JP6527626B1 - Carbon nanotube dispersion liquid and use thereof - Google Patents
Carbon nanotube dispersion liquid and use thereof Download PDFInfo
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- JP6527626B1 JP6527626B1 JP2018153799A JP2018153799A JP6527626B1 JP 6527626 B1 JP6527626 B1 JP 6527626B1 JP 2018153799 A JP2018153799 A JP 2018153799A JP 2018153799 A JP2018153799 A JP 2018153799A JP 6527626 B1 JP6527626 B1 JP 6527626B1
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- carbon nanotube
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- dispersion liquid
- nanotube dispersion
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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
- Compositions Of Macromolecular Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
【課題】本発明では、カーボンナノチューブの濃度が高くても低粘度、且つ分散性と分散液の貯蔵安定性に優れた、水を溶剤とするカーボンナノチューブ分散液を提供することを目的とする。また、均質で良好な塗膜物性と、電池特性に優れる電池電極合剤層を提供することを目的とする。【解決手段】カーボンナノチューブ（Ａ）と、ポリビニルピロリドン（Ｂ）と、水（Ｃ）と、アミン系化合物（Ｄ）と、アセチレン系界面活性剤（Ｅ）とを含有してなり、前記カーボンナノチューブ（Ａ）１００重量部に対して、前記アミン系化合物（Ｄ）を０．５重量部以上、５重量部以下含有し、かつ前記アセチレン系界面活性剤（Ｅ）を１重量部以上、１０重量部以下含有することを特徴とする、カーボンナノチューブ分散液。【選択図】なしAn object of the present invention is to provide a carbon nanotube dispersion liquid using water as a solvent, which has low viscosity even when the concentration of carbon nanotube is high, and is excellent in dispersibility and storage stability of the dispersion liquid. Another object of the present invention is to provide a battery electrode mixture layer which is homogeneous and has excellent coating film properties and battery characteristics. A carbon nanotube (A), polyvinyl pyrrolidone (B), water (C), an amine compound (D), and an acetylenic surfactant (E) are contained, (A) The amine compound (D) is contained in an amount of 0.5 to 5 parts by weight with respect to 100 parts by weight, and 1 to 10 parts by weight of the acetylene-based surfactant (E) Carbon nanotube dispersion liquid characterized by containing less than part. 【Selection chart】 None
Description
本発明は、分散性、貯蔵安定性に優れたカーボンナノチューブ分散液に関する。また、該分散液を使用した電池電極合剤層およびリチウムイオン二次電池に関する。 The present invention relates to a carbon nanotube dispersion excellent in dispersibility and storage stability. The present invention also relates to a battery electrode mixture layer and a lithium ion secondary battery using the dispersion.
近年、携帯電話やノート型パーソナルコンピューターなどの普及に伴って、リチウム二次電池の開発が活発に行われている。さらに、リチウムイオン二次電池は、ハイブリット自動車、プラグインハイブリッド自動車、あるいは電気自動車の電源として大きな市場の伸張が期待されている。これらの用途では、軽量・コンパクト化、特に電気自動車においては、一度の充電での走行距離の大幅な改善が求められており、この課題の解決のためには、それぞれの電池材料における更なる高容量化対策が必要である。 2. Description of the Related Art In recent years, with the spread of mobile phones and notebook personal computers, development of lithium secondary batteries has been actively conducted. Furthermore, lithium ion secondary batteries are expected to be a significant market growth as a power source for hybrid vehicles, plug-in hybrid vehicles, or electric vehicles. In these applications, light weight and compactness, in particular, in electric vehicles, significant improvement in the distance traveled by one charge is required, and in order to solve this problem, each battery material has a higher height. Measures to increase capacity are needed.
リチウム二次電池の電極としては、リチウムイオンを含む正極活物質と導電助剤と有機バインダーなどからなる電極合剤を金属箔の集電体の表面に固着させた正極、及び、リチウムイオンの脱挿入可能な負極活物質と導電助剤と有機バインダーなどからなる電極合剤を金属箔の集電体の表面に固着させた負極が使用されている。正極、負極共に、導電材の配合により活物質の導電性が高められるが、導電材としては、カーボンブラック、ケッチェンブラック、フラーレン、グラフェン、微細炭素材料等が検討されている。特に微細炭素繊維の一種であるカーボンナノチューブは、直径１μｍ以下の太さのチューブ状のカーボンであり、その特異な構造に基づく高い導電性などからリチウムイオン電池用の導電助剤としての使用が検討されている。 As an electrode of a lithium secondary battery, a positive electrode in which an electrode mixture comprising a positive electrode active material containing lithium ions, a conductive additive and an organic binder is fixed to the surface of a current collector of metal foil, lithium ions are removed There is used a negative electrode in which an electrode mixture comprising an insertable negative electrode active material, a conductive additive, an organic binder and the like is fixed to the surface of a current collector of metal foil. The conductivity of the active material is enhanced by blending the conductive material in both the positive electrode and the negative electrode, and carbon black, ketjen black, fullerene, graphene, a fine carbon material, and the like have been studied as the conductive material. In particular, carbon nanotubes, which are a type of fine carbon fibers, are tube-shaped carbons with a diameter of 1 μm or less, and their use as a conductive agent for lithium ion batteries is examined because of their high conductivity based on their unique structure. It is done.
また、近年、特に環境や生産コストへの配慮から、リチウム二次電池電極用塗工液に使用する溶媒を、Ｎ−メチル−２−ピロリドンから水へと切り替えることが強く求められている。Ｎ−メチル−２−ピロリドンは、一般的な溶剤と比較して単に高価なだけでなく、沸点が２００℃以上と非常に高いために溶剤を乾燥する際に多くのエネルギーを必要とし、さらには生体に対して特に有害である懸念が各国で指摘され始めている。 In recent years, it has been strongly demanded to switch the solvent used for the coating solution for lithium secondary battery electrodes from N-methyl-2-pyrrolidone to water, in particular, in consideration of the environment and production cost. N-methyl-2-pyrrolidone is not only expensive compared to common solvents, but also requires a lot of energy when drying the solvent because its boiling point is so high as 200 ° C. or more, and further, Concerns that are particularly harmful to the organism are beginning to be pointed out in each country.
カーボンナノチューブの中でも、外径１０ｎｍ〜数１０ｎｍの多層カーボンナノチューブは比較的安価になりつつあり、リチウムイオン電池用途での実用化が期待されている。平均外径が細いカーボンナノチューブを用いると、少量で効率的に導電ネットワークを形成することができ、リチウムイオン電池の電極中に含まれる導電材量を低減することが期待される。しかしながら、平均外径が細いカーボンナノチューブは凝集力が強いため、十分な分散性を有するカーボンナノチューブ分散液を得ることが難しいという問題がある。 Among carbon nanotubes, multi-walled carbon nanotubes with an outer diameter of 10 nm to several tens of nm are becoming relatively inexpensive, and their practical use in lithium ion battery applications is expected. The use of a carbon nanotube having a narrow average outer diameter can efficiently form a conductive network in a small amount, and is expected to reduce the amount of conductive material contained in an electrode of a lithium ion battery. However, since the carbon nanotubes having a narrow average outer diameter have strong cohesion, there is a problem that it is difficult to obtain a carbon nanotube dispersion having sufficient dispersibility.
上述の問題に対して、様々な分散剤を用いてカーボンナノチューブを分散安定化する方法が提案されている。例えば、特許文献１には、水溶性高分子ポリビニルピロリドン（以下、ＰＶＰ）を用いたＮＭＰへの分散が提案されている。また、特許文献２には、ＰＶＰに代表される非イオン性の樹脂型分散剤を用いた分散が記載されている。さらに、特許文献３には、カーボンブラックと、分散剤と、水系溶媒とを含有するカーボンブラック分散液が提案されている。しかし、水系溶媒及びこれらの樹脂型分散剤を用いて高濃度なカーボンナノチューブ分散液を作製した場合、十分な分散度が得られない場合があるとともに、得られる分散液の粘度が非常に高くなる問題がある。カーボンナノチューブ分散液の粘度が非常に高い場合、分散液の流動性が悪いために、他のバインダー成分や活物質を添加した上での、液の加工性や均質性、塗工性を確保することが困難となり、均一な塗工層を得る事が困難になる。 To address the above-mentioned problems, methods have been proposed for dispersing and stabilizing carbon nanotubes using various dispersants. For example, Patent Document 1 proposes dispersion in NMP using a water-soluble polymer polyvinyl pyrrolidone (hereinafter, PVP). Further, Patent Document 2 describes dispersion using a nonionic resin-type dispersant represented by PVP. Furthermore, Patent Document 3 proposes a carbon black dispersion containing carbon black, a dispersant, and an aqueous solvent. However, when a high concentration carbon nanotube dispersion is prepared using an aqueous solvent and these resin type dispersants, a sufficient degree of dispersion may not be obtained, and the viscosity of the obtained dispersion becomes extremely high. There's a problem. When the viscosity of the carbon nanotube dispersion is very high, the fluidity of the dispersion is poor, so the processability, homogeneity, and coatability of the liquid after adding other binder components and active materials are secured. It becomes difficult to obtain a uniform coating layer.
以上の状況を鑑み、本発明では、カーボンナノチューブの濃度が高くても低粘度、且つ分散性と分散液の貯蔵安定性に優れた、水を溶剤とするカーボンナノチューブ分散液を提供することを目的とする。また、均質で良好な塗膜物性と、電池特性に優れる電池電極合剤層を提供することを目的とする。 In view of the above situation, the object of the present invention is to provide a carbon nanotube dispersion liquid using water as a solvent, which has low viscosity even when the concentration of carbon nanotube is high, and which is excellent in dispersibility and storage stability of dispersion liquid. I assume. Another object of the present invention is to provide a battery electrode mixture layer which is homogeneous and has excellent coating film properties and battery characteristics.
本発明者らは、上記目的を達成するため鋭意検討を行った結果、カーボンナノチューブを水に分散させる際に、分散剤としてポリビニルピロリドン（ＰＶＰ）および、添加剤としてアミン系化合物およびアセチレン系界面活性剤を使用することで高濃度、低粘度、かつ長期保存安定性が良好且つ、リチウムイオン電池の電極用途に好適なカーボンナノチューブ分散液を製造できることを見出し、本発明の完成に至った。 The inventors of the present invention conducted intensive studies to achieve the above object, and as a result, when dispersing carbon nanotubes in water, polyvinyl pyrrolidone (PVP) as a dispersing agent, an amine compound as an additive, and an acetylene based surfactant It has been found that the use of an agent makes it possible to produce a carbon nanotube dispersion which is high in concentration, low in viscosity and excellent in long-term storage stability and suitable for use as an electrode of a lithium ion battery.
