JP5978824B2 - Fine carbon dispersion, method for producing the same, electrode paste using the same, and electrode for lithium ion battery - Google Patents
Fine carbon dispersion, method for producing the same, electrode paste using the same, and electrode for lithium ion battery Download PDFInfo
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- JP5978824B2 JP5978824B2 JP2012161077A JP2012161077A JP5978824B2 JP 5978824 B2 JP5978824 B2 JP 5978824B2 JP 2012161077 A JP2012161077 A JP 2012161077A JP 2012161077 A JP2012161077 A JP 2012161077A JP 5978824 B2 JP5978824 B2 JP 5978824B2
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- Prior art keywords
- fine carbon
- carbon fiber
- dispersion
- dispersant
- fine
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- 229940117986 sulfobetaine Drugs 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
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- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
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- 125000003944 tolyl group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
本発明は、微細炭素繊維分散液及びその製造方法に関する。さらに微細炭素繊維分散液を用いた電極ペースト及び微細炭素被覆活物質に関する。 The present invention relates to a fine carbon fiber dispersion and a method for producing the same. Further, the present invention relates to an electrode paste using a fine carbon fiber dispersion and a fine carbon-coated active material.
カーボンブラック類、ケッチェンブラック（登録商標）、フラーレン、グラフェン、カーボンナノチューブ等の微細炭素材料は、その電気的特性、熱伝導性から、エレクトロニクス、エネルギー分野等の幅広い分野へ利用されている。特に微細炭素繊維の一種であるカーボンナノチューブ類は、直径１μｍ以下の太さのチューブ状のカーボンであり、その特異な構造に基づく高い導電性、引張り強度、耐熱性などから各種用途へのさらなる利用拡大が期待されている。ナノチューブ類の中でも直径１０ｎｍ〜数十ｎｍの多層カーボンナノチューブ（以下、ＭＷＮＴ）などの微細炭素繊維は比較的安価であり、リチウムイオン電池用の導電助剤や帯電防止コーティング等、様々な分野での実用化が期待されている。 Fine carbon materials such as carbon blacks, ketjen black (registered trademark) , fullerene, graphene, and carbon nanotubes are used in a wide range of fields such as electronics and energy due to their electrical properties and thermal conductivity. In particular, carbon nanotubes, a type of fine carbon fiber, are tube-like carbon with a diameter of 1 μm or less, and can be used in various applications due to their high conductivity, tensile strength, heat resistance, etc. based on their unique structure. Expansion is expected. Among the nanotubes, fine carbon fibers such as multi-walled carbon nanotubes (hereinafter referred to as MWNT) having a diameter of 10 nm to several tens of nm are relatively inexpensive, and are used in various fields such as conductive assistants and antistatic coatings for lithium ion batteries. Practical use is expected.
前記微細炭素繊維の特性を有効に活用するためには、微細炭素繊維が凝集する事なく、均一に分散していることが好ましい。しかしながら、一般的なＭＷＮＴは、互いの凝集力（ファンデルワールス力）によって束状及び縄状のバンドルと呼ばれる凝集体や、成長過程にチューブ同士が絡まった凝集体として得られる為、これら凝集したナノチューブを解し、分散媒に均一に分散させることは非常に困難である。 In order to effectively utilize the characteristics of the fine carbon fibers, it is preferable that the fine carbon fibers are uniformly dispersed without agglomeration. However, since general MWNTs are obtained as aggregates called bundles and rope-like bundles due to mutual cohesion (van der Waals force), and aggregates in which tubes are entangled in the growth process, these aggregates It is very difficult to break the nanotubes and uniformly disperse them in the dispersion medium.
これまでに、微細炭素繊維の分散媒に対する分散性を改善する為、様々な試みがなされている。カーボンナノチューブ類の分散について例を挙げると、まず、超音波をかけながらカーボンナノチューブをアセトン中に分散させる方法（特許文献１）が提案されている。しかし、超音波を照射している間は分散できても照射が終了するとカーボンナノチューブの凝集が始まり、カーボンナノチューブの濃度が高くなると凝集してしまう。 Various attempts have been made so far to improve the dispersibility of fine carbon fibers in a dispersion medium. As an example of the dispersion of