JP2016021390A - Conductive material fluid dispersion for electrochemical devices, slurry for electrochemical device positive electrodes, positive electrode for electrochemical devices, and electrochemical device - Google Patents
Conductive material fluid dispersion for electrochemical devices, slurry for electrochemical device positive electrodes, positive electrode for electrochemical devices, and electrochemical device Download PDFInfo
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- JP2016021390A JP2016021390A JP2015123149A JP2015123149A JP2016021390A JP 2016021390 A JP2016021390 A JP 2016021390A JP 2015123149 A JP2015123149 A JP 2015123149A JP 2015123149 A JP2015123149 A JP 2015123149A JP 2016021390 A JP2016021390 A JP 2016021390A
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- Prior art keywords
- conductive material
- positive electrode
- polymer
- electrochemical
- slurry
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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
- Y02E60/13—Energy storage using capacitors
Abstract
Description
本発明は、電気化学素子用導電材分散液、電気化学素子正極用スラリー、電気化学素子用正極および電気化学素子に関するものである。 The present invention relates to a conductive material dispersion for an electrochemical element, a slurry for an electrochemical element positive electrode, a positive electrode for an electrochemical element, and an electrochemical element.
リチウムイオン二次電池、リチウムイオンキャパシタおよび電気二重層キャパシタなどの電気化学素子は、小型で軽量、且つ、エネルギー密度が高く、更に繰り返し充放電が可能という特性があり、幅広い用途に使用されている。ここで、例えばリチウムイオン二次電池用の電極は、通常、集電体と、集電体上に形成された電極合材層とを備えている。そして、電極合材層、例えば正極合材層は、通常、正極活物質に加え、導電性を向上させるための導電材、これらの成分を結着するための結着材を分散媒中に含んでなる正極用スラリーを集電体上に塗布し、乾燥させることにより形成されている。 Electrochemical elements such as lithium ion secondary batteries, lithium ion capacitors, and electric double layer capacitors are small and light, have high energy density, and can be repeatedly charged and discharged, and are used in a wide range of applications. . Here, for example, an electrode for a lithium ion secondary battery usually includes a current collector and an electrode mixture layer formed on the current collector. In addition to the positive electrode active material, the electrode mixture layer, for example, the positive electrode mixture layer usually contains a conductive material for improving conductivity and a binder for binding these components in the dispersion medium. The positive electrode slurry is applied on a current collector and dried.
ここで、電気化学素子の性能向上を達成すべく、従来から正極用スラリー等の電極用スラリーを改良する試みがなされている。具体的には、凝集し易いカーボンブラックなどの導電材の分散性を改良して電気化学素子の性能を向上させるべく、導電材、分散剤、および分散媒を予混合してなる導電材分散液と、電極活物質とを併せて電極用スラリーとし、当該電極用スラリーを用いて電極を形成する技術が提案されている。 Here, attempts have been made to improve electrode slurries such as positive electrode slurries in order to achieve improved performance of electrochemical devices. Specifically, a conductive material dispersion liquid obtained by premixing a conductive material, a dispersant, and a dispersion medium in order to improve the dispersibility of a conductive material such as carbon black that easily aggregates and improve the performance of an electrochemical device. And an electrode active material are combined to form an electrode slurry, and a technique for forming an electrode using the electrode slurry has been proposed.
例えば、特許文献１では、導電材としてのカーボンブラックと、分散剤としての特定の性状を有するポリビニルアルコール樹脂と、分散媒としてのＮ−メチル−２−ピロリドン（ＮＭＰ）を含む導電材分散液をリチウムイオン二次電池の電極合材層の形成に用いることが提案されている。そして、特許文献１では、この導電材分散液はカーボンブラックの分散性と貯蔵安定性に優れ、かつ、当該分散液に電極活物質を加えた電極用スラリーを用いて均質な塗膜を塗布可能であり、当該電極用スラリーから表面抵抗の低い電極合材層を形成することができると報告されている。 For example, in Patent Document 1, a conductive material dispersion containing carbon black as a conductive material, a polyvinyl alcohol resin having specific properties as a dispersant, and N-methyl-2-pyrrolidone (NMP) as a dispersion medium. It has been proposed to be used for forming an electrode mixture layer of a lithium ion secondary battery. And in patent document 1, this electroconductive material dispersion liquid is excellent in the dispersibility and storage stability of carbon black, and can apply | coat a homogeneous coating film using the slurry for electrodes which added the electrode active material to the said dispersion liquid It is reported that an electrode mixture layer having a low surface resistance can be formed from the electrode slurry.
また例えば、特許文献２では、導電材としてのカーボンブラックと、分散剤としてのポリビニルアセタール樹脂と、分散媒としてのＮＭＰと含む導電材分散液をリチウムイオン二次電池の電極合材層の形成に用いることが提案されている。そして、特許文献２では、この導電材分散液はカーボンブラックの分散性と貯蔵安定性に優れ、当該分散液に電極活物質を加えた電極用スラリーを用いることで、内部抵抗の低減が可能な電極合材層を形成することができると報告されている。 Further, for example, in Patent Document 2, a conductive material dispersion containing carbon black as a conductive material, polyvinyl acetal resin as a dispersant, and NMP as a dispersion medium is used to form an electrode mixture layer of a lithium ion secondary battery. It has been proposed to use. And in patent document 2, this electrically conductive material dispersion liquid is excellent in the dispersibility and storage stability of carbon black, and internal resistance can be reduced by using the slurry for electrodes which added the electrode active material to the said dispersion liquid. It has been reported that an electrode mixture layer can be formed.
しかしながら、上記従来の技術では、導電材分散液および電極用スラリー中において、分散剤の導電材分散能が十分に発揮されない場合があり、経時による粘度変化により導電材の分散性が損なわれる虞、即ち、保存安定性が低下する虞があった。また、導電材分散液を含む電極用スラリーを集電体上に塗布して塗膜を形成する際に、当該塗膜の厚みを十分に均一に出来ない場合があった。そして、このような導電材分散液および電極用スラリーを用いて形成される電極合材層は、厚みが一様となり難く、また、当該電極合材層中で好適な導電材ネットワークが形成され難い場合があり、電気化学素子に十分な出力特性を発揮させることができなかった。
したがって、上記従来の技術には、導電材分散液の保存安定性を確保しつつ、当該導電材分散液を含む正極用スラリーの塗工性を改良し、そして電気化学素子の出力特性を向上させるという点において未だ改善の余地があった。
However, in the conventional technique, in the conductive material dispersion and the electrode slurry, the conductive material dispersibility of the dispersant may not be sufficiently exhibited, and the dispersibility of the conductive material may be impaired due to a change in viscosity over time. That is, storage stability may be reduced. Moreover, when the electrode slurry containing the conductive material dispersion is applied on the current collector to form a coating film, the thickness of the coating film may not be sufficiently uniform. The electrode mixture layer formed using such a conductive material dispersion and the electrode slurry is unlikely to have a uniform thickness, and a suitable conductive material network is not easily formed in the electrode mixture layer. In some cases, the electrochemical device could not exhibit sufficient output characteristics.
Therefore, the above conventional technique improves the coating property of the slurry for the positive electrode containing the conductive material dispersion and improves the output characteristics of the electrochemical device while ensuring the storage stability of the conductive material dispersion. There was still room for improvement.
そこで、本発明は、保存安定性に優れ、電気化学素子電極用スラリーに良好な塗工性を付与しつつ、電気化学素子に優れた出力特性を発揮させることが可能な電気化学素子用導電材分散液を提供することを目的とする。
また、本発明は、保存安定性および塗工性に優れ、電気化学素子に優れた出力特性を発揮させることが可能な電気化学素子正極用スラリーを提供することを目的とする。
更に、本発明は、電気化学素子に優れた出力特性を発揮させることが可能な電気化学素子用正極、および出力特性に優れる電気化学素子を提供することを目的とする。
Therefore, the present invention is an electrochemical element conductive material that is excellent in storage stability and can give excellent output characteristics to an electrochemical element while imparting good coating properties to the slurry for an electrochemical element electrode. The object is to provide a dispersion.
Another object of the present invention is to provide a slurry for an electrochemical device positive electrode that is excellent in storage stability and coating properties and can exhibit excellent output characteristics in an electrochemical device.
Furthermore, an object of the present invention is to provide a positive electrode for an electrochemical element capable of exhibiting excellent output characteristics of the electrochemical element, and an electrochemical element excellent in output characteristic.
本発明者らは、上記課題を解決することを目的として鋭意検討を行った。そして、本発明者らは、分散媒としてピロリドン系溶媒を使用した導電材分散液において、分散剤としてニトリル基含有単量体単位およびアルキレン構造単位を含み、そしてヨウ素価が特定の範囲内である重合体を特定量用い、かつ導電材分散液を特定の粘度以下の低粘度とすることで、導電材の保存安定性を優れたものとしつつ、この導電材分散液を含んでなる電極用スラリーの塗工性を向上させ、さらには、当該電極用スラリーを用いて形成される電極を備える電気化学素子の出力特性を高めることができることを見出し、本発明を完成させるに至った。 The present inventors have intensively studied for the purpose of solving the above problems. Then, the present inventors include a conductive material dispersion using a pyrrolidone-based solvent as a dispersion medium, which includes a nitrile group-containing monomer unit and an alkylene structural unit as a dispersant, and an iodine value within a specific range. A slurry for an electrode comprising the conductive material dispersion liquid while using a specific amount of the polymer and the conductive material dispersion liquid having a low viscosity equal to or lower than a specific viscosity to improve the storage stability of the conductive material. It has been found that the output characteristics of an electrochemical device comprising an electrode formed using the electrode slurry can be improved, and the present invention has been completed.
即ち、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の電気化学素子用導電材分散液は、導電材、重合体Ｘ、およびピロリドン系溶媒を含む電気化学素子用導電材分散液であって、前記重合体Ｘは、ニトリル基含有単量体単位およびアルキレン構造単位を含み、ヨウ素価が２０ｍｇ/１００ｍｇ以下であり、前記導電材１００質量部当たり、前記重合体Ｘを２質量部以上３０質量部以下含み、そして、粘度が８００ｍＰａ・ｓ以下であることを特徴とする。このように、分散媒としてピロリドン系溶媒を使用した導電材分散液において上述した重合体Ｘを特定量使用し、さらに当該導電材分散液の粘度を特定の範囲内とすれば、導電材分散液の保存安定性を高めつつ、電気化学素子電極用スラリーに良好な塗工性を付与することができ、さらには、電気化学素子に優れた出力特性を発揮させることができる。
なお、本発明において重合体Ｘのヨウ素価は、重合体Ｘの水分散液または溶液１００ｇを、メタノール１リットルで凝固した後、６０℃で１２時間真空乾燥して得られる乾燥した重合体Ｘのヨウ素価を、ＪＩＳ Ｋ６２３５（２００６）に従って測定することで得ることができる。
また、本発明において導電材分散液の粘度は、Ｂ型粘度計を用いて、温度２５℃、回転速度６０ｒｐｍ、回転時間６０秒の条件で測定することができる。
That is, the present invention aims to advantageously solve the above problems, and the electroconductive material dispersion for an electrochemical element of the present invention is an electrochemistry containing an electroconductive material, a polymer X, and a pyrrolidone-based solvent. A conductive material dispersion for an element, wherein the polymer X includes a nitrile group-containing monomer unit and an alkylene structural unit, has an iodine value of 20 mg / 100 mg or less, and per 100 parts by mass of the conductive material. It is characterized in that it comprises 2 to 30 parts by mass of coalescence X and has a viscosity of 800 mPa · s or less. As described above, when a specific amount of the polymer X described above is used in a conductive material dispersion using a pyrrolidone-based solvent as a dispersion medium, and the viscosity of the conductive material dispersion is within a specific range, the conductive material dispersion In addition, it is possible to impart good coating properties to the slurry for an electrochemical element electrode while improving the storage stability of the electrochemical element, and to exhibit excellent output characteristics for the electrochemical element.
In the present invention, the iodine value of the polymer X is the same as that of the dried polymer X obtained by coagulating 100 g of an aqueous dispersion or solution of the polymer X with 1 liter of methanol and then vacuum drying at 60 ° C. for 12 hours. The iodine value can be obtained by measuring according to JIS K6235 (2006).
In the present invention, the viscosity of the conductive material dispersion can be measured using a B-type viscometer under conditions of a temperature of 25 ° C., a rotation speed of 60 rpm, and a rotation time of 60 seconds.
ここで、本発明の電気化学素子用導電材分散液は、前記重合体Ｘが、ニトリル基含有単量体単位を１５質量％以上５０質量％以下含み、アルキレン構造単位を５０質量％以上８５質量％以下含むことが好ましい。ニトリル基含有単量体単位とアルキレン構造単位を上述の範囲内で含む重合体Ｘは、導電材分散能とピロリドン系溶媒への溶解性をバランスよく備え、当該重合体Ｘを含む導電材分散液の保存安定性を更に向上させることができるからである。 Here, in the conductive material dispersion for an electrochemical element of the present invention, the polymer X contains 15% by mass to 50% by mass of a nitrile group-containing monomer unit, and 50% by mass to 85% by mass of an alkylene structural unit. % Or less is preferable. The polymer X containing a nitrile group-containing monomer unit and an alkylene structural unit within the above-mentioned range has a well-balanced conductive material dispersion ability and solubility in a pyrrolidone-based solvent, and a conductive material dispersion containing the polymer X This is because the storage stability of can be further improved.
そして、本発明の電気化学素子用導電材分散液は、さらにフッ素樹脂Ｙを含むことが好ましい。フッ素樹脂Ｙを使用することで、導電材分散液から形成される電極合材層と集電体の密着性が確保され、電気化学素子の出力特性などの電気的特性を更に向上させることができるからである。 And it is preferable that the electrically conductive material dispersion liquid for electrochemical elements of this invention contains the fluororesin Y further. By using the fluororesin Y, the adhesion between the electrode mixture layer formed from the conductive material dispersion and the current collector is ensured, and the electrical characteristics such as the output characteristics of the electrochemical element can be further improved. Because.
また、本発明の電気化学素子正極用スラリーは、上述の何れかの電気化学素子用導電材分散液および正極活物質を含むことを特徴とする。上述したいずれかの導電材分散液を用いて調製された正極用スラリーは、保存安定性および塗工性に優れる。また、当該正極用スラリーを用いて調製した正極を使用すれば、電気化学素子に優れた出力特性を発揮させることができる。 Moreover, the slurry for electrochemical element positive electrodes of this invention is characterized by including one of the above-mentioned electroconductive element dispersions for electrochemical elements and a positive electrode active material. The positive electrode slurry prepared using any of the conductive material dispersions described above is excellent in storage stability and coatability. Moreover, if the positive electrode prepared using the said slurry for positive electrodes is used, the output characteristic excellent in the electrochemical element can be exhibited.
また、本発明の電気化学素子用正極は、上述の電気化学素子正極用スラリーを用いて調製した正極合材層を、集電体上に備えることを特徴とする。上述の正極用スラリーから形成された正極合材層を備える正極は、電気化学素子に優れた出力特性を発揮させることができる。 Moreover, the positive electrode for electrochemical devices of this invention is equipped with the positive electrode compound-material layer prepared using the above-mentioned slurry for positive electrodes of electrochemical devices on a collector. A positive electrode including a positive electrode mixture layer formed from the above-described positive electrode slurry can exhibit excellent output characteristics in an electrochemical element.
また、本発明の電気化学素子は、上述の電気化学素子用正極を備えることを特徴とする。上述の電気化学素子用正極を備える電気化学素子は、優れた出力特性を発揮する。 Moreover, the electrochemical element of this invention is provided with the above-mentioned positive electrode for electrochemical elements. An electrochemical element provided with the above-mentioned positive electrode for an electrochemical element exhibits excellent output characteristics.
本発明によれば、保存安定性に優れ、電気化学素子電極用スラリーに良好な塗工性を付与しつつ、電気化学素子に優れた出力特性を発揮させることが可能な電気化学素子用導電材分散液を提供することができる。
本発明によれば、保存安定性および塗工性に優れ、電気化学素子に優れた出力特性を発揮させることが可能な電気化学素子正極用スラリーを提供することができる。
更に、本発明によれば、電気化学素子に優れた出力特性を発揮させることが可能な電気化学素子用正極、および出力特性に優れる電気化学素子を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, it is excellent in storage stability, and the electroconductive element for electrochemical elements which can make the electrochemical element exhibit the outstanding output characteristic, providing the favorable coating property to the slurry for electrochemical element electrodes A dispersion can be provided.