すなわち本発明はカーボンナノチューブ（Ａ）と、ポリビニルピロリドン（Ｂ）と、水（Ｃ）と、アミン系化合物（Ｄ）と、アセチレン系界面活性剤（Ｅ）とを含有してなり、
前記カーボンナノチューブ（Ａ）１００重量部に対して、前記アミン系化合物（Ｄ）を０．５重量部以上、５重量部以下含有し、かつ前記アセチレン系界面活性剤（Ｅ）を１重量部以上、１０重量部以下含有することを特徴とする、カーボンナノチューブ分散液に関する。
That is, the present invention comprises carbon nanotubes (A), polyvinyl pyrrolidone (B), water (C), an amine compound (D), and an acetylene surfactant (E),
The amine compound (D) is contained in an amount of 0.5 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the carbon nanotube (A), and 1 part by weight or more of the acetylene surfactant (E) The present invention relates to a carbon nanotube dispersion liquid containing 10 parts by weight or less.
また、本発明は、前記ポリビニルピロリドン（Ｂ）を、前記カーボンナノチューブ（Ａ）１００重量部に対して、１０重量部以上、４０重量部以下含有することを特徴とする、上記カーボンナノチューブ分散液に関する。 Further, the present invention relates to the carbon nanotube dispersion, wherein the polyvinyl pyrrolidone (B) is contained in an amount of 10 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the carbon nanotube (A). .
また、本発明は、アミン系化合物（Ｄ）が、脂肪族１級アミン、脂肪族２級アミン、脂肪族３級アミン、アミノ酸、アルカノールアミン、および脂環式含窒素複素環化合物からなる群より選ばれた１種以上のアミン系化合物であることを特徴とする、上記カーボンナノチューブ分散液に関する。 Further, according to the present invention, the amine compound (D) is selected from the group consisting of aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, amino acids, alkanolamines, and alicyclic nitrogen-containing heterocyclic compounds. The present invention relates to the above-described carbon nanotube dispersion liquid, which is characterized by being one or more selected amine compounds.
また、本発明は、アセチレン系界面活性剤（Ｅ）が、少なくともアセチレン部位と水酸基とを有し、ＨＬＢ値が８以下であることを特徴とする、上記カーボンナノチューブ分散液に関する。 The present invention also relates to the carbon nanotube dispersion liquid, wherein the acetylene-based surfactant (E) has at least an acetylene site and a hydroxyl group, and has an HLB value of 8 or less.
また、本発明は、上記カーボンナノチューブ分散液と、電極活物質とを含有してなる電極用カーボンナノチューブ分散液に関する。 The present invention also relates to a carbon nanotube dispersion liquid for electrode, which contains the above-mentioned carbon nanotube dispersion liquid and an electrode active material.
また、本発明は、上記電極用カーボンナノチューブ分散液を層状に形成してなる電池電極合剤層に関する。 The present invention also relates to a battery electrode mixture layer formed by forming the above-described carbon nanotube dispersion liquid for electrodes into a layer.
また、本発明は、上記電池電極合剤層を備えてなるリチウムイオン二次電池に関する。
The present invention also relates to a lithium ion secondary battery comprising the battery electrode mixture layer.
本発明の好ましい実施態様によれば、高濃度、低粘度、且つ長期保存安定性が良好なカーボンナノチューブ分散液を得ることができる。特に、リチウムイオン電池の電極用途では、当該分散液を使用することで、均質で極板抵抗の低い電池電極合剤層が得られる為、リチウムイオン電池の特性向上に寄与する。 According to a preferred embodiment of the present invention, it is possible to obtain a carbon nanotube dispersion having high concentration, low viscosity, and long-term storage stability. In particular, in the electrode application of a lithium ion battery, by using the dispersion liquid, a battery electrode mixture layer which is homogeneous and has a low electrode plate resistance can be obtained, which contributes to the improvement of the characteristics of the lithium ion battery.
本発明におけるカーボンナノチューブ分散液は、カーボンナノチューブと、ポリビニルピロリドンと、アミン系化合物と、水とを含むことを特徴とする。以下にその詳細を説明する。尚、本明細書では、「カーボンナノチューブ分散液」、「電池用カーボンナノチューブ分散液」を「分散液」と略記することがある。 The carbon nanotube dispersion in the present invention is characterized by containing carbon nanotubes, polyvinyl pyrrolidone, an amine compound, and water. The details will be described below. In the present specification, "carbon nanotube dispersion" and "battery carbon nanotube dispersion" may be abbreviated as "dispersion".
＜カーボンナノチューブ（Ａ）＞
本発明に用いるカーボンナノチューブ（Ａ）は、平面的なグラファイトを円筒状に巻いた形状を有している。カーボンナノチューブは多層カーボンナノチューブまたは、単層カーボンナノチューブもしくはこれらが混在するものであってもよい。単層カーボンナノチューブは一層のグラファイトが巻かれた構造を有する。多層カーボンナノチューブは、二または三以上の層のグラファイトが巻かれた構造を有する。また、カーボンナノチューブ（Ａ）の側壁はグラファイト構造でなくともよい。例えば、アモルファス構造を有する側壁を備えるカーボンナノチューブをカーボンナノチューブ（Ａ）として用いることもできる。
<Carbon nanotube (A)>
The carbon nanotube (A) used in the present invention has a shape in which planar graphite is cylindrically wound. The carbon nanotubes may be multi-walled carbon nanotubes, single-walled carbon nanotubes, or a mixture of these. Single-walled carbon nanotubes have a structure in which one layer of graphite is wound. Multi-walled carbon nanotubes have a structure in which two or more layers of graphite are wound. In addition, the side wall of the carbon nanotube (A) may not have a graphite structure. For example, a carbon nanotube provided with a sidewall having an amorphous structure can also be used as the carbon nanotube (A).
本実施形態のカーボンナノチューブ（Ａ）の形状は限定されない。かかる形状としては、針状、円筒チューブ状、魚骨状（フィッシュボーン又はカップ積層型）、トランプ状（プレートレット）及びコイル状を含む様々な形状が挙げられる。本実施形態においてカーボンナノチューブ（Ａ）の形状は、中でも、針状、又は、円筒チューブ状であることが好ましい。カーボンナノチューブ（Ａ）は、単独の形状、または２種以上の形状の組合せであってもよい。 The shape of the carbon nanotube (A) of the present embodiment is not limited. Such shapes include various shapes including needle-like, cylindrical tube-like, fish-bone-like (fishbone or cup-stacked), card-like (platelet) and coil-like. Among them, the shape of the carbon nanotube (A) in the present embodiment is preferably a needle shape or a cylindrical tube shape. The carbon nanotube (A) may have a single shape or a combination of two or more shapes.
本実施形態のカーボンナノチューブ（Ａ）の外径は５〜２５ｎｍであることが好ましく、８〜２０ｎｍであることがより好ましく、１０〜１５ｎｍであることがさらに好ましい。 The outer diameter of the carbon nanotube (A) of the present embodiment is preferably 5 to 25 nm, more preferably 8 to 20 nm, and still more preferably 10 to 15 nm.
このようなカーボンナノチューブ（Ａ）としては、例えば、単層カーボンナノチューブとして、日本ゼオン社製ＺＥＯＮＡＮＯ ＳＧ１０１（外径：３〜５ｎｍ）、ＯＣＳｉＡｌ社製 ＴＵＢＡＬＬ（外径：約２ｎｍ）等が挙げられるが、これらに限定されるものではない。また、多層カーボンナノチューブとしては、ＡＲＫＥＭＡ社製 Ｇｒａｐｈｉｓｔｒｅｎｇｔｈ（外径：１０〜１５ｎｍ）、ＳＵＳＵＮ Ｓｉｎｏｔｅｃｈ Ｎｅｗ Ｍａｔｅｒｉａｌｓ社製 ＨＣＮＴｓ１０（外径：１０〜２０ｎｍ）、ＨＣＮＴｓ４０（外径：３０〜５０ｎｍ）、Ｎａｎｏｃｙｌ社製 ＮＣ７０００（外径：１０ｎｍ）、ＮＸ７１００（外径：１０ｎｍ）、ＪＥＩＯ社製 ＪＥＮＯＴＵＢＥ８Ａ（外径：６〜９ｎｍ）、ＪＥＮＯＴＵＢＥ１０Ａ（外径：７〜２０ｎｍ）、ＪＥＮＯＴＵＢＥ１０Ｂ（外径：７〜１０ｎｍ）、Ｃｎａｎｏ社製 ＦｌｏＴｕｂｅ９１００（外径：１０〜１５ｎｍ）、ＦｌｏＴｕｂｅ９１１０（外径：１０〜１５ｎｍ）、ＦｌｏＴｕｂｅ７０１０（外径：７〜１１ｎｍ）、Ｋｕｍｈｏ Ｐｅｔｒｏｃｈｅｍｉｃａｌ社製 Ｋ−Ｎａｎｏｓ１００Ｐ（外径：１０〜１５ｎｍ）、Ｋ−Ｎａｎｏｓ１００Ｔ（外径：１０〜１５ｎｍ）、Ｋ−Ｎａｎｏｓ２００Ｐ（外径：５〜１５ｎｍ）等が挙げられるが、これらに限定されるものではない。 Examples of such carbon nanotubes (A) include ZEONANO SG101 (outer diameter: 3 to 5 nm) manufactured by Zeon Corporation, TUBALL (outer diameter: about 2 nm) manufactured by OCSiAl, and the like as single-walled carbon nanotubes. Not limited to these. As multi-walled carbon nanotubes, Graphistrength (outer diameter: 10 to 15 nm) manufactured by ARKEMA, HCNTs 10 (outer diameter: 10 to 20 nm) manufactured by SUSUN Sinotech New Materials, HCNTs 40 (outer diameter: 30 to 50 nm), manufactured by Nanocyl NC7000 (outside diameter: 10 nm), NX7100 (outside diameter: 10 nm), JENOTIO's JENOTUBE 8A (outside diameter: 6 to 9 nm), JENOTUBE 10A (outside diameter: 7 to 20 nm), JENOTUBE 10B (outside diameter: 7 to 10 nm), Cnano FloTube 9100 (OD: 10-15 nm), FloTube 9110 (OD: 10-15 nm), FloTube 7010 (OD: 7-11 nm), Kumho Petrochemic l K-Nanos 100 P (outer diameter: 10 to 15 nm), K-Nanos 100 T (outer diameter: 10 to 15 nm), K-Nanos 200 P (outer diameter: 5 to 15 nm), etc., but are limited thereto is not.
