JP2000348537A - Conductive paste, manufacture thereof, and conductive auxiliary agent for secondary battery - Google Patents
Conductive paste, manufacture thereof, and conductive auxiliary agent for secondary batteryInfo
- Publication number
- JP2000348537A JP2000348537A JP11244229A JP24422999A JP2000348537A JP 2000348537 A JP2000348537 A JP 2000348537A JP 11244229 A JP11244229 A JP 11244229A JP 24422999 A JP24422999 A JP 24422999A JP 2000348537 A JP2000348537 A JP 2000348537A
- Authority
- JP
- Japan
- Prior art keywords
- carbon black
- paste
- conductive paste
- conductive
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、導電性粉末として
カーボンブラックを含有する優れた保存安定性を有する
導電性ペースト及び該ペーストを効率良く製造する方法
並びに二次電池用導電助剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive paste containing carbon black as a conductive powder and having excellent storage stability, a method for efficiently producing the paste, and a conductive auxiliary for a secondary battery.
【０００２】[0002]
【従来技術及び発明が解決しようとする課題】従来か
ら、導電性ペースト組成物は、例えばプリント配線など
電気回路の形成、又は電気的な接続部の構成材料として
使用されている。また、近年の電子産業技術の発展に伴
って各種二次電池の正極、負極の導電助剤、導電塗料な
どの用途にも広がりつつある。2. Description of the Related Art Conventionally, a conductive paste composition has been used as a material for forming an electric circuit such as a printed wiring or as a constituent material of an electric connection portion. In addition, with the recent development of electronics industry technology, it has been spreading to applications such as a conductive auxiliary for a positive electrode and a negative electrode of various secondary batteries, and a conductive paint.
【０００３】上記導電性ペースト組成物には、導電性を
付与するため、カーボンブラック、グラファイト等の炭
素材料、Ａｇ、Ｎｉ等の金属材料などの導電粉末が添加
されており、これらの中でも、カーボンブラックは一般
に数十ｎｍの一次粒子が集まったストラクチャーと呼ば
れる鎖状の二次粒子構造を形成することにより、優れた
導電性を有し、好適なものである。[0003] The conductive paste composition contains a conductive powder such as a carbon material such as carbon black and graphite, and a metal material such as Ag and Ni in order to impart conductivity. Black is preferable because it has excellent conductivity by forming a chain-like secondary particle structure called a structure in which primary particles of several tens of nm are gathered.
【０００４】上記カーボンブラック含有ペーストの導電
性は、カーボンブラックの添加量、粒子径、比表面積、
及びＤＢＰ吸油量などにより、大きく左右すると共に、
カーボンブラックのペースト中での分散状態によって、
かなり変化することが知られている。The conductivity of the carbon black-containing paste is determined by the amount of carbon black added, the particle size, the specific surface area,
And DBP oil absorption, etc.
Depending on the dispersion state of the carbon black in the paste,
It is known to vary considerably.
【０００５】このため、カーボンブラック含有ペースト
には、優れた導電性能を発揮する上において、カーボン
ブラックの添加量、粒子径、比表面積、及びＤＢＰ吸油
量などの要素以外にも、ペースト中でカーボンブラック
が最適な分散状態を維持しつつ、経時により沈降しない
こと（沈降安定性）、凝集しないこと（凝集安定性）と
いう良好な保存安定性を有することが望まれている。[0005] Therefore, in order to exhibit excellent conductivity, carbon black-containing paste contains carbon black in the paste in addition to factors such as the amount of added carbon black, particle size, specific surface area, and DBP oil absorption. It is desired that black has good storage stability such that it does not settle with time (sedimentation stability) and does not aggregate (aggregation stability) while maintaining an optimal dispersion state.
【０００６】しかしながら、カーボンブラックは元来比
表面積が大きく、細孔容積が大きいという特徴を有する
ため、通常の攪拌分散方法を行った場合には時間かかる
上に、均一に分散させることが困難であり、経時により
ペースト中に凝集物が生じ、この凝集物の存在により、
導電性能が低下したり、保存安定性が損われてしまうと
いう問題があった。However, since carbon black is originally characterized by a large specific surface area and a large pore volume, it takes time and is difficult to uniformly disperse it when a normal stirring and dispersion method is performed. Yes, aggregates are generated in the paste over time, and due to the presence of the aggregates,
There have been problems that the conductive performance is reduced and the storage stability is impaired.
【０００７】かかる問題点を解決すべく、サンドミール
やボールミルなどを用いて強い機械力を与えることによ
り攪拌分散する方法も検討されているが、これらの方法
では、カーボンブラックの優れた導電性をもたらすスト
ラクチャー構造を破壊してしまい、導電性能が低下する
上に、ペーストが沈降し易くなってしまうという問題が
ある。[0007] In order to solve such problems, methods of stirring and dispersing by applying a strong mechanical force using a sand meal, a ball mill or the like have been studied. However, in these methods, the excellent conductivity of carbon black is considered. There is a problem that the resulting structure structure is destroyed, the conductive performance is reduced, and the paste is liable to settle.
【０００８】本発明は、上記問題点を解決するためにな
されたもので、保存安定性（凝集安定性、沈降安定性）
の改良された高い導電性を有するカーボンブラック含有
導電性ペースト及び該ペーストを効率良く製造する方法
並びに二次電池用導電助剤を提供することを目的とす
る。The present invention has been made to solve the above problems, and has storage stability (aggregation stability, sedimentation stability).
It is an object of the present invention to provide an improved carbon black-containing conductive paste having high conductivity, a method for efficiently producing the paste, and a conductive auxiliary for a secondary battery.
【０００９】[0009]
【課題を解決するための手段及び発明の実施の形態】本
発明者は、上記目的を達成するため鋭意検討を重ねた結
果、カーボンブラックと、分散媒とを含む導電性ペース
トにおいて、上記カーボンブラックの比表面積が７００
〜１５００ｍ2／ｇ、一次粒子径が１０〜４０ｎｍ、Ｄ
ＢＰ吸油量が３００〜６００ｍＬ／１００ｇであると共
に、上記ペーストの粘度が１０００〜１０００００ｍＰ
ａ・ｓであるカーボンブラック含有導電性ペーストが、
ペースト中に均一に分散したカーボンブラックの経時に
よる粒径の変化が極めて少なく、また経時でのカーボン
ブラックの沈降が少ないという優れた凝集安定性、沈降
安定性と高い導電性とを併せ持つことを知見した。Means for Solving the Problems and Embodiments of the Invention As a result of extensive studies to achieve the above object, the present inventor has found that the conductive paste containing carbon black and a dispersion medium contains the carbon black. Has a specific surface area of 700
１1500 m 2 / g, primary particle diameter 10-40 nm, D
The BP oil absorption is 300 to 600 mL / 100 g, and the viscosity of the paste is 1,000 to 100,000 mP.
a · s carbon black-containing conductive paste,
It has been found that carbon black uniformly dispersed in the paste has very little change in particle size over time, and also has excellent aggregation stability, sedimentation stability and high conductivity, with little sedimentation of carbon black over time. did.
【００１０】また、本発明の導電性ペーストの製造方法
によれば、円板の外周縁から中心に向かう切り込みを所
定間隔で偶数本形成することによって得られた偶数個の
切片の基端部を交互に上下方向に向けて折り曲げてなる
攪拌羽根を具備した攪拌翼を有する攪拌機を用いること
により、この攪拌翼全体の高い攪拌力と、全体混合と局
所剪断との両機能が効果的に作用して、従来は極めて困
難であったカーボンブラックのペースト中への添加、均
一分散を短時間に効率良く行うことができ、高い導電性
と保存安定性が飛躍的に向上し、二次電池用導電助剤と
して好適なカーボンブラック含有導電性ペーストが得ら
れることを見出し、本発明をなすに至った。Further, according to the method for producing a conductive paste of the present invention, the base end portion of an even number of cuts obtained by forming an even number of cuts from the outer peripheral edge of the disk toward the center at predetermined intervals is formed. By using a stirrer having stirring blades provided with stirring blades alternately bent in the vertical direction, the high stirring force of the entire stirring blade, and both functions of overall mixing and local shearing effectively act. Therefore, carbon black can be efficiently added and uniformly dispersed in a paste in a short time, which has been extremely difficult in the past, and high conductivity and storage stability have been dramatically improved. The present inventors have found that a carbon black-containing conductive paste suitable as an auxiliary agent can be obtained, and have accomplished the present invention.