ADVANTAGE OF THE INVENTION According to this invention, the slurry for electrochemical element positive electrodes which is excellent in storage stability and coating property, and can exhibit the output characteristic excellent in the electrochemical element can be provided.
Furthermore, according to the present invention, it is possible to provide a positive electrode for an electrochemical element capable of exhibiting excellent output characteristics of the electrochemical element, and an electrochemical element excellent in output characteristic.
以下、本発明の実施形態について詳細に説明する。
ここで、本発明の電気化学素子用導電材分散液は、電気化学素子電極用スラリー、好ましくは電気化学素子正極用スラリーを製造する際の材料として用いられる。そして、本発明の電気化学素子正極用スラリーは、本発明の電気化学素子用導電材分散液を用いて形成される。加えて、本発明の電気化学素子用正極は、本発明の電気化学素子正極用スラリーを用いて形成された正極合材層を備えることを特徴とする。また、本発明の電気化学素子は、本発明の電気化学素子用正極を備えることを特徴とする。
Hereinafter, embodiments of the present invention will be described in detail.
Here, the electroconductive element-use conductive material dispersion liquid of the present invention is used as a material for producing an electrochemical element electrode slurry, preferably an electrochemical element positive electrode slurry. And the slurry for electrochemical element positive electrodes of this invention is formed using the electrically conductive material dispersion liquid for electrochemical elements of this invention. In addition, the positive electrode for electrochemical devices of the present invention is characterized by including a positive electrode mixture layer formed using the slurry for positive electrodes of electrochemical devices of the present invention. Moreover, the electrochemical element of this invention is equipped with the positive electrode for electrochemical elements of this invention, It is characterized by the above-mentioned.
（電気化学素子用導電材分散液）
本発明の電気化学素子用導電材分散液は、ピロリドン系溶媒中に、導電材に加え、ニトリル基含有単量体単位およびアルキレン構造単位を含み、ヨウ素価が２０ｍｇ/１００ｍｇ以下である重合体Ｘを含み、任意にフッ素樹脂Ｙを更に含有する。そして、本発明の電気化学素子用導電材分散液は、重合体Ｘの配合量が、導電材１００質量部当たり、２〜３０質量部であり、そして、粘度が８００ｍＰａ・ｓ以下であることを特徴とする。
このように、上述した重合体Ｘを特定の割合で含み、粘度が８００ｍＰａ・ｓ以下である導電材分散液は、保存安定性に優れる上、当該導電材分散液を含む電極用スラリーの塗工性を向上させ、集電体上に均一な塗膜を形成することができる。そして、当該塗膜を乾燥等して形成された電極合材層を備える電極は、電気化学素子に優れた出力特性を発揮させることができる。
なお、本発明において「単量体単位を含む」とは、「その単量体を用いて得た重合体中に単量体由来の繰り返し単位が含まれている」ことを意味する。
また、本発明において「アルキレン構造単位を含む」とは、「重合体中に一般式−ＣｎＨ２ｎ−［但し、ｎは２以上の整数］で表わされるアルキレン構造のみで構成される繰り返し単位が含まれている」ことを意味する。
(Conductive material dispersion for electrochemical devices)
In the pyrrolidone-based solvent, the conductive material dispersion for an electrochemical element of the present invention contains a nitrile group-containing monomer unit and an alkylene structural unit in addition to the conductive material, and has an iodine value of 20 mg / 100 mg or less. And optionally further containing a fluororesin Y. And as for the electrically conductive material dispersion liquid for electrochemical elements of this invention, the compounding quantity of the polymer X is 2-30 mass parts per 100 mass parts of electrically conductive materials, and viscosity is 800 mPa * s or less. Features.
As described above, the conductive material dispersion liquid containing the polymer X described above at a specific ratio and having a viscosity of 800 mPa · s or less is excellent in storage stability and is coated with the electrode slurry containing the conductive material dispersion liquid. And a uniform coating film can be formed on the current collector. And the electrode provided with the electrode compound-material layer formed by drying the said coating film can exhibit the output characteristic excellent in the electrochemical element.
In the present invention, “comprising a monomer unit” means “a repeating unit derived from a monomer is contained in a polymer obtained using the monomer”.
In the present invention, “including an alkylene structural unit” means “a repeating unit composed of only an alkylene structure represented by the general formula —C n H 2n — [wherein n is an integer of 2 or more] in the polymer. Is included. ”
＜導電材＞
導電材は、電極合材層中で電極活物質同士の電気的接触を確保するためのものである。そして、本発明の導電材分散液に用いる導電材としては、特に限定されることなく、カーボンブラック（例えば、アセチレンブラック、ケッチェンブラック（登録商標）、ファーネスブラックなど）、単層または多層カーボンナノチューブ（多層カーボンナノチューブにはカップスタック型が含まれる）、カーボンナノホーン、気相成長炭素繊維、ポリマー繊維を焼成後に破砕して得られるミルドカーボン繊維、単層または多層グラフェン、ポリマー繊維からなる不織布を焼成して得られるカーボン不織布シートなどの導電性炭素材料、並びに各種金属のファイバー又は箔などを用いることができる。これらは一種単独で、または、二種以上を組み合わせて用いることができる。これらの中でも、化学的安定性に優れるという点で、導電性炭素材料が好ましい。また、近接する導電性炭素材料同士の接触頻度を高め、安定した導電パスを形成しつつ高効率での電子授受を達成して、優れた導電性を発現させる観点からは、カーボンブラックや、繊維状又はシート状である導電性炭素材料がより好ましい。
ここで、本発明において導電性炭素材料が「繊維状」であるとは、透過型電子顕微鏡（ＴＥＭ）で測定した導電性炭素材料のアスペクト比が１０以上であることをいい、繊維状導電性炭素材料としては、例えば、上述した単層または多層カーボンナノチューブ、カーボンナノホーン、気相成長炭素繊維、ミルドカーボン繊維などが挙げられる。
また、本発明において導電性炭素材料が「シート状」であるとは、導電性炭素材料が平面状に広がる構造を有することをいい、シート状導電性炭素材料としては、例えば、上述した単層または多層グラフェン、カーボン不織布シートなどが挙げられる。なお、平面状に広がる構造を有するシート状導電性炭素材料には、繊維状導電性炭素材料は含まれないものとする。
<Conductive material>
The conductive material is for ensuring electrical contact between the electrode active materials in the electrode mixture layer. The conductive material used in the conductive material dispersion of the present invention is not particularly limited, and carbon black (for example, acetylene black, ketjen black (registered trademark), furnace black, etc.), single-walled or multi-walled carbon nanotubes (Multi-walled carbon nanotubes include cup-stacked types), carbon nanohorns, vapor-grown carbon fibers, milled carbon fibers obtained by crushing polymer fibers after firing, single-layer or multilayer graphene, and nonwoven fabrics made of polymer fibers A conductive carbon material such as a carbon non-woven sheet obtained as well as various metal fibers or foils can be used. These can be used individually by 1 type or in combination of 2 or more types. Among these, a conductive carbon material is preferable because it is excellent in chemical stability. Also, from the viewpoint of increasing the contact frequency between adjacent conductive carbon materials, achieving highly efficient electron transfer while forming a stable conductive path, and exhibiting excellent conductivity, carbon black and fibers A conductive carbon material that is in the form of a sheet or a sheet is more preferable.
Here, in the present invention, that the conductive carbon material is “fibrous” means that the aspect ratio of the conductive carbon material measured by a transmission electron microscope (TEM) is 10 or more, and the fibrous conductivity. Examples of the carbon material include the single-walled or multi-walled carbon nanotubes, carbon nanohorns, vapor-grown carbon fibers, and milled carbon fibers described above.
Further, in the present invention, the conductive carbon material being “sheet-like” means that the conductive carbon material has a structure spreading in a plane, and the sheet-like conductive carbon material includes, for example, the single layer described above. Or a multilayer graphene, a carbon nonwoven fabric sheet, etc. are mentioned. The sheet-like conductive carbon material having a structure extending in a planar shape does not include a fibrous conductive carbon material.
カーボンブラックの平均粒子径は、好ましくは１０ｎｍ以上、より好ましくは１５ｎｍ以上、更に好ましくは２０ｎｍ以上であり、好ましくは１００ｎｍ以下、より好ましくは７０ｎｍ以下、更に好ましくは５０ｎｍ以下である。カーボンブラックの平均粒子径が上述の範囲内であれば、導電材であるカーボンブラックの分散性を確保しつつ電極合材層中において良好な導電パスを形成することができるため、導電材分散液の保存安定性、電極用スラリーの塗工性および電気化学素子の出力特性を更に向上させることができる。
なお、本発明において「カーボンブラックの平均粒子径」は、ＴＥＭを用いて無作為に選択されたカーボンブラック粒子１００個の粒子径（個々の粒子の外縁上の２点を結ぶ線分の長さのうち、最大の長さ）を測定して求めることができる。
The average particle size of carbon black is preferably 10 nm or more, more preferably 15 nm or more, still more preferably 20 nm or more, preferably 100 nm or less, more preferably 70 nm or less, and even more preferably 50 nm or less. If the average particle diameter of the carbon black is within the above range, a conductive material dispersion liquid can be formed in the electrode mixture layer while ensuring the dispersibility of the carbon black as a conductive material. Storage stability, electrode slurry coating properties, and electrochemical device output characteristics can be further improved.
In the present invention, the “average particle diameter of carbon black” means the particle diameter of 100 carbon black particles randomly selected using TEM (the length of a line segment connecting two points on the outer edge of each particle). Can be obtained by measuring the maximum length).
導電材の比表面積は、好ましくは２０ｍ２／ｇ以上、より好ましくは３５ｍ２／ｇ以上であり、好ましくは１０００ｍ２／ｇ以下、より好ましくは８００ｍ２／ｇ以下、更に好ましくは５００ｍ２／ｇ以下、特に好ましくは１００ｍ２／ｇ以下、最も好ましくは６０ｍ２／ｇ以下である。導電材の比表面積が上述の範囲内であれば、導電材の分散性を確保しつつ電極合材層中において良好な導電パスを形成することができるため、導電材分散液の保存安定性、電極用スラリーの塗工性および電気化学素子の出力特性を更に向上させることができる。特に導電材の比表面積が６０ｍ２／ｇ以下である場合は、保存安定性に優れた導電材分散液を容易に得ることができる。
なお、本発明において「導電材の比表面積」とは、窒素吸着法によるＢＥＴ比表面積のことであり、ＡＳＴＭ Ｄ３０３７−８１に準拠して測定することができる。
The specific surface area of the conductive material is preferably 20 m 2 / g or more, more preferably 35 m 2 / g or more, preferably 1000 m 2 / g or less, more preferably 800 m 2 / g or less, and still more preferably 500 m 2 / g. Hereinafter, it is particularly preferably 100 m 2 / g or less, most preferably 60 m 2 / g or less. If the specific surface area of the conductive material is within the above range, it is possible to form a good conductive path in the electrode mixture layer while ensuring the dispersibility of the conductive material, so that the storage stability of the conductive material dispersion liquid, The coating properties of the electrode slurry and the output characteristics of the electrochemical device can be further improved. In particular, when the conductive material has a specific surface area of 60 m 2 / g or less, a conductive material dispersion excellent in storage stability can be easily obtained.
In the present invention, the “specific surface area of the conductive material” is a BET specific surface area by a nitrogen adsorption method, and can be measured in accordance with ASTM D3037-81.
導電材の密度は、好ましくは０．０１ｇ／ｃｍ３以上、より好ましくは０．０２ｇ／ｃｍ３以上であり、好ましくは０．５ｇ／ｃｍ３以下、より好ましくは０．３ｇ／ｃｍ３以下、更に好ましくは０．２ｇ／ｃｍ３以下である。導電材の密度が上述の範囲内であれば、導電材分散液調製時における導電材の飛散が抑制され、作業性を確保することができる。また分散性を確保しつつ電極合材層中において良好な導電パスを形成することができるため、導電材分散液の保存安定性、電極用スラリーの塗工性および電気化学素子の出力特性を更に向上させることができる。
なお、本発明において「導電材の密度」とは、かさ密度のことであり、ＪＩＳ Ｚ ８９０１に準拠して測定することができる。
The density of the conductive material is preferably 0.01 g / cm 3 or more, more preferably 0.02 g / cm 3 or more, preferably 0.5 g / cm 3 or less, more preferably 0.3 g / cm 3 or less. More preferably, it is 0.2 g / cm 3 or less. When the density of the conductive material is within the above range, scattering of the conductive material during preparation of the conductive material dispersion is suppressed, and workability can be ensured. In addition, since a good conductive path can be formed in the electrode mixture layer while ensuring dispersibility, the storage stability of the conductive material dispersion, the coating property of the slurry for the electrode, and the output characteristics of the electrochemical device are further improved. Can be improved.
In the present invention, the “density of the conductive material” is a bulk density and can be measured according to JIS Z 8901.
＜重合体Ｘ＞
重合体Ｘは、ニトリル基含有単量体単位およびアルキレン構造単位を含む共重合体であり、任意に、ニトリル基含有単量体単位およびアルキレン構造単位以外のその他の単量体単位（繰り返し単位）を含んでいてもよい。そして重合体Ｘは、本発明の導電材分散液において、導電材を分散させる分散剤として機能しうる。
<Polymer X>
The polymer X is a copolymer containing a nitrile group-containing monomer unit and an alkylene structural unit, and optionally other monomer units (repeating units) other than the nitrile group-containing monomer unit and the alkylene structural unit. May be included. The polymer X can function as a dispersant for dispersing the conductive material in the conductive material dispersion of the present invention.
このように、重合体Ｘがニトリル基含有単量体単位およびアルキレン構造単位を含むことで、重合体Ｘの導電材分散能およびピロリドン系溶媒に対する溶解性が確保されるため、導電材分散液中で導電材を良好に分散させることができ、しかも経時による導電材の凝集が抑制されて導電材分散液の保存安定性を向上させることができる。加えて、重合体Ｘの寄与により、本発明の導電材分散液は導電材の凝集などによる高粘度化が抑制されるため、導電材分散液を適度に低粘度とすることができる。このような低粘度の導電材分散液からは、電極用スラリーを容易に調製することができ、当該電極用スラリーも適度に低粘度とすることができる。そのような低粘度の電極用スラリーは、集電体上に均一に塗布することが可能となり、塗布むらが抑制される。そして、このような導電材分散液を用いて形成される電極合材層は、導電性に優れしかも均一な厚みを有し、電気化学素子に優れた出力特性などの電気的特性を発揮させることができる。
以下、重合体Ｘに含まれるニトリル基含有単量体単位、アルキレン構造単位、および任意のその他の単量体単位について詳述する。
Thus, since the polymer X contains a nitrile group-containing monomer unit and an alkylene structural unit, the conductive material dispersibility of the polymer X and the solubility in a pyrrolidone-based solvent are ensured. Thus, the conductive material can be well dispersed, and the aggregation of the conductive material over time can be suppressed, and the storage stability of the conductive material dispersion can be improved. In addition, due to the contribution of the polymer X, the conductive material dispersion of the present invention is prevented from increasing in viscosity due to aggregation of the conductive material, and thus the conductive material dispersion can be appropriately reduced in viscosity. From such a low-viscosity conductive material dispersion, an electrode slurry can be easily prepared, and the electrode slurry can also have a reasonably low viscosity. Such a low-viscosity electrode slurry can be uniformly applied on the current collector, and uneven application is suppressed. The electrode mixture layer formed using such a conductive material dispersion liquid has excellent conductivity and uniform thickness, and exhibits electrical characteristics such as excellent output characteristics for electrochemical devices. Can do.
Hereinafter, the nitrile group-containing monomer unit, the alkylene structural unit, and any other monomer unit contained in the polymer X will be described in detail.