＜ポリビニルピロリドン（Ｂ）＞
ポリビニルピロリドン（Ｂ）（以下、ＰＶＰともいう）としては、重量平均分子量（粘度測定法）が８０００〜３００万の範囲のものが好ましく、具体的には、ＢＡＳＦジャパン社製、商品名：ルビテック（Ｌｕｖｉｔｅｃ）Ｋ１７（Ｋ値：１５．０〜１９．０、低分子量）、Ｋ３０（Ｋ値２７．０〜３３．０）、Ｋ８０（Ｋ値７４．０〜８２．０）、Ｋ８５（Ｋ値８４．０〜８８．０）、Ｋ９０（Ｋ値８８．０〜９２．０）、Ｋ９０ＨＭ（Ｋ値９２．０〜９６．０、高分子量）、ＩＳＰ社製、Ｋ１５、Ｋ３０、Ｋ９０、Ｋ１２０、日本触媒社製、商品名：ポリビニルピロリドンＫ３０（Ｋ値２７．０〜３３．０）、Ｋ８５（Ｋ値８４．０〜８８．０）、Ｋ９０（Ｋ値８８．０〜９６．０）などが挙げられる。ポリビニルピロリドンは、粘度上昇防止の観点から、好ましくは、Ｋ値が１５０以下、さらには、Ｋ値が１００以下である。
<Polyvinylpyrrolidone (B)>
As polyvinyl pyrrolidone (B) (hereinafter, also referred to as PVP), those having a weight average molecular weight (viscosity measurement method) in the range of 8,000 to 3,000,000 are preferable, and specifically, BASF Japan Co., Ltd., trade name: Rubitec ( Luvitec) K17 (K value: 15.0 to 19.0, low molecular weight), K30 (K value 27.0 to 33.0), K80 (K value 74.0 to 82.0), K85 (K value 84) .0 to 88.0), K90 (K value 88.0 to 92.0), K90HM (K value 92.0 to 96.0, high molecular weight), manufactured by ISP, K15, K30, K90, K120, Japan Catalyst company make, trade name: polyvinyl pyrrolidone K30 (K value 27.0-33.0), K85 (K value 84.0-88.0), K90 (K value 88.0-96.0), etc. are mentioned. Be The polyvinyl pyrrolidone preferably has a K value of 150 or less, and further, a K value of 100 or less, from the viewpoint of preventing viscosity increase.
＜水（Ｃ）＞
本発明で用いる水（Ｃ）は、分散液の分散媒として用いる。種々のイオンを含有する一般の水ではなく、イオン交換水（脱イオン水）を使用するのが好ましい。分散媒として、本発明では、ＰＶＰの分散剤としての性能、電池性能を損なわない範囲で、他の溶剤を１種類以上併用しても良いが、本発明の想定する産業上の利用可能性から、水を単独で用いることが好ましい。
<Water (C)>
Water (C) used in the present invention is used as a dispersion medium for the dispersion. It is preferred to use ion-exchanged water (deionized water) rather than general water containing various ions. As the dispersion medium, in the present invention, one or more other solvents may be used in combination as long as the performance of the PVP as a dispersant and the battery performance are not impaired, but from the industrial applicability assumed by the present invention It is preferable to use water alone.
＜アミン系化合物（Ｄ）＞
本発明には、アミン系化合物（Ｄ）を用いる。アミン系化合物（Ｄ）としては、第１アミン（１級アミン）、第２アミン（２級アミン）、第３アミン（３級アミン）が用いられ、アンモニアや第４級アンモニウム化合物は含まない。アミン系化合物は、モノアミン以外にも、分子内に複数のアミノ基を有するジアミン、トリアミン、テトラミンといったアミン系化合物を用いることができる。また、上記以外のものとして、アミノ酸や脂環式含窒素複素環化合物等も使用することができる。よって、本明細書中のアミノ基は１級、２級または３級の官能基である。
<Amine compound (D)>
An amine compound (D) is used in the present invention. As the amine compound (D), primary amines (primary amines), secondary amines (secondary amines) and tertiary amines (tertiary amines) are used, and ammonia and quaternary ammonium compounds are not included. As the amine compound, in addition to monoamines, amine compounds such as diamine, triamine and tetramine having a plurality of amino groups in the molecule can be used. In addition to the above, amino acids and alicyclic nitrogen-containing heterocyclic compounds can also be used. Thus, the amino group in the present specification is a primary, secondary or tertiary functional group.
本発明で用いるアミン系化合物（Ｄ）は、脂肪族１級アミン、脂肪族２級アミン、脂肪族３級アミン、アミノ酸、アルカノールアミン、脂環式含窒素複素環化合物からなる群より選ばれた１種以上のアミン系化合物が好ましく、アミノ基を１つのみ有する、脂肪族１級アミン、脂肪族２級アミン、脂肪族３級アミン、アルカノールアミン、からなる群より選ばれた１種以上のアミン系化合物がより好ましい。 The amine compound (D) used in the present invention is selected from the group consisting of aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, amino acids, alkanolamines and alicyclic nitrogen-containing heterocyclic compounds. One or more kinds of amine compounds are preferable, and one or more kinds selected from the group consisting of aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, and alkanolamines having only one amino group. An amine compound is more preferable.
本発明で使用するアミン系化合物（Ｄ）は、市販品、合成品に関わらず、単独もしくは２種類以上併せて使用することができる。 The amine compound (D) used in the present invention can be used singly or in combination of two or more, regardless of whether it is a commercial product or a synthetic product.
具体的には、例えば、メチルアミン、エチルアミン、ブチルアミン、オクチルアミンなどの脂肪族１級アミン、ジメチルアミン、ジエチルアミン、ジブチルアミンなどの脂肪族２級アミン、トリメチルアミン、トリエチルアミン、ジメチルオクチルアミンなどの脂肪族３級アミン、アラニン、メチオニン、プロリン、セリン、アスパラギン、グルタミン、リシン、アルギニン、ヒスチジン、アスパラギン酸、グルタミン酸、システインなどのアミノ酸、ジメチルアミノエタノール、モノエタノールアミン、ジエタノールアミン、メチルエタノールアミン、トリエタノールアミンなどのアルカノールアミン、ヘキサメチレンテトラミン、モルホリン、ピペリジンなどの脂環式含窒素複素環化合物等が挙げられるが、これらに限定されるものではない。 Specifically, for example, aliphatic primary amines such as methylamine, ethylamine, butylamine and octylamine, aliphatic secondary amines such as dimethylamine, diethylamine and dibutylamine, and aliphatics such as trimethylamine, triethylamine and dimethyloctylamine Tertiary amines, alanine, methionine, proline, serine, asparagine, glutamine, lysine, arginine, histidine, aspartic acid, glutamic acid, amino acids such as cysteine, dimethylaminoethanol, monoethanolamine, diethanolamine, methylethanolamine, triethanolamine, etc. Alkanolamines of the following, alicyclic nitrogen-containing heterocyclic compounds such as hexamethylenetetramine, morpholine, piperidine, etc .; There.
アミン系化合物（Ｄ）の分子量は、１０以上、２０００以下のものが好ましく、１０以上、１０００以下のものがより好ましく、２０以上、５００以下のものがさらに好ましく、３０以上、２００以下のものが特に好ましい。 The molecular weight of the amine compound (D) is preferably 10 or more and 2000 or less, more preferably 10 or more and 1000 or less, still more preferably 20 or more and 500 or less, and 30 or more and 200 or less. Particularly preferred.
アミン系化合物（Ｄ）の炭素数は、１以上、１００以下のものが好ましく、１以上、５０以下のものがより好ましく、１以上、３０以下のものがさらに好ましく、１以上、１０以下のものが特に好ましい。 The carbon number of the amine compound (D) is preferably 1 or more and 100 or less, more preferably 1 or more and 50 or less, still more preferably 1 or more and 30 or less, and 1 or more and 10 or less Is particularly preferred.
アミン系化合物（Ｄ）が脂肪族アミンの場合には、炭素数が１以上４０以下であるものが好ましく、１以上３６以下であるものがより好ましく、１以上２４以下であるものが特に好ましい。 When the amine compound (D) is an aliphatic amine, it preferably has 1 to 40 carbon atoms, more preferably 1 to 36 carbon atoms, and particularly preferably 1 to 24 carbon atoms.
アミン系化合物（Ｄ）の酸解離定数（ｐＫａ）は、６以上、１２以下であることが好ましく、７以上、１１以下であることがより好ましく、８以上、１０．５以下であることが特に好ましい。なお、酸解離定数は、２５℃の水溶液における値である。 The acid dissociation constant (pKa) of the amine compound (D) is preferably 6 or more and 12 or less, more preferably 7 or more and 11 or less, and particularly preferably 8 or more and 10.5 or less preferable. The acid dissociation constant is a value in an aqueous solution at 25 ° C.
アミン系化合物（Ｄ）が有するアミノ基の数は、分散液の貯蔵安定性の観点から、１以上、４以下であることが好ましく、１以上、２以下であることがより好ましく、１であることが特に好ましい。 The number of amino groups contained in the amine compound (D) is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less, from the viewpoint of storage stability of the dispersion. Is particularly preferred.
＜アセチレン系界面活性剤（Ｅ）＞
本発明で用いるアセチレン系界面活性剤（Ｅ）は、顔料の分散性を妨げないものであればよく特に限定されないが、水に溶解するものであることが好ましい。アセチレン系界面活性剤（Ｅ）を用いることにより、カーボンナノチューブ（Ａ）の分散性を高め、分散後の再凝集をより効果的に防止することができる。
<Acetylene-based surfactant (E)>
The acetylene-based surfactant (E) used in the present invention is not particularly limited as long as it does not prevent the dispersibility of the pigment, but is preferably soluble in water. By using the acetylene-based surfactant (E), the dispersibility of the carbon nanotube (A) can be enhanced, and reaggregation after dispersion can be more effectively prevented.
アセチレン系界面活性剤（Ｅ）は、アセチレングリコール系界面活性剤、またはアセチレンアルコール系界面活性剤が好ましい。アセチレングリコール系界面活性剤、またはアセチレンアルコール系界面活性剤としては、２，４，７，９−テトラメチル−５−デシン−４，７−ジオール及び２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのアルキレンオキシド付加物、２，４−ジメチル−５−デシン−４−オール及び２，４−ジメチル−５−デシン−４−オールのアルキレンオキシド付加物から選ばれた１種以上が好ましい。 The acetylene-based surfactant (E) is preferably an acetylene glycol-based surfactant or an acetylene alcohol-based surfactant. As an acetylene glycol surfactant or an acetylene alcohol surfactant, 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5 Alkylene oxide adducts of -decyne-4,7-diol, selected from alkylene oxide adducts of 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol One or more are preferable.