【００１１】従って、本発明は、（１）カーボンブラッ
クと、分散媒とを含む導電性ペーストにおいて、上記カ
ーボンブラックが比表面積７００〜１５００ｍ2／ｇ、
一次粒子径１０〜４０ｎｍ、ＤＢＰ吸油量３００〜６０
０ｍＬ／１００ｇであると共に、上記ペーストの粘度が
１０００〜１０００００ｍＰａ・ｓであることを特徴と
する導電性ペースト、（２）上記導電性ペーストからな
る二次電池用導電助剤、（３）上記導電性ペーストを製
造する方法であって、円板の外周縁から中心に向かう切
り込みを所定間隔で偶数本形成することによって得られ
た偶数個の切片の基端部を交互に上下方向に向けて折り
曲げてなる攪拌羽根を具備した攪拌翼を有する攪拌機を
用いて、上記カーボンブラック、分散媒等の導電性ペー
スト材料を攪拌混合することを特徴とする導電性ペース
トの製造方法、及び（４）上記（３）方法により得られ
た導電性ペーストからなる二次電池用導電助剤を提供す
る。Therefore, the present invention provides (1) a conductive paste containing carbon black and a dispersion medium, wherein the carbon black has a specific surface area of 700 to 1500 m 2 / g;
Primary particle diameter 10 to 40 nm, DBP oil absorption 300 to 60
0 mL / 100 g, and the paste has a viscosity of 1,000 to 100,000 mPa · s; (2) a conductive auxiliary for the secondary battery comprising the conductive paste; A method for producing a conductive paste, wherein the base ends of an even number of pieces obtained by forming an even number of cuts from the outer peripheral edge of the disk toward the center at predetermined intervals are alternately bent in the vertical direction. And (4) a method for producing a conductive paste, wherein the conductive paste material such as the carbon black and the dispersion medium is stirred and mixed using a stirrer having stirring blades provided with stirring blades. 3) A conductive assistant for a secondary battery comprising a conductive paste obtained by the method is provided.
【００１２】以下、本発明につき更に詳しく説明する。
本発明の導電性ペーストは、カーボンブラックと、分散
媒と、必要に応じて分散剤とを含むものである。Hereinafter, the present invention will be described in more detail.
The conductive paste of the present invention contains carbon black, a dispersion medium, and, if necessary, a dispersant.
【００１３】ここで、上記カーボンブラックは、例えば
ファーネスブラックのように平均一次粒子径が約１０〜
４０ｎｍ、好ましくは２０〜３５ｎｍの炭素原子が鎖状
に二次凝集した構造を有し、かつ比表面積が７００〜１
５００ｍ2／ｇ、好ましくは８００〜１３００ｍ2／ｇで
あり、ＤＢＰ吸油量が３００〜６００ｍＬ／１００ｇ、
好ましくは３５０〜５００ｍＬ／１００ｇである。この
ような二次粒子構造を持つカーボンブラックは、導電剤
として導電性に優れるものである。このカーボンブラッ
クの製造方法は、特に制限されないが、例えば石油など
の炭化水素を燃焼させることにより得ることができる。Here, the carbon black has an average primary particle diameter of about 10 to 10 like, for example, furnace black.
It has a structure in which carbon atoms of 40 nm, preferably 20 to 35 nm are secondarily aggregated in a chain, and has a specific surface area of 700 to 1
500m 2 / g, preferably 800~1300m 2 / g, DBP oil absorption amount 300~600mL / 100g,
Preferably it is 350-500 mL / 100 g. Carbon black having such a secondary particle structure has excellent conductivity as a conductive agent. The method for producing the carbon black is not particularly limited, but can be obtained by burning a hydrocarbon such as petroleum.
【００１４】このカーボンブラックの添加量はペースト
１００重量部に対して０．５〜２５重量部、より好まし
くは２〜１０重量部である。カーボンブラックの添加量
が少なすぎると導電性能が発現し得なくなる場合があ
る。一方、多すぎると分散媒の大部分がカーボンブラッ
クに吸収されてしまい、流動性がなくなり、ハンドリン
グ性が著しく困難になる場合がある。The amount of carbon black added is 0.5 to 25 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the paste. If the added amount of carbon black is too small, the conductive performance may not be able to be exhibited. On the other hand, if the content is too large, most of the dispersion medium is absorbed by the carbon black, the fluidity is lost, and the handling property may be extremely difficult.
【００１５】上記分散媒は、主に導電性ペーストの用途
によって決定される。例えば、ニッケル水素二次電池に
代表される金属酸化物−水素二次電池用途では電解質が
ＫＯＨのような水溶液であるため、主として水が用いら
れる。また、リチウムイオン二次電池のように非水系電
解質を用いる二次電池ではＮ−メチル−２−ピロリドン
（ＮＭＰ）、ジメチルホルムアミド、ジメチルアセトア
ミド、ジメチルスルホアミド等の極性溶媒のように、フ
ッ素系のバインダーを溶解し得る分散媒が用いられ、特
にＮＭＰが好ましい。また、ポリフッ化ビニリデン（Ｐ
ＶＤＦ）等を５〜２０重量％、好ましくは１０〜１５重
量％溶解したＮＭＰを用いることもできる。更に、一般
の導電塗料として用いる場合には分散媒としては水の他
に、メタノール、エタノール、イソプロピルアルコール
（ＩＰＡ）等のアルコール系溶媒、エチレングリコー
ル、ジエチレングリコール、ブチルセロソルブ、ブチル
カルビトール、グリセリンなどが好適である。[0015] The dispersion medium is mainly determined by the use of the conductive paste. For example, in a metal oxide-hydrogen secondary battery application represented by a nickel hydride secondary battery, water is mainly used because the electrolyte is an aqueous solution such as KOH. In a secondary battery using a non-aqueous electrolyte such as a lithium ion secondary battery, a fluorine-based solvent such as a polar solvent such as N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, and dimethylsulfamide is used. A dispersion medium that can dissolve the binder is used, and NMP is particularly preferable. In addition, polyvinylidene fluoride (P
VMP) or the like may be used in an amount of 5 to 20% by weight, preferably 10 to 15% by weight. Further, when used as a general conductive paint, as a dispersion medium, in addition to water, alcoholic solvents such as methanol, ethanol, isopropyl alcohol (IPA), ethylene glycol, diethylene glycol, butyl cellosolve, butyl carbitol, and glycerin are preferable. It is.
【００１６】分散媒として水を用いた場合（カーボンブ
ラック含有導電性水ペースト）は、分散剤を用いること
が好ましい。この分散剤はカーボンブラックと水とのぬ
れ性を向上させ、分散を容易にする機能と、系の粘度を
増大させ、カーボンブラック含有導電性ペーストの保存
安定性を良好に保つ機能を有するものである。When water is used as the dispersion medium (conductive water paste containing carbon black), it is preferable to use a dispersant. This dispersant has the function of improving the wettability of carbon black and water, facilitating dispersion, and the function of increasing the viscosity of the system and keeping the storage stability of the carbon black-containing conductive paste in good condition. is there.
【００１７】上記分散剤としては、例えばカルボキシメ
チルセルロース（ＣＭＣ）、ヒドロキシエチルセルロー
ス等のセルロース系高分子、ポリアクリル酸ナトリウム
等のアクリル酸系高分子、キサンタンガム、グアガム等
のガム系高分子などが用いられ、これらの１種を単独で
又は２種以上を組み合わせて使用することができる。中
でもセルロース系高分子が好ましい。Examples of the dispersant include cellulosic polymers such as carboxymethyl cellulose (CMC) and hydroxyethyl cellulose, acrylic polymers such as sodium polyacrylate, and gum polymers such as xanthan gum and guar gum. These may be used alone or in combination of two or more. Among them, cellulosic polymers are preferred.
【００１８】上記分散剤の添加量はペースト１００重量
部に対して０．０１〜１５重量部、好ましくは０．０２
〜１２重量部である。分散剤の添加量が少なすぎると分
散剤の性能が不十分となる場合がある。一方、多すぎる
とカーボンブラックに対する分散剤の比率が高くなりす
ぎてカーボンブラックの性能を十分に引き出せない場合
がある。The dispersant is added in an amount of 0.01 to 15 parts by weight, preferably 0.02 parts by weight, per 100 parts by weight of the paste.
