未満である場合には、当該ポリマーがべとつき易くなり、十分なプレス加工性を得難い傾向がある。一方、ガラス転移点が１００℃を超える場合には、ポリマーが硬くなり過ぎて、得られる電極は、柔軟性に乏しいものとなってしまう傾向がある。
また、ラテックス中の固形分濃度は、３０〜７０質量％であることが好ましく、より好ましくは４０〜６０質量％である。
〔latex〕
The latex constituting the electrode binder of the present invention preferably has an average particle size of dispersed particles of 50 to 150 nm, more preferably 70 to 140 nm. When the average particle diameter is less than 50 nm, polymer migration tends to occur in the drying step when forming the electrode, and the resulting electrode tends to be non-uniform in composition. On the other hand, when the number average particle diameter exceeds 150 nm, it tends to be difficult to obtain a sufficient number of effective adhesion points between the materials in the obtained electrode.
Moreover, it is preferable that the glass transition point of the polymer which comprises latex is -100-100 degreeC, More preferably, it is -50-70 degreeC. When the glass transition point is less than −100 ° C., the polymer tends to be sticky, and it is difficult to obtain sufficient press workability. On the other hand, when the glass transition point exceeds 100 ° C., the polymer becomes too hard and the obtained electrode tends to be poor in flexibility.
Moreover, it is preferable that the solid content concentration in latex is 30-70 mass%, More preferably, it is 40-60 mass%.
このようなラテックスよりなる電極用バインダーによれば、後述する実施例から明らかなように、プレス加工における剥離または破壊が生じることがなくて良好なプレス加工性が得られ、しかも、集電体に対する密着性が高い電極層を形成することができる。 According to the electrode binder made of such a latex, as will be apparent from Examples described later, exfoliation or breakage in press working does not occur, and good press workability can be obtained. An electrode layer with high adhesion can be formed.
〔電極用組成物〕
本発明の電極用バインダーにおいては、電極活物質と混合されることによって、エネルギーデバイス電極用組成物（以下、「電極用組成物」という。）が調製される。
電極活物質は、特に限定されるものではないが、リチウムイオン二次電池電極に用いる場合には、負極用として、カーボン、例えばフェノール樹脂、ポリアクリロニトリル、セルロース等の有機高分子化合物を焼成することにより得られる炭素材料、コークスやピッチを焼成することにより得られる炭素材料、人造グラファイト、天然グラファイトなどを用いることができ、また、電気二重層キャパシタ電極に用いる場合には、活性炭、活性炭繊維、シリカ、アルミナなどを用いることができ、また、リチウムイオンキャパシタ電極に用いる場合には、黒鉛、難黒鉛化炭素、ハードカーボン、コークスなとの炭素材料や、ポリアセン系有機半導体（ＰＡＳ）などを用いることができる。
また、電極用組成物には、増粘剤、ヘキサメタリン酸ソーダ、トリポリリン酸ソーダ、ポリアクリル酸ソーダなどの分散剤、ラテックスの安定化剤としてのノニオン性またはアニオン性界面活性剤、消泡剤などの添加剤が含有されていてもよい。
(Electrode composition)
In the electrode binder of the present invention, an energy device electrode composition (hereinafter referred to as “electrode composition”) is prepared by mixing with an electrode active material.
The electrode active material is not particularly limited, but when used for a lithium ion secondary battery electrode, an organic polymer compound such as carbon, for example, phenol resin, polyacrylonitrile, cellulose, etc. is fired for the negative electrode. Can be used, carbon materials obtained by firing coke or pitch, artificial graphite, natural graphite, etc., and when used for electric double layer capacitor electrodes, activated carbon, activated carbon fiber, silica Alumina, etc. can be used, and when used for lithium ion capacitor electrodes, carbon materials such as graphite, non-graphitizable carbon, hard carbon, coke, polyacene organic semiconductor (PAS), etc. should be used. Can do.
In addition, the electrode composition includes a thickener, a dispersant such as sodium hexametaphosphate, sodium tripolyphosphate, sodium polyacrylate, a nonionic or anionic surfactant as a latex stabilizer, an antifoaming agent, etc. The additive may be contained.
電極用組成物においては、電極活物質１００質量部に対して、電極用バインダーにおける固形分が０．１〜１０質量部の割合で含有されていることが好ましく、より好ましくは０．３〜４質量部である。電極用バインダーの固形分の割合が過小である場合には、良好な密着性が得られなくなる傾向にある。一方、電極用バインダーの固形分の割合が過大である場合には、過電圧が上昇して電池特性に影響を及ぼす傾向にある。 In the electrode composition, the solid content in the electrode binder is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 4 parts per 100 parts by mass of the electrode active material. Part by mass. When the ratio of the solid content of the electrode binder is too small, good adhesion tends not to be obtained. On the other hand, when the ratio of the solid content of the binder for electrodes is excessive, the overvoltage tends to increase and affect the battery characteristics.