このようなアセチレン系界面活性剤（Ｅ）としては、例えば、日信化学工業社製のサーフィノール１０４シリーズが挙げられる。より具体的には、サーフィノール１０４Ｅ、サーフィノール１０４Ｈ、サーフィノール１０４Ａ、サーフィノール１０４ＢＣ、サーフィノール１０４ＤＰＭ、サーフィノール１０４ＰＡ、サーフィノール１０４ＰＧ−５０、サーフィノール４２０、サーフィノール４４０、サーフィノール４６５、のオルフィンＥ１００４、オルフィンＥ１０１０、オルフィンＥ１０２０、オルフィンＰＤ−００１、オルフィンＰＤ−００２Ｗ、オルフィンＰＤ−００４、オルフィンＰＤ−００５、オルフィンＥＸＰ．４００１、オルフィンＥＸＰ．４２００、オルフィンＥＸＰ．４１２３、オルフィンＥＸＰ．４３００などが挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 As such an acetylene-based surfactant (E), for example, Surfynol 104 series manufactured by Nisshin Chemical Industry Co., Ltd. can be mentioned. More specifically, Olfine of Surfynol 104 E, Surfynol 104 H, Surfynol 104 A, Surfynol 104 BC, Surfynol 104 DPM, Surfynol 104 PA, Surfynol 104 PG-50, Surfynol 420, Surfynol 440, Surfynol 465, E1004, Orphin E1010, Orphin E1020, Orphin PD-001, Orphin PD-002W, Orphin PD-004, Orphin PD-005, Orphin EXP. 4001, Olfin EXP. 4200, Olfin EXP. 4123, Olfin EXP. 4300 and the like. These may be used alone or in combination of two or more.
アセチレン系界面活性剤（Ｅ）のＨＬＢ値は、８以下であることが好ましく、６以下であることがより好ましい。ＨＬＢ値を８以下とすることで、脱泡性及び塗膜の結着性に優れたカーボンナノチューブ分散液を得ることができる。
尚、ＨＬＢ値は、以下の式により定義されるグリフィン法により求めることができる。 ＨＬＢ値＝２０×親水基の分子量の和／界面活性剤の分子量
The HLB value of the acetylene-based surfactant (E) is preferably 8 or less, more preferably 6 or less. By setting the HLB value to 8 or less, it is possible to obtain a carbon nanotube dispersion excellent in defoaming property and binding property of the coating film.
The HLB value can be determined by the Griffin method defined by the following equation. HLB value = 20 × sum of molecular weight of hydrophilic group / molecular weight of surfactant
＜カーボンナノチューブ分散液の製造方法＞
本発明の分散液は、ポリビニルピロリドン（Ｂ）を分散剤として、アミン系化合物（Ｄ）、アセチレン系界面活性剤（Ｅ）を添加剤として用いてカーボンナノチューブ（Ａ）を水（Ｃ）中に分散したものである。この場合、ポリビニルピロリドン（Ｂ）とカーボンナノチューブ（Ａ）を同時、または順次添加し、混合することで、ポリビニルピロリドン（Ｂ）をカーボンナノチューブ（Ａ）に作用（吸着）させつつ分散する。但し、カーボンナノチューブ分散液の製造をより容易に行うためには、ポリビニルピロリドン（Ｂ）およびアセチレン系界面活性剤（Ｅ）を水（Ｃ）中に溶解、膨潤、または分散させ、その後、液中にカーボンナノチューブ（Ａ）を添加し、混合することでポリビニルピロリドン（Ｂ）をカーボンナノチューブ（Ａ）に作用（吸着）させることが、より好ましい。また、カーボンナノチューブ（Ａ）以外の粉体として、例えば二次電池用電極活物質等を添加して、電極用合剤スラリーとして使用する場合、水（Ｃ）中にポリビニルピロリドン（Ｂ）とカーボンナノチューブ（Ａ）と電極活物質とを同時に仕込み分散処理を行っても良い。
<Production Method of Carbon Nanotube Dispersion>
The dispersion liquid of the present invention contains carbon nanotubes (A) in water (C) using polyvinyl pyrrolidone (B) as a dispersant, an amine compound (D) and an acetylene surfactant (E) as an additive. It is dispersed. In this case, polyvinyl pyrrolidone (B) and carbon nanotubes (A) are simultaneously or sequentially added and mixed to disperse polyvinyl pyrrolidone (B) while acting (adsorbing) on carbon nanotubes (A). However, for easier production of the carbon nanotube dispersion, the polyvinyl pyrrolidone (B) and the acetylenic surfactant (E) are dissolved, swollen or dispersed in water (C), and then in the liquid It is more preferable to cause the polyvinyl pyrrolidone (B) to act (adsorb) on the carbon nanotube (A) by adding the carbon nanotube (A) to the mixture and mixing them. In addition, when using as an electrode mixture slurry, for example, by adding an electrode active material for a secondary battery as powder other than carbon nanotubes (A), polyvinyl pyrrolidone (B) and carbon in water (C) The nanotube (A) and the electrode active material may be simultaneously charged and dispersed.
なお、アミン系化合物（Ｄ）の添加は、ポリビニルピロリドン（Ｂ）をカーボンナノチューブ（Ａ）に作用させる前に行っても良いし、分散処理が終了した後で行っても良く、どちらの場合についても好適な効果が得られる。 The addition of the amine compound (D) may be carried out before the polyvinyl pyrrolidone (B) is allowed to act on the carbon nanotube (A), or may be carried out after the dispersion treatment is completed, in either case. Also suitable effects can be obtained.
分散装置としては、顔料分散等に通常用いられている分散機を使用することができる。例えば、ディスパー、ホモミキサー、プラネタリーミキサー等のミキサー類、ホモジナイザー（エム・テクニック社製「クレアミックス」、ＰＲＩＭＩＸ社「フィルミックス」等、シルバーソン社製「アブラミックス」等）類、ペイントコンディショナー（レッドデビル社製）、コロイドミル（ＰＵＣ社製「ＰＵＣコロイドミル」、ＩＫＡ社製「コロイドミルＭＫ」）類、コーンミル（ＩＫＡ社製「コーンミルＭＫＯ」等）、ボールミル、サンドミル（シンマルエンタープライゼス社製「ダイノミル」等）、アトライター、パールミル（アイリッヒ社製「ＤＣＰミル」等）、コボールミル等のメディア型分散機、湿式ジェットミル（ジーナス社製「ジーナスＰＹ」、スギノマシン社製「スターバースト」、ナノマイザー社製「ナノマイザー」等）、エム・テクニック社製「クレアＳＳ−５」、奈良機械社製「ＭＩＣＲＯＳ」等のメディアレス分散機、その他ロールミル等が挙げられるが、これらに限定されるものではない。 As a dispersing apparatus, a dispersing machine usually used for pigment dispersion etc. can be used. For example, mixers such as disper, homomixer, and planetary mixer, Homogenizers ("CLEARMIX" manufactured by M. Technic Co., Ltd., "ABRAMIX" manufactured by PRIMERX "Pillmix", etc.), paint conditioners (eg Red Devil, Colloid Mill (PUC Colloid Mill, IKA Colloid Mill MK), Corn Mill (IKA Corn Mill MKO, etc.), Ball Mill, Sandal Enterprises Co., Ltd. Made by "Dino mill" etc., Atelier, Pearl mill ("DCP mill" made by Eirich Co., Ltd.), Media type dispersing machine such as co-ball mill, wet jet mill ("Genas PY" made by Genas, "Starburst" made by Sugino Machine Co.) , Nanomizer "Nanomizer" ), M Technique Co., Ltd. "Claire SS-5", Nara Machinery Co., Ltd. "MICROS" media-less dispersing machine such as, but other roll mill, and the like, but is not limited to these.
本発明において、カーボンナノチューブ（Ａ）に対する分散剤としてのポリビニルピロリドン（Ｂ）の添加量は特に限定されないが、カーボンナノチューブ（Ａ）１００重量部に対して、１０重量部以上、４０重量部以下であることが好ましく、その中でも１０重量部以上、２５重量部以下がより好ましく、１５重量部以上、２２重量部以下が特に好ましい。 In the present invention, the amount of polyvinyl pyrrolidone (B) added as a dispersant to carbon nanotubes (A) is not particularly limited, but 10 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of carbon nanotubes (A). Among these, 10 parts by weight or more and 25 parts by weight or less are more preferable, and 15 parts by weight or more and 22 parts by weight or less are particularly preferable.
本発明において、カーボンブナノチューブ（Ａ）に対するアミン系化合物（Ｄ）の添加量は、カーボンナノチューブ（Ａ）１００重量部に対して、０．５重量部以上、５重量部以下であり、０．８重量部以上、５重量部以下が好ましい。 In the present invention, the addition amount of the amine compound (D) to the carbon nanotube (A) is 0.5 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the carbon nanotube (A). 8 parts by weight or more and 5 parts by weight or less are preferable.
本発明において、カーボンブナノチューブ（Ａ）に対するアセチレン界面活性剤（Ｅ）の添加量は、カーボンナノチューブ（Ａ）１００重量部に対して、１重量部以上、１０重量部以下であり、２重量部以上、５重量部以下が好ましい。 In the present invention, the addition amount of the acetylene surfactant (E) to the carbon nanotube (A) is 1 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the carbon nanotube (A), and 2 parts by weight Above, 5 parts by weight or less is preferable.
このような比率で配合することにより、本発明が解決しようとする課題であるカーボンナノチューブ分散液の低粘度化が可能となり、高濃度で分散性と貯蔵安定性に優れた分散液を得ることが容易となる。 By blending at such a ratio, it is possible to reduce the viscosity of the carbon nanotube dispersion, which is the problem to be solved by the present invention, and to obtain a dispersion having excellent dispersibility and storage stability at high concentration. It becomes easy.
＜カーボンナノチューブ分散液の用途＞
本発明のカーボンナノチューブ分散液の利用分野としては特に制限はないが、遮光性、導電性、耐久性、漆黒性等が要求される分野、例えば、グラビアインキ、オフセットインキ、磁気記録媒体用バックコート、静電トナー、インクジェット、自動車塗料、繊維・プラスチック形成材料、電子写真用シームレスベルト、電池用電極において、安定かつ均一な組成物を提供し得るものである。
<Application of Carbon Nanotube Dispersion>
The application field of the carbon nanotube dispersion of the present invention is not particularly limited, but fields requiring light shielding property, conductivity, durability, jet-blackness, etc., for example, gravure ink, offset ink, back coat for magnetic recording media A stable and uniform composition can be provided in electrostatic toners, inkjets, automobile paints, fiber / plastic forming materials, seamless belts for electrophotography, and electrodes for batteries.