１２12 parts by weight. If the amount of the dispersant is too small, the performance of the dispersant may be insufficient. On the other hand, if the amount is too large, the ratio of the dispersant to the carbon black may be too high, and the performance of the carbon black may not be sufficiently obtained.
【００１９】一方、分散媒として非水溶媒を用いた場合
（カーボンブラック含有導電性非水ペースト）、ペース
ト１００重量部に対してカーボンブラック０．５〜２５
重量部、より好ましくは２〜１０重量部と、非水溶媒７
５〜９９．５重量部、より好ましくは９０〜９８重量部
とを含有することが好ましい。On the other hand, when a non-aqueous solvent is used as a dispersion medium (a conductive non-aqueous paste containing carbon black), 0.5 to 25 parts of carbon black is added to 100 parts by weight of the paste.
Parts by weight, more preferably 2 to 10 parts by weight,
It is preferable to contain 5 to 99.5 parts by weight, more preferably 90 to 98 parts by weight.
【００２０】本発明のカーボンブラック含有導電性ペー
ストの粘度は、２５℃において１０００〜１０００００
ｍＰａ・ｓ、好ましくは２０００〜８００００ｍＰａ・
ｓである。粘度が小さすぎると保存安定性が低下し、一
方、大きすぎるとペースト中にカーボンブラックの凝集
物が生じ、凝集安定性が低下する上に、ペースト製造及
びハンドリング性が著しく困難となる。The carbon black-containing conductive paste of the present invention has a viscosity of 1,000 to 100,000 at 25 ° C.
mPa · s, preferably 2000 to 80000 mPa · s
s. If the viscosity is too low, the storage stability decreases, while if it is too high, aggregates of carbon black are formed in the paste, and the aggregation stability decreases, and the paste production and handling properties become extremely difficult.
【００２１】次に、本発明のカーボンブラック含有導電
性ペーストは、通常の攪拌翼（例えばアンカー型、ディ
スクタービン型）を有する攪拌機では製造するのに長時
間を要する上に、均一に攪拌混合することが困難である
ため、高い攪拌力と、全体混合と局所剪断との両機能を
併せ持つ攪拌翼を有する攪拌機を用いて製造することが
好ましい。Next, the carbon black-containing conductive paste of the present invention requires a long time to be manufactured by a stirrer having ordinary stirring blades (eg, anchor type, disk turbine type), and is uniformly stirred and mixed. Therefore, it is preferable to use a stirrer having a stirring blade having both high stirring power and both functions of total mixing and local shearing.
【００２２】このような攪拌翼の一例として図１に示し
たように、円板の外周縁から中心に向かう切り込みを所
定間隔で偶数本形成することによって得られた偶数個の
切片の基端部を交互に上下方向に向けて折り曲げてなる
攪拌羽根を備えた攪拌翼が用いられる。As an example of such a stirring blade, as shown in FIG. 1, a base end portion of an even number of slices obtained by forming an even number of cuts from the outer peripheral edge toward the center at predetermined intervals. Are provided with stirring blades which are alternately bent in the vertical direction.
【００２３】図１に示したように、この攪拌翼１は、円
板基体の周方向に沿って互いに等間隔離間した偶数箇所
の外周縁位置からそれぞれ中心部近傍に至る偶数個の切
り込みを径方向に形成することにより、略扇形状の偶数
個の切片を形成すると共に、これら切片の基端部を交互
に上下方向に向けて折曲することにより、攪拌羽根３を
形成し、且つ上記円板基体の中心部に貫通孔（図示せ
ず）を穿設し、この貫通孔の周縁部に円筒状の攪拌軸取
り付け部２を突設してなるものである。As shown in FIG. 1, the stirring blade 1 has an even number of incisions extending from the outer peripheral edge positions at even locations which are equally spaced apart from each other along the circumferential direction of the disk base to the vicinity of the center. And forming the stirring blades 3 by bending the base ends of these sections alternately in the vertical direction, thereby forming the stirring blades 3. A through hole (not shown) is formed in the center of the plate base, and a cylindrical stirring shaft mounting portion 2 is protruded from the periphery of the through hole.
【００２４】ここで、攪拌羽根３の枚数は、偶数枚であ
れば、特に制限されるものではないが、６〜１６枚、特
に８〜１２枚であることが好ましい。枚数が少なすぎる
と本発明の効果が十分得られない場合があり、一方、多
すぎると攪拌羽根の製作加工が困難となる場合がある。The number of the stirring blades 3 is not particularly limited as long as it is an even number, but is preferably 6 to 16, especially 8 to 12. If the number is too small, the effect of the present invention may not be sufficiently obtained. On the other hand, if the number is too large, manufacturing and processing of the stirring blade may be difficult.
【００２５】そして、各攪拌羽根３の上方向、下方向へ
の折り曲げ角度θ（図２参照）としては、羽根面が水平
面Ａ（図２参照）、即ち攪拌軸５の軸方向に対し直交す
る面に対してそれぞれ上方向又は下方向に２０〜４５°
の角度を有するように上記切片の基端部を上方向又は下
方向に折り曲げることが好ましい。上記範囲以外では、
攪拌羽根の用をなさない場合がある。As the upward and downward bending angles θ (see FIG. 2) of each stirring blade 3, the blade surface is perpendicular to the horizontal plane A (see FIG. 2), that is, the axial direction of the stirring shaft 5. 20-45 ° upward or downward with respect to the plane
It is preferable to bend the base end of the section upward or downward so as to have an angle of? Outside the above range,
The use of stirring blades may not be used.
【００２６】ここで、本発明の攪拌翼１の場合、攪拌の
目的によっては、このようにして上記切片を交互に上下
方向に折り曲げた各攪拌羽根３の内の上側の攪拌羽根
３、下側の攪拌羽根３又は全ての攪拌羽根３を、それぞ
れ各羽根面の先端側をねじって、プロペラ羽根のように
羽根面を先端部から基端部にかけて水平面に対し斜め方
向に傾斜させることもできる。この場合、傾斜角度とし
ては、羽根面先端部における水平面に対する傾斜角度が
３０〜６０°となるように先端部をねじると好適であ
る。この角度が小さすぎると十分な流動が得られなくな
る場合があり、一方、大きすぎると下向きの流動が得ら
れなくなる場合がある。なお、高剪断を付与する攪拌を
目的とする場合には、下側の攪拌羽根３は傾斜させない
で、上側の攪拌羽根３のみを傾斜させることが好まし
い。下側の攪拌羽根３を傾斜させると流体が固体回転
（回転流れのみで軸方向の流動がない）を起こし、剪断
がかからない場合がある。Here, in the case of the stirring blade 1 of the present invention, depending on the purpose of stirring, the upper stirring blade 3 and the lower stirring blade 3 of the respective stirring blades 3 obtained by alternately bending the above-mentioned section in the vertical direction are used. The stirring blade 3 or all the stirring blades 3 may be twisted at the tip end side of each blade surface, and the blade surface may be inclined obliquely to the horizontal plane from the tip end to the base end like a propeller blade. In this case, it is preferable that the tip be twisted such that the tip of the blade face has an angle of 30 to 60 ° with respect to the horizontal plane at the tip of the blade surface. If the angle is too small, sufficient flow may not be obtained, while if it is too large, downward flow may not be obtained. In addition, when aiming the stirring which gives high shear, it is preferable not to incline the lower stirring blade 3 but to incline only the upper stirring blade 3. When the lower stirring blade 3 is tilted, the fluid may cause a solid rotation (only the rotational flow and no axial flow), so that the fluid may not be sheared.
【００２７】上記攪拌翼１は、図２に示すように、カー
ボンブラック、分散媒等のペースト用材料を仕込む攪拌
槽４内に垂下される攪拌軸５を上記攪拌軸取り付け部２
及び貫通孔に挿通した後、攪拌軸５の先端部で固定され
て攪拌機６を構成する。攪拌装置７は上記攪拌槽４と攪
拌機６とを具備し、攪拌機６は図示しないモータの作動
によって攪拌軸５を回転させ、これと一体に攪拌翼１を
回転させることによって攪拌槽４内に仕込まれたカーボ
ンブラック、分散媒等のペースト用材料を混合、分散さ
せて、導電性ペーストを製造するものである。As shown in FIG. 2, the stirring blade 1 is provided with a stirring shaft 5 suspended in a stirring tank 4 for charging a paste material such as carbon black and a dispersion medium.