［ニトリル基含有単量体単位］
ニトリル基含有単量体単位を形成しうるニトリル基含有単量体としては、α，β−エチレン性不飽和ニトリル単量体が挙げられる。そして、α，β−エチレン性不飽和ニトリル単量体としては、ニトリル基を有するα，β−エチレン性不飽和化合物であれば特に限定されないが、例えば、アクリロニトリル；α−クロロアクリロニトリル、α−ブロモアクリロニトリルなどのα−ハロゲノアクリロニトリル；メタクリロニトリル、α−エチルアクリロニトリルなどのα−アルキルアクリロニトリル；などが挙げられる。なかでも、重合体Ｘのピロリドン系溶媒への溶解性を高める観点からは、ニトリル基含有単量体としては、アクリロニトリルおよびメタクリロニトリルが好ましく、アクリロニトリルがより好ましい。
これらは一種単独で、または、２種以上を組み合わせて用いることができる。
[Nitrile group-containing monomer unit]
Examples of the nitrile group-containing monomer that can form a nitrile group-containing monomer unit include α, β-ethylenically unsaturated nitrile monomers. The α, β-ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an α, β-ethylenically unsaturated compound having a nitrile group. For example, acrylonitrile; α-chloroacrylonitrile, α-bromo Α-halogenoacrylonitrile such as acrylonitrile; α-alkylacrylonitrile such as methacrylonitrile and α-ethylacrylonitrile; and the like. Especially, from a viewpoint of improving the solubility to the pyrrolidone-type solvent of the polymer X, as a nitrile group containing monomer, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is more preferable.
These can be used alone or in combination of two or more.
そして、上記重合体Ｘ中でのニトリル基含有単量体単位の含有割合は、重合体Ｘ中の全繰り返し単位を１００質量％とした場合に、１５質量％以上が好ましく、２５質量％以上がより好ましく、３０質量％以上が特に好ましく、５０質量％以下が好ましく、４０質量％以下がより好ましい。重合体Ｘ中のニトリル基含有単量体単位の含有割合を１５質量％以上とすることで、重合体Ｘのピロリドン系溶媒への溶解性を向上させることができ、５０質量％以下とすることで、重合体Ｘの導電材分散能を向上させることができる。従って、重合体Ｘ中のニトリル基含有単量体単位の含有割合を上述の範囲内とすることで、導電材分散液の保存安定性を更に向上させることができる。そして、導電材分散液を用いて形成される電極合材層中で導電材を良好に分散させて、導電性を向上させる（即ち、内部抵抗を低減する）ことができ、本発明の導電材分散液を用いて製造された電極を備える電気化学素子の出力特性などの電気的特性を更に向上させることができる。 The content ratio of the nitrile group-containing monomer unit in the polymer X is preferably 15% by mass or more, and 25% by mass or more when the total repeating unit in the polymer X is 100% by mass. More preferably, 30% by mass or more is particularly preferable, 50% by mass or less is preferable, and 40% by mass or less is more preferable. By setting the content ratio of the nitrile group-containing monomer unit in the polymer X to 15% by mass or more, the solubility of the polymer X in the pyrrolidone-based solvent can be improved, and it should be 50% by mass or less. Thus, the conductive material dispersibility of the polymer X can be improved. Therefore, when the content ratio of the nitrile group-containing monomer unit in the polymer X is within the above range, the storage stability of the conductive material dispersion can be further improved. Then, the conductive material can be well dispersed in the electrode mixture layer formed using the conductive material dispersion to improve conductivity (that is, reduce internal resistance), and the conductive material of the present invention It is possible to further improve electrical characteristics such as output characteristics of an electrochemical device including an electrode manufactured using the dispersion.
［アルキレン構造単位］
アルキレン構造単位は、直鎖状であっても分岐状であってもよいが、導電材分散液の保存安定性を向上させる観点からは、アルキレン構造単位は直鎖状、すなわち直鎖アルキレン構造単位であることが好ましい。
そして、重合体Ｘへのアルキレン構造単位の導入方法は、特に限定はされないが、例えば以下の（１）、（２）の方法：
（１）共役ジエン単量体を含む単量体組成物から重合体を調製し、当該重合体に水素添加することで、共役ジエン単量体単位をアルキレン構造単位に変換する方法
（２）１−オレフィン単量体を含む単量体組成物から重合体を調製する方法
が挙げられる。これらの中でも、（１）の方法が重合体Ｘの製造が容易であり好ましい。
[Alkylene structural unit]
The alkylene structural unit may be linear or branched, but from the viewpoint of improving the storage stability of the conductive material dispersion, the alkylene structural unit is linear, that is, a linear alkylene structural unit. It is preferable that
The method for introducing an alkylene structural unit into the polymer X is not particularly limited. For example, the following methods (1) and (2):
(1) A method of converting a conjugated diene monomer unit into an alkylene structural unit by preparing a polymer from a monomer composition containing a conjugated diene monomer and hydrogenating the polymer (2) 1 -The method of preparing a polymer from the monomer composition containing an olefin monomer is mentioned. Among these, the method (1) is preferable because the production of the polymer X is easy.
ここで、共役ジエン単量体としては、たとえば、１，３−ブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエンなどの炭素数４以上の共役ジエン化合物が挙げられる。中でも、１，３−ブタジエンが好ましい。すなわち、アルキレン構造単位は、共役ジエン単量体単位を水素化して得られる構造単位（共役ジエン水素化物単位）であることが好ましく、１,３−ブタジエン単量体単位を水素化して得られる構造単位（１,３−ブタジエン水素化物単位）であることがより好ましい。
また、１−オレフィン単量体としては、例えば、エチレン、プロピレン、１−ブテンなどが挙げられる。
これらの共役ジエン単量体や１−オレフィン単量体は、一種単独で、または、２種以上を組み合わせて用いることができる
Here, examples of the conjugated diene monomer include conjugated diene compounds having 4 or more carbon atoms such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. It is done. Of these, 1,3-butadiene is preferred. That is, the alkylene structural unit is preferably a structural unit (conjugated diene hydride unit) obtained by hydrogenating a conjugated diene monomer unit, and a structure obtained by hydrogenating a 1,3-butadiene monomer unit. More preferred is a unit (1,3-butadiene hydride unit).
Moreover, as a 1-olefin monomer, ethylene, propylene, 1-butene etc. are mentioned, for example.
These conjugated diene monomers and 1-olefin monomers can be used alone or in combination of two or more.
そして、上記重合体Ｘ中でのアルキレン構造単位の含有割合は、重合体Ｘ中の全繰り返し単位（単量体単位と構造単位との合計）を１００質量％とした場合に、５０質量％以上が好ましく、６０質量％以上がより好ましく、８５質量％以下が好ましく、７５質量％以下がより好ましく、７０質量％以下が特に好ましい。重合体Ｘ中でのアルキレン構造単位の含有割合を５０質量％以上とすることで、重合体Ｘの導電材分散能を向上させることができ、８５質量％以下とすることで、重合体Ｘのピロリドン系溶媒への溶解性を向上させることができる。従って、重合体Ｘ中のアルキレン構造単位の含有割合を上述の範囲内とすることで、導電材分散液の保存安定性を更に向上させることができる。そして、導電材分散液を用いて形成される電極合材層中で導電材を良好に分散させて、導電性を向上させる（即ち、内部抵抗を低減する）ことができ、本発明の導電材分散液を用いて製造された電極を備える電気化学素子の出力特性などの電気的特性を更に向上させることができる。 And the content rate of the alkylene structural unit in the said polymer X is 50 mass% or more when all the repeating units (the sum total of a monomer unit and a structural unit) in the polymer X are 100 mass%. 60 mass% or more is more preferable, 85 mass% or less is preferable, 75 mass% or less is more preferable, and 70 mass% or less is especially preferable. By setting the content ratio of the alkylene structural unit in the polymer X to 50% by mass or more, the conductive material dispersibility of the polymer X can be improved, and by setting the content rate of the polymer X to 85% by mass or less, The solubility in the pyrrolidone solvent can be improved. Therefore, when the content ratio of the alkylene structural unit in the polymer X is within the above range, the storage stability of the conductive material dispersion can be further improved. Then, the conductive material can be well dispersed in the electrode mixture layer formed using the conductive material dispersion to improve conductivity (that is, reduce internal resistance), and the conductive material of the present invention It is possible to further improve electrical characteristics such as output characteristics of an electrochemical device including an electrode manufactured using the dispersion.
［その他の単量体単位］
重合体Ｘは、上述したニトリル基含有単量体単位、アルキレン構造単位以外に、その他の単量体単位を含んでいてもよい。そのようなその他の単量体単位としては、（メタ）アクリル酸エステル単量体単位、親水性基含有単量体単位などが挙げられる。
なお本発明において「（メタ）アクリル」とは、アクリルおよび／またはメタクリルを意味する。
[Other monomer units]
The polymer X may contain other monomer units in addition to the nitrile group-containing monomer units and alkylene structural units described above. Examples of such other monomer units include (meth) acrylate monomer units and hydrophilic group-containing monomer units.
In the present invention, “(meth) acryl” means acrylic and / or methacrylic.
［［（メタ）アクリル酸エステル単量体単位］］
（メタ）アクリル酸エステル単量体単位を形成しうる（メタ）アクリル酸エステル単量体としては、アクリル酸アルキルエステル、メタクリル酸アルキルエステルを用いることができる。
これらの単量体の具体例としては、国際公開第２０１３／０８０９８９号に記載のものが挙げられる。
[[(Meth) acrylic acid ester monomer unit]]
As the (meth) acrylic acid ester monomer that can form a (meth) acrylic acid ester monomer unit, an alkyl acrylate ester or an alkyl methacrylate ester can be used.
Specific examples of these monomers include those described in International Publication No. 2013/080989.
ここで、特にブチルアクリレート等の（メタ）アクリル酸エステル単量体は、重合体Ｘの柔軟性に寄与し得る一方、導電材分散能には寄与し難いため、本発明の導電材分散液を用いて製造した電気化学素子の出力特性が損なわれる場合がある。したがって、重合体Ｘ中での（メタ）アクリル酸エステル単量体単位の含有割合は、アルキレン構造単位の含有割合を十分に確保し、導電材分散能を向上させる観点から、重合体Ｘ中の全繰り返し単位を１００質量％とした場合に、３５質量％以下が好ましく、１０質量％以下がより好ましく、０．０５質量％未満（実質的に含まない）が更に好ましく、０質量％が特に好ましい。 Here, in particular, (meth) acrylic acid ester monomers such as butyl acrylate can contribute to the flexibility of the polymer X, but hardly contribute to the conductive material dispersibility. The output characteristics of the electrochemical device manufactured using the same may be impaired. Therefore, the content ratio of the (meth) acrylic acid ester monomer unit in the polymer X is sufficient from the viewpoint of ensuring a sufficient content ratio of the alkylene structural unit and improving the conductive material dispersibility. When the total repeating unit is 100% by mass, it is preferably 35% by mass or less, more preferably 10% by mass or less, still more preferably less than 0.05% by mass (substantially free), and particularly preferably 0% by mass. .
［［親水性基含有単量体単位］］
親水性基含有単量体単位を形成しうる親水性基含有単量体としては、カルボン酸基を有する単量体、スルホン酸基を有する単量体、リン酸基を有する単量体および水酸基を有する単量体を用いることができる。
これらの単量体の具体例としては、国際公開第２０１３／０８０９８９号に記載のものが挙げられる。
なお本発明において、上述した（メタ）アクリル酸エステル単量体、ニトリル基含有単量体には、カルボン酸基、スルホン酸基、リン酸基および水酸基は含まれないものとする。
[[Hydrophilic group-containing monomer unit]]
Examples of the hydrophilic group-containing monomer that can form a hydrophilic group-containing monomer unit include a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, a monomer having a phosphate group, and a hydroxyl group A monomer having can be used.
Specific examples of these monomers include those described in International Publication No. 2013/080989.
In the present invention, the above-mentioned (meth) acrylic acid ester monomer and nitrile group-containing monomer do not include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group and a hydroxyl group.
ここで、特にカルボン酸基を有する単量体などの親水性基含有単量体は、重合体Ｘの製造安定性の向上に寄与し得る一方、親水性基含有単量体単位を重合体Ｘに含めると、重合体Ｘが有する導電材分散能が損なわれる虞がある。したがって、導電材分散液の保存安定性を確保する観点から、重合体Ｘ中での親水性基含有単量体単位の含有割合は、重合体Ｘ中の全繰り返し単位を１００質量％とした場合に、０．０５質量％未満（実質的に含まない）が好ましく、０質量％がより好ましい。 Here, in particular, the hydrophilic group-containing monomer such as a monomer having a carboxylic acid group can contribute to the improvement of the production stability of the polymer X, while the hydrophilic group-containing monomer unit is converted to the polymer X. If included in, the conductive material dispersibility of the polymer X may be impaired. Therefore, from the viewpoint of ensuring the storage stability of the conductive material dispersion, the content ratio of the hydrophilic group-containing monomer unit in the polymer X is when the total repeating unit in the polymer X is 100% by mass. Is preferably less than 0.05% by mass (substantially free), more preferably 0% by mass.
［重合体Ｘの調製方法］
重合体Ｘの製造方法は特に限定されないが、例えば、上述した単量体を含む単量体組成物を重合して重合体を得て、任意に、得られた重合体を水素添加することで調製することができる。
ここで、本発明において単量体組成物中の各単量体の含有割合は、重合体Ｘおける各単量体単位および構造単位（繰り返し単位）の含有割合に準じて定めることができる。
重合様式は、特に制限なく、溶液重合法、懸濁重合法、塊状重合法、乳化重合法などのいずれの方法も用いることができる。各重合法において、必要に応じて既知の乳化剤や重合開始剤を使用することができる。
水素添加の方法は、特に制限なく、触媒を用いる一般的な方法（例えば、国際公開第２０１２／１６５１２０号、国際公開第２０１３／０８０９８９号および特開２０１３−８４８５号公報参照）を使用することができる。
[Method for Preparing Polymer X]
Although the manufacturing method of the polymer X is not specifically limited, For example, by polymerizing the monomer composition containing the monomer mentioned above to obtain a polymer, and optionally hydrogenating the obtained polymer Can be prepared.
Here, in the present invention, the content ratio of each monomer in the monomer composition can be determined according to the content ratio of each monomer unit and structural unit (repeating unit) in the polymer X.
The polymerization mode is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used. In each polymerization method, known emulsifiers and polymerization initiators can be used as necessary.
The hydrogenation method is not particularly limited, and a general method using a catalyst (for example, see International Publication No. 2012/165120, International Publication No. 2013/088099 and JP2013-8485A) may be used. it can.
［重合体Ｘのヨウ素価］
なお、重合体Ｘのヨウ素価は２０ｍｇ／１００ｍｇ以下である必要があり、１８ｍｇ／１００ｍｇ以下であることが好ましく、１０ｍｇ／１００ｍｇ以下であることが更に好ましく、一方、５ｍｇ／１００ｍｇ以上であることが好ましい。重合体Ｘのヨウ素価が２０ｍｇ／１００ｍｇ超であると、導電材分散液の保存安定性が確保できず、電気化学素子の出力特性が低下してしまう。一方、５ｍｇ／１００ｍｇ以上であることで、重合体Ｘのピロリドン系溶媒への溶解性が向上する。そして、重合体Ｘのヨウ素価を上述の範囲内とすることで、導電材の分散性が確保され、電気化学素子の出力特性を向上させることができる。
[Iodine value of polymer X]
The iodine value of polymer X needs to be 20 mg / 100 mg or less, preferably 18 mg / 100 mg or less, more preferably 10 mg / 100 mg or less, and on the other hand, 5 mg / 100 mg or more. preferable. When the iodine value of the polymer X is more than 20 mg / 100 mg, the storage stability of the conductive material dispersion cannot be ensured, and the output characteristics of the electrochemical device are deteriorated. On the other hand, the solubility to the pyrrolidone-type solvent of the polymer X improves because it is 5 mg / 100 mg or more. And by making the iodine value of the polymer X into the above-mentioned range, the dispersibility of a electrically conductive material is ensured and the output characteristic of an electrochemical element can be improved.