＜電極用カーボンナノチューブ分散液＞
本発明の電極用カーボンナノチューブ分散液は、必要に応じて、さらに、バインダー、電極活物質（正極活物質または負極活物質）を添加してもよい。
例えば、更にカルボキシメチルセルロース、ポリフッ化ビニリデン等のバインダーを添加してリチウムイオン二次電池用電極や電気二重層キャパシタ用電極、リチウムイオンキャパシタ用電極のプライマー層としたり、更にコバルト酸リチウム、マンガン酸リチウム等のリチウム遷移金属複合酸化物、黒鉛、活性炭、グラファイト、カーボンナノチューブやカーボンナノファイバーなどの正極活物質や負極活物質を添加してリチウムイオン二次電池用電極や電気二重層キャパシタ用電極、リチウムイオンキャパシタ用電極の電極層を製造することができる。
<Carbon nanotube dispersion liquid for electrode>
A binder and an electrode active material (a positive electrode active material or a negative electrode active material) may be further added to the carbon nanotube dispersion for an electrode of the present invention, as necessary.
For example, a binder such as carboxymethyl cellulose or polyvinylidene fluoride is further added to form an electrode for a lithium ion secondary battery, an electrode for an electric double layer capacitor, or a primer layer of an electrode for a lithium ion capacitor, or lithium cobaltate or lithium manganate Lithium transition metal complex oxide such as graphite, activated carbon, graphite, carbon nanotube or carbon nanofibers, and other positive electrode active materials or negative electrode active materials to be used as electrodes for lithium ion secondary batteries, electrodes for electric double layer capacitors, lithium The electrode layer of the electrode for ion capacitors can be manufactured.
＜活物質＞
リチウムイオン二次電池用の正極活物質としては、特に限定はされないが、リチウムイオンをドーピングまたはインターカレーション可能な金属酸化物、金属硫化物等の金属化合物、および導電性高分子等を使用することができる。
<Active material>
The positive electrode active material for lithium ion secondary batteries is not particularly limited, but metal oxides such as metal oxides which can be doped or intercalated with lithium ions, metal compounds such as metal sulfides, and conductive polymers are used. be able to.
例えば、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｎ等の遷移金属の酸化物、リチウムとの複合酸化物、遷移金属硫化物等の無機化合物等が挙げられる。具体的には、ＭｎＯ、Ｖ2Ｏ5、Ｖ6Ｏ13、ＴｉＯ2等の遷移金属酸化物粉末、層状構造のニッケル酸リチウム、コバルト酸リチウム、マンガン酸リチウム、スピネル構造のマンガン酸リチウムなどのリチウムと遷移金属との複合酸化物粉末、オリビン構造のリン酸化合物であるリン酸鉄リチウム系材料、ＴｉＳ2、ＦｅＳなどの遷移金属硫化物粉末等が挙げられる。また、ポリアニリン、ポリアセチレン、ポリピロール、ポリチオフェン等の導電性高分子を使用することもできる。また、上記の無機化合物や有機化合物を混合して用いてもよい。 For example, oxides of transition metals such as Fe, Co, Ni, and Mn, composite oxides with lithium, inorganic compounds such as transition metal sulfides, and the like can be mentioned. Specifically, transition metal oxide powder such as MnO, V 2 O 5 , V 6 O 13 , TiO 2 , lithium nickelate having a layered structure, lithium cobaltate, lithium manganate, lithium manganate having a spinel structure, etc. Composite oxide powder of lithium and transition metal, lithium iron phosphate material which is a phosphate compound having an olivine structure, transition metal sulfide powder such as TiS 2 , FeS, and the like can be mentioned. In addition, conductive polymers such as polyaniline, polyacetylene, polypyrrole and polythiophene can also be used. Moreover, you may mix and use said inorganic compound and organic compound.
リチウムイオン二次電池用の負極活物質としては、リチウムイオンをドーピングまたはインターカレーション可能なものであれば特に限定されない。例えば、金属Li、その合金であるスズ合金、シリコン合金、鉛合金等の合金系、ＬｉXＦｅ2Ｏ3（この段落で、Ｘは、０＜Ｘ≦４を表す。）、ＬｉXＦｅ3Ｏ4、ＬｉXＷＯ2、チタン酸リチウム、バナジウム酸リチウム、ケイ素酸リチウム等の金属酸化物系、ポリアセチレン、ポリ−ｐ−フェニレン等の導電性高分子系、ソフトカーボンやハードカーボンといった、アモルファス系炭素質材料や、高黒鉛化炭素材料等の人造黒鉛、あるいは天然黒鉛等の炭素質粉末、カーボンブラック、メソフェーズカーボンブラック、樹脂焼成炭素材料、気層成長炭素繊維、炭素繊維などの炭素系材料が挙げられる。これら負極活物質は、１種または複数を組み合わせて使用することもできる。 The negative electrode active material for a lithium ion secondary battery is not particularly limited as long as it can be doped or intercalated with lithium ions. For example, metal Li, alloy thereof such as tin alloy, silicon alloy, lead alloy, Li x Fe 2 O 3 (in this paragraph, X represents 0 <x ≦ 4), Li x Fe 3 Metal oxides such as O 4 , Li x WO 2 , lithium titanate, lithium vanadate and lithium siliconate, conductive polymers such as polyacetylene and poly-p-phenylene, amorphous such as soft carbon and hard carbon Carbonaceous material, artificial graphite such as highly graphitized carbon material, carbonaceous powder such as natural graphite, carbon black, mesophase carbon black, resin-fired carbon material, carbon-based material such as air-grown carbon fiber, carbon fiber It can be mentioned. These negative electrode active materials can be used alone or in combination of two or more.
これら活物質は、平均粒径が０．０５〜１００μｍの範囲内であることが好ましく、さらに好ましくは、０．１〜５０μｍの範囲内である。本明細書でいう活物質の平均粒径とは、活物質を電子顕微鏡で測定した粒子径の平均値である。 The average particle diameter of these active materials is preferably in the range of 0.05 to 100 μm, and more preferably in the range of 0.1 to 50 μm. The average particle size of the active material as referred to in the present specification is an average value of particle sizes of the active material measured by an electron microscope.
合剤インキ中のバインダーとは、活物質や導電性の炭素材料などの粒子同士、あるいは導電性の炭素材料と集電体を結着させるために使用されるものである。 The binder in the mixture ink is used to bind particles of an active material or a conductive carbon material, or a conductive carbon material and a current collector.
合剤インキ中で使用されるバインダーとしては、例えば、アクリル樹脂、ポリウレタン樹脂、ポリエステル樹脂、フェノール樹脂、エポキシ樹脂、フェノキシ樹脂、尿素樹脂、メラミン樹脂、アルキッド樹脂、ホルムアルデヒド樹脂、シリコン樹脂、フッ素樹脂、カルボキシメチルセルロース等のセルロース樹脂、スチレンブタジエンゴムやフッ素ゴム等の合成ゴム、ポリアニリンやポリアセチレン等の導電性樹脂等、ポリフッ化ビニリデン、ポリフッ化ビニル、及びテトラフルオロエチレン等のフッ素原子を含む高分子化合物が挙げられる。また、これらの樹脂の変性物、混合物、又は共重合体でも良い。これらバインダーは、１種または複数を組み合わせて使用することも出来る。また、水性の合剤インキ中で好適に使用されるバインダーとしては水媒体のものが好ましく、水媒体のバインダーの形態としては、水溶性型、エマルション型、ハイドロゾル型等が挙げられ、適宜選択することができる。 Examples of the binder used in the mixture ink include acrylic resin, polyurethane resin, polyester resin, phenol resin, epoxy resin, phenoxy resin, phenoxy resin, urea resin, melamine resin, alkyd resin, formaldehyde resin, silicone resin, fluorine resin, Cellulose resins such as carboxymethyl cellulose, synthetic rubbers such as styrene butadiene rubber and fluorine rubber, conductive resins such as polyaniline and polyacetylene, etc., and polymers containing fluorine atoms such as polyvinylidene fluoride, polyvinyl fluoride, and tetrafluoroethylene It can be mentioned. In addition, modified products, mixtures or copolymers of these resins may be used. These binders may be used alone or in combination of two or more. Moreover, as a binder suitably used in aqueous | water-based mixture ink, the thing of an aqueous medium is preferable, As a form of the binder of an aqueous medium, a water-soluble type, an emulsion type, a hydrosol type etc. are mentioned, It selects suitably. be able to.
さらに、合剤インキには、成膜助剤、消泡剤、レベリング剤、防腐剤、ｐＨ調整剤、粘性調整剤などを必要に応じて配合できる。 Furthermore, a film forming aid, an antifoaming agent, a leveling agent, a preservative, a pH adjusting agent, a viscosity adjusting agent and the like can be added to the mixture ink as required.
＜電池電極合剤層＞
本発明の電池電極合剤層は、電極用カーボンチューブ分散液を層状に形成してなる。集電体上に電極用カーボンチューブ分散液を塗工・乾燥し、電池電極合剤層を形成することで電池用電極を得ることができる。
<Battery electrode mixture layer>
The battery electrode mixture layer of the present invention is formed by forming a carbon tube dispersion liquid for an electrode into a layer. The electrode for a battery can be obtained by coating and drying a carbon tube dispersion for an electrode on a current collector and forming a battery electrode mixture layer.
（集電体）
電極に使用する集電体の材質や形状は特に限定されず、各種電池にあったものを適宜選択することができる。例えば、集電体の材質としては、アルミニウム、銅、ニッケル、チタン、又はステンレス等の金属や合金が挙げられる。また、形状としては、一般的には平板上の箔が用いられるが、表面を粗面化したものや、穴あき箔状のもの、及びメッシュ状の集電体も使用できる。
(Current collector)
The material and shape of the current collector used for the electrode are not particularly limited, and materials suitable for various batteries can be appropriately selected. For example, as a material of the current collector, a metal or alloy such as aluminum, copper, nickel, titanium, or stainless steel can be mentioned. In general, a flat plate foil is used as the shape, but it is also possible to use a roughened surface, a perforated foil, or a mesh current collector.
集電体上に電極用カーボンチューブ分散液を塗工する方法としては、特に制限はなく公知の方法を用いることができる。具体的には、ダイコーティング法、ディップコーティング法、ロールコーティング法、ドクターコーティング法、ナイフコーティング法、スプレーコティング法、グラビアコーティング法、スクリーン印刷法または静電塗装法等が挙げる事ができ、乾燥方法としては放置乾燥、送風乾燥機、温風乾燥機、赤外線加熱機、遠赤外線加熱機などが使用できるが、特にこれらに限定されるものではない。 There is no restriction | limiting in particular as a method of coating the carbon tube dispersion liquid for electrodes on a collector, A well-known method can be used. Specifically, die coating method, dip coating method, roll coating method, doctor coating method, knife coating method, spray coating method, gravure coating method, screen printing method or electrostatic coating method can be mentioned, and drying is possible. As the method, although it is possible to use standing drying, a fan drier, a hot air drier, an infrared heater, a far infrared heater, etc., it is not particularly limited thereto.