After being inserted through the through-hole, it is fixed at the tip of the stirring shaft 5 to form the stirrer 6. The stirrer 7 is provided with the stirring tank 4 and the stirrer 6. The stirrer 6 rotates the stirring shaft 5 by the operation of a motor (not shown), and the stirring blade 1 is rotated integrally with the stirring shaft 5. The conductive paste is produced by mixing and dispersing paste materials such as carbon black and a dispersion medium.
【００２８】本発明の攪拌翼を備えた攪拌機を用いた導
電性ペーストの製造方法によれば、偶数枚の攪拌羽根の
各先端部が交互に上下になっているので、攪拌翼全体と
しての攪拌力が従来に比べて増大すると共に、全体混合
と局所剪断の両機能を併せ持つため、ペースト中にカー
ボンブラックが均一に分散した導電性ペーストを短時間
に効率よく製造することができるものである。According to the method of the present invention for producing a conductive paste using a stirrer provided with stirring blades, the tips of the even number of stirring blades are alternately turned up and down. Since the force is increased as compared with the related art, and both functions of total mixing and local shearing are provided, a conductive paste in which carbon black is uniformly dispersed in the paste can be efficiently produced in a short time.
【００２９】本発明のカーボンブラック含有導電性ペー
ストの製造方法は、分散媒中に分散剤が必要な場合は分
散剤を溶解後、所定量のカーボンブラックを添加して、
上記攪拌翼を有する攪拌機を用いて、回転数１００〜１
０００ｒｐｍ、通常３０分〜５時間混合、攪拌すること
により、粘度が１０００〜１０００００ｍＰａ・ｓであ
るカーボンブラック含有導電性ペーストを製造できるも
のである。In the method for producing a carbon black-containing conductive paste of the present invention, when a dispersant is required in a dispersion medium, the dispersant is dissolved, and a predetermined amount of carbon black is added.
Using a stirrer having the stirring blade, the number of rotations is 100 to 1
By mixing and stirring at 000 rpm, usually for 30 minutes to 5 hours, a carbon black-containing conductive paste having a viscosity of 1,000 to 100,000 mPa · s can be produced.
【００３０】本発明のカーボンブラック含有導電性ペー
ストは、高い導電性と優れた保存安定性（凝集安定性、
沈降安定性）を有しており、プリント配線など電気回路
の形成、又は電気的な接続部の構成材料、各種二次電池
の正極、負極の導電助剤としての用途、一般の導電塗料
などの用途に好適なものであり、特にニッケル水素二次
電池、リチウムイオン二次電池等の二次電池の正極、負
極の導電助剤として用いた場合、優れた電池特性を有す
る二次電池が得られるものである。The carbon black-containing conductive paste of the present invention has high conductivity and excellent storage stability (aggregation stability,
Sedimentation stability), forming electrical circuits such as printed wiring, or constituting materials for electrical connections, applications as conductive aids for the positive and negative electrodes of various secondary batteries, and general conductive paints. Suitable for use, especially when used as a conductive assistant for the positive electrode and negative electrode of secondary batteries such as nickel-metal hydride secondary batteries and lithium ion secondary batteries, a secondary battery having excellent battery characteristics is obtained. Things.
【００３１】[0031]
【実施例】以下、実施例と比較例とを示し、本発明を更
に具体的に説明するが、本発明は下記実施例に制限され
るものではない。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
【００３２】〔実施例１〕導電性カーボンブラックとし
てケッチェンブラックＥＣ（ケッチェンブラックインタ
ーナショナル株式会社製；以下ＥＣという）及びケッチ
ェンブラックＥＣ６００ＪＤ（ケッチェンブラックイン
ターナショナル株式会社製；以下６００ＪＤという）を
準備した。これらの代表的な性状を下記表１に示す。Example 1 Ketjen Black EC (Ketjen Black International, Inc .; hereinafter referred to as EC) and Ketjen Black EC600JD (Ketjen Black International, Ltd .; hereafter referred to as 600 JD) were prepared as conductive carbon blacks. did. The typical properties are shown in Table 1 below.
【００３３】[0033]
【表１】 ＊ＤＢＰ（ジブチルフタレート）給油量：ＡＳＴＭ Ｄ
−２４１４−７９に準拠し測定した。 ＊比表面積：ＢＥＴ法にて測定した。 ＊一次粒子径：ＴＥＭにより測定した。[Table 1] * DBP (dibutyl phthalate) lubrication amount: ASTM D
It measured based on -2144-79. * Specific surface area: measured by the BET method. * Primary particle diameter: Measured by TEM.
【００３４】次に、３Ｌのガラス製ビーカーに表２に示
した所定量の分散媒と必要に応じて分散剤を配合し、図
１に示した攪拌翼（以下、ディスプロ型という）を有す
る攪拌機を用いて混合溶解した。続いて、表２に示した
所定量のカーボンブラックを添加し、分散させることに
より組成１〜６のカーボンブラック含有ペーストを調製
した。Next, a predetermined amount of the dispersion medium shown in Table 2 and a dispersant as required are mixed in a 3 L glass beaker, and a stirrer having a stirring blade (hereinafter referred to as a dispro type) shown in FIG. Was used for mixing and dissolution. Subsequently, a predetermined amount of carbon black shown in Table 2 was added and dispersed to prepare carbon black-containing pastes having compositions 1 to 6.
【００３５】[0035]
【表２】 ＊ＮＭＰ：Ｎ−メチル−２−ピロリドン ＊ＩＰＡ：イソプロピルアルコール ＊ＣＭＣ：カルボキシメチルセルロース（日本製紙株式
会社製サンローズ） ＊ＨＥＣ：ヒドロキシエチルセルロース（ユニオンカー
バイド社製ＱＰシリーズ）[Table 2] * NMP: N-methyl-2-pyrrolidone * IPA: Isopropyl alcohol * CMC: Carboxymethyl cellulose (Sunrose manufactured by Nippon Paper Industries Co., Ltd.) * HEC: Hydroxyethyl cellulose (QP series manufactured by Union Carbide)
【００３６】得られた組成１〜６のカーボンブラック含
有ペーストの粘度及び保存安定性を下記方法により測定
した。結果を表３に示す。粘度 ＢＲＯＯＫＦＩＥＬＤ社製のＲＶＦ型粘度計を用いて、
２５℃でＮｏ．６ロータ又はＮｏ．７ロータのうち適当
なロータを使用して２０ｒｐｍで測定した。保存安定性 ２０℃で１週間静置保存後の凝集安定性及び沈降安定性
を下記方法により測定した。 ・凝集安定性は、経時での粒子径の変化から下記式によ
り算出した。なお、カーボンブラックペーストの粒子径
はヨシミツ精機製の粒ゲージＣ型を用いて測定した。 凝集安定性＝１週間後の粒子径（μｍ）÷調製直後の粒
子径（μｍ） 凝集安定性は１．０が経時による粒径の変化がなく、良
好な凝集安定性を有することを示し、１．０を超えるほ
ど経時により凝集物が生じ、凝集安定性が劣ることを示
す。 ・沈降安定性は、経時での沈降度合いで表され、プラス
チック製５００ｍＬの広口ボトルに４００ｇのカーボン
ブラックペーストを入れ、１週間後の上部と底部の固形
分濃度を測定し、下記式により沈降安定性を算出した。
なお、カーボンブラックペースト中の固形分濃度は乾燥
減量法で測定した。 沈降安定性（％）＝底部固形分濃度（％）−上部固形分
濃度（％） 沈降安定性の値が大きいほど、経時により沈降が生じて
いることを示し、０（ゼロ）は沈降が生じていないこと
を示す。The viscosity and storage stability of the obtained carbon black-containing pastes having compositions 1 to 6 were measured by the following methods. Table 3 shows the results. Using a viscosity BROOKFIELD Co., Ltd. of RVF-type viscometer,
No. at 25 ° C. No. 6 rotor or No. 6 The measurement was performed at 20 rpm using an appropriate rotor among the seven rotors. Storage stability Aggregation stability and sedimentation stability after storage for 1 week at 20 ° C. were measured by the following methods. -Aggregation stability was calculated from the change in particle diameter over time by the following equation. The particle size of the carbon black paste was measured using a particle gauge C type manufactured by Yoshimitsu Seiki. Aggregation stability = particle size (μm) after one week 粒子 particle size immediately after preparation (μm) Aggregation stability of 1.0 indicates that there is no change in particle size over time and that the composition has good aggregation stability. Aggregates are formed over time as the ratio exceeds 1.0, indicating that the aggregation stability is poor.・ The sedimentation stability is expressed by the degree of sedimentation over time. 400 g of carbon black paste is placed in a plastic 500 mL wide-mouth bottle, and the solid content concentration at the top and bottom after one week is measured. Sex was calculated.