［好適な重合体Ｘの構造］
そして、重合体Ｘとしては、導電材分散液を用いて形成される電極合材層中で導電材を良好に分散させて、電極合材層の導電性を向上させる観点から、単量体として、ニトリル基含有単量体としてのアクリロニトリルと、共役ジエン単量体としての１，３−ブタジエンを含む単量体組成物を重合してなる重合体に、さらに水素添加することで得られる重合体が好ましい。くわえて、重合体Ｘとしては、上述と同様の観点から、単量体として、ニトリル基含有単量体としてのアクリロニトリルと、共役ジエン単量体としての１，３−ブタジエンのみを含む単量体組成物を重合してなる重合体に、さらに水素添加することで得られる重合体がより好ましい。
[Preferable Structure of Polymer X]
And as a polymer X, from a viewpoint of disperse | distributing a conductive material favorably in the electrode compound-material layer formed using a conductive-material dispersion liquid, and improving the electroconductivity of an electrode compound-material layer, as a monomer A polymer obtained by further hydrogenating a polymer obtained by polymerizing a monomer composition containing acrylonitrile as a nitrile group-containing monomer and 1,3-butadiene as a conjugated diene monomer Is preferred. In addition, the polymer X is a monomer containing only acrylonitrile as a nitrile group-containing monomer and 1,3-butadiene as a conjugated diene monomer from the same viewpoint as described above. A polymer obtained by further hydrogenating a polymer obtained by polymerizing the composition is more preferable.
［重合体Ｘの配合量］
導電材分散液中における重合体Ｘの配合量は、導電材１００質量部当たり、２質量部以上３０質量部以下であることが必要であり、好ましくは５質量部以上であり、より好ましくは６質量部以上であり、好ましくは２５質量部以下である。導電材分散液中の重合体Ｘの配合量が２質量部未満であると、導電材分散液中の導電材の分散性を十分に確保することができない。一方、導電材分散液中の重合体Ｘの配合量が３０質量部超であると、導電材の分散液の粘度が増加することで電極用スラリーの良好な塗工性が確保できず、また、重合体Ｘの配合量の増加に見合う分散性の向上効果が得られなくなると共に、導電材分散液から形成された電極合材層を備える電極を有する電気化学素子において、内部抵抗が上昇し、出力特性などの電気的特性が低下する。
よって、重合体Ｘの配合量を、導電材１００質量部当たり、２質量部以上３０質量部以下とすることで、電極用スラリーの良好な塗工性および電極合材層中の導電材の分散性が確保され、電気化学素子の出力特性を向上させることができる。
[Blending amount of polymer X]
The blending amount of the polymer X in the conductive material dispersion liquid needs to be 2 parts by mass or more and 30 parts by mass or less, preferably 5 parts by mass or more, more preferably 6 parts per 100 parts by mass of the conductive material. It is at least part by mass, preferably at most 25 parts by mass. When the blending amount of the polymer X in the conductive material dispersion is less than 2 parts by mass, the dispersibility of the conductive material in the conductive material dispersion cannot be sufficiently ensured. On the other hand, when the blending amount of the polymer X in the conductive material dispersion is more than 30 parts by mass, the viscosity of the conductive material dispersion cannot be increased so that good coatability of the electrode slurry cannot be secured. In addition, in the electrochemical element having an electrode provided with an electrode mixture layer formed from a conductive material dispersion liquid, the internal resistance increases, while the improvement effect of dispersibility commensurate with the increase in the blending amount of the polymer X cannot be obtained. Electrical characteristics such as output characteristics deteriorate.
Therefore, by setting the blending amount of the polymer X to 2 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the conductive material, good coating property of the electrode slurry and dispersion of the conductive material in the electrode mixture layer And the output characteristics of the electrochemical device can be improved.
＜フッ素樹脂Ｙ＞
本発明の導電材分散液は、任意に、結着材として機能しうるフッ素樹脂Ｙを含有してもよい。結着材として機能しうるフッ素樹脂Ｙを使用することで、当該導電材分散液から形成される電極合材層と集電体の密着性が確保され、出力特性などの電気化学素子の電気的特性を向上させることができる。
なお、上記重合体Ｘも結着性を発揮するが、上述した通り、導電材の分散性、電極用スラリーの塗工性、および電気化学素子の電気的特性の全てを確保する観点からは、重合体Ｘの配合量には限界がある。そこで、本発明の導電材分散液では、重合体Ｘ以外に結着材として機能しうるフッ素樹脂Ｙを使用することで、電極合材層と集電体の密着性を確保することが好ましい。
<Fluorine resin Y>
The conductive material dispersion of the present invention may optionally contain a fluororesin Y that can function as a binder. By using the fluororesin Y that can function as a binder, the adhesion between the electrode mixture layer formed from the conductive material dispersion and the current collector is secured, and the electrical characteristics of the electrochemical device such as output characteristics Characteristics can be improved.
In addition, although the polymer X also exhibits binding properties, as described above, from the viewpoint of ensuring all of the dispersibility of the conductive material, the coating property of the slurry for electrodes, and the electrical characteristics of the electrochemical element, There is a limit to the blending amount of the polymer X. Therefore, in the conductive material dispersion of the present invention, it is preferable to secure the adhesion between the electrode mixture layer and the current collector by using a fluororesin Y that can function as a binder in addition to the polymer X.
フッ素樹脂Ｙは、フッ素含有単量体単位を含む重合体である。具体的には、フッ素樹脂Ｙとしては、１種類以上のフッ素含有単量体の単独重合体または共重合体や、１種類以上のフッ素含有単量体とフッ素を含有しない単量体（以下、「フッ素非含有単量体」と称する。）との共重合体が挙げられる。
なお、フッ素樹脂Ｙにおけるフッ素含有単量体単位の割合は、通常７０質量％以上、好ましくは８０質量％以上である。また、フッ素樹脂Ｙにおけるフッ素非含有単量体単位の割合は、通常３０質量％以下、好ましくは２０質量％以下である。
The fluororesin Y is a polymer containing a fluorine-containing monomer unit. Specifically, as the fluororesin Y, a homopolymer or copolymer of one or more fluorine-containing monomers, one or more fluorine-containing monomers and a monomer not containing fluorine (hereinafter, And a copolymer thereof (referred to as “fluorine-free monomer”).
In addition, the ratio of the fluorine-containing monomer unit in the fluororesin Y is usually 70% by mass or more, and preferably 80% by mass or more. Moreover, the ratio of the fluorine-free monomer unit in the fluororesin Y is usually 30% by mass or less, preferably 20% by mass or less.
ここで、フッ素含有単量体単位を形成し得るフッ素含有単量体としては、フッ化ビニリデン、テトラフルオロエチレン、ヘキサフルオロプロピレン、三フッ化塩化ビニル、フッ化ビニル、パーフルオロアルキルビニルエーテルなどが挙げられる。これらの中でも、フッ素含有単量体としては、フッ化ビニリデンが好ましい。 Here, examples of the fluorine-containing monomer that can form a fluorine-containing monomer unit include vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, vinyl trifluoride chloride, vinyl fluoride, and perfluoroalkyl vinyl ether. It is done. Among these, as the fluorine-containing monomer, vinylidene fluoride is preferable.
また、フッ素非含有単量体単位を形成し得るフッ素非含有単量体としては、フッ素含有単量体と共重合可能なフッ素を含まない単量体、例えば、エチレン、プロピレン、１−ブテンなどの１−オレフィン；スチレン、α−メチルスチレン、ｐ−ｔ−ブチルスチレン、ビニルトルエン、クロロスチレンなどの芳香族ビニル化合物；（メタ）アクリロニトリルなどの不飽和ニトリル化合物；（メタ）アクリル酸メチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシルなどの（メタ）アクリル酸エステル化合物；（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミドなどの（メタ）アクリルアミド化合物；（メタ）アクリル酸、イタコン酸、フマル酸、クロトン酸、マレイン酸などのカルボキシル基を含有するビニル化合物；アリルグリシジルエーテル、（メタ）アクリル酸グリシジルなどのエポキシ基含有不飽和化合物；（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジエチルアミノエチルなどのアミノ基含有不飽和化合物；スチレンスルホン酸、ビニルスルホン酸、（メタ）アリルスルホン酸などのスルホン酸基含有不飽和化合物；３−アリロキシ−２−ヒドロキシプロパン硫酸などの硫酸基含有不飽和化合物；（メタ）アクリル酸−３−クロロ−２−リン酸プロピル、３−アリロキシ−２−ヒドロキシプロパンリン酸などのリン酸基含有不飽和化合物などが挙げられる。 Examples of the fluorine-free monomer that can form a fluorine-free monomer unit include a fluorine-free monomer copolymerizable with the fluorine-containing monomer, such as ethylene, propylene, and 1-butene. 1-olefin; aromatic vinyl compounds such as styrene, α-methylstyrene, pt-butylstyrene, vinyltoluene, chlorostyrene; unsaturated nitrile compounds such as (meth) acrylonitrile; methyl (meth) acrylate, ( (Meth) acrylic acid ester compounds such as (meth) butyl acrylate and (meth) acrylic acid 2-ethylhexyl; (meth) such as (meth) acrylamide, N-methylol (meth) acrylamide and N-butoxymethyl (meth) acrylamide Acrylamide compounds; (meth) acrylic acid, itaconic acid, fumaric acid, crotonic acid, Vinyl compounds containing carboxyl groups such as oleic acid; epoxy group-containing unsaturated compounds such as allyl glycidyl ether and glycidyl (meth) acrylate; amino such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate Group-containing unsaturated compounds; sulfonic acid group-containing unsaturated compounds such as styrene sulfonic acid, vinyl sulfonic acid and (meth) allyl sulfonic acid; sulfate group-containing unsaturated compounds such as 3-allyloxy-2-hydroxypropanesulfuric acid; ) Phosphoric acid group-containing unsaturated compounds such as acrylic acid-3-chloro-2-phosphate and 3-allyloxy-2-hydroxypropanephosphoric acid.
そして、フッ素樹脂Ｙとしては、フッ素含有単量体としてフッ化ビニリデンを用いた重合体およびフッ素含有単量体としてフッ化ビニルを用いた重合体が好ましく、フッ素含有単量体としてフッ化ビニリデンを用いた重合体がより好ましい。
具体的には、フッ素樹脂Ｙとしては、フッ化ビニリデンの単独重合体（ポリフッ化ビニリデン）、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体およびポリフッ化ビニルが好ましく、ポリフッ化ビニリデン（ＰＶＤＦ）がより好ましい。
なお、上述したフッ素樹脂Ｙは、単独で使用してもよいし、２種以上を併用してもよい。
The fluororesin Y is preferably a polymer using vinylidene fluoride as the fluorine-containing monomer and a polymer using vinyl fluoride as the fluorine-containing monomer, and vinylidene fluoride is used as the fluorine-containing monomer. The polymer used is more preferred.
Specifically, as the fluororesin Y, a homopolymer of vinylidene fluoride (polyvinylidene fluoride), a copolymer of vinylidene fluoride and hexafluoropropylene, and polyvinyl fluoride are preferable, and polyvinylidene fluoride (PVDF) is preferable. More preferred.
In addition, the fluororesin Y mentioned above may be used independently and may use 2 or more types together.
ここで、フッ素樹脂Ｙが１２質量％の濃度でＮＭＰに溶解した溶液の粘度は、好ましくは１０ｍＰａ・ｓ以上、より好ましくは１００ｍＰａ・ｓ以上であり、好ましくは１８００ｍＰａ・ｓ以下、より好ましくは１３００ｍＰａ・ｓ以下、更に好ましくは６００ｍＰａ・ｓ以下である。フッ素樹脂Ｙの１２質量％ＮＭＰ溶液の粘度が１０ｍＰａ・ｓ以上であることで、導電材分散液から形成される電極合材層と集電体との密着性を向上させることができ、１８００ｍＰａ・ｓ以下であることで、導電材分散液の粘度が過剰に上昇することにより導電材の分散性が損なわれることもない。そして、フッ素樹脂Ｙの１２質量％ＮＭＰ溶液の粘度が上述の範囲内であることにより、当該フッ素樹脂Ｙを用いた導電材分散液から形成された電極合材層を備える電極を有する電気化学素子の、出力特性などの電気的特性を向上させることができる。
なお、フッ素樹脂Ｙの１２質量％ＮＭＰ溶液の粘度は、Ｂ型粘度計を用いて、温度２５℃、回転速度６０ｒｐｍ、回転時間６０秒の条件で測定することができる。
Here, the viscosity of the solution in which the fluororesin Y is dissolved in NMP at a concentration of 12% by mass is preferably 10 mPa · s or more, more preferably 100 mPa · s or more, preferably 1800 mPa · s or less, more preferably 1300 mPa. · S or less, more preferably 600 mPa · s or less. When the viscosity of the 12 mass% NMP solution of the fluororesin Y is 10 mPa · s or more, the adhesion between the electrode mixture layer formed from the conductive material dispersion and the current collector can be improved, and 1800 mPa · s. By being less than s, the dispersibility of the conductive material is not impaired by excessive increase in the viscosity of the conductive material dispersion. And the electrochemical element which has an electrode provided with the electrode compound-material layer formed from the electrically conductive material dispersion liquid using the said fluororesin Y because the viscosity of the 12 mass% NMP solution of fluororesin Y is in the above-mentioned range. The electrical characteristics such as the output characteristics can be improved.
In addition, the viscosity of the 12 mass% NMP solution of the fluororesin Y can be measured using a B-type viscometer under conditions of a temperature of 25 ° C., a rotation speed of 60 rpm, and a rotation time of 60 seconds.
ここで、上述したフッ素樹脂Ｙの製造方法は特に限定はされず、例えば、溶液重合法、懸濁重合法、塊状重合法、乳化重合法などのいずれの方法も用いることができる。
また、重合方法としては、イオン重合、ラジカル重合、リビングラジカル重合などの付加重合を用いることができる。また、重合開始剤としては、既知の重合開始剤を用いることができる。
Here, the manufacturing method of the fluororesin Y mentioned above is not specifically limited, For example, any methods, such as a solution polymerization method, suspension polymerization method, block polymerization method, and emulsion polymerization method, can be used.
As the polymerization method, addition polymerization such as ionic polymerization, radical polymerization, living radical polymerization and the like can be used. Moreover, as a polymerization initiator, a known polymerization initiator can be used.
そして、フッ素樹脂Ｙは、分散媒に分散された分散液または溶解された溶液の状態で導電材分散液の調製に使用される。導電材分散液の調製に使用するフッ素樹脂Ｙの分散媒としては、フッ素樹脂Ｙを均一に分散または溶解し得るものであれば、特に制限されず、水や有機溶媒を用いることができ、有機溶媒を用いることが好ましい。なお、有機溶媒としては、特に限定されることなく、本発明の導電材分散液の分散媒として用いるピロリドン系溶媒を用いることができる。 The fluororesin Y is used for the preparation of a conductive material dispersion in the state of a dispersion or a solution dissolved in a dispersion medium. The dispersion medium of the fluororesin Y used for the preparation of the conductive material dispersion is not particularly limited as long as the fluororesin Y can be uniformly dispersed or dissolved, and water or an organic solvent can be used. It is preferable to use a solvent. In addition, as an organic solvent, it does not specifically limit, The pyrrolidone type solvent used as a dispersion medium of the electrically conductive material dispersion liquid of this invention can be used.