電極用組成物の調製において、電極用バインダーと、電極活物質と、必要に応じて用いられる添加剤とを混合する手段としては、攪拌機、脱泡機、ビーズミル、高圧ホモジナイザーなどを利用することができる。
また、電極用組成物の調製においては、減圧下で行うことができ、これにより、得られる電極層内に気泡が生じることを防止することができる。
In the preparation of the electrode composition, as a means for mixing the electrode binder, the electrode active material, and the additive used as necessary, a stirrer, a defoamer, a bead mill, a high-pressure homogenizer, or the like can be used. it can.
In addition, the preparation of the electrode composition can be carried out under reduced pressure, thereby preventing bubbles from being generated in the obtained electrode layer.
〔エネルギーデバイス電極〕
本発明においては、上記の電極用組成物を集電体の表面に塗布して乾燥処理し、得られる塗膜をプレス加工することにより、当該集電体の表面に電極層が形成され、以て、エネルギーデバイス電極が得られる。
集電体としては、金属箔、エッチング金属箔、エキスパンドメタルなどからなるもの用いることができ、集電体を構成する材料としては、アルミニウム、銅、ニッケル、タンタル、ステンレス、チタンなどの金属材料から目的とするエネルギーデバイスの種類に応じて適宜選択して用いることができる。また、集電体の厚みは、例えばリチウム二次電池用の電極を構成する場合には、５〜３０μｍ、好ましくは８〜２５μｍであり、例えば電気二重層キャパシタ用の電極を構成する場合には、５〜１００μｍ、好ましくは１０〜７０μｍ、より好ましくは１５〜３０μｍである。
電極用スラリーを塗布する手段としては、ドクターブレード法、リバースロール法、コンマバー法、グラビヤ法、エアーナイフ法などを利用することができる。
また、電極用組成物の塗布膜の乾燥処理の条件としては、処理温度が例えば２０〜２５０℃であることが好ましく、５０〜１５０℃であることが更に好ましい。また、処理時間が例えば１〜１２０分間であることが好ましく、５〜６０分間であることが更に好ましい。
また、プレス加工する手段としては、高圧スーパープレス、ソフトカレンダー、１トンプレス機などを利用することができる。
プレス加工の条件としては、用いる加工機に応じて適宜設定される。
このようにして形成される電極層は、例えば厚みが４０〜１００μｍであり、密度が１．３〜２．０ｇ／ｃｍ2 である。
[Energy device electrode]
In the present invention, an electrode layer is formed on the surface of the current collector by applying the electrode composition to the surface of the current collector and drying, and pressing the resulting coating film. Thus, an energy device electrode is obtained.
As the current collector, a metal foil, an etching metal foil, an expanded metal or the like can be used. As a material constituting the current collector, a metal material such as aluminum, copper, nickel, tantalum, stainless steel, titanium or the like can be used. It can be appropriately selected and used according to the type of the target energy device. Further, the thickness of the current collector is, for example, 5 to 30 μm, preferably 8 to 25 μm when constituting an electrode for a lithium secondary battery. For example, when constituting an electrode for an electric double layer capacitor. 5 to 100 μm, preferably 10 to 70 μm, more preferably 15 to 30 μm.
As a means for applying the electrode slurry, a doctor blade method, a reverse roll method, a comma bar method, a gravure method, an air knife method, or the like can be used.
Moreover, as conditions for the drying process of the coating film of the composition for electrodes, it is preferable that processing temperature is 20-250 degreeC, for example, and it is still more preferable that it is 50-150 degreeC. Moreover, it is preferable that processing time is 1 to 120 minutes, for example, and it is still more preferable that it is 5 to 60 minutes.
Moreover, as a means to press-work, a high pressure super press, a soft calendar, a 1-ton press machine, etc. can be utilized.
The press working conditions are appropriately set according to the processing machine to be used.
Thus the electrode layer thus formed is, for example, a thickness of 40 to 100 [mu] m, density of 1.3~2.0g / cm 2.