In addition, the solid content concentration in the carbon black paste was measured by a drying loss method. Sedimentation stability (%) = bottom solids concentration (%)-top solids concentration (%) A larger value of sedimentation stability indicates that sedimentation occurs over time, and 0 (zero) indicates sedimentation Not indicate.
【００３７】[0037]
【表３】 [Table 3]
【００３８】[比較例１]表４に示した組成Ａ〜Ｄのカー
ボンブラック含有ペーストを実施例１と同様に調製し
た。得られたペーストの粘度、凝集安定性、及び沈降安
定性を実施例１と同様に測定した。結果を表５に示す。Comparative Example 1 Carbon black-containing pastes having compositions A to D shown in Table 4 were prepared in the same manner as in Example 1. The viscosity, aggregation stability, and sedimentation stability of the obtained paste were measured in the same manner as in Example 1. Table 5 shows the results.
【００３９】[0039]
【表４】 [Table 4]
【００４０】[0040]
【表５】 [Table 5]
【００４１】表３，５の結果から、ペースト粘度が本発
明の好適範囲を下回ると（組成Ｂ，Ｃ）凝集安定性は良
好であるが、沈降安定性が劣る。一方、好適範囲を上回
ると（組成Ａ，Ｄ）沈降安定性は良好であるが、凝集安
定性が劣り、いすれも経時の保存安定性（凝集安定性、
沈降安定性）が劣ることが認められた。これに対して、
本発明品（組成１〜６）はいずれも良好な経時の保存安
定性（凝集安定性、沈降安定性）を有することが確認で
きた。From the results in Tables 3 and 5, when the paste viscosity is lower than the preferred range of the present invention (compositions B and C), the aggregation stability is good, but the sedimentation stability is poor. On the other hand, if it exceeds the preferred range (compositions A and D), the sedimentation stability is good, but the cohesion stability is inferior, and the storage stability (coagulation stability,
(Sedimentation stability) was found to be inferior. On the contrary,
It was confirmed that all of the products of the present invention (compositions 1 to 6) had good storage stability over time (aggregation stability and sedimentation stability).
【００４２】[実施例２]上記実施例１の組成１のカーボ
ンブラック含有ペーストをディスプロ翼（図１）、アン
カー翼（図３）及びディスクタービン翼（図４）を有す
る攪拌装置を用いて、下記攪拌条件により製造した。攪拌条件 攪拌翼径ｄ：５０ｍｍ 攪拌槽の直径Ｄ：１５０ｍｍ 回転数：１０００ｒｐｍExample 2 The carbon black-containing paste of composition 1 of Example 1 was applied to a stirrer having a dispersing blade (FIG. 1), an anchor blade (FIG. 3) and a disk turbine blade (FIG. 4). It was manufactured under the following stirring conditions. Stirring conditions Stirring blade diameter d: 50 mm Stirring tank diameter D: 150 mm Number of rotations: 1000 rpm
【００４３】この際、ペーストの調製はＣＭＣ溶解工
程、カーボンブラック添加工程、カーボンブラック分散
工程に分けられ、各工程におけるペースト中に凝集物の
存在しなくなるまでの時間を下記方法により測定した。
結果を表６に示す。At this time, the preparation of the paste was divided into a CMC dissolving step, a carbon black adding step, and a carbon black dispersing step, and the time required until no aggregate was present in the paste in each step was measured by the following method.
Table 6 shows the results.
【００４４】なお、ＣＭＣ溶解工程とは、ＣＭＣ添加後
に目視判定でＣＭＣが溶解するまでの工程である。カー
ボンブラック添加工程とは、所定量のカーボンブラック
を添加後にビーカー上部の粉体が完全にペースト中に巻
き込まれるまでの工程である。カーボンブラック分散工
程とは、ペースト中に１ｍｍ以上の凝集物が存在しなく
なるまでの工程である。The CMC dissolving step is a step until the CMC is dissolved by visual judgment after the addition of the CMC. The carbon black adding step is a step after the addition of a predetermined amount of carbon black until the powder at the top of the beaker is completely caught in the paste. The carbon black dispersion step is a step until no aggregates of 1 mm or more are present in the paste.
【００４５】凝集物が存在しなくなるまでの時間の測定
方法 ペースト中の凝集物の測定は、１０ｃｍ×１０ｃｍのガ
ラス板２枚の間に各工程で得られたカーボンブラック含
有ペーストを０．５ｇ秤り取り、ガラス板に１０ｋｇの
荷重を６０秒間かけた。その後、１ｍｍ以上の凝集物の
個数を数えることにより行った。この操作を３回繰り返
し、３回とも凝集物の個数が０個になった時を終点と判
定し、それまでに要した時間で表した。 Measurement of time until no aggregate is present
Method For the measurement of aggregates in the paste, 0.5 g of the carbon black-containing paste obtained in each step was weighed between two glass plates of 10 cm × 10 cm, and a load of 10 kg was applied to the glass plate for 60 seconds. . Thereafter, the counting was performed by counting the number of aggregates of 1 mm or more. This operation was repeated three times, and the time when the number of aggregates became 0 was determined to be the end point in all three times, and was represented by the time required until then.
【００４６】[0046]
【表６】 [Table 6]
【００４７】表６の結果から、本発明の攪拌翼（ディス
プロ型）を用いた場合には、各工程の凝集物が存在しな
くなるまでの時間、特にカーボンブラック分散工程の所
要時間が従来の攪拌翼を用いた場合に比べて大幅に短縮
できることが確認できた。From the results shown in Table 6, when the stirring blade (displo type) of the present invention was used, the time required for eliminating the aggregates in each step, particularly the time required for the carbon black dispersing step, was the same as the conventional stirring method. It was confirmed that the time can be significantly reduced compared to the case using wings.
【００４８】〔実施例３、比較例２〕 Ｎｉ−水素蓄電
池（負極）への応用 まず、ＬｍＮｉ4.2Ｍｎ0.3Ａｌ0.3Ｃｏ0.2（Ｌｍはラン
タノイド希土類元素群から選ばれる一種以上の元素から
なる）を使用前にガス状水素の吸蔵放出を繰り返すこと
によって微粉化し、平均粒径２０μｍの水素吸蔵合金粉
末を用意した。この用意した水素吸蔵合金粉末１００重
量部に、ポリアクリル酸ナトリウムを０．５重量部、ポ
リテトラフルオロエチレンの水分散液（比重が１．５
で、固形分の割合が６０重量％のもの）を１重量部、水
を２５重量部添加し、更に、表２記載の組成１〜３（実
施例３）及び表４記載の組成Ａ，Ｂ（比較例２）のカー
ボンペーストを調製直後と調製後１週間経過したものを
それぞれ２５重量部添加し、一定の攪拌条件で混練して
合計１０種類のペーストを調製した。引き続いて、導電
性基板としてパンチドメタルを前記各ペーストが収容さ
れた塗布槽中に浸漬し、この塗布槽から垂直方向に引き
上げた後、スリットを通して余分なペーストを除去する
ことにより、パンチドメタル表面にペーストを塗布し、
これを８０℃で乾燥後、ローラプレスすることにより、
容量が２０００ｍＡｈの１０種類の負極を作成した。Example 3, Comparative Example 2 Ni-hydrogen storage
Application to a pond (negative electrode) First, LmNi 4.2 Mn 0.3 Al 0.3 Co 0.2 (Lm is composed of one or more elements selected from the group consisting of lanthanoid rare earth elements) is pulverized by repeated storage and release of gaseous hydrogen before use. A hydrogen storage alloy powder having an average particle diameter of 20 μm was prepared. To 100 parts by weight of the prepared hydrogen storage alloy powder, 0.5 part by weight of sodium polyacrylate and an aqueous dispersion of polytetrafluoroethylene (specific gravity: 1.5
1% by weight), 25 parts by weight of water, and compositions 1 to 3 (Example 3) shown in Table 2 and compositions A and B shown in Table 4. 25 parts by weight of each of the carbon pastes of (Comparative Example 2) immediately after preparation and one week after preparation were added, and kneaded under constant stirring conditions to prepare a total of 10 types of pastes. Subsequently, the punched metal as a conductive substrate was immersed in a coating tank containing each of the pastes described above, pulled up vertically from the coating tank, and removed through a slit to remove excess paste. Apply paste on the surface,
After drying this at 80 ° C., by roller pressing,
Ten types of negative electrodes having a capacity of 2000 mAh were prepared.