そして、本発明の導電材分散液は、導電材１００質量部当たり、フッ素樹脂Ｙを好ましくは１０質量部以上含み、好ましくは２００質量部以下、より好ましくは１００質量部以下、更に好ましくは５０質量部以下含む。フッ素樹脂Ｙの配合量が導電材１００質量部当たり１０質量部以上であることで、導電材分散液から形成される電極合材層と集電体との密着性を向上させることができる。一方、フッ素樹脂Ｙの配合量が導電材１００質量部当たり２００質量部以下であることで、当該導電材分散液から形成された電極合材層を備える電極を有する電気化学素子において、フッ素樹脂Ｙの量が過剰となることに起因する内部抵抗の上昇が抑制され、出力特性などの電気的特性を確保することができる。加えて、導電材分散液の粘度が過剰に高粘度とならず、電極用スラリーの調製が容易であり、また、電極用スラリーの集電体上への塗工性が向上する。さらに、導電材分散液中での導電材の分散性を確保することができる。
なお、本発明の導電材分散液は、重合体Ｘの量とフッ素樹脂Ｙの量の合計中、フッ素樹脂Ｙの量が占める割合は、好ましくは６０質量％以上、より好ましくは６５質量％以上であり、好ましくは９０質量％以下、より好ましくは８７質量％以下である。重合体Ｘとフッ素樹脂Ｙの合計量中のフッ素樹脂Ｙの割合が上述の範囲内であることで、重合体Ｘおよびフッ素樹脂Ｙにより得られる結着能と、重合体Ｘにより得られる導電材分散能のバランスが良好となり、導電材分散液の保存安定性、そして当該導電材分散液から形成された電極合材層を備える電極を有する電気化学素子の、出力特性などの電気的特性を更に向上させることができる。加えて、重合体Ｘとフッ素樹脂Ｙの合計量中のフッ素樹脂Ｙの割合が上述の範囲内であることで、電極用スラリーの集電体上への塗工性を更に向上させることができる。
The conductive material dispersion of the present invention preferably contains 10 parts by mass or more, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 50 parts by mass, per 100 parts by mass of the conductive material. Including parts. When the blending amount of the fluororesin Y is 10 parts by mass or more per 100 parts by mass of the conductive material, the adhesion between the electrode mixture layer formed from the conductive material dispersion and the current collector can be improved. On the other hand, in the electrochemical element having an electrode including an electrode mixture layer formed from the conductive material dispersion, the blending amount of the fluororesin Y is 200 parts by mass or less per 100 parts by mass of the conductive material. An increase in internal resistance due to an excessive amount of is suppressed, and electrical characteristics such as output characteristics can be secured. In addition, the viscosity of the conductive material dispersion does not become excessively high, and the preparation of the electrode slurry is easy, and the coating property of the electrode slurry on the current collector is improved. Furthermore, the dispersibility of the conductive material in the conductive material dispersion can be ensured.
In the conductive material dispersion of the present invention, the proportion of the amount of the fluororesin Y in the total amount of the polymer X and the fluororesin Y is preferably 60% by mass or more, more preferably 65% by mass or more. Preferably, it is 90 mass% or less, More preferably, it is 87 mass% or less. When the ratio of the fluororesin Y in the total amount of the polymer X and the fluororesin Y is within the above range, the binding ability obtained by the polymer X and the fluororesin Y and the conductive material obtained by the polymer X The balance of the dispersibility becomes good, the storage stability of the conductive material dispersion, and the electrical characteristics such as the output characteristics of the electrochemical device having the electrode with the electrode mixture layer formed from the conductive material dispersion are further improved. Can be improved. In addition, when the ratio of the fluororesin Y in the total amount of the polymer X and the fluororesin Y is within the above range, the coating property of the electrode slurry onto the current collector can be further improved. .
＜ピロリドン系溶媒＞
本発明の導電材分散液において、分散媒としてピロリドン系溶媒を用いる。ピロリドン系溶媒は、重合体Ｘの溶解度が高いため、重合体Ｘの導電材分散能を十分に発揮させることができるからである。具体的なピロリドン系溶媒としては、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、Ｎ−エチル−２−ピロリドン（ＮＥＰ）が挙げられる。これらの中でも、フッ素樹脂Ｙの溶解性の観点からＮＭＰが好ましい。
なお、これらのピロリドン系溶媒は、単独で使用してもよいし、２種以上を混合して使用してもよい。
<Pyrrolidone solvent>
In the conductive material dispersion of the present invention, a pyrrolidone solvent is used as a dispersion medium. This is because the pyrrolidone-based solvent has a high solubility of the polymer X, so that the conductive material dispersibility of the polymer X can be sufficiently exhibited. Specific examples of the pyrrolidone solvent include N-methyl-2-pyrrolidone (NMP) and N-ethyl-2-pyrrolidone (NEP). Among these, NMP is preferable from the viewpoint of solubility of the fluororesin Y.
These pyrrolidone solvents may be used alone or in combination of two or more.
＜導電材分散液の調製方法＞
上述の導電材、重合体Ｘ、任意のフッ素樹脂Ｙ、およびピロリドン系溶媒を混合して導電材分散液を得るにあたり、混合方法には特に制限は無く、例えば、ディスパー、ミル、ニーダーなどの一般的な混合装置を用いることができる。例えば、ディスパーを使用する場合には、１０００ｒｐｍ以上５０００ｒｐｍ以下で、５分以上６０分以下攪拌することが好ましい。
また、導電材分散液を得るにあたり、混合手順も特に制限はなく、例えば、（Ａ）ピロリドン系溶媒に重合体Ｘを溶解後、導電材を添加し、上述の混合装置および混合条件で混合してもよいし、（Ｂ）導電材、重合体Ｘおよびピロリドン系溶媒を上述の混合装置および混合条件で一括混合してもよい。これらの中でも、（Ａ）の混合手順が好ましい。
更に、フッ素樹脂Ｙを導電材分散液に添加する場合は、導電材分散液の保存安定性を一層向上させる観点から、導電材、重合体Ｘおよびピロリドン系溶媒を例えば上述の混合装置および混合条件で予混合した後に、フッ素樹脂Ｙを添加することが好ましい。そして、フッ素樹脂Ｙを添加後、例えば上述の混合装置および混合条件でさらに混合することが好ましい。フッ素樹脂Ｙの添加に先んじて、導電材、重合体Ｘおよびピロリドン系溶媒を混合することで、分散剤としての重合体Ｘを優先して導電材に吸着させることができ、重合体Ｘの導電材分散能を十分に発揮させることができるからである。なお、フッ素樹脂Ｙは、電気化学素子正極用スラリーの調製段階で添加してもよい。
<Method for preparing conductive material dispersion>
When the conductive material, the polymer X, the optional fluororesin Y, and the pyrrolidone-based solvent are mixed to obtain a conductive material dispersion, there is no particular limitation on the mixing method. For example, general disperser, mill, kneader, etc. A typical mixing device can be used. For example, when using a disper, it is preferable to stir at 1000 rpm to 5000 rpm for 5 minutes to 60 minutes.
In addition, there is no particular limitation on the mixing procedure for obtaining the conductive material dispersion. For example, after dissolving the polymer X in the (A) pyrrolidone-based solvent, the conductive material is added and mixed using the above-described mixing apparatus and mixing conditions. Alternatively, (B) the conductive material, the polymer X, and the pyrrolidone-based solvent may be mixed together using the above-described mixing apparatus and mixing conditions. Among these, the mixing procedure (A) is preferable.
Further, when the fluororesin Y is added to the conductive material dispersion, from the viewpoint of further improving the storage stability of the conductive material dispersion, the conductive material, the polymer X and the pyrrolidone-based solvent are mixed, for example, with the above-described mixing apparatus and mixing conditions. It is preferable to add the fluororesin Y after premixing in step (b). And after adding fluororesin Y, it is preferable to mix further, for example with the above-mentioned mixing apparatus and mixing conditions. Prior to the addition of the fluororesin Y, the conductive material, the polymer X and the pyrrolidone-based solvent are mixed so that the polymer X as a dispersant can be preferentially adsorbed on the conductive material. This is because the material dispersibility can be sufficiently exhibited. In addition, you may add the fluororesin Y in the preparation stage of the slurry for electrochemical element positive electrodes.
そして、得られる導電材分散液の粘度は、８００ｍＰａ・ｓ以下である必要があり、７５０ｍＰａ・ｓ以下であることが好ましく、７００ｍＰａ・ｓ以下であることがより好ましく、３００ｍＰａ・ｓ以上であることが好ましい。導電材分散液の粘度が８００ｍＰａ・ｓ超であると、当該導電材分散液を含む電極用スラリーの塗工性が損なわれ、集電体上に塗布した際にむらが生じ、電気化学素子の出力特性などの電気的特性が低下する。一方、導電材分散液の粘度が３００ｍＰａ・ｓ以上であれば、電極用スラリーの塗布の際に生じるハジキを抑制することができる。
また、得られる導電材分散液のＴＩ値（チクソトロピックインデックス値）は、０．８０以上であることが好ましく、０．９５以上であることがより好ましく、３．５０以下であることが好ましく、２．０以下であることがより好ましい。ＴＩ値が上述の範囲内であれば、電極用スラリーの塗工性が向上し、電気化学素子の出力特性などの電気的特性を一層高めることができる。
ここで、ＴＩ値は、Ｂ型粘度計を用いて、温度２５℃、回転速度６０ｒｐｍ、回転時間６０秒の条件で測定される導電材分散液の粘度η６０に対する、回転速度を６ｒｐｍとした以外はη６０と同様にして測定される導電材分散液の粘度η６の比（η６／η６０）として求めることができる。
The viscosity of the obtained conductive material dispersion liquid needs to be 800 mPa · s or less, preferably 750 mPa · s or less, more preferably 700 mPa · s or less, and 300 mPa · s or more. Is preferred. When the viscosity of the conductive material dispersion is more than 800 mPa · s, the coating property of the electrode slurry containing the conductive material dispersion is impaired, and unevenness occurs when applied on the current collector. Electrical characteristics such as output characteristics deteriorate. On the other hand, if the viscosity of the conductive material dispersion is 300 mPa · s or more, repelling that occurs during application of the electrode slurry can be suppressed.
Further, the TI value (thixotropic index value) of the obtained conductive material dispersion is preferably 0.80 or more, more preferably 0.95 or more, and preferably 3.50 or less, More preferably, it is 2.0 or less. If the TI value is within the above range, the coating property of the electrode slurry can be improved, and the electrical characteristics such as the output characteristics of the electrochemical element can be further enhanced.
Here, the TI value is obtained by using a B-type viscometer, except that the rotation speed is 6 rpm with respect to the viscosity η60 of the conductive material dispersion measured at a temperature of 25 ° C., a rotation speed of 60 rpm, and a rotation time of 60 seconds. It can be determined as the ratio (η6 / η60) of the viscosity η6 of the conductive material dispersion measured in the same manner as η60.
（電気化学素子正極用スラリー）
本発明の電気化学素子正極用スラリーは、上述した電気化学素子用導電材分散液および正極活物質を含む。即ち、導電材と、重合体Ｘと、正極活物質と、ピロリドン系溶媒と、任意にフッ素樹脂Ｙとを含む。
このように、上述した電気化学素子用導電材分散液を含む電気化学素子正極用スラリーは、本発明の導電材分散液を用いて調製されているため、保存安定性および塗工性に優れる。したがって、そのような正極用スラリーから形成される正極合材層は、その中で導電材が良好に分散しかつ均一な厚みを有し、そして電気化学素子に優れた出力特性を発揮させることができる。
(Slurry for electrochemical element positive electrode)
The slurry for an electrochemical element positive electrode of the present invention contains the above-described conductive material dispersion for an electrochemical element and a positive electrode active material. That is, a conductive material, a polymer X, a positive electrode active material, a pyrrolidone-based solvent, and optionally a fluororesin Y are included.
Thus, since the slurry for electrochemical element positive electrodes containing the electrically conductive material dispersion liquid for electrochemical elements mentioned above is prepared using the electrically conductive material dispersion liquid of this invention, it is excellent in storage stability and coating property. Therefore, the positive electrode mixture layer formed from such a positive electrode slurry has a conductive material dispersed well therein and a uniform thickness, and can exhibit excellent output characteristics in an electrochemical device. it can.
＜正極活物質＞
電気化学素子正極用スラリーに配合する正極活物質としては、特に限定されることなく、既知の正極活物質を用いることができる。
例えばリチウムイオン二次電池に用いられる正極活物質としては、特に限定されることなく、リチウム含有コバルト酸化物（ＬｉＣｏＯ２）、マンガン酸リチウム（ＬｉＭｎ２Ｏ４）、リチウム含有ニッケル酸化物（ＬｉＮｉＯ２）、Ｃｏ−Ｎｉ−Ｍｎのリチウム含有複合酸化物、Ｎｉ−Ｍｎ−Ａｌのリチウム含有複合酸化物、Ｎｉ−Ｃｏ−Ａｌのリチウム含有複合酸化物、オリビン型リン酸鉄リチウム（ＬｉＦｅＰＯ４）、オリビン型リン酸マンガンリチウム（ＬｉＭｎＰＯ４）、Ｌｉ１＋ｘＭｎ２−ｘＯ４（０＜Ｘ＜２）で表されるリチウム過剰のスピネル化合物、Ｌｉ［Ｎｉ０．１７Ｌｉ０．２Ｃｏ０．０７Ｍｎ０．５６］Ｏ２、ＬｉＮｉ０．５Ｍｎ１．５Ｏ４等が挙げられる。
また例えばリチウムイオンキャパシタや電気二重層キャパシタに用いられる正極活物質としては、特に限定されることなく、炭素の同素体が挙げられる。炭素の同素体の具体例としては、活性炭、ポリアセン、カーボンウィスカ及びグラファイト等が挙げられ、これらの粉末または繊維を使用することができる。
<Positive electrode active material>
As a positive electrode active material mix | blended with the slurry for electrochemical element positive electrodes, it is not specifically limited, A known positive electrode active material can be used.
For example, a positive electrode active material used for a lithium ion secondary battery is not particularly limited, and lithium-containing cobalt oxide (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), lithium-containing nickel oxide (LiNiO 2). ), Co—Ni—Mn lithium-containing composite oxide, Ni—Mn—Al lithium-containing composite oxide, Ni—Co—Al lithium-containing composite oxide, olivine-type lithium iron phosphate (LiFePO 4 ), olivine Type lithium lithium phosphate (LiMnPO 4 ), Li 1 + x Mn 2−x O 4 (0 <X <2), an excess lithium spinel compound, Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 , LiNi 0.5 Mn 1.5 O 4 and the like.
Further, for example, a positive electrode active material used for a lithium ion capacitor or an electric double layer capacitor is not particularly limited, and includes an allotrope of carbon. Specific examples of the allotrope of carbon include activated carbon, polyacene, carbon whisker, and graphite, and these powders or fibers can be used.
上述した中でも、リチウムイオン二次電池において電池容量などを向上させる観点からは、正極活物質としてリチウム含有コバルト酸化物（ＬｉＣｏＯ２）、リチウム含有ニッケル酸化物（ＬｉＮｉＯ２）、Ｃｏ−Ｎｉ−Ｍｎのリチウム含有複合酸化物、Ｎｉ−Ｃｏ−Ａｌのリチウム含有複合酸化物、Ｌｉ［Ｎｉ０．１７Ｌｉ０．２Ｃｏ０．０７Ｍｎ０．５６］Ｏ２またはＬｉＮｉ０．５Ｍｎ１．５Ｏ４を用いることが好ましい。
なお、正極活物質の粒径は、特に限定されることなく、従来使用されている正極活物質と同様とすることができる。
そして、本発明の電気化学素子正極用スラリーは、導電材１００質量部当たり、正極活物質を好ましくは１０００質量部以上、より好ましくは２０００質量部以上含み、好ましくは１００００質量部以下、より好ましくは５０００質量部以下含む。上述の範囲内で正極活物質を含むことで、導電材の分散性を向上させつつ正極用スラリーを用いて形成される正極合材層の導電性を優れたものとすることができる。
Among the above, from the viewpoint of improving battery capacity and the like in a lithium ion secondary battery, lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), and Co—Ni—Mn are used as the positive electrode active material. Lithium-containing composite oxide, lithium-containing composite oxide of Ni—Co—Al, Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 or LiNi 0.5 Mn 1.5 O 4 Is preferably used.
The particle size of the positive electrode active material is not particularly limited, and can be the same as that of a positive electrode active material conventionally used.
The slurry for an electrochemical device positive electrode of the present invention preferably contains 1000 parts by mass or more, more preferably 2000 parts by mass or more, preferably 10,000 parts by mass or less, more preferably 100 parts by mass or more of the positive electrode active material per 100 parts by mass of the conductive material. Including 5000 parts by mass or less. By including the positive electrode active material within the above range, the conductivity of the positive electrode mixture layer formed using the positive electrode slurry can be improved while improving the dispersibility of the conductive material.