また、塗布後に平版プレスやカレンダーロール等による圧延処理を行っても良い。 In addition, a rolling process using a lithographic press or a calender roll may be performed after the application.
＜リチウムイオン二次電池＞
本発明の電池電極合剤層からなる電極、対極、電解質、セパレータ等を用いて、リチウムイオン二次電池などの、各種電池とすることができる。
<Lithium ion secondary battery>
It is possible to make various batteries such as a lithium ion secondary battery by using an electrode comprising a battery electrode mixture layer of the present invention, a counter electrode, an electrolyte, a separator and the like.
（電解液）
リチウムイオン二次電池の場合を例にとって説明する。電解液としては、リチウムを含んだ解質を非水系の溶剤に溶解したものを用いる。電解質としては、ＬｉＢＦ4、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＣＦ3ＳＯ3、Ｌｉ（ＣＦ3ＳＯ2）2Ｎ、ＬｉＣ4Ｆ9ＳＯ3、Ｌｉ（ＣＦ3ＳＯ2）3Ｃ、ＬｉＩ、ＬｉＢｒ、ＬｉＣｌ、ＬｉＡｌＣｌ、ＬｉＨＦ2、ＬｉＳＣＮ、またはＬｉＢＰｈ4等が挙げられるがこれらに限定されない。
(Electrolyte solution)
The case of a lithium ion secondary battery will be described as an example. As the electrolytic solution, one obtained by dissolving a lithium-containing powder in a non-aqueous solvent is used. As the electrolyte, LiBF 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 3 C, LiI, LiBr, LiCl, LiAlCl, LiHF 2 , LiSCN, or it LiBPh 4 and the like without limitation.
非水系の溶剤としては特に限定はされないが、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、エチルメチルカーボネート、及びジ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、γ−バレロラクトン、及びγ−オクタノイックラクトン等のラクトン類；テトラヒドロフラン、２−メチルテトラヒドロフラン、１，３−ジオキソラン、４−メチル−１，３−ジオキソラン、１，２−メトキシエタン、１，２−エトキシエタン、及び １，２−ジブトキシエタン等のグライム類；メチルフォルメート、メチルアセテート、及びメチルプロピオネート等のエステル類；ジメチルスルホキシド、及びスルホラン等のスルホキシド類；並びに、アセトニトリル等のニトリル類等が挙げられる。また、これらの溶剤は、それぞれ単独で使用しても良いが、２種以上を混合して使用しても良い。さらに上記電解液を、ポリマーマトリクスに保持しゲル状とした高分子電解質とすることもできる。ポリマーマトリクスとしては、ポリアルキレンオキシドセグメントを有するアクリレート系樹脂、ポリアルキレンオキシドセグメントを有するポリホスファゼン系樹脂、及びポリアルキレンオキシドセグメントを有するポリシロキサン等が挙げられるがこれらに限定されない。 The non-aqueous solvent is not particularly limited, but examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and carbonates such as diethyl carbonate; γ-butyrolactone, γ-valerolactone, and γ- Lactones such as octanoic lactone; tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, and 1,2 -Glymes such as dibutoxy ethane; esters such as methyl formate, methyl acetate and methyl propionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and nitriles such as acetonitrile It can be mentioned. Moreover, although these solvents may be used independently, respectively, you may mix and use 2 or more types. Furthermore, the above-mentioned electrolytic solution can be held in a polymer matrix to form a gel-like polymer electrolyte. Examples of the polymer matrix include, but are not limited to, acrylate resins having a polyalkylene oxide segment, polyphosphazene resins having a polyalkylene oxide segment, and polysiloxanes having a polyalkylene oxide segment.
（セパレータ）
セパレータとしては、例えば、ポリエチレン不織布、ポリプロピレン不織布、ポリアミド不織布及びそれらに親水性処理を施したものが挙げられるが、特にこれらに限定されるものではない。
(Separator)
Examples of the separator include polyethylene non-woven fabric, polypropylene non-woven fabric, polyamide non-woven fabric and those obtained by subjecting them to hydrophilic treatment, but not limited thereto.
以下、実施例に基づき、本発明を詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。本実施例中、部は重量部を、％は重量％をそれぞれ表す。
実施例及び比較例で使用したカーボンナノチューブ（Ａ）（「ＣＮＴ」と略記することがある）、ポリビニルピロリドン（Ｂ）（「ＰＶＰ」と略記することがある）、アミン系化合物（Ｄ）、電極活物質等を以下に示す。また、各表には、各原料の組成のみを記載しているが、特に記載の無い残りの成分は、全て水である。
Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In the examples, parts represent parts by weight and% represents weight%.
Carbon nanotubes (A) (sometimes abbreviated as "CNT"), polyvinyl pyrrolidone (B) (sometimes abbreviated as "PVP"), amine compounds (D), electrodes used in Examples and Comparative Examples Active materials and the like are shown below. Moreover, in each table | surface, although only the composition of each raw material is described, all the remaining components which are not indicated in particular are all water.
＜カーボンナノチューブ（Ａ）＞
・ＪＥＮＯＴＵＢＥ８Ａ：ＪＥＩＯ社製、多層ＣＮＴ、外径６〜９ｎｍ。
・Ｋ−Ｎａｎｏｓ １００Ｔ：Ｋｕｍｈｏ Ｐｅｔｒｏｃｈｅｍｉｃａｌ社製、多層ＣＮＴ、外径１０〜１５ｎｍ、以下１００Ｔと略記する。
<Carbon nanotube (A)>
-JENOTUBE 8A: manufactured by JEIO, multilayer CNT, outer diameter 6 to 9 nm.
K-Nanos 100T: manufactured by Kumho Petrochemical, multilayer CNT, outer diameter 10 to 15 nm, hereinafter abbreviated as 100T.
＜ポリビニルピロリドン（Ｂ）＞
・ＰＶＰ Ｋ−１２０（ＩＳＰ社製）
・ＰＶＰ Ｋ−９０（ＩＳＰ社製 ）
・ＰＶＰ Ｋ−３０（日本触媒社製）：Ｋ値２７．０〜３３．０
<Polyvinylpyrrolidone (B)>
・ PVP K-120 (made by ISP)
・ PVP K-90 (made by ISP)
PVP K-30 (manufactured by Nippon Shokubai Co., Ltd.): K value 27.0 to 33.0
＜アミン系化合物（Ｄ）＞
・ｎ−ブチルアミン：脂肪族１級アミン。Ｃ4Ｈ9ＮＨ2。分子量７３。以下、ブチルアミンと略記する。
・ジエチルアミン：脂肪族２級アミン。分子式Ｃ4Ｈ11Ｎ。分子量７３。
・トリエチルアミン：脂肪族３級アミン。分子式Ｃ6Ｈ15Ｎ。分子量１０１。
・メタノールアミン：アルカノールアミン系１級アミン。分子式ＣＨ5ＮＯ、分子量４７。
・エタノールアミン：アルカノールアミン系１級アミン。分子式Ｃ2Ｈ7ＮＯ、分子量６１。
・３−アミノ−１−プロパノール：アルカノールアミン系１級アミン。分子式Ｃ3Ｈ9ＮＯ、分子量７５。以下、プロパノールアミンと略記する。
・Ｎ−メチルエタノールアミン：アルコールアミン系２級アミン。分子式Ｃ3Ｈ9ＮＯ、分子量７５。以下、メチルエタノールアミンと略記する。
・トリエタノールアミン：アルカノールアミン系３級アミン。分子式Ｃ6Ｈ15ＮＯ3。ｐＫａ＝７．６。
・ヘキサメチレンテトラミン：脂環式含窒素複素環化合物（３級アミン）。分子式Ｃ6Ｈ12Ｎ4。
・Ｌ−アスパラギン酸：酸性アミノ酸。分子式Ｃ4Ｈ7ＮＯ2。以下、アスパラギン酸と略記する。
・Ｌ−アスパラギン１水和物：中性アミノ酸。分子式Ｃ4Ｈ8Ｎ2Ｏ3。以下、アスパラギンと略記する。
<Amine compound (D)>
N-butylamine: aliphatic primary amine. C 4 H 9 NH 2 . Molecular weight 73. Hereinafter, it is abbreviated as butylamine.
-Diethylamine: Aliphatic secondary amine. Molecular formula C 4 H 11 N. Molecular weight 73.
Triethylamine: aliphatic tertiary amine. Molecular formula C 6 H 15 N. Molecular weight 101.
-Methanol amine: Alkanol amine primary amine. Molecular formula CH 5 NO, molecular weight 47.
-Ethanolamine: Alkanolamine primary amine. Molecular formula C 2 H 7 NO, molecular weight 61.
3-Amino-1-propanol: Alkanolamine primary amine. Molecular formula C 3 H 9 NO, molecular weight 75. Hereinafter, it is abbreviated as propanolamine.
N-methyl ethanolamine: alcohol amine secondary amine. Molecular formula C 3 H 9 NO, molecular weight 75. Hereinafter, it is abbreviated as methylethanolamine.
Triethanolamine: Alkanolamine tertiary amine. Molecular formula C 6 H 15 NO 3 . pKa = 7.6.
Hexamethylenetetramine: alicyclic nitrogen-containing heterocyclic compound (tertiary amine). Molecular formula C 6 H 12 N 4 .
L-aspartic acid: acidic amino acid. Molecular formula C 4 H 7 NO 2 . Hereinafter, it is abbreviated as aspartic acid.
L-asparagine monohydrate: neutral amino acid. Molecular formula C 4 H 8 N 2 O 3 . Hereinafter, it is abbreviated as asparagine.
＜アセチレン系界面活性剤（Ｅ）＞
・サーフィノール１０４Ｅ（日信化学工業社製）；ＨＬＢ４
・サーフィノール４６５（日信化学工業社製）；ＨＬＢ１３
<Acetylene-based surfactant (E)>
· Surfynol 104E (made by Nisshin Chemical Industry Co., Ltd.); HLB 4
· Surfynol 465 (made by Nisshin Chemical Industry Co., Ltd.); HLB 13
＜バインダー＞
・ＣＭＣダイセル＃１１９０（ダイセル化学工業社製）：カルボキシメチルセルロース（ＣＭＣ）。以下、ＣＭＣと略記する。
・ＴＲＤ２００１（ＪＳＲ社製）：スチレンブタジエンエマルション（固形分４８％水分散液）。以下、ＳＢＲと略記する。
・ＫＦポリマーＷ７３００（クレハ社製）：ポリフッ化ビニリデン（ＰＶＤＦ）、重量平均分子量約１００００００。以下、ＰＶＤＦと略記する。
<Binder>
CMC Daicel # 1190 (manufactured by Daicel Chemical Industries, Ltd.): carboxymethylcellulose (CMC). Hereinafter, it is abbreviated as CMC.