【００４９】また、水酸化ニッケル粉末９０重量部及び
酸化コバルト粉末１０重量部からなる混合粉体にカルボ
キシメチルセルロース３重量部、ポリテトラフルオロエ
チレン５重量部、純水４５重量部を添加して混練するこ
とにより、ペーストを調製した。このペーストを焼結繊
維基板内へ充填した後、更に、その両表面にペーストを
塗布し、乾燥後、ローラプレスによって圧延することに
より、容量が１２００ｍＡｈのペースト式ニッケル正極
を作成した。Also, 3 parts by weight of carboxymethyl cellulose, 5 parts by weight of polytetrafluoroethylene, and 45 parts by weight of pure water are added to a mixed powder composed of 90 parts by weight of nickel hydroxide powder and 10 parts by weight of cobalt oxide powder and kneaded. Thus, a paste was prepared. After filling this paste into the sintered fiber substrate, the paste was further applied to both surfaces thereof, dried, and then rolled by a roller press to prepare a paste-type nickel positive electrode having a capacity of 1200 mAh.
【００５０】次いで、作成した各負極と正極との間にポ
リアミド繊維製の不織布からなるセパレータを介して渦
巻状に電極群を作成した。これら電極群を圧力検出器を
付けたアクリル樹脂製容器のＡＡサイズの空間に挿入
し、この空間に８規定のＫＯＨ水溶液からなる電解液を
注入して封ロし、図５に示したような１０種類の試験セ
ルを組み立てた。具体的には、図５に示したように、各
試験セルは、アクリル樹脂製のケース本体８とキャップ
９とからなる電池ケースを備えており、ケース本体８の
中心部には、ＡＡサイズの電池の金属容器と同一の内径
及び高さを有する空間１０が形成されている。この空間
１０内部には、電極群１１が収納され、電解液が収容さ
れている。前記ケース本体８上には、キャップ９がゴム
シート１２及びＯリング１３を介してボルト１４及びナ
ット１５により気密に固定されている。なお、キャップ
９には、圧力検出器１６が取り付けられている。負極リ
ード１７は、一端が負極に取り付けられ、かつ他端がゴ
ムシート１２とＯリング１３との間を通して導出されて
いる。正極リード１８は、一端が正極に取り付けられ、
かつ他端がゴムシート１２とＯリング１３との間を通し
て導出されている。Next, an electrode group was spirally formed between each of the prepared negative and positive electrodes with a separator made of a nonwoven fabric made of polyamide fiber interposed therebetween. These electrode groups were inserted into an AA-size space of an acrylic resin container provided with a pressure detector, and an electrolytic solution consisting of an 8N aqueous KOH solution was injected into this space and sealed, as shown in FIG. Ten types of test cells were assembled. Specifically, as shown in FIG. 5, each test cell includes a battery case including a case body 8 made of acrylic resin and a cap 9, and the center of the case body 8 has an AA size. A space 10 having the same inner diameter and height as the metal container of the battery is formed. Inside the space 10, an electrode group 11 is accommodated, and an electrolytic solution is accommodated. A cap 9 is hermetically fixed on the case main body 8 by a bolt 14 and a nut 15 via a rubber sheet 12 and an O-ring 13. Note that a pressure detector 16 is attached to the cap 9. One end of the negative electrode lead 17 is attached to the negative electrode, and the other end is led out between the rubber sheet 12 and the O-ring 13. One end of the positive electrode lead 18 is attached to the positive electrode,
The other end is led out between the rubber sheet 12 and the O-ring 13.
【００５１】得られた実施例３の組成１〜３及び比較例
２の組成Ａ，Ｂのペーストを用いて作成した１０種類の
試験セルについて、１Ｃの電流で０．８Ｖまで放電する
充放電サイクル試験を行い、５０サイクル目の電池内圧
を測定した。結果を表７に示す。A charge / discharge cycle in which 10 types of test cells prepared using the pastes of the obtained compositions 1 to 3 of Example 3 and the compositions A and B of Comparative Example 2 were discharged at a current of 1 C to 0.8 V. The test was performed, and the internal pressure of the battery at the 50th cycle was measured. Table 7 shows the results.
【００５２】[0052]
【表７】 [Table 7]
【００５３】表７の結果から、実施例３の組成１〜３の
導電性ペーストを含む負極を備えた二次電池は、調製直
後、１週間経過後共に、過充電時の内圧が低いものであ
る。これは、導電性ペーストの経時安定性が良好である
ために、１週間経過後の導電性ペーストを用いても、負
極中にカーボンブラックが均一に分散されているためで
ある。このことから、カーボンブラックが負極の水素吸
蔵合金中に均一に分散することにより、水素吸蔵合金粉
末間の導通性が向上し、二次電池が過充電された際に、
正極から発生する酸素ガスと水素吸蔵合金粉末との反応
性が向上し、過充電時に電池内圧が上昇するのを抑制で
きることが確認できた。From the results in Table 7, it can be seen that the secondary battery provided with the negative electrode containing the conductive pastes of the compositions 1 to 3 of Example 3 had a low internal pressure at the time of overcharge immediately after preparation and one week later. is there. This is because carbon black is uniformly dispersed in the negative electrode even if the conductive paste after one week is used because the conductive paste has good stability over time. From this, by the carbon black is uniformly dispersed in the hydrogen storage alloy of the negative electrode, the conductivity between the hydrogen storage alloy powder is improved, when the secondary battery is overcharged,
It was confirmed that the reactivity between the oxygen gas generated from the positive electrode and the hydrogen-absorbing alloy powder was improved, and it was possible to suppress an increase in battery internal pressure during overcharge.
【００５４】これに対し、比較例２の組成Ａ，Ｂの導電
性ペーストは、調製直後のペーストを含む負極を備えた
二次電池の過充電時の内圧は低かったが、１週間経過後
のペーストを含む負極を備えた二次電池の過充電時の内
圧が高いものである。これは、導電性ペーストの凝集安
定性及び沈降安定性が不良であるために、それを用いて
調製した負極中にカーボンブラックが凝集しているか、
又は不足しているためである。On the other hand, in the conductive pastes of compositions A and B of Comparative Example 2, the internal pressure at the time of overcharging of the secondary battery provided with the negative electrode including the paste immediately after preparation was low, but after one week. The internal pressure at the time of overcharging of the secondary battery including the negative electrode including the paste is high. This is because the aggregation stability and sedimentation stability of the conductive paste are poor, so that carbon black is aggregated in the negative electrode prepared using it,
Or because of lack.
【００５５】〔実施例４、比較例３〕 Ｌｉイオン電池
（正極）への応用 正極活物質となるＬｉＣｏＯ2９１重量部に、ポリフッ
化ビニリデン（ＰＶＤＦ）を３重量部添加し、更に、表
２の組成４，５（実施例４）及び表４の組成Ｃ（比較例
３）のカーボンペーストを調製直後と調製後１週間経過
したものをそれぞれ１５０重量部添加し、一定の攪拌条
件で混練して合計６種類の正極合剤ペーストを調製し
た。Example 4, Comparative Example 3 Li-ion battery
Application to (Positive Electrode) To 91 parts by weight of LiCoO 2 serving as a positive electrode active material, 3 parts by weight of polyvinylidene fluoride (PVDF) was added. Further, the compositions 4 and 5 in Table 2 (Example 4) and the compositions in Table 4 were added. C (Comparative Example 3), 150 parts by weight of carbon paste immediately after preparation and one week after preparation, were added and kneaded under constant stirring conditions to prepare a total of six types of positive electrode mixture pastes.