＜その他の成分＞
電気化学素子正極用スラリーには、上記成分の他に、例えば、フッ素樹脂Ｙ以外の結着材、粘度調整剤、補強材、酸化防止剤、電解液の分解を抑制する機能を有する電解液添加剤などの成分を混合してもよい。これらの他の成分は、公知のものを使用することができる。また、これらの他の成分は、上述した本発明の電気化学素子用導電材分散液に配合してもよい。
<Other ingredients>
In addition to the above components, for example, a binder other than the fluororesin Y, a viscosity modifier, a reinforcing material, an antioxidant, and an electrolyte solution having a function of suppressing decomposition of the electrolyte solution are added to the slurry for the electrochemical device positive electrode You may mix components, such as an agent. As these other components, known ones can be used. Moreover, you may mix | blend these other components with the electrically conductive material dispersion liquid for electrochemical elements of this invention mentioned above.
＜電気化学素子正極用スラリーの調製方法＞
導電材分散液に対して、上述の正極活物質と、任意に、その他の成分および追加のピロリドン系溶媒とを混合して電気化学素子正極用スラリーを得るにあたり、混合方法には特に制限は無く、例えば、ディスパー、ミル、ニーダーなどの一般的な混合装置を用いることができる。例えば、ディスパーを使用する場合には、２０００ｒｐｍ以上５０００ｒｐｍ以下で、５分以上１２０分以下攪拌することが好ましい。
<Method for preparing slurry for electrochemical element positive electrode>
There is no particular limitation on the mixing method for obtaining the slurry for the positive electrode of the electrochemical device by mixing the above-mentioned positive electrode active material and optionally other components and an additional pyrrolidone-based solvent with respect to the conductive material dispersion. For example, a general mixing apparatus such as a disper, a mill, or a kneader can be used. For example, when using a disper, it is preferable to stir at 2000 rpm or more and 5000 rpm or less for 5 minutes or more and 120 minutes or less.
（電気化学素子用正極）
本発明の電気化学素子用正極は、本発明の電気化学素子正極用スラリーを使用して製造することができる。
そして、本発明の電気化学素子用正極は、集電体と、集電体上に形成された正極合材層とを備え、正極合材層には、少なくとも、正極活物質と、導電材と、重合体Ｘとが含まれ、任意にフッ素樹脂Ｙが含まれている。なお、正極合材層中に含まれている正極活物質、導電材および重合体Ｘは、本発明の電気化学素子用導電材分散液および電気化学素子正極用スラリー中に含まれていたものであり、それら各成分の好適な存在比は、本発明の電気化学素子用導電材分散液および電気化学素子正極用スラリー中の各成分の好適な存在比と同じである。
(Positive electrode for electrochemical devices)
The positive electrode for electrochemical devices of the present invention can be produced using the slurry for positive electrodes of electrochemical devices of the present invention.
And the positive electrode for electrochemical devices of the present invention comprises a current collector and a positive electrode mixture layer formed on the current collector. The positive electrode mixture layer includes at least a positive electrode active material, a conductive material, and And a polymer X, and optionally a fluororesin Y. The positive electrode active material, conductive material, and polymer X contained in the positive electrode mixture layer were those contained in the electrochemical element conductive material dispersion and electrochemical element positive electrode slurry of the present invention. The preferred abundance ratios of these components are the same as the preferred abundance ratios of the respective components in the conductive material dispersion for electrochemical devices and the slurry for positive electrodes of electrochemical devices of the present invention.
そして、上述した電気化学素子正極用スラリーから形成される正極合材層は、導電材が良好に分散し内部抵抗の上昇が抑制されているとともに、均一な厚みを有する。従って、そのような正極合材層を備える本発明の電気化学素子用正極を有する電気化学素子は、出力特性などの電気的特性に優れる。 And the positive mix layer formed from the slurry for electrochemical element positive electrodes mentioned above has a uniform thickness while the conductive material is well dispersed and the increase in internal resistance is suppressed. Therefore, the electrochemical device having the positive electrode for an electrochemical device of the present invention having such a positive electrode mixture layer is excellent in electrical characteristics such as output characteristics.
＜電気化学素子用正極の製造方法＞
本発明の電気化学素子用正極の製造方法は、本発明の電気化学素子正極用スラリーを、集電体の少なくとも一方の面に塗布し、乾燥して正極合材層を形成する工程を含む。より詳細には、当該製造方法は、電気化学素子正極用スラリーを集電体の少なくとも一方の面に塗布する工程（塗布工程）と、集電体の少なくとも一方の面に塗布された電気化学素子正極用スラリーを乾燥して集電体上に正極合材層を形成する工程（乾燥工程）とを含む。
<Method for producing positive electrode for electrochemical device>
The manufacturing method of the positive electrode for electrochemical devices of this invention includes the process of apply | coating the slurry for electrochemical device positive electrodes of this invention to at least one surface of a collector, and drying, and forming a positive mix layer. More specifically, the manufacturing method includes a step of applying the electrochemical device positive electrode slurry to at least one surface of the current collector (application step), and an electrochemical device applied to at least one surface of the current collector. And a step of drying the positive electrode slurry to form a positive electrode mixture layer on the current collector (drying step).
［塗布工程］
上記電気化学素子正極用スラリーを集電体上に塗布する方法としては、特に限定されず公知の方法を用いることができる。具体的には、塗布方法としては、ドクターブレード法、ディップ法、リバースロール法、ダイレクトロール法、グラビア法、エクストルージョン法、ハケ塗り法などを用いることができる。この際、電気化学素子正極用スラリーを集電体の片面だけに塗布してもよいし、両面に塗布してもよい。塗布後乾燥前の集電体上のスラリー膜の厚みは、乾燥して得られる正極合材層の厚みに応じて適宜に設定しうる。
[Coating process]
The method for coating the electrochemical device positive electrode slurry on the current collector is not particularly limited, and a known method can be used. Specifically, as a coating method, a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating method, or the like can be used. At this time, the electrochemical device positive electrode slurry may be applied to only one surface of the current collector, or may be applied to both surfaces. The thickness of the slurry film on the current collector after application and before drying can be appropriately set according to the thickness of the positive electrode mixture layer obtained by drying.
ここで、電気化学素子正極用スラリーを塗布する集電体としては、電気導電性を有し、かつ、電気化学的に耐久性のある材料が用いられる。具体的には、集電体としては、アルミニウムまたはアルミニウム合金からなる集電体を用い得る。この際、アルミニウムとアルミニウム合金とを組み合わせて用いてもよく、種類が異なるアルミニウム合金を組み合わせて用いてもよい。アルミニウムおよびアルミニウム合金は耐熱性を有し、電気化学的に安定であるため、優れた集電体材料である。 Here, as the current collector on which the slurry for the electrochemical device positive electrode is applied, a material having electrical conductivity and electrochemical durability is used. Specifically, a current collector made of aluminum or an aluminum alloy can be used as the current collector. At this time, aluminum and an aluminum alloy may be used in combination, or different types of aluminum alloys may be used in combination. Aluminum and aluminum alloys are excellent current collector materials because they have heat resistance and are electrochemically stable.
［乾燥工程］
集電体上の電気化学素子正極用スラリーを乾燥する方法としては、特に限定されず公知の方法を用いることができ、例えば温風、熱風、低湿風による乾燥、真空乾燥、赤外線や電子線などの照射による乾燥法が挙げられる。このように集電体上の電気化学素子正極用スラリーを乾燥することで、集電体上に正極合材層を形成し、集電体と正極合材層とを備える電気化学素子用正極を得ることができる。
[Drying process]
The method for drying the slurry for the electrochemical device positive electrode on the current collector is not particularly limited, and a known method can be used, for example, drying with hot air, hot air, low-humidity air, vacuum drying, infrared rays, electron beam, etc. And a drying method by irradiation. Thus, by drying the slurry for the electrochemical device positive electrode on the current collector, a positive electrode composite material layer is formed on the current collector, and the positive electrode for an electrochemical device comprising the current collector and the positive electrode composite material layer is provided. Can be obtained.
なお、乾燥工程の後、金型プレスまたはロールプレスなどを用い、正極合材層に加圧処理を施してもよい。加圧処理により、正極合材層と集電体との密着性を向上させることができる。
さらに、正極合材層が硬化性の重合体を含む場合は、正極合材層の形成後に前記重合体を硬化させることが好ましい。
Note that after the drying step, the positive electrode mixture layer may be subjected to pressure treatment using a die press or a roll press. By the pressure treatment, the adhesion between the positive electrode mixture layer and the current collector can be improved.
Furthermore, when the positive electrode mixture layer contains a curable polymer, the polymer is preferably cured after the positive electrode mixture layer is formed.
（電気化学素子）
本発明の電気化学素子は、特に限定されることなく、リチウムイオン二次電池、リチウムイオンキャパシタや電気二重層キャパシタであり、好ましくはリチウムイオン二次電池である。そして、本発明の電気化学素子は、本発明の電気化学素子用正極を備えることを特徴とする。このような電気化学素子は、出力特性などの電気的特性に優れる。
(Electrochemical element)
The electrochemical device of the present invention is not particularly limited, and is a lithium ion secondary battery, a lithium ion capacitor or an electric double layer capacitor, preferably a lithium ion secondary battery. And the electrochemical element of this invention is equipped with the positive electrode for electrochemical elements of this invention, It is characterized by the above-mentioned. Such an electrochemical element is excellent in electrical characteristics such as output characteristics.
ここで、以下では、本発明の電気化学素子の一例としてのリチウムイオン二次電池の構成について説明する。このリチウムイオン二次電池は、通常、上記本発明の電気化学素子用正極に加え、負極、電解液、セパレーターを備える。以下、上記各構成について説明する。 Here, below, the structure of the lithium ion secondary battery as an example of the electrochemical element of this invention is demonstrated. This lithium ion secondary battery usually includes a negative electrode, an electrolytic solution, and a separator in addition to the positive electrode for an electrochemical element of the present invention. Hereafter, each said structure is demonstrated.
＜負極＞
リチウムイオン二次電池の負極としては、リチウムイオン二次電池用負極として用いられる既知の負極を用いることができる。具体的には、負極としては、例えば、金属リチウムの薄板よりなる負極や、負極合材層を集電体上に形成してなる負極を用いることができる。
なお、集電体としては、鉄、銅、アルミニウム、ニッケル、ステンレス鋼、チタン、タンタル、金、白金等の金属材料からなるものを用いることができる。また、負極合材層としては、負極活物質と結着材とを含む層を用いることができる。更に、結着材としては、特に限定されず、任意の既知の材料を用いうる。
<Negative electrode>
As a negative electrode of a lithium ion secondary battery, a known negative electrode used as a negative electrode for a lithium ion secondary battery can be used. Specifically, as the negative electrode, for example, a negative electrode made of a thin plate of metallic lithium or a negative electrode formed by forming a negative electrode mixture layer on a current collector can be used.
In addition, as a collector, what consists of metal materials, such as iron, copper, aluminum, nickel, stainless steel, titanium, a tantalum, gold | metal | money, platinum, can be used. As the negative electrode mixture layer, a layer containing a negative electrode active material and a binder can be used. Furthermore, the binder is not particularly limited, and any known material can be used.
＜電解液＞
電解液としては、通常、有機溶媒に支持電解質を溶解した有機電解液が用いられる。支持電解質としては、例えば、リチウム塩が用いられる。リチウム塩としては、例えば、ＬｉＰＦ６、ＬｉＡｓＦ６、ＬｉＢＦ４、ＬｉＳｂＦ６、ＬｉＡｌＣｌ４、ＬｉＣｌＯ４、ＣＦ３ＳＯ３Ｌｉ、Ｃ４Ｆ９ＳＯ３Ｌｉ、ＣＦ３ＣＯＯＬｉ、（ＣＦ３ＣＯ）２ＮＬｉ、（ＣＦ３ＳＯ２）２ＮＬｉ、（Ｃ２Ｆ５ＳＯ２）ＮＬｉなどが挙げられる。なかでも、溶媒に溶けやすく高い解離度を示すので、ＬｉＰＦ６、ＬｉＣｌＯ４、ＣＦ３ＳＯ３Ｌｉが好ましく、ＬｉＰＦ６が特に好ましい。なお、電解質は１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。通常は、解離度の高い支持電解質を用いるほどリチウムイオン伝導度が高くなる傾向があるので、支持電解質の種類によりリチウムイオン伝導度を調節することができる。
<Electrolyte>
As the electrolytic solution, an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used. For example, a lithium salt is used as the supporting electrolyte. Examples of the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like. Among them, LiPF 6 , LiClO 4 , and CF 3 SO 3 Li are preferable, and LiPF 6 is particularly preferable because it is easily dissolved in a solvent and exhibits a high degree of dissociation. In addition, electrolyte may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. Usually, the lithium ion conductivity tends to increase as the supporting electrolyte having a higher degree of dissociation is used, so that the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
電解液に使用する有機溶媒としては、支持電解質を溶解できるものであれば特に限定されないが、例えば、ジメチルカーボネート（ＤＭＣ）、エチレンカーボネート（ＥＣ）、ジエチルカーボネート（ＤＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレンカーボネート（ＢＣ）、メチルエチルカーボネート（ＥＭＣ）等のカーボネート類；γ−ブチロラクトン、ギ酸メチル等のエステル類；１，２−ジメトキシエタン、テトラヒドロフラン等のエーテル類；スルホラン、ジメチルスルホキシド等の含硫黄化合物類；などが好適に用いられる。またこれらの溶媒の混合液を用いてもよい。中でも、誘電率が高く、安定な電位領域が広いのでカーボネート類を用いることが好ましく、エチレンカーボネートとエチルメチルカーボネートとの混合物を用いることが更に好ましい。
なお、電解液中の電解質の濃度は適宜調整することができ、例えば０．５〜１５質量％することが好ましく、２〜１３質量％とすることがより好ましく、５〜１０質量％とすることが更に好ましい。また、電解液には、既知の添加剤、例えばフルオロエチレンカーボネートやエチルメチルスルホンなどを添加してもよい。
The organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte. For example, dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), Carbonates such as butylene carbonate (BC) and methyl ethyl carbonate (EMC); esters such as γ-butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide Etc. are preferably used. Moreover, you may use the liquid mixture of these solvents. Among them, it is preferable to use carbonates because they have a high dielectric constant and a wide stable potential region, and it is more preferable to use a mixture of ethylene carbonate and ethyl methyl carbonate.
In addition, the density | concentration of the electrolyte in electrolyte solution can be adjusted suitably, for example, it is preferable to set it as 0.5-15 mass%, it is more preferable to set it as 2-13 mass%, and it shall be 5-10 mass%. Is more preferable. Further, known additives such as fluoroethylene carbonate and ethyl methyl sulfone may be added to the electrolytic solution.
＜セパレーター＞
セパレーターとしては、特に限定されることなく、例えば特開２０１２−２０４３０３号公報に記載のものを用いることができる。これらの中でも、セパレーター全体の膜厚を薄くすることができ、これにより、リチウムイオン二次電池内の電極活物質の比率を高くして体積あたりの容量を高くすることができるという点より、ポリオレフィン系（ポリエチレン、ポリプロピレン、ポリブテン、ポリ塩化ビニル）の樹脂からなる微多孔膜が好ましい。
<Separator>
As a separator, it does not specifically limit, For example, the thing of Unexamined-Japanese-Patent No. 2012-204303 can be used. Among these, the thickness of the entire separator can be reduced, thereby increasing the ratio of the electrode active material in the lithium ion secondary battery and increasing the capacity per volume. A microporous membrane made of a resin of the type (polyethylene, polypropylene, polybutene, polyvinyl chloride) is preferable.
＜リチウムイオン二次電池の製造方法＞
本発明に従うリチウムイオン二次電池は、例えば、正極と、負極とを、セパレーターを介して重ね合わせ、これを必要に応じて電池形状に応じて巻く、折るなどして電池容器に入れ、電池容器に電解液を注入して封口することにより製造することができる。二次電池の内部の圧力上昇、過充放電等の発生を防止するために、必要に応じて、ヒューズ、ＰＴＣ素子等の過電流防止素子、エキスパンドメタル、リード板などを設けてもよい。二次電池の形状は、例えば、コイン型、ボタン型、シート型、円筒型、角形、扁平型など、何れであってもよい。
<Method for producing lithium ion secondary battery>
The lithium ion secondary battery according to the present invention includes, for example, a positive electrode and a negative electrode that are overlapped via a separator and wound into a battery container according to the battery shape as necessary. It can manufacture by inject | pouring electrolyte solution into and sealing. In order to prevent an increase in pressure inside the secondary battery, overcharge / discharge, and the like, a fuse, an overcurrent prevention element such as a PTC element, an expanded metal, a lead plate, and the like may be provided as necessary. The shape of the secondary battery may be any of, for example, a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, and a flat shape.