〔エネルギーデバイス〕
このようにして得られるエネルギーデバイス電極は、例えばリチウムイオン二次電池、電気二重層キャパシタ、リチウムイオンキャパシタなどのエネルギーデバイスの電極として好適に用いることができる。
本発明によって得られるエネルギーデバイス電極を用いてリチウムイオン二次電池を構成する場合には、電解液として、リチウム化合物からなる電解質が溶媒中に溶解されてなるものが用いられる。
電解質の具体例としては、ＬｉＣｌＯ4 、ＬｉＢＦ4 、ＬｉＩ、ＬｉＰＦ6 、ＬｉＣＦ3 ＳＯ3 、ＬｉＡｓＦ6 、ＬｉＳｂＦ6 、ＬｉＡｌＣｌ4 、ＬｉＣｌ、ＬｉＢｒ、ＬｉＢ（Ｃ2 Ｈ5 ）4 、ＬｉＣＨ3 ＳＯ3 、ＬｉＣ4 Ｆ9 ＳＯ3 、Ｌｉ（Ｃ4 Ｆ3 ＳＯ2 ）2 Ｎ、Ｌｉ［（ＣＯ2 ）2 ］2 Ｂなどが挙げられる。
溶媒の具体例としては、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート等のカーボネート類、γ−ブチロラクトン等のラクトン類、トリメトキシシラン、１，２−ジメトキシエタン、ジエチルエーテル、２−エトキシエタン、テトラヒドロフラン、２−メチルテトラヒドロフラン等のエーテル類、ジメチルスルホキシド等のスルホキシド類、１，３−ジオキソラン、４−メチル−１，３−ジオキソラン等のオキソラン類、アセトニトリル、ニトロメタン等の窒素含有化合物、ギ酸メチル、酢酸メチル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチル、リン酸トリエステル等のエステル類、ジグライム、トリグライム、テトラグライム等のグライム類、アセトン、ジエチルケトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、スルホラン等のスルホン類、２−メチル−２−オキサゾリジノン等のオキサゾリジノン類、１，３−プロパンスルトン、４−ブタンスルトン、ナフタスルトン等のスルトン類などが挙げられる。
また、本発明によって得られるエネルギーデバイス電極を用いて電気二重層キャパシタを構成する場合には、電解液として、上記の溶媒中に、テトラエチルアンモニウムテトラフルオロボレート、トリエチルメチルアンモニウムテトラフルオロボレート、テトラエラルアンモニウムヘキサフルオロホスフェート等の電解質が溶解されてなるものが用いられる。
また、本発明によって得られるエネルギーデバイス電極を用いてリチウムイオンキャパシタを構成する場合には、電解液として、上記のリチウムイオン二次電池を構成する場合と同様のものを用いることができる。
[Energy device]
The energy device electrode thus obtained can be suitably used as an electrode of an energy device such as a lithium ion secondary battery, an electric double layer capacitor, or a lithium ion capacitor.
When a lithium ion secondary battery is configured using the energy device electrode obtained by the present invention, an electrolyte solution in which an electrolyte made of a lithium compound is dissolved in a solvent is used.
Specific examples of the electrolyte, LiClO 4, LiBF 4, LiI , LiPF 6, LiCF 3 SO 3, LiAsF 6, LiSbF 6, LiAlCl 4, LiCl, LiBr, LiB (C 2 H 5) 4, LiCH 3 SO 3, Examples include LiC 4 F 9 SO 3 , Li (C 4 F 3 SO 2 ) 2 N, Li [(CO 2 ) 2 ] 2 B, and the like.
Specific examples of the solvent include carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; lactones such as γ-butyrolactone; trimethoxysilane, 1,2-dimethoxyethane, diethyl Ethers, ethers such as 2-ethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, sulfoxides such as dimethyl sulfoxide, oxolanes such as 1,3-dioxolane, 4-methyl-1,3-dioxolane, acetonitrile, nitromethane, etc. Nitrogen-containing compounds, methyl formate, methyl acetate, butyl acetate, methyl propionate, ethyl propionate, phosphate triesters, diglyme, triglyme, tetragram Grimes such as acetone, ketones such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, sulfones such as sulfolane, oxazolidinones such as 2-methyl-2-oxazolidinone, 1,3-propane sultone, 4-butane sultone, And sultone such as naphtha sultone.
In the case where an electric double layer capacitor is constituted using the energy device electrode obtained by the present invention, tetraethylammonium tetrafluoroborate, triethylmethylammonium tetrafluoroborate, tetraethylammonium in the above-mentioned solvent as an electrolytic solution. A material in which an electrolyte such as hexafluorophosphate is dissolved is used.
Moreover, when comprising a lithium ion capacitor using the energy device electrode obtained by this invention, the thing similar to the case where said lithium ion secondary battery is comprised can be used as electrolyte solution.
以下、本発明の具体的な実施例について説明するが、本発明は、これらの実施例に限定されるものではない。なお、以下において、「部」は「質量部」を意味する。
また、以下の実施例および比較例において、分散粒子の平均粒子径およびポリマーのガラス転移点は、下記の方法によって測定した。
（１）分散粒子の平均粒子径：
大塚電子（株）製レーザー粒径解析システムＬＰＡ−３０００ｓ／３１００を用いて粒子径を測定した。
（２）ガラス転移点（Ｔｇ）：
電極用バインダーをガラス板に塗布し、１２０℃で１時間乾燥することにより、重合体フィルムを形成し、得られたフィルムを、セイコー電子工業（株）製示差走査熱量計を用いてガラス転移点（Ｔｇ）を測定した。
Specific examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “part” means “part by mass”.