【００５６】この正極合剤ペーストを、正極集電体とな
る厚さ２０μｍの帯状アルミニウム箔に塗布、乾燥させ
ることで正極合剤層を形成した。次いで、この正極合剤
層をローラプレス機により圧縮成型して帯状にし、更
に、円筒型のカッターを用いて切断加工することで、直
径１５．５ｍｍの円筒型正極を作成し、図６に示したよ
うな６種類の非水電解液二次電池を組み立てた。具体的
には、図６に示したように、作成した正極２１をカソー
ド缶２２に設置し、その上にセパレータ２３を載せて非
水電解液を注入した。次に、金属リチウム２０が圧着さ
れたアノードカップ１９を金属リチウム２０の露出する
側がセパレータ側となるようにセパレータ２３上に載置
し、アノードカップ１９とカソード缶２２とを絶縁封ロ
ガスケット２４を介してかしめることによって、直径２
０ｍｍ、高さ１．６ｍｍのコイン型非水電解液二次電池
を作成した。This positive electrode mixture paste was applied to a 20 μm-thick strip-shaped aluminum foil serving as a positive electrode current collector, and dried to form a positive electrode mixture layer. Next, the positive electrode mixture layer was compression-molded by a roller press into a belt shape, and further cut using a cylindrical cutter to form a cylindrical positive electrode having a diameter of 15.5 mm, as shown in FIG. Six types of such non-aqueous electrolyte secondary batteries were assembled. Specifically, as shown in FIG. 6, the prepared positive electrode 21 was placed in a cathode can 22, a separator 23 was placed thereon, and a non-aqueous electrolyte was injected. Next, the anode cup 19 to which the metallic lithium 20 has been pressed is placed on the separator 23 such that the exposed side of the metallic lithium 20 is on the separator side, and the anode cup 19 and the cathode can 22 are insulated and sealed with a gasket 24. By swaging through, the diameter 2
A coin-type non-aqueous electrolyte secondary battery having a thickness of 0 mm and a height of 1.6 mm was prepared.
【００５７】実施例４の組成４，５及び比較例３の組成
Ｃのペーストを用いて作成した６種類の非水電解液二次
電池について、正極の空孔率、直流抵抗を調べた。結果
を表８に示す。なお、空孔率は正極に電解液を含浸させ
たときの電解液の含浸量を測定し、この電解液の含浸量
を空孔体積として求めた。また、直流抵抗は満充電状態
で測定した。With respect to six types of nonaqueous electrolyte secondary batteries prepared using the pastes of Compositions 4 and 5 of Example 4 and Composition C of Comparative Example 3, the porosity and DC resistance of the positive electrode were examined. Table 8 shows the results. The porosity was obtained by measuring the impregnation amount of the electrolytic solution when the positive electrode was impregnated with the electrolytic solution, and determining the impregnated amount of the electrolytic solution as a pore volume. The DC resistance was measured in a fully charged state.
【００５８】[0058]
【表８】 [Table 8]
【００５９】表８の結果から、実施例４の組成４，５の
導電性ペーストペーストを含む非水電解液二次電池は、
調製直後、１週間経過後共に、正極の空孔率が大きく、
直流抵抗が低くなった。これは、導電性ペーストの経時
安定性が良好であるために、１週間経過後の導電性ペー
ストを用いても、正極中にカーボンブラックが均一に分
散されているためである。From the results shown in Table 8, the non-aqueous electrolyte secondary battery containing the conductive paste pastes of compositions 4 and 5 of Example 4 is as follows.
Immediately after the preparation and one week after, the porosity of the positive electrode is large,
DC resistance is low. This is because carbon black is uniformly dispersed in the positive electrode even if the conductive paste after one week has been used because the conductive paste has good temporal stability.
【００６０】これに対し、比較例３の組成Ｃの導電性ペ
ーストは、調製直後のペーストを含む正極の空孔率は大
きく、直流抵抗は低かったが、１週間経過後のペースト
を含む正極の空孔率は低く、直流抵抗が高くなった。こ
れは、導電性ペーストの沈降安定性が不良であるため
に、それを用いて調製した正極中にカーボンブラックが
不足しているためである。On the other hand, in the conductive paste of the composition C of Comparative Example 3, the porosity of the positive electrode including the paste immediately after preparation was large and the DC resistance was low, but the positive electrode including the paste after one week had passed. The porosity was low and the DC resistance was high. This is because carbon black is insufficient in the positive electrode prepared using the conductive paste because the sedimentation stability of the conductive paste is poor.
【００６１】〔実施例５、比較例４〕 Ｌｉイオン電池
（負極）への応用 負極活物質となる人造黒鉛材料８７重量部、ポリフッ化
ビニリデン（ＰＶＤＦ）１０重量部混合し、更に、表２
の組成４，５（実施例５）及び表４の組成Ｃ（比較例
４）のカーボンペーストを調製直後と調製後１週間経過
したものをそれぞれ１００重量部添加し、一定の攪拌条
件で混練して合計６種類の負極合剤ペーストを調製し
た。Example 5, Comparative Example 4 Li-ion battery
Application to (Negative Electrode) 87 parts by weight of an artificial graphite material serving as a negative electrode active material and 10 parts by weight of polyvinylidene fluoride (PVDF) were mixed.
100 parts by weight of each of carbon pastes having compositions 4 and 5 (Example 5) and a composition C (Comparative Example 4) in Table 4 immediately after and one week after the preparation were added and kneaded under constant stirring conditions. Thus, a total of six types of negative electrode mixture pastes were prepared.
【００６２】この負極合剤ペーストを負極集電体となる
厚さ２０μｍの帯状銅箔に塗布、乾燥後、ローラープレ
スにより圧縮成型して帯状負極を作成し、円型のカッタ
ーを用いて切断加工することで直径１０ｍｍの円型負極
を作成した。この円型負極をニッケル金網で挟み込み、
周囲を溶接することにより、６種類の試験電極を作成し
た。The negative electrode mixture paste is applied to a 20 μm-thick strip-shaped copper foil serving as a negative electrode current collector, dried, compression-molded by a roller press to form a strip-shaped negative electrode, and cut using a circular cutter. Thus, a circular negative electrode having a diameter of 10 mm was prepared. This circular negative electrode is sandwiched between nickel wire mesh,
By welding the surroundings, six types of test electrodes were prepared.
【００６３】得られた各試験電極を３電極式ガラスセル
にセットし、対極、参照極に金属リチウムをセットし、
電解液として炭酸エチレンとジエチルカーボネートの混
合溶媒（容量比で１：１）にＬｉＣｌＯ4を１ｍｏｌ／
Ｌの濃度で溶解したものを用いて、走査速度１ｍＶ／ｓ
ｅｃ、走査範囲１０ｍＶ〜２Ｖ（ｖｓ．Ｌｉ／Ｌｉ+）
の条件で電位走査法により放電容量性能を調べた。結果
を表９に示す。Each of the test electrodes thus obtained was set in a three-electrode glass cell, and metallic lithium was set in the counter electrode and the reference electrode.
LiClO 4 in a mixed solvent of ethylene carbonate and diethyl carbonate (1: 1 by volume ratio) as an electrolyte was 1 mol / mol.
Using a solution dissolved at a concentration of L, a scanning speed of 1 mV / s
ec, scanning range 10 mV to 2 V (vs. Li / Li + )
The discharge capacity performance was examined by the potential scanning method under the following conditions. Table 9 shows the results.