以下、本発明について実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、以下の説明において、量を表す「％」及び「部」は、特に断らない限り、質量基準である。
実施例および比較例において、導電材分散液の保存安定性、正極用スラリーの塗工性およびリチウムイオン二次電池の出力特性は、それぞれ以下の方法を使用して評価した。
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the following description, “%” and “part” representing amounts are based on mass unless otherwise specified.
In Examples and Comparative Examples, the storage stability of the conductive material dispersion, the coating property of the positive electrode slurry, and the output characteristics of the lithium ion secondary battery were evaluated using the following methods, respectively.
＜導電材分散液の保存安定性＞
調製直後の導電材分散液の粘度η１を、Ｂ型粘度計（東機産業社製、ＲＢ―８０Ｌ）を用いて、温度２５℃、回転速度６０ｒｐｍ、回転時間６０秒で測定した。その後、導電材分散液を、２５℃環境下で３０日間保管後、そのまま上述のη１と同様にして、粘度η２を測定し、粘度変化Δη（％）＝（｜η１−η２｜／η１）×１００を求めた。そして下記基準で導電材分散液の保存安定性を評価した。粘度変化Δηが小さいほど、導電材分散液の粘度が安定であり、導電材の分散状態を良好に維持することができることを示す。
Ａ：粘度変化Δηが５％未満である。
Ｂ：粘度変化Δηが５％以上１０％未満である。
Ｃ：粘度変化Δηが１０％以上３０％未満である。
Ｄ：粘度変化Δηが３０％以上である。
＜正極用スラリーの塗工性＞
正極用スラリーを集電体としてのアルミニウム箔上に塗工し、乾燥して得られた正極を切り出して、大きさ０．５ｍ２の試験片を１０枚準備した。そして、試験片の正極合材層の表面を目視により観察し、ピンホール、ハジキが存在する試験片の枚数をカウントし、以下の指標で塗工性を評価した。ピンホール、ハジキが少ないほど、正極用スラリーの塗工性が優れることを示す。
Ａ：１０枚中、全てにピンホールおよびハジキの双方がみられない。
Ｂ：１０枚中、１〜２枚に、ピンホールおよび／またはハジキがみられる。
Ｃ：１０枚中、３〜４枚に、ピンホールおよび／またはハジキがみられる。
Ｄ：１０枚中、５枚以上に、ピンホールおよび／またはハジキがみられる。
＜リチウムイオン二次電池の出力特性＞
作製したラミネート型リチウムイオン二次電池を、２５℃環境下、電流１４０ｍＡで電圧が４．２Ｖになるまで定電流充電し、電圧４．２Ｖで充電電流が１４ｍＡになるまで定電圧充電を行った。続いて、電流１４０ｍＡで電池電圧が３Ｖになるまで定電流放電を行い、初期容量とした。
初期容量を測定したラミネート型リチウムイオン二次電池を、２５℃環境下、０．２Ｃで電池電圧が４．２Ｖになるまで定電流充電し、電圧４．２Ｖで充電電流が０．０２Ｃになるまで定電圧充電を行った。続いて、電流２Ｃで電池電圧が３．０Ｖになるまで定電流放電を行い、２Ｃ容量とした。｛（２Ｃ容量）／（初期容量）｝×１００（％）の値を出力特性とし、下記基準で評価を行った。この値が高いほど、初期出力特性に優れ、すなわち内部抵抗が小さいことを意味する。
Ａ：出力特性が９０％以上である。
Ｂ：出力特性が８７％以上９０％未満である。
Ｃ：出力特性が８４％以上８７％未満である。
Ｄ：出力特性が８０％以上８４％未満である。
Ｅ：出力特性が８０％未満である。
<Storage stability of conductive material dispersion>
The viscosity η1 of the electrically conductive material dispersion immediately after preparation was measured at a temperature of 25 ° C., a rotation speed of 60 rpm, and a rotation time of 60 seconds using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., RB-80L). Then, after storing the conductive material dispersion in an environment of 25 ° C. for 30 days, the viscosity η2 is measured in the same manner as η1 as described above, and the viscosity change Δη (%) = (| η1−η2 | / η1) × 100 was determined. Then, the storage stability of the conductive material dispersion was evaluated according to the following criteria. It shows that the smaller the viscosity change Δη is, the more stable the viscosity of the conductive material dispersion liquid is, and the better the dispersion state of the conductive material can be maintained.
A: Viscosity change Δη is less than 5%.
B: Viscosity change Δη is 5% or more and less than 10%.
C: Viscosity change Δη is 10% or more and less than 30%.
D: The viscosity change Δη is 30% or more.
<Coating properties of slurry for positive electrode>
The positive electrode slurry obtained by coating the slurry for positive electrode on the aluminum foil as a current collector and drying was prepared, and 10 test pieces having a size of 0.5 m 2 were prepared. Then, the surface of the positive electrode composite material layer of the test piece was visually observed, the number of test pieces having pinholes and repellencies was counted, and the coating property was evaluated using the following indices. It shows that the coating property of the slurry for positive electrodes is excellent, so that there are few pinholes and repellency.
A: Neither pinholes nor repellencies are seen in all 10 sheets.
B: A pinhole and / or a repellency are seen in 1-2 sheets out of 10 sheets.
C: Pinholes and / or repellencies are observed in 3 to 4 of 10 sheets.
D: Pinholes and / or repellencies are observed on 5 or more of 10 sheets.
<Output characteristics of lithium ion secondary battery>
The manufactured laminated lithium ion secondary battery was charged at a constant current at a current of 140 mA until the voltage reached 4.2 V in a 25 ° C. environment, and was charged at a voltage of 4.2 V until the charging current reached 14 mA. . Subsequently, constant current discharge was performed until the battery voltage became 3 V at a current of 140 mA to obtain an initial capacity.
The laminated lithium ion secondary battery whose initial capacity was measured was charged at a constant current until the battery voltage was 4.2 V at 0.2 C in an environment of 25 ° C., and the charging current was 0.02 C at a voltage of 4.2 V. Until constant voltage charging. Subsequently, constant current discharge was performed until the battery voltage reached 3.0 V at a current of 2 C, to obtain a 2 C capacity. A value of {(2C capacity) / (initial capacity)} × 100 (%) was used as an output characteristic, and evaluation was performed according to the following criteria. The higher this value, the better the initial output characteristics, that is, the smaller the internal resistance.
A: The output characteristic is 90% or more.
B: Output characteristics are 87% or more and less than 90%.
C: The output characteristic is 84% or more and less than 87%.
D: The output characteristic is 80% or more and less than 84%.
E: The output characteristic is less than 80%.
（実施例１）
＜重合体Ｘの調製＞
撹拌機付きのオートクレーブに、イオン交換水２４０部、乳化剤としてアルキルベンゼンスルホン酸ナトリウム２．５部、ニトリル基含有単量体としてアクリロニトリル（ＡＮ）３６部をこの順で入れ、ボトル内を窒素で置換した後、共役ジエン単量体として１，３−ブタジエン（ＢＤ）６４部（単量体としてＡＮ，ＢＤのみを含む単量体組成物を構成）を圧入し、重合開始剤として過硫酸アンモニウム０．２５部を添加して反応温度４０℃で重合反応させ、共役ジエン単量体単位およびニトリル基含有単量体単位を含んでなる重合体を得た。重合転化率は８５％であった。
Example 1
<Preparation of polymer X>
In an autoclave equipped with a stirrer, 240 parts of ion-exchanged water, 2.5 parts of sodium alkylbenzenesulfonate as an emulsifier, and 36 parts of acrylonitrile (AN) as a nitrile group-containing monomer were placed in this order, and the inside of the bottle was replaced with nitrogen. Thereafter, 64 parts of 1,3-butadiene (BD) (a monomer composition containing only AN and BD as monomers) is injected as a conjugated diene monomer, and ammonium persulfate 0.25 is used as a polymerization initiator. A polymer comprising a conjugated diene monomer unit and a nitrile group-containing monomer unit was obtained. The polymerization conversion rate was 85%.
得られた重合体に対してイオン交換水を添加して全固形分濃度を１２質量％に調整した４００ミリリットル（全固形分４８グラム）の溶液を、撹拌機付きの１リットルオートクレーブに投入し、窒素ガスを１０分間流して溶液中の溶存酸素を除去した後、水素添加反応触媒として、酢酸パラジウム７５ｍｇを、パラジウム（Ｐｄ）に対して４倍モルの硝酸を添加したイオン交換水１８０ｍＬに溶解して、添加した。系内を水素ガスで２回置換した後、３ＭＰａまで水素ガスで加圧した状態でオートクレーブの内容物を５０℃に加温し、６時間水素添加反応（第一段階の水素添加反応）させた。 400 ml (total solid content 48 grams) of a solution obtained by adding ion-exchanged water to the obtained polymer to adjust the total solid content concentration to 12% by mass was charged into a 1 liter autoclave equipped with a stirrer. After removing dissolved oxygen in the solution by flowing nitrogen gas for 10 minutes, as a hydrogenation reaction catalyst, 75 mg of palladium acetate was dissolved in 180 mL of ion-exchanged water added with 4-fold molar nitric acid with respect to palladium (Pd). And added. After the inside of the system was replaced with hydrogen gas twice, the content of the autoclave was heated to 50 ° C. while being pressurized with hydrogen gas to 3 MPa, and subjected to hydrogenation reaction (first stage hydrogenation reaction) for 6 hours. .
次いで、オートクレーブを大気圧にまで戻し、更に水素添加反応触媒として、酢酸パラジウム２５ｍｇを、Ｐｄに対して４倍モルの硝酸を添加したイオン交換水６０ｍＬに溶解して、添加した。系内を水素ガスで２回置換した後、３ＭＰａまで水素ガスで加圧した状態でオートクレーブの内容物を５０℃に加温し、６時間水素添加反応（第二段階の水素添加反応）させた。 Next, the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 mL of ion-exchanged water added with 4-fold mol of nitric acid with respect to Pd and added. After the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. under pressure with hydrogen gas up to 3 MPa and subjected to hydrogenation reaction (second stage hydrogenation reaction) for 6 hours. .
その後、内容物を常温に戻し、系内を窒素雰囲気とした後、エバポレータを用いて、固形分濃度が４０％となるまで濃縮して重合体Ｘの水分散液を得た。また、この重合体Ｘの水分散液１００部にＮＭＰ３２０部を加え、減圧下に水を蒸発させて、ニトリル基含有単量体単位およびアルキレン構造単位を含み、ヨウ素価が６ｍｇ／１００ｍｇである重合体ＸのＮＭＰ溶液を得た。 Thereafter, the contents were returned to room temperature, the inside of the system was made into a nitrogen atmosphere, and then concentrated using an evaporator until the solid content concentration became 40% to obtain an aqueous dispersion of polymer X. Also, 320 parts of NMP was added to 100 parts of this aqueous dispersion of polymer X, and water was evaporated under reduced pressure to contain a nitrile group-containing monomer unit and an alkylene structural unit, and an iodine value of 6 mg / 100 mg. An NMP solution of union X was obtained.
＜導電材分散液の製造＞
導電材としてのカーボンブラックα（電気化学工業（株）製、ＨＳ−１００、アセチレンブラック、平均粒子径：４８ｎｍ、比表面積：３９ｍ２／ｇ、密度：０．１５ｇ／ｃｍ３）１００部と、上述のようにして得た重合体ＸのＮＭＰ溶液を固形分相当量で１０部と、適量のＮＭＰとをディスパーにて攪拌（２０００ｒｐｍ、６０分）した。その後、固形分濃度が１０質量％になるように適量のＮＭＰを入れてディスパーで撹拌（２０００ｒｐｍ、１０分）し、さらにフッ素樹脂ＹとしてのＰＶＤＦ１（クレハ(株)製 Ｌ＃１１２０ １２％ＮＭＰ溶液の粘度：５５０ｍＰａ・ｓ）２０部を添加し、ディスパーで撹拌することにより、導電材分散液を製造した。調製直後の導電材分散液の粘度を測定し、またこの導電材分散液の保存安定性を評価した。結果を表１に示す。
<Manufacture of conductive material dispersion>
100 parts of carbon black α (manufactured by Denki Kagaku Kogyo Co., Ltd., HS-100, acetylene black, average particle size: 48 nm, specific surface area: 39 m 2 / g, density: 0.15 g / cm 3 ) as a conductive material, The NMP solution of polymer X obtained as described above was stirred with a disper (2000 rpm, 60 minutes) with 10 parts of solid content equivalent amount and NMP. Thereafter, an appropriate amount of NMP is added so that the solid content concentration becomes 10% by mass, stirred with a disper (2000 rpm, 10 minutes), and further PVDF1 as a fluororesin Y (Kureha Co., Ltd. L # 1120 12% NMP solution) Viscosity: 550 mPa · s) 20 parts was added and stirred with a disper to produce a conductive material dispersion. The viscosity of the conductive material dispersion immediately after preparation was measured, and the storage stability of this conductive material dispersion was evaluated. The results are shown in Table 1.
＜正極用スラリーおよび正極の製造＞
得られた導電材分散液に正極活物質としてのＬｉＣｏＯ２２０００部を添加し、ディスパーを用いて２５００ｒｐｍで３０分間攪拌撹拌することで正極用スラリーを得た。この正極用スラリーの粘度は１５００ｍＰａ・sであった。
この正極用スラリーを、コンマコーターで、集電体である厚さ１８μｍのアルミニウム箔の上に塗布量が２０ｍｇ／ｃｍ２となるように塗布した。その後、正極用スラリーが塗布されたアルミ箔を、雰囲気温度１２０℃で３０分乾燥して、正極原反を得た。得られた正極原反をロールプレス機にて密度が３．８ｇ／ｃｍ３となるようにプレスし、正極（正極合材層の厚みが５３μｍ）を得た。この正極を用いて、正極用スラリーの塗工性を評価した。結果を表１に示す。
<Production of slurry for positive electrode and positive electrode>
To the obtained conductive material dispersion, 2000 parts of LiCoO 2 as a positive electrode active material was added, and a slurry for positive electrode was obtained by stirring and stirring at 2500 rpm for 30 minutes using a disper. The viscosity of this positive electrode slurry was 1500 mPa · s.
This positive electrode slurry was applied with a comma coater onto an aluminum foil having a thickness of 18 μm, which was a current collector, so that the amount applied was 20 mg / cm 2 . Thereafter, the aluminum foil coated with the positive electrode slurry was dried at an ambient temperature of 120 ° C. for 30 minutes to obtain a positive electrode original fabric. The obtained positive electrode original fabric was pressed with a roll press machine so that the density was 3.8 g / cm 3, and a positive electrode (the thickness of the positive electrode mixture layer was 53 μm) was obtained. Using this positive electrode, the coatability of the positive electrode slurry was evaluated. The results are shown in Table 1.
＜負極用スラリーおよび負極の製造＞
負極活物質として人造黒鉛（平均粒子径：２４．５μｍ、黒鉛層間距離（Ｘ線回折法による（００２）面の面間隔（ｄ値）：０．３５４ｎｍ）９６部と、粘度調整剤としてのカルボキシメチルセルロースの１．５％水溶液（日本製紙社製、「ＭＡＣ３５０」）を固形分相で１．０部とをディスパーで混合し、さらにイオン交換水を固形分濃度が４５％となるように加え、混合分散した。次に結着材としてのスチレン−ブタジエン共重合体（日本ゼオン（株）製、ＢＭ−４００Ｂ）をさらに固形分相当で３．０部混合して最終固形分濃度が４０％の負極用スラリーを得た。
この負極用スラリーを、コンマコーターで、集電体である厚さ１８μｍの銅箔の上に塗布量が９ｍｇ／ｃｍ２となるように塗布した。その後、負極用スラリーが塗布された銅箔を、雰囲気温１２０℃で３０分間乾燥して、負極原反を得た。得られた負極原反をロールプレス機にて密度が１．６ｇ／ｃｍ３となるようにプレスし、負極（負極合材層の厚みが５６μｍ）を得た。
<Manufacture of slurry for negative electrode and negative electrode>
Artificial graphite as the negative electrode active material (average particle size: 24.5 μm, graphite interlayer distance (space (d) value of (002) plane by X-ray diffraction method (d value): 9654 nm)) 96 parts, and carboxy as a viscosity modifier A 1.5% aqueous solution of methylcellulose (manufactured by Nippon Paper Industries Co., Ltd., “MAC350”) was mixed with 1.0 part of a solid phase with a disper, and ion-exchanged water was added so that the solid content concentration was 45%. Next, a styrene-butadiene copolymer (manufactured by Zeon Corporation, BM-400B) as a binder was further mixed in an amount of 3.0 parts corresponding to the solid content, so that the final solid content concentration was 40%. A slurry for negative electrode was obtained.