In the following Examples and Comparative Examples, the average particle diameter of dispersed particles and the glass transition point of the polymer were measured by the following methods.
(1) Average particle diameter of dispersed particles:
The particle size was measured using a laser particle size analysis system LPA-3000s / 3100 manufactured by Otsuka Electronics Co., Ltd.
(2) Glass transition point (Tg):
An electrode binder is applied to a glass plate and dried at 120 ° C. for 1 hour to form a polymer film, and the obtained film is subjected to a glass transition point using a differential scanning calorimeter manufactured by Seiko Instruments Inc. (Tg) was measured.
〈実施例１〜５〉
（１）第１段階の乳化重合工程：
撹拌機を備えた、温度調節の可能なオートクレーブ中に、水２００部、ドデシルベンゼンスルホン酸ナトリウム０．５部、過硫酸カリウム１．０部、重亜硫酸ナトリウム０．５部、並びに下記表１に示す分子量調節剤および単量体混合物（Ｘ）を一括して仕込み、５０℃で６．５時間の条件で乳化重合を行い、重合転化率が７０％以上であることを確認した。
（２）第２段階の乳化重合工程：
上記第１段階の乳化重合工程に続き、下記表１に示す分子量調節剤および単量体混合物（Ｙ）を５５℃で２時間にわたって連続的に添加して乳化重合を行った。
（３）第３段階の乳化重合工程：
上記第２段階の乳化重合工程に続き、下記表１に示す分子量調節剤および単量体混合物（Ｚ）を６０℃で８時間にわたって連続的に添加して乳化重合を行うことにより、ラテックスを得た。最終的な重合添加率は、９３〜９９％であった。
（４）電極用バインダーの調製：
以上のようにして得られたラテックスに対し、水酸化ナトリウム水溶液により、ｐＨを７．２に調整した後、減圧処理によって濃縮することにより、固形分濃度が４９質量％の電極用バインダーを調製した。
<Examples 1-5>
(1) First stage emulsion polymerization step:
In a temperature-controllable autoclave equipped with a stirrer, 200 parts of water, 0.5 part of sodium dodecylbenzenesulfonate, 1.0 part of potassium persulfate, 0.5 part of sodium bisulfite and the following Table 1 The molecular weight regulator and monomer mixture (X) shown were charged all at once, and emulsion polymerization was carried out at 50 ° C. for 6.5 hours, and it was confirmed that the polymerization conversion was 70% or more.
(2) Second stage emulsion polymerization step:
Following the emulsion polymerization step in the first stage, emulsion polymerization was carried out by continuously adding the molecular weight regulator and monomer mixture (Y) shown in Table 1 below at 55 ° C. over 2 hours.
(3) Third stage emulsion polymerization step:
Following the second stage emulsion polymerization step, the molecular weight regulator and monomer mixture (Z) shown in Table 1 below are continuously added at 60 ° C. over 8 hours to carry out emulsion polymerization to obtain a latex. It was. The final polymerization addition rate was 93 to 99%.
(4) Preparation of electrode binder:
The latex obtained as described above was adjusted to pH 7.2 with an aqueous sodium hydroxide solution and then concentrated by decompression to prepare a binder for an electrode having a solid content concentration of 49% by mass. .
〈実施例６〉
（１）第１段階の乳化重合工程：
撹拌機を備えた、温度調節の可能なオートクレーブ中に、水２００部、ドデシルベンゼンスルホン酸ナトリウム０．５部、過硫酸カリウム１．０部、重亜硫酸ナトリウム０．５部、並びに下記表１に示す分子量調節剤および単量体混合物（Ｘ）を一括して仕込み、４０℃で６．５時間の条件で乳化重合を行い、重合転化率が７０％以上であることを確認した。
（２）第２段階の乳化重合工程：
上記第１段階の乳化重合工程に続き、下記表１に示す分子量調節剤および単量体混合物（Ｙ）を５０℃で２時間にわたって連続的に添加して乳化重合を行った。
（３）第３段階の乳化重合工程：
上記第２段階の乳化重合工程に続き、下記表１に示す分子量調節剤および単量体混合物（Ｚ）を５５℃で８時間にわたって連続的に添加して乳化重合を行うことにより、ラテックスを得た。最終的な重合添加率は、９３〜９９％であった。
（４）電極用バインダーの調製：
以上のようにして得られたラテックスに対し、水酸化ナトリウム水溶液により、ｐＨを７．２に調整した後、減圧処理によって濃縮することにより、固形分濃度が４９質量％の電極用バインダーを調製した。
得られた電極用バインダーにおける分散粒子の平均粒子径およびポリマーのガラス転移点を下記表１に示す。
<Example 6>
(1) First stage emulsion polymerization step:
In a temperature-controllable autoclave equipped with a stirrer, 200 parts of water, 0.5 part of sodium dodecylbenzenesulfonate, 1.0 part of potassium persulfate, 0.5 part of sodium bisulfite and the following Table 1 The molecular weight regulator and the monomer mixture (X) shown were charged all at once, and emulsion polymerization was carried out at 40 ° C. for 6.5 hours, and it was confirmed that the polymerization conversion was 70% or more.
(2) Second stage emulsion polymerization step:
Following the emulsion polymerization step in the first stage, the molecular weight regulator and monomer mixture (Y) shown in Table 1 below were continuously added at 50 ° C. over 2 hours to carry out emulsion polymerization.
(3) Third stage emulsion polymerization step:
Following the second stage emulsion polymerization step, latex is obtained by performing emulsion polymerization by continuously adding the molecular weight regulator and monomer mixture (Z) shown in Table 1 below at 55 ° C. over 8 hours. It was. The final polymerization addition rate was 93 to 99%.
(4) Preparation of electrode binder:
The latex obtained as described above was adjusted to pH 7.2 with an aqueous sodium hydroxide solution and then concentrated by decompression to prepare a binder for an electrode having a solid content concentration of 49% by mass. .
The average particle diameter of the dispersed particles and the glass transition point of the polymer in the obtained binder for electrodes are shown in Table 1 below.
〈実施例７〉
（１）第１段階の乳化重合工程：
撹拌機を備えた、温度調節の可能なオートクレーブ中に、水２００部、ドデシルベンゼンスルホン酸ナトリウム０．５部、過硫酸カリウム１．０部、重亜硫酸ナトリウム０．５部、並びに下記表１に示す分子量調節剤および単量体混合物（Ｘ）を一括して仕込み、５５℃で６．５時間の条件で乳化重合を行い、重合転化率が７０％以上であることを確認した。
（２）第２段階の乳化重合工程：
上記第１段階の乳化重合工程に続き、下記表１に示す分子量調節剤および単量体混合物（Ｙ）を６０℃で２時間にわたって連続的に添加して乳化重合を行った。
（３）第３段階の乳化重合工程：
上記第２段階の乳化重合工程に続き、下記表１に示す分子量調節剤および単量体混合物（Ｚ）を６５℃で８時間にわたって連続的に添加して乳化重合を行うことにより、ラテックスを得た。最終的な重合添加率は、９３〜９９％であった。
（４）電極用バインダーの調製：
以上のようにして得られたラテックスに対し、水酸化ナトリウム水溶液により、ｐＨを７．２に調整した後、減圧処理によって濃縮することにより、固形分濃度が４９質量％の電極用バインダーを調製した。
得られた電極用バインダーにおける分散粒子の平均粒子径およびポリマーのガラス転移点を下記表１に示す。
<Example 7>
(1) First stage emulsion polymerization step:
In a temperature-controllable autoclave equipped with a stirrer, 200 parts of water, 0.5 part of sodium dodecylbenzenesulfonate, 1.0 part of potassium persulfate, 0.5 part of sodium bisulfite and the following Table 1 The molecular weight regulator and monomer mixture (X) shown were charged all at once, and emulsion polymerization was carried out at 55 ° C. for 6.5 hours, and it was confirmed that the polymerization conversion was 70% or more.
(2) Second stage emulsion polymerization step:
Following the emulsion polymerization step in the first stage, the molecular weight regulator and monomer mixture (Y) shown in Table 1 below were continuously added at 60 ° C. over 2 hours to carry out emulsion polymerization.
(3) Third stage emulsion polymerization step:
Following the second stage emulsion polymerization step, latex is obtained by performing emulsion polymerization by continuously adding the molecular weight regulator and monomer mixture (Z) shown in Table 1 below at 65 ° C. over 8 hours. It was. The final polymerization addition rate was 93 to 99%.
(4) Preparation of electrode binder:
The latex obtained as described above was adjusted to pH 7.2 with an aqueous sodium hydroxide solution and then concentrated by decompression to prepare a binder for an electrode having a solid content concentration of 49% by mass. .
The average particle diameter of the dispersed particles and the glass transition point of the polymer in the obtained binder for electrodes are shown in Table 1 below.