-TRD 2001 (manufactured by JSR Corporation): styrene butadiene emulsion (solid content 48% aqueous dispersion). Hereinafter, it is abbreviated as SBR.
KF polymer W7300 (manufactured by Kureha): polyvinylidene fluoride (PVDF), weight average molecular weight about 1,000,000. Hereinafter, it is abbreviated as PVDF.
＜電極活物質＞
・正極活物質：コバルト酸リチウム（ＬｉＣｏＯ4）、平均一次粒子径１１μｍ。
・負極活物質：人造黒鉛、平均粒子径１２μｍ。以下、黒鉛と略記する。
<Electrode active material>
-Positive electrode active material: Lithium cobaltate (LiCoO 4 ), average primary particle diameter 11 μm.
-Negative electrode active material: Artificial graphite, average particle diameter 12 micrometers. Hereinafter, it is abbreviated as graphite.
＜カーボンナノチューブ分散液の評価＞
実施例、比較例で得られたカーボンナノチューブ分散液の評価は、粘度値を測定することにより行った。
<Evaluation of carbon nanotube dispersion liquid>
The carbon nanotube dispersions obtained in Examples and Comparative Examples were evaluated by measuring viscosity values.
粘度値の測定は、Ｂ型粘度計（東機産業社製「ＢＬ」）を用いて、分散液温度２５℃、Ｂ型粘度計ローター回転速度６０ｒｐｍにて、分散液をヘラで充分に撹拌した後、直ちに行った。測定に使用したローターは、粘度値が１００ｍＰａ・ｓ未満の場合はＮｏ．１を、１００ｍＰａ・ｓ以上５００ｍＰａ・ｓ未満の場合はＮｏ．２を、５００ｍＰａ・ｓ以上２０００ｍＰａ・ｓ未満の場合はＮｏ．３を、２０００ｍＰａ・ｓ以上１００００ｍＰａ・ｓ未満の場合はＮｏ．４のものをそれぞれ用いた。低粘度であるほど分散性が良好であり、高粘度であるほど分散性が不良である。 To measure the viscosity value, the dispersion was sufficiently stirred with a spatula using a B-type viscometer ("BL" manufactured by Toki Sangyo Co., Ltd.) at a dispersion temperature of 25 ° C and a B-type viscometer rotor rotational speed of 60 rpm. I went right away. The rotor used for the measurement had No. 1 when the viscosity value was less than 100 mPa · s. No. 1 in the case of 100 mPa · s or more and less than 500 mPa · s. No. 2 in the case of 500 mPa · s or more and less than 2000 mPa · s. No. 3 in the case of 2000 mPa · s or more and less than 10000 mPa · s. Each of 4 was used. The lower the viscosity, the better the dispersibility, and the higher the viscosity, the poorer the dispersibility.
貯蔵安定性の評価は、カーボンナノチューブ分散液を５０℃にて、３日間静置して保存した後の、粘度値の変化から評価した。変化の少ないものほど安定性が良好であることを示す。以下の基準で評価した結果を表２に示す。
○（良好）；粘度変化率の絶対値が５０％以下
△（やや不良）；粘度変化率の絶対値が５０％を超えて１００％以下
×（不良）；粘度変化率の絶対値が１００％超え、もしくはゲル化
The storage stability was evaluated from the change in viscosity value after the carbon nanotube dispersion was stored at 50 ° C. for 3 days. The less change, the better the stability. The results evaluated based on the following criteria are shown in Table 2.
○ (Good): Absolute value of viscosity change rate is 50% or less Δ (Slightly poor); Absolute value of viscosity change rate is over 50% to 100% or less × (Defect); Absolute value of viscosity change rate is 100% Or gelation
＜カーボンナノチューブ分散液の調製＞
［実施例１−１〜１−２５］
表１に示す組成に従い、ガラス瓶に水（Ｃ）と各種ポリビニルピロリドン（Ｂ）と各種アミン系化合物（Ｄ）とアセチレン系界面活性剤（Ｅ）とを仕込み、充分に混合溶解、または混合分散した後、各種カーボンナノチューブ（Ａ）を加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントシェーカーで７時間分散し、各カーボンナノチューブ分散液を得た。いずれも低粘度かつ、貯蔵安定性も良好であった。評価結果を表２に示す。
<Preparation of Carbon Nanotube Dispersion>
[Examples 1-1 to 1-25]
According to the composition shown in Table 1, water (C), various polyvinyl pyrrolidones (B), various amine compounds (D) and acetylenic surfactants (E) were charged in a glass bottle and thoroughly mixed, dissolved or mixed and dispersed. Thereafter, various carbon nanotubes (A) were added, and dispersion was performed for 7 hours with a paint shaker using 1.25 mmφ zirconia beads as a medium, to obtain each carbon nanotube dispersion liquid. Both were low in viscosity and good in storage stability. The evaluation results are shown in Table 2.
［比較例１−１〜１−６］
表１に示す組成に従い、ガラス瓶に水（Ｃ）と、ポリビニルピロリドン（Ｂ）としてＫ−３０とを仕込み、充分に混合溶解、または混合分散した後、カーボンナノチューブ（Ａ）として表１に示すＣＮＴを加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントシェーカーで７時間分散した。しかし、得られた分散液は、いずれも高粘度な状態であったことから、カーボンナノチューブを十分に分散する事が出来ていないことがわかる。評価結果を表２に示す。この結果から、ＰＶＰを分散剤として単独で用いた場合には、所望とする高濃度かつ低粘度のカーボンナノチューブ分散液を得る事ができないことが明らかとなった。
Comparative Examples 1-1 to 1-6
According to the composition shown in Table 1, water (C) and K-30 as polyvinyl pyrrolidone (B) are charged in a glass bottle, sufficiently mixed and dissolved, or mixed and dispersed, and then CNT shown in Table 1 as carbon nanotube (A) And dispersed with a paint shaker for 7 hours using 1.25 mmφ zirconia beads as a medium. However, since all of the obtained dispersions were in a high viscosity state, it can be understood that carbon nanotubes can not be sufficiently dispersed. The evaluation results are shown in Table 2. From this result, it is clear that it is not possible to obtain the desired high concentration and low viscosity carbon nanotube dispersion liquid when PVP is used alone as the dispersant.
＜電極活物質含むカーボンナノチューブ分散液（電極用合剤スラリー）の調製＞
＜負極用合剤スラリー＞
［実施例２−１〜２−２５、比較例２−１〜２−６］
表３に示す組成に従い、１００ｍＬの容器に実施例１−１〜１−２５、および比較例１−１〜１−６で調製した各種カーボンナノチューブ分散液と、バインダーとしてカルボキシメチルセルロース１．５％水溶液（固形分として１質量部）を仕込み、プラネタリーミキサーに入れて混練し、さらに水、スチレンブタジエンエマルション４８％水系分散液を混合しつつ電極活物質として人造黒鉛を徐々に添加し、混合して電極用合剤スラリーを得た。電極用合剤スラリーの粘度評価結果を表３に示す。
<Preparation of carbon nanotube dispersion liquid (mixture slurry for electrode) containing electrode active material>
<Mixture slurry for negative electrode>
[Examples 2-1 to 2-25, Comparative Examples 2-1 to 2-6]
According to the composition shown in Table 3, various carbon nanotube dispersions prepared in Examples 1-1 to 1-25 and Comparative Examples 1-1 to 1-6 in a 100 mL container, and a 1.5% aqueous solution of carboxymethyl cellulose as a binder (1 part by mass as solid content) charged, put into a planetary mixer and kneaded, and further, artificial graphite as an electrode active material is gradually added while mixing water and a 48% aqueous dispersion of styrene butadiene emulsion and mixed An electrode mixture slurry was obtained. The evaluation results of the viscosity of the electrode mixture slurry are shown in Table 3.
＜正極用合剤スラリー＞
後述の電池評価で負極と組み合わせる正極用合剤スラリーの調製を以下に示す。
プラネタリーミキサーに、正極活物質としてＬｉＣｏＯ4９５部、導電助剤であるアセチレンブラック５部（デンカ株式会社製ＨＳ−１００）、ＫＦポリマーＷ７３００（ＰＶＤＦ）３部、さらにＮＭＰを加えて混合し、固形分濃度６７％の正極用合剤スラリーを調製した。
<Slurry for positive electrode mixture>
The preparation of the positive electrode mixture slurry to be combined with the negative electrode in the below-described battery evaluation is shown below.
In a planetary mixer, 95 parts of LiCoO 4 as a positive electrode active material, 5 parts of acetylene black as a conduction aid (HS-100 manufactured by Denka Co., Ltd.), 3 parts of KF polymer W7300 (PVDF), and NMP are further added and mixed. A positive electrode mixture slurry was prepared with a solid content concentration of 67%.
＜電極用合剤スラリーの評価＞
実施例、比較例で得られた電極用合剤スラリーの評価は、粘度値を測定することにより行った。
<Evaluation of mixture slurry for electrode>
Evaluation of the electrode mixture slurry obtained in Examples and Comparative Examples was carried out by measuring viscosity values.
粘度値の測定は、Ｂ型粘度計（東機産業社製「ＢＬ」）を用いて、分散液温度２５℃、Ｂ型粘度計ローター回転速度６０ｒｐｍにて、分散液をヘラで充分に撹拌した後、直ちに行った。測定に使用したローターは、粘度値が１００ｍＰａ・ｓ未満の場合はＮｏ．１を、１００ｍＰａ・ｓ以上５００ｍＰａ・ｓ未満の場合はＮｏ．２を、５００ｍＰａ・ｓ以上２０００ｍＰａ・ｓ未満の場合はＮｏ．３を、２０００ｍＰａ・ｓ以上１００００ｍＰａ・ｓ未満の場合はＮｏ．４のものをそれぞれ用いた。得られた粘度値が１００００ｍＰａ・ｓ以上の場合については、「＞１００００」と記載したが、これは評価に用いたＢ型粘度計では評価不可能なほどに高粘度であったことを表す。低粘度であるほど分散性が良好であり、高粘度であるほど分散性が不良である。合剤スラリーの粘度は後述の電池電極合剤層を作製する際の塗工特性に影響し、３０００ｍＰａ・ｓ以上６０００ｍＰａ・ｓ以下の範囲にあるものがより好ましい。 To measure the viscosity value, the dispersion was sufficiently stirred with a spatula using a B-type viscometer ("BL" manufactured by Toki Sangyo Co., Ltd.) at a dispersion temperature of 25 ° C and a B-type viscometer rotor rotational speed of 60 rpm. I went right away. The rotor used for the measurement had No. 1 when the viscosity value was less than 100 mPa · s. No. 1 in the case of 100 mPa · s or more and less than 500 mPa · s. No. 2 in the case of 500 mPa · s or more and less than 2000 mPa · s. No. 3 in the case of 2000 mPa · s or more and less than 10000 mPa · s. Each of 4 was used. Although the case where the obtained viscosity value is 10000 mPa · s or more was described as "> 10000", this indicates that the viscosity was so high that it could not be evaluated by the B-type viscometer used for the evaluation. The lower the viscosity, the better the dispersibility, and the higher the viscosity, the poorer the dispersibility. The viscosity of the mixture slurry affects the coating characteristics when producing a battery electrode mixture layer described later, and it is more preferable that the viscosity be in the range of 3000 mPa · s to 6000 mPa · s.