This negative electrode slurry was applied with a comma coater on a 18 μm-thick copper foil as a current collector so that the amount applied was 9 mg / cm 2 . Thereafter, the copper foil coated with the negative electrode slurry was dried at an ambient temperature of 120 ° C. for 30 minutes to obtain a negative electrode raw material. The obtained negative electrode original fabric was pressed with a roll press so that the density was 1.6 g / cm 3 to obtain a negative electrode (the thickness of the negative electrode mixture layer was 56 μm).
＜セパレーターの用意＞
単層のポリプロピレン製セパレーター（幅６５ｍｍ、長さ５００ｍｍ、厚さ２５μｍ、乾式法により製造、気孔率５５％）を、５ｃｍ×５ｃｍの正方形に切り抜いた。
<Preparation of separator>
A single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 μm, produced by a dry method, porosity 55%) was cut into a 5 cm × 5 cm square.
＜リチウムイオン二次電池の製造＞
電池の外装として、アルミ包材外装を用意した。上記で得られた正極を、４ｃｍ×４ｃｍの正方形に切り出し、集電体側の表面がアルミ包材外装に接するように配置した。正極の正極合材層の面上に、上記で得られた正方形のセパレーターを配置した。さらに、上記で得られた負極を、４．２ｃｍ×４．２ｃｍの正方形に切り出し、これをセパレーター上に、負極合材層側の表面がセパレーターに向かい合うように配置した。更に、ビニレンカーボネートを２．０％含有する、濃度１．０ＭのＬｉＰＦ６溶液を充填した。このＬｉＰＦ６溶液の溶媒はエチレンカーボネート（ＥＣ）とエチルメチルカーボネート（ＥＭＣ）との混合溶媒（ＥＣ／ＥＭＣ＝３／７（体積比））である。さらに、アルミニウム包材の開口を密封するために、１５０℃でヒートシールをしてアルミニウム外装を閉口し、ラミネート型のリチウムイオン二次電池を製造した。得られたリチウムイオン二次電池について出力特性を評価した。結果を表１に示す。
<Manufacture of lithium ion secondary batteries>
An aluminum packaging exterior was prepared as the battery exterior. The positive electrode obtained above was cut into a 4 cm × 4 cm square and arranged so that the current collector-side surface was in contact with the aluminum packaging exterior. The square separator obtained above was disposed on the surface of the positive electrode mixture layer of the positive electrode. Furthermore, the negative electrode obtained above was cut into a square of 4.2 cm × 4.2 cm, and this was placed on the separator so that the surface on the negative electrode mixture layer side faces the separator. Further, a LiPF 6 solution having a concentration of 1.0 M and containing 2.0% of vinylene carbonate was charged. The solvent of this LiPF 6 solution is a mixed solvent (EC / EMC = 3/7 (volume ratio)) of ethylene carbonate (EC) and ethyl methyl carbonate (EMC). Furthermore, in order to seal the opening of the aluminum packaging material, heat sealing was performed at 150 ° C. to close the aluminum exterior, and a laminate type lithium ion secondary battery was manufactured. The output characteristics of the obtained lithium ion secondary battery were evaluated. The results are shown in Table 1.
（実施例２、３、１０）
重合体Ｘの製造時に、表１の単量体を表１の量で含む単量体組成物を使用し、ヨウ素価が実施例１と同様となるよう水素添加条件を適宜変更した以外は、実施例１と同様にして、導電材分散液、正極用スラリー、負極用スラリー、正極、負極およびリチウムイオン二次電池を製造した。そして、実施例１と同様にして各種評価を行った。結果を表１に示す。
(Examples 2, 3, and 10)
Except for using the monomer composition containing the monomers shown in Table 1 in the amounts shown in Table 1 during the production of the polymer X, and changing the hydrogenation conditions appropriately so that the iodine value is the same as in Example 1, In the same manner as in Example 1, a conductive material dispersion, a positive electrode slurry, a negative electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
（実施例４）
導電材分散液の製造時に、重合体Ｘの配合量を表１のように変更した以外は、実施例１と同様にして、導電材分散液、正極用スラリー、負極用スラリー、正極、負極およびリチウムイオン二次電池を製造した。そして、実施例１と同様にして各種評価を行った。結果を表１に示す。
Example 4
The conductive material dispersion, the positive electrode slurry, the negative electrode slurry, the positive electrode, the negative electrode, and the negative electrode slurry were changed in the same manner as in Example 1 except that the amount of the polymer X was changed as shown in Table 1 when the conductive material dispersion was produced. A lithium ion secondary battery was manufactured. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
（実施例５）
重合体Ｘの製造時に、表１の単量体を表１の量で含む単量体組成物を使用（（メタ）アクリル酸エステル単量体としてブチルアクリレート（ＢＡ）を使用）し、さらに、導電材分散液の製造時に重合体Ｘの配合量を表１のように変更した以外は、実施例１と同様にして、導電材分散液、正極用スラリー、負極用スラリー、正極、負極およびリチウムイオン二次電池を製造した。そして、実施例１と同様にして各種評価を行った。結果を表１に示す。
(Example 5)
At the time of production of the polymer X, a monomer composition containing the monomers shown in Table 1 in the amounts shown in Table 1 is used (using butyl acrylate (BA) as the (meth) acrylic acid ester monomer), Except having changed the compounding quantity of the polymer X at the time of manufacture of a electrically conductive material dispersion like Table 1, it is the same as that of Example 1, and electrically conductive material dispersion liquid, the slurry for positive electrodes, the slurry for negative electrodes, the positive electrode, the negative electrode, and lithium An ion secondary battery was manufactured. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
（実施例６〜８）
導電材分散液の製造時に、ＰＶＤＦ１（フッ素樹脂Ｙ）の配合量を表１のように変更した以外は、実施例１と同様にして、導電材分散液、正極用スラリー、負極用スラリー、正極、負極およびリチウムイオン二次電池を製造した。そして、実施例１と同様にして各種評価を行った。結果を表１に示す。
(Examples 6 to 8)
The conductive material dispersion, the positive electrode slurry, the negative electrode slurry, and the positive electrode were the same as in Example 1 except that the amount of PVDF1 (fluororesin Y) was changed as shown in Table 1 when the conductive material dispersion was produced. A negative electrode and a lithium ion secondary battery were manufactured. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
（実施例９）
導電材分散液の製造時に、ＰＶＤＦ１に替えてＰＶＤＦ２（クレハ(株)製 Ｌ＃１３２０ １２％ＮＭＰ溶液の粘度：１１５０ｍＰａ・ｓ）を使用した以外は、実施例１と同様にして、導電材分散液、正極用スラリー、負極用スラリー、正極、負極およびリチウムイオン二次電池を製造した。そして、実施例１と同様にして各種評価を行った。結果を表１に示す。
Example 9
Conductive material dispersion was performed in the same manner as in Example 1 except that PVDF2 (Viscosity of L # 1320 12% NMP solution: 1150 mPa · s manufactured by Kureha Co., Ltd.) was used instead of PVDF1 during the production of the conductive material dispersion. A liquid, a positive electrode slurry, a negative electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
（実施例１１）
ピロリドン系溶媒としてのＮＭＰに替えて、ＮＥＰを使用した以外は、実施例１と同様にして、導電材分散液、正極用スラリー、負極用スラリー、正極、負極およびリチウムイオン二次電池を製造した。そして、実施例１と同様にして各種評価を行った。結果を表１に示す。
(Example 11)
A conductive material dispersion, a positive electrode slurry, a negative electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 1 except that NEP was used instead of NMP as the pyrrolidone solvent. . Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
(実施例１２)
導電材分散液の製造時に、重合体Ｘの配合量およびフッ素樹脂Ｙの配合量を表１のように変更した以外は、実施例１と同様にして、導電材分散液、正極用スラリー、負極用スラリー、正極、負極およびリチウムイオン二次電池を製造した。そして、実施例１と同様にして各種評価を行った。結果を表１に示す。
(Example 12)
The conductive material dispersion, the positive electrode slurry, the negative electrode were prepared in the same manner as in Example 1 except that the blending amount of the polymer X and the blending amount of the fluororesin Y were changed as shown in Table 1 during the production of the conductive material dispersion. Slurry, positive electrode, negative electrode and lithium ion secondary battery were produced. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
（実施例１３）
導電材としてのカーボンブラックαに替えて、カーボンブラックβ（電気化学工業（株）製、デンカブラック、粉状品、平均粒子径：３５ｎｍ、比表面積：６８ｍ２／ｇ、密度０．０４ｇ／ｃｍ３）を使用した以外は、実施例１と同様にして、導電材分散液、正極用スラリー、負極用スラリー、正極、負極およびリチウムイオン二次電池を製造した。そして、実施例１と同様にして各種評価を行った。結果を表１に示す。
(Example 13)
Instead of carbon black α as a conductive material, carbon black β (manufactured by Denki Kagaku Kogyo Co., Ltd., Denka Black, powdered product, average particle size: 35 nm, specific surface area: 68 m 2 / g, density 0.04 g / cm 3 ) A conductive material dispersion, a positive electrode slurry, a negative electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 1 except that 3 ) was used. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
（比較例１）
重合体Ｘの製造時に、水素添加を行わずＮＭＰに溶媒置換し、共役ジエン単量体単位およびニトリル基含有単量体単位を含む重合体を重合体Ｘとして使用した以外は、実施例１と同様にして、導電材分散液、正極用スラリー、負極用スラリー、正極、負極およびリチウムイオン二次電池を製造した。そして、実施例１と同様にして各種評価を行った。結果を表１に示す。
(Comparative Example 1)
Example 1 except that during the production of the polymer X, the solvent was replaced with NMP without hydrogenation and a polymer containing a conjugated diene monomer unit and a nitrile group-containing monomer unit was used as the polymer X. Similarly, a conductive material dispersion, a positive electrode slurry, a negative electrode slurry, a positive electrode, a negative electrode, and a lithium ion secondary battery were produced. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
（比較例２）
導電材分散液の製造時に、重合体Ｘの配合量を表１のように変更した以外は、実施例１と同様にして、導電材分散液、正極用スラリー、負極用スラリー、正極、負極およびリチウムイオン二次電池を製造した。そして、実施例１と同様にして各種評価を行った。結果を表１に示す。
(Comparative Example 2)
The conductive material dispersion, the positive electrode slurry, the negative electrode slurry, the positive electrode, the negative electrode, and the negative electrode slurry were changed in the same manner as in Example 1 except that the amount of the polymer X was changed as shown in Table 1 when the conductive material dispersion was produced. A lithium ion secondary battery was manufactured. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
表１より、実施例１〜１３および比較例１、２より、実施例１〜１３では、保存安定性に優れた導電材分散液が得られ、正極用スラリーの塗工性も良好であり、そして、リチウムイオン二次電池に優れた出力特性を発揮させることができることがわかる。
また、表１の実施例１〜５、１０より、重合体Ｘの組成、配合量を変更することで、導電材分散液の保存安定性、正極用スラリーの塗工性およびリチウムイオン二次電池の出力特性をより向上させ得ることがわかる。
さらに、表１の実施例１、６〜９より、フッ素樹脂Ｙの配合量、１２質量％ＮＭＰ溶液の粘度を変更することで、正極用スラリーの塗工性およびリチウムイオン二次電池の出力特性をより向上させ得ることがわかる。
加えて、表１の実施例１、１１より、ピロリドン系溶媒としてＮＥＰを用いた場合でも、保存安定性に優れた導電材分散液が得られ、正極用スラリーの塗工性を良好とすることができ、そして、リチウムイオン二次電池に優れた出力特性を発揮させることができることがわかる。
そして、表１の実施例１、１２より、重合体Ｘの配合量およびフッ素樹脂Ｙの配合量を変更することで、正極用スラリーの塗工性およびリチウムイオン二次電池の出力特性をより向上させ得ることがわかる。
また、表１の実施例１、１３より、導電材の種類を変更することで、導電材分散液の保存安定性をより向上させ得ることがわかる。
From Table 1, from Examples 1 to 13 and Comparative Examples 1 and 2, in Examples 1 to 13, a conductive material dispersion excellent in storage stability was obtained, and the coatability of the positive electrode slurry was also good. And it turns out that the output characteristic excellent in the lithium ion secondary battery can be exhibited.
Further, from Examples 1 to 5 and 10 in Table 1, by changing the composition and blending amount of the polymer X, the storage stability of the conductive material dispersion, the coating property of the positive electrode slurry, and the lithium ion secondary battery It can be seen that the output characteristics can be further improved.
Furthermore, from Examples 1 and 6 to 9 in Table 1, the coating amount of the positive electrode slurry and the output characteristics of the lithium ion secondary battery were changed by changing the blending amount of the fluororesin Y and the viscosity of the 12 mass% NMP solution. It can be seen that can be further improved.
In addition, from Examples 1 and 11 in Table 1, even when NEP is used as the pyrrolidone-based solvent, a conductive material dispersion excellent in storage stability is obtained, and the coating property of the positive electrode slurry is improved. It can be seen that the lithium ion secondary battery can exhibit excellent output characteristics.
Then, from Examples 1 and 12 in Table 1, the coating amount of the positive electrode slurry and the output characteristics of the lithium ion secondary battery are further improved by changing the blending amount of the polymer X and the blending amount of the fluororesin Y. You can see that
Moreover, from Examples 1 and 13 in Table 1, it can be seen that the storage stability of the conductive material dispersion can be further improved by changing the type of the conductive material.
本発明によれば、保存安定性に優れ、電気化学素子電極用スラリーに良好な塗工性を付与しつつ、電気化学素子に優れた出力特性を発揮させることが可能な電気化学素子用導電材分散液を提供することができる。
本発明によれば、保存安定性および塗工性に優れ、電気化学素子に優れた出力特性を発揮させることが可能な電気化学素子正極用スラリーを提供することができる。
更に、本発明によれば、電気化学素子に優れた出力特性を発揮させることが可能な電気化学素子用正極、および出力特性に優れる電気化学素子を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, it is excellent in storage stability, and the electroconductive element for electrochemical elements which can make the electrochemical element exhibit the outstanding output characteristic, providing the favorable coating property to the slurry for electrochemical element electrodes A dispersion can be provided.
ADVANTAGE OF THE INVENTION According to this invention, the slurry for electrochemical element positive electrodes which is excellent in storage stability and coating property, and can exhibit the output characteristic excellent in the electrochemical element can be provided.
Furthermore, according to the present invention, it is possible to provide a positive electrode for an electrochemical element capable of exhibiting excellent output characteristics of the electrochemical element, and an electrochemical element excellent in output characteristic.
Claims (6)
前記重合体Ｘは、ニトリル基含有単量体単位およびアルキレン構造単位を含み、ヨウ素価が２０ｍｇ/１００ｍｇ以下であり、
前記導電材１００質量部当たり、前記重合体Ｘを２質量部以上３０質量部以下含み、
そして、粘度が８００ｍＰａ・ｓ以下である、電気化学素子用導電材分散液。 A conductive material dispersion for an electrochemical device comprising a conductive material, a polymer X, and a pyrrolidone-based solvent,
The polymer X includes a nitrile group-containing monomer unit and an alkylene structural unit, and has an iodine value of 20 mg / 100 mg or less,
2 parts by mass or more and 30 parts by mass or less of the polymer X per 100 parts by mass of the conductive material,
And the electrically conductive material dispersion liquid for electrochemical elements whose viscosity is 800 mPa * s or less.
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