【００６４】[0064]
【表９】 [Table 9]
【００６５】表９の結果から、実施例５の組成４，５の
導電性ペーストを含むＬｉイオン電池は、調製直後、１
週間経過後共に、負極の放電容量が大きくなった。これ
は、導電性ペーストの経時安定性が良好であるために、
１週間経過後の導電性ペーストを用いても、負極中にカ
ーボンブラックが均一に分散されているためである。こ
れに対し、比較例４の組成Ｃの導電性ペーストは、調製
直後のペーストを含む負極の放電容量は大きかったが、
１週間経時後のペーストを含む負極の放電容量は小さく
なった。これは、導電性ペーストの沈降安定性が不良で
あるために、それを用いて調製した負極中にカーボンブ
ラックが不足しているためである。From the results in Table 9, it can be seen that the Li-ion battery containing the conductive pastes of compositions 4 and 5 of Example 5 was obtained immediately after the preparation.
After a lapse of a week, the discharge capacity of the negative electrode increased. This is because the stability over time of the conductive paste is good,
This is because carbon black is uniformly dispersed in the negative electrode even when the conductive paste after one week has elapsed is used. On the other hand, in the conductive paste of the composition C of Comparative Example 4, although the discharge capacity of the negative electrode including the paste immediately after preparation was large,
After one week, the discharge capacity of the negative electrode including the paste became small. This is because carbon black is insufficient in the negative electrode prepared using the conductive paste because the sedimentation stability of the conductive paste is poor.
【００６６】[0066]
【発明の効果】本発明によれば、高い導電性と優れた保
存安定性（沈降安定性、凝集安定性）を有するカーボン
ブラック含有導電性ペーストを得ることができる。ま
た、本発明の製造方法は、特殊形状の攪拌翼を用いるこ
とにより、従来は困難であったカーボンブラックのペー
スト中へ添加し、均一分散を短時間に過不足なく行うこ
とができ、二次電池用導電助剤として好適なものであ
る。According to the present invention, it is possible to obtain a carbon black-containing conductive paste having high conductivity and excellent storage stability (sedimentation stability, aggregation stability). Further, the production method of the present invention, by using a stirring blade of a special shape, can be added to the paste of carbon black, which was conventionally difficult, and can be uniformly dispersed in a short time without excess or shortage. It is suitable as a conductive assistant for batteries.
【図１】本発明の一実施例に係る攪拌翼（ディスプロ
型）の斜視図である。FIG. 1 is a perspective view of a stirring blade (displo type) according to an embodiment of the present invention.
【図２】同攪拌装置の一例を説明するための説明図であ
るFIG. 2 is an explanatory diagram for explaining an example of the stirring device.
【図３】従来のアンカー型の攪拌翼の斜視図である。FIG. 3 is a perspective view of a conventional anchor-type stirring blade.
【図４】同ディスクタービン型の攪拌翼の斜視図であ
る。FIG. 4 is a perspective view of the disk turbine type stirring blade.
【図５】本発明の実施例３及び比較例２で用いられる試
験セルを示した断面図である。FIG. 5 is a sectional view showing a test cell used in Example 3 and Comparative Example 2 of the present invention.
【図６】本発明の実施例４及び比較例３で用いられる非
水電解質二次電池の一構成例を示した概略断面図であ
る。FIG. 6 is a schematic sectional view showing a configuration example of a nonaqueous electrolyte secondary battery used in Example 4 and Comparative Example 3 of the present invention.
１ 攪拌翼 ３ 攪拌羽根 ４ 攪拌槽 ５ 攪拌軸 ６ 攪拌機 ７ 攪拌装置 DESCRIPTION OF SYMBOLS 1 Stirrer blade 3 Stirrer blade 4 Stirrer tank 5 Stirrer shaft 6 Stirrer 7 Stirrer
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｃ 1/48 Ｃ０９Ｃ 1/48 Ｃ０９Ｄ 5/24 Ｃ０９Ｄ 5/24 (72)発明者 白石 昭夫 東京都墨田区本所１丁目３番７号 ライオ ン株式会社内 Ｆターム(参考） 4G078 AA02 AB20 BA05 DA03 DA30 4J037 AA02 CA07 CB15 CB21 CC01 CC02 CC14 DD05 DD07 DD13 DD17 DD24 EE08 EE28 FF11 4J038 BA021 BA091 BA181 CD111 CG111 HA026 KA06 KA09 MA08 NA20 PB09 5G301 DA18 DA42 DA60 DD01 DE01 5H003 AA01 AA04 BA01 BA02 BA03 BA05 BB15 BC01 BD05 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09C 1/48 C09C 1/48 C09D 5/24 C09D 5/24 (72) Inventor Akio Shiraishi Sumida-ku, Tokyo 1- 3-7 Honjo F-term in Lion Corporation (reference) 4G078 AA02 AB20 BA05 DA03 DA30 4J037 AA02 CA07 CB15 CB21 CC01 CC02 CC14 DD05 DD07 DD13 DD17 DD24 EE08 EE28 FF11 4J038 BA021 BA091 BA181 CD111 CG111 HA0926 KA111 NA20 PB09 5G301 DA18 DA42 DA60 DD01 DE01 5H003 AA01 AA04 BA01 BA02 BA03 BA05 BB15 BC01 BD05
Claims (6)
電性ペーストにおいて、上記カーボンブラックが比表面
積７００〜１５００ｍ2／ｇ、一次粒子径１０〜４０ｎ
ｍ、ＤＢＰ吸油量３００〜６００ｍＬ／１００ｇである
と共に、上記ペーストの粘度が１０００〜１０００００
ｍＰａ・ｓであることを特徴とする導電性ペースト。1. In a conductive paste containing carbon black and a dispersion medium, the carbon black has a specific surface area of 700 to 1500 m 2 / g and a primary particle diameter of 10 to 40 n.
m, the DBP oil absorption is 300 to 600 mL / 100 g, and the viscosity of the paste is 1,000 to 100,000.
A conductive paste having a mPa · s.
重量部に対してカーボンブラック０．５〜２５重量部
と、分散剤０．０１〜１５重量部とを含有する請求項１
記載の導電性ペースト。2. The paste according to claim 1, wherein the dispersion medium is water.
2. The composition according to claim 1, wherein the composition contains 0.5 to 25 parts by weight of carbon black and 0.01 to 15 parts by weight of a dispersant.
The conductive paste as described in the above.
１００重量部に対してカーボンブラック０．５〜２５重
量部と、非水溶媒７５〜９９．５重量部とを含有する請
求項１記載の導電性ペースト。3. The dispersion medium is a non-aqueous solvent, and contains 0.5 to 25 parts by weight of carbon black and 75 to 99.5 parts by weight of a non-aqueous solvent based on 100 parts by weight of the paste. The conductive paste as described in the above.
トからなる二次電池用導電助剤。4. A conductive auxiliary for a secondary battery, comprising the conductive paste according to claim 1, 2, or 3.
トを製造する方法であって、円板の外周縁から中心に向
かう切り込みを所定間隔で偶数本形成することによって
得られた偶数個の切片の基端部を交互に上下方向に向け
て折り曲げてなる攪拌羽根を具備した攪拌翼を有する攪
拌機を用いて、上記カーボンブラック、分散媒等の導電
性ペースト材料を攪拌混合することを特徴とする導電性
ペーストの製造方法。5. The method for producing a conductive paste according to claim 1, 2 or 3, wherein an even number of cuts are formed at predetermined intervals from the outer peripheral edge of the disk toward the center. Using a stirrer having stirring blades provided with stirring blades formed by alternately bending the base ends of the pieces in the vertical direction, stirring and mixing the conductive paste material such as the carbon black and the dispersion medium. A method for producing a conductive paste.
性ペーストからなる二次電池用導電助剤。6. A conductive auxiliary for a secondary battery, comprising a conductive paste obtained by the method according to claim 5.
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| JP24422999A JP3856074B2 (en) | 1999-03-31 | 1999-08-31 | Conductive paste, method for producing the same, and conductive additive for secondary battery |
| KR1020000016079A KR20000063047A (en) | 1999-03-31 | 2000-03-29 | Electroconductive carbon pastes, their manufacturing process, electrode of lithium secondary batteries and electroconductive assisting additives for secondary batteries |
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|---|---|---|---|
| JP9108899 | 1999-03-31 | ||
| JP11-91088 | 1999-03-31 | ||
| JP24422999A JP3856074B2 (en) | 1999-03-31 | 1999-08-31 | Conductive paste, method for producing the same, and conductive additive for secondary battery |
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|---|---|
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| JP3856074B2 JP3856074B2 (en) | 2006-12-13 |
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