＜電池電極合剤層の作製＞
［実施例３−１〜３−２５］および［比較例３−１〜３−６］
上記の各実施例２−１〜２−２５および、比較例２−１〜２−６で得られた電極活物質含むカーボンナノチューブ分散液を電池電極用合剤スラリーとして、負極用として銅箔（厚み１８μｍ）に、それぞれドクターブレードを用いて所定の厚みに塗布した。これを１２０℃で１時間真空乾燥し、１８ｍｍΦに打ち抜いた。さらに、打ち抜いた電極を超鋼製プレス板で挟み、プレス圧が電極に対して１０００〜３０００ｋｇ／ｃｍ2となるようにプレスし、目付け量７〜９ｍｇ／ｃｍ2、厚さ４０〜６０μｍで、電極密度を１．６ｇ／ｃｍ3とした。その後、真空乾燥機で１２０℃１２時間乾燥し、評価用負極とした。
<Fabrication of battery electrode mixture layer>
[Examples 3-1 to 3-25] and [Comparative Examples 3-1 to 3-6]
The carbon nanotube dispersion containing the electrode active material obtained in each of the above Examples 2-1 to 2-25 and Comparative Examples 2-1 to 2-6 is used as a mixture slurry of a battery electrode and is used as a negative electrode for copper foil ( It applied to a predetermined thickness to a thickness of 18 μm using a doctor blade, respectively. It was vacuum dried at 120 ° C. for 1 hour and punched into 18 mm diameter. Furthermore, the punched out electrode is sandwiched by a super steel press plate, and pressed so that the pressing pressure is 1000 to 3000 kg / cm 2 against the electrode, and the coating weight is 7 to 9 mg / cm 2 and the thickness is 40 to 60 μm, The electrode density was 1.6 g / cm 3 . Thereafter, it was dried at 120 ° C. for 12 hours with a vacuum dryer to obtain a negative electrode for evaluation.
上記方法にて作製した負極と合わせる正極は、先に調製した正極用合剤スラリーをアルミ箔（厚み２５μｍ）に、ドクターブレードを用いて所定の厚みに塗布した。これを１２０℃で１時間真空乾燥し、１８ｍｍΦに打ち抜いた。さらに、打ち抜いた電極を超鋼製プレス板で挟み、プレス圧が電極に対して１０００〜３０００ｋｇ／ｃｍ2となるようにプレスした。その後、真空乾燥機で１２０℃１２時間乾燥し、評価用正極とした。厚さ約８０μｍ、電極密度は約３．５ｇ／ｃｍ3であった。 The positive electrode combined with the negative electrode produced by the said method apply | coated the positive mix slurry prepared previously to aluminum foil (25 micrometers in thickness) to predetermined thickness using a doctor blade. It was vacuum dried at 120 ° C. for 1 hour and punched into 18 mm diameter. Furthermore, the punched-out electrode was sandwiched by a super steel press plate and pressed so that the pressing pressure was 1000 to 3000 kg / cm 2 with respect to the electrode. Thereafter, it was dried at 120 ° C. for 12 hours with a vacuum dryer to obtain a positive electrode for evaluation. The thickness was about 80 μm, and the electrode density was about 3.5 g / cm 3 .
＜リチウムイオン電池試験用セルの組み立て＞
上記で作製した銅箔付き負極とアルミ箔付き正極を多孔質ポリプロピレンフィルムからなるセパレーター（厚さ２０μｍ、空孔率５０％）で挿入積層し、電解液（エチレンカーボネートとジエチルカーボネートを容量比１:１で混合した混合溶媒にＬｉＰＦ6を１Ｍの濃度で溶解させた非水電解液）を満たして二極密閉式金属セル（宝泉社製ＨＳフラットセル）を組み立てた。セルの組み立ては、アルゴンガス置換したグローブボックス内で行った。
<Assembly of lithium ion battery test cell>
The copper foil-coated negative electrode and the aluminum foil-coated positive electrode are inserted and laminated with a separator (20 μm in thickness, 50% porosity) made of a porous polypropylene film, and an electrolyte (ethylene carbonate and diethyl carbonate in a volume ratio of 1: A non-aqueous electrolytic solution in which LiPF 6 was dissolved at a concentration of 1 M was filled in the mixed solvent mixed in 1) to assemble a bipolar sealed metal cell (HS flat cell manufactured by Hosen Co., Ltd.). The cell assembly was performed in an argon gas-replaced glove box.
＜電池特性評価＞
（高率放電容量保持率）
上記で作製したリチウムイオン電池試験用セルを用い、定電流電圧充放電試験を行った。
充電はレストポテンシャルから２ｍＶまで０．２ｍＡ／ｃｍ2で定電流充電を行った。次に２ｍＶで定電圧充電に切り替え、電流値が１２．０μＡに低下した時点で停止させた。放電は各電流密度（０．２ｍＡ／ｃｍ2（０．１Ｃに相当）、及び４．０ｍＡ／ｃｍ2（２．０Ｃに相当））でそれぞれ定電流放電を行い、電圧１．５Ｖでカットオフした。０．１Ｃ時の放電容量に対する２．０Ｃ時の放電容量の割合を、高率放電容量保持率として評価を行った。以下の基準で評価した結果を表４に示す。
◎（優秀）：高率放電容量保持率が９５％以上
○（良好）：高率放電容量保持率が９０％以上、９５％未満
△（やや不良）：高率放電容量保持率が８０％以上、９０％未満
×（不良）：高率放電容量保持率が８０％未満
<Battery characteristic evaluation>
(High rate discharge capacity retention rate)
The constant current voltage charge / discharge test was performed using the lithium ion battery test cell manufactured above.
For charging, constant current charging was performed at 0.2 mA / cm 2 to 2 mV from the rest potential. Next, switching to constant voltage charging was performed at 2 mV and stopped when the current value dropped to 12.0 μA. Discharging was conducted with each constant current discharging at each current density (0.2mA / cm 2 (equivalent to 0.1 C), and 4.0 mA / cm 2 (equivalent to 2.0 C)), cut off at a voltage of 1.5V did. The ratio of the discharge capacity at 2.0 C to the discharge capacity at 0.1 C was evaluated as the high-rate discharge capacity retention rate. The results evaluated based on the following criteria are shown in Table 4.
((Excellent): high-rate discharge capacity retention 95% or more ○ (good): high-rate discharge capacity retention 90% or more, less than 95% Δ (slightly poor): high-rate discharge capacity retention 80% or more , Less than 90% × (defect): High-rate discharge capacity retention rate less than 80%
（サイクル容量維持率）
作製した評価用セルを３０℃で、充放電装置（北斗電工社製ＳＭ−８）を使用して、充電レート１．０Ｃの定電流定電圧充電（上限電圧４．２Ｖ）で満充電とし、充電時と同じレートの定電流で、放電下限電圧３．０Ｖまで放電を行う充放電を１サイクル（充放電間隔休止時間３０分）とし、このサイクルを合計５０サイクル行い、充放電を行った。サイクル特性は容量維持率により評価した。容量維持率は、１サイクル目の放電容量に対する５０サイクル目の放電容量の百分率であり、数値が１００％に近いものほど良好であることを示す。以下の基準で評価した結果を表４に示す。
◎（優秀）：サイクル容量維持率が９５％以上
○（良好）：サイクル容量維持率が９０％以上、９５％未満
△（やや不良）：サイクル容量維持率が８０％以上、９０％未満
−（不良）：集電体からの塗膜の剥離やショート等により正常な充放電曲線が得られず、容量が求められなかった場合
(Cycle capacity maintenance rate)
Using the charge / discharge device (SM-8 manufactured by Hokuto Denko) at 30 ° C, the prepared evaluation cell is fully charged at a constant current / constant voltage charge (upper limit voltage 4.2 V) at a charge rate of 1.0 C. The charge / discharge cycle was a total of 50 cycles, in which charge / discharge was performed for 1 cycle (charge / discharge interval rest time: 30 minutes), at a constant current of the same rate as charge, and discharging to a discharge lower limit voltage of 3.0 V. The cycle characteristics were evaluated by the capacity retention rate. The capacity retention rate is a percentage of the discharge capacity at the 50th cycle to the discharge capacity at the 1st cycle, and it is shown that the closer the value to 100%, the better. The results evaluated based on the following criteria are shown in Table 4.
優秀 (excellent): cycle capacity retention rate is 95% or more ○ (good): cycle capacity retention rate is 90% or more and less than 95% Δ (slightly poor): cycle capacity retention rate is 80% or more and less than 90%-( Poor): When a normal charge / discharge curve can not be obtained due to peeling of the coating film from the current collector, short circuit, etc.
表４より、本発明の電極を使用した実施例３−１〜実施例３−２５は、比較例３−１〜３−６と比較して、高率放電容量や、５０サイクル後の容量維持率についても、良好な結果であった。 From Table 4, Example 3-1 to Example 3-25 using the electrode of the present invention have high-rate discharge capacity and capacity maintenance after 50 cycles as compared with Comparative Examples 3-1 to 3-6. The rate was also good.
Claims (6)
前記カーボンナノチューブ（Ａ）１００重量部に対して、前記ポリビニルピロリドン（Ｂ）を１０重量部以上、４０重量部以下含有し、前記アミン系化合物（Ｄ）を０．５重量部以上、５重量部以下含有し、かつ前記アセチレン系界面活性剤（Ｅ）を１重量部以上、１０重量部以下含有することを特徴とする、カーボンナノチューブ分散液。 Containing carbon nanotubes (A), polyvinyl pyrrolidone (B), water (C), an amine compound (D), and an acetylene surfactant (E),
The polyvinyl pyrrolidone (B) is contained in an amount of 10 to 40 parts by weight with respect to 100 parts by weight of the carbon nanotube (A), and 0.5 to 5 parts by weight of the amine compound (D) A carbon nanotube dispersion liquid comprising the following and containing 1 part by weight or more and 10 parts by weight or less of the acetylene-based surfactant (E).
A lithium ion secondary battery comprising the battery electrode mixture layer according to claim 5 .
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