〈実施例８〉
（１）第１段階の乳化重合工程：
撹拌機を備えた、温度調節の可能なオートクレーブ中に、水２００部、ドデシルベンゼンスルホン酸ナトリウム０．５部、過硫酸カリウム１．０部、重亜硫酸ナトリウム０．５部、並びに下記表１に示す分子量調節剤および単量体混合物（Ｘ）を一括して仕込み、７０℃で６．５時間の条件で乳化重合を行い、重合転化率が７０％以上であることを確認した。
（２）第２段階の乳化重合工程：
上記第１段階の乳化重合工程に続き、下記表１に示す分子量調節剤および単量体混合物（Ｙ）を７５℃で２時間にわたって連続的に添加して乳化重合を行った。
（３）第３段階の乳化重合工程：
上記第２段階の乳化重合工程に続き、下記表１に示す分子量調節剤および単量体混合物（Ｚ）を８０℃で８時間にわたって連続的に添加して乳化重合を行うことにより、ラテックスを得た。最終的な重合添加率は、９３〜９９％であった。
（４）電極用バインダーの調製：
以上のようにして得られたラテックスに対し、水酸化ナトリウム水溶液により、ｐＨを７．２に調整した後、減圧処理によって濃縮することにより、固形分濃度が４９質量％の電極用バインダーを調製した。
得られた電極用バインダーにおける分散粒子の平均粒子径およびポリマーのガラス転移点を下記表１に示す。
<Example 8>
(1) First stage emulsion polymerization step:
In a temperature-controllable autoclave equipped with a stirrer, 200 parts of water, 0.5 part of sodium dodecylbenzenesulfonate, 1.0 part of potassium persulfate, 0.5 part of sodium bisulfite and the following Table 1 The molecular weight regulator shown and the monomer mixture (X) were charged all at once, and emulsion polymerization was performed at 70 ° C. for 6.5 hours, and it was confirmed that the polymerization conversion was 70% or more.
(2) Second stage emulsion polymerization step:
Following the emulsion polymerization step in the first stage, the molecular weight regulator and monomer mixture (Y) shown in Table 1 below were continuously added at 75 ° C. over 2 hours to carry out emulsion polymerization.
(3) Third stage emulsion polymerization step:
Following the emulsion polymerization step in the second stage, a latex is obtained by continuously adding a molecular weight regulator and a monomer mixture (Z) shown in Table 1 below at 80 ° C. over 8 hours to carry out emulsion polymerization. It was. The final polymerization addition rate was 93 to 99%.
(4) Preparation of electrode binder:
The latex obtained as described above was adjusted to pH 7.2 with an aqueous sodium hydroxide solution and then concentrated by decompression to prepare a binder for an electrode having a solid content concentration of 49% by mass. .
The average particle diameter of the dispersed particles and the glass transition point of the polymer in the obtained binder for electrodes are shown in Table 1 below.
〈比較例１〉
撹拌機を備えた、温度調節の可能なオートクレーブ中に、水２００部、ドデシルベンゼンスルホン酸ナトリウム０．５部、過硫酸カリウム１．０部、重亜硫酸ナトリウム０．５部、並びに下記表１に示す分子量調節剤および単量体混合物（Ｘ）を一括して仕込み、５０℃で１１時間、次いで５５℃で６時間の条件で乳化重合を行うことにより、ラテックスを得た。最終的な重合添加率は、９３〜９９％であった。
以上のようにして得られたラテックスに対し、水酸化ナトリウム水溶液により、ｐＨを７．２に調整した後、減圧処理によって濃縮することにより、固形分濃度が４９質量％の電極用バインダーを調製した。
得られた電極用バインダーにおける分散粒子の平均粒子径およびポリマーのガラス転移点を下記表１に示す。
<Comparative example 1>
In a temperature-controllable autoclave equipped with a stirrer, 200 parts of water, 0.5 part of sodium dodecylbenzenesulfonate, 1.0 part of potassium persulfate, 0.5 part of sodium bisulfite and the following Table 1 The molecular weight regulator and monomer mixture (X) shown were charged all at once, and emulsion polymerization was carried out at 50 ° C. for 11 hours and then at 55 ° C. for 6 hours to obtain a latex. The final polymerization addition rate was 93 to 99%.
The latex obtained as described above was adjusted to pH 7.2 with an aqueous sodium hydroxide solution and then concentrated by decompression to prepare a binder for an electrode having a solid content concentration of 49% by mass. .
The average particle diameter of the dispersed particles and the glass transition point of the polymer in the obtained binder for electrodes are shown in Table 1 below.
〈比較例２〉
撹拌機を備えた、温度調節の可能なオートクレーブ中に、水２００部、ドデシルベンゼンスルホン酸ナトリウム０．５部、過硫酸カリウム１．０部、重亜硫酸ナトリウム０．５部、並びに下記表１に示す分子量調節剤および単量体混合物（Ｘ）を一括して仕込み、７０℃で１１時間、次いで７５℃で６時間の条件で乳化重合を行うことにより、ラテックスを得た。最終的な重合添加率は、９３〜９９％であった。
以上のようにして得られたラテックスに対し、水酸化ナトリウム水溶液により、ｐＨを７．２に調整した後、減圧処理によって濃縮することにより、固形分濃度が４９質量％の電極用バインダーを調製した。
得られた電極用バインダーにおける分散粒子の平均粒子径およびポリマーのガラス転移点を下記表１に示す。
<Comparative example 2>
In a temperature-controllable autoclave equipped with a stirrer, 200 parts of water, 0.5 part of sodium dodecylbenzenesulfonate, 1.0 part of potassium persulfate, 0.5 part of sodium bisulfite and the following Table 1 A latex was obtained by batch charging the molecular weight regulator and the monomer mixture (X) shown, and performing emulsion polymerization at 70 ° C. for 11 hours and then at 75 ° C. for 6 hours. The final polymerization addition rate was 93 to 99%.
The latex obtained as described above was adjusted to pH 7.2 with an aqueous sodium hydroxide solution and then concentrated by decompression to prepare a binder for an electrode having a solid content concentration of 49% by mass. .
The average particle diameter of the dispersed particles and the glass transition point of the polymer in the obtained binder for electrodes are shown in Table 1 below.
上記表１において、「ＢＤ」は１，３−ブタジエン、「ＳＴ」はスチレン、「ＭＭＡ」はメタクリル酸メチル、「ＡＮ」はアクリロニトリル、「ＡＡ」はアクリル酸、「ＩＡ」はイタコン酸、「ｔ−ＤＭ」はｔ−ドデシルメルカプタン、「α−ＭＳＤ」はα−メチルスチレンダイマーを示す。 In Table 1 above, “BD” is 1,3-butadiene, “ST” is styrene, “MMA” is methyl methacrylate, “AN” is acrylonitrile, “AA” is acrylic acid, “IA” is itaconic acid, “ “t-DM” represents t-dodecyl mercaptan, and “α-MSD” represents α-methylstyrene dimer.
実施例１〜８および比較例１〜２で得られた電極用バインダーについて、以下のようにして、電極用組成物を調製してその評価を行った。結果を下記表２に示す。
（１）電極用組成物の調製：
リチウムイオン二次電池用黒鉛（平均粒径２０μｍ）１００質量部と、電極用バインダー１質量部と、固形分で１重量部のカルボキシメチルセルロース水溶液と混合することにより、電極用組成物を調製した。
（２）密着強度：
厚さが５０μｍの銅箔よりなる集電体の表面に、電極用組成物を単位面積当たりの質量が２００ｇ／ｍ2 となるよう、ロールコーターによって塗工し、７０℃で２０分間乾燥し、さらに１２０℃で２０分間乾燥した後、塗膜を室温でプレスすることにより、厚さが９０μｍの電極層を有する電極を作製した。得られた電極について、テスター産業（株）製の９０°剥離試験機により、集電体に対する電極層の密着強度を測定した。
（３）プレス加工性：
上記（１）と同様にして電極を作製し、得られた電極を、テスター産業（株）の小型プレス機により、５００ｋｇ／ｃｍの荷重で厚み方向に加圧し、電極層の剥離状態および破壊状態を目視で観察し、電極層の剥離および破壊が認められない場合を「○」、微小および部分的な電極層の剥離および破壊が認められた場合を「△」、全体および大部分の電極層剥離および破壊が認められた場合を「×」として評価した。
About the binder for electrodes obtained in Examples 1-8 and Comparative Examples 1-2, the composition for electrodes was prepared and evaluated as follows. The results are shown in Table 2 below.
(1) Preparation of electrode composition:
An electrode composition was prepared by mixing 100 parts by weight of graphite for lithium ion secondary batteries (average particle size 20 μm), 1 part by weight of an electrode binder, and 1 part by weight of a carboxymethylcellulose aqueous solution in solid content.
(2) Adhesion strength:
On the surface of the current collector made of copper foil having a thickness of 50 μm, the electrode composition was applied by a roll coater so that the mass per unit area was 200 g / m 2, and dried at 70 ° C. for 20 minutes. After further drying at 120 ° C. for 20 minutes, the coating film was pressed at room temperature to produce an electrode having an electrode layer having a thickness of 90 μm. About the obtained electrode, the adhesion strength of the electrode layer with respect to an electrical power collector was measured with the 90 degree peeling tester by a tester industry Co., Ltd. product.
(3) Press workability:
An electrode was produced in the same manner as in (1) above, and the obtained electrode was pressed in the thickness direction with a load of 500 kg / cm by a small press machine of Tester Sangyo Co., Ltd. Is observed when the electrode layer is not peeled off or broken, and “△” is marked when a minute or partial peeling of the electrode layer is observed. The case where peeling and destruction were observed was evaluated as “x”.
表２の結果から明らかなように、実施例に係る電極用バインダーによれば、プレス加工における剥離または破壊が生じることがなくて良好なプレス加工性が得られ、しかも、集電体に対する密着性が高い電極層を形成することができることが確認された。 As is apparent from the results in Table 2, the electrode binder according to the example provides good press workability without causing peeling or breakage in press work, and has good adhesion to the current collector. It was confirmed that a high electrode layer can be formed.
Claims (7)
第１段階の乳化重合による重合体成分が、芳香族ビニル化合物、共役ジエン化合物、（メタ）アクリル酸エステルおよびシアン化ビニル化合物を含有する単量体混合物から得られるものであり、
他の段階の乳化重合による重合体成分が、芳香族ビニル化合物、共役ジエン化合物および（メタ）アクリル酸エステルを含有する単量体混合物から得られるものである
ことを特徴とするエネルギーデバイス電極用バインダー。 It consists of latex obtained by multistage emulsion polymerization,
The polymer component by emulsion polymerization in the first stage is obtained from a monomer mixture containing an aromatic vinyl compound, a conjugated diene compound, a (meth) acrylic acid ester and a vinyl cyanide compound,
The binder for an energy device electrode, wherein the polymer component obtained by emulsion polymerization in another stage is obtained from a monomer mixture containing an aromatic vinyl compound, a conjugated diene compound and a (meth) acrylic acid ester. .
第１段階の乳化重合による重合体成分が、芳香族ビニル化合物、共役ジエン化合物、（メタ）アクリル酸エステルおよびシアン化ビニル化合物を含有する単量体混合物（Ｘ）から得られるものであり、
第２段階の乳化重合による重合体成分が、芳香族ビニル化合物、共役ジエン化合物および（メタ）アクリル酸エステルを含有する単量体混合物（Ｙ）から得られるものであり、 第３段階の乳化重合による重合体成分が、芳香族ビニル化合物、共役ジエン化合物および（メタ）アクリル酸エステルを含有する単量体混合物（Ｚ）から得られるものであることを特徴とするエネルギーデバイス電極用バインダー。 It consists of a latex obtained by three-stage emulsion polymerization,
The polymer component by the first stage emulsion polymerization is obtained from a monomer mixture (X) containing an aromatic vinyl compound, a conjugated diene compound, a (meth) acrylic acid ester and a vinyl cyanide compound,
The polymer component by the second stage emulsion polymerization is obtained from a monomer mixture (Y) containing an aromatic vinyl compound, a conjugated diene compound and a (meth) acrylic acid ester, and the third stage emulsion polymerization. A binder for an energy device electrode, wherein the polymer component is obtained from a monomer mixture (Z) containing an aromatic vinyl compound, a conjugated diene compound and a (meth) acrylic acid ester.
この工程（１）に続き、反応系中に、芳香族ビニル化合物、共役ジエン化合物および（メタ）アクリル酸エステルを含有する単量体混合物を連続的にまたは断続的に添加しながら乳化重合する工程（２）と
を有することを特徴とするエネルギーデバイス電極用バインダーの製造方法。 (1) emulsion polymerizing a monomer mixture containing an aromatic vinyl compound, a conjugated diene compound, a (meth) acrylic acid ester and a vinyl cyanide compound;
Following this step (1), a step of emulsion polymerization while continuously or intermittently adding a monomer mixture containing an aromatic vinyl compound, a conjugated diene compound and a (meth) acrylic acid ester to the reaction system. (2) The manufacturing method of the binder for energy device electrodes characterized by having.
を有することを特徴とする請求項３乃至請求項５のいずれかに記載のエネルギーデバイス電極用バインダーの製造方法。 Following the step (2), a step of emulsion polymerization while continuously or intermittently adding a monomer mixture containing an aromatic vinyl compound, a conjugated diene compound and a (meth) acrylic acid ester to the reaction system ( 3)
The method for producing a binder for an energy device electrode according to any one of claims 3 to 5, wherein:
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| KR20180059433A (en) | 2015-09-28 | 2018-06-04 | 니폰 제온 가부시키가이샤 | A binder composition for a non-aqueous secondary battery electrode, a slurry composition for a non-aqueous secondary battery electrode, an electrode for a non-aqueous secondary battery, |
| CN107338011A (en) * | 2016-08-16 | 2017-11-10 | 南京工业大学 | A kind of water-dispersed polymer particulate emulsion binder and preparation method thereof |
| CN107338011B (en) * | 2016-08-16 | 2019-06-07 | 南京工业大学 | A kind of water-dispersed polymer particulate emulsion binder and preparation method thereof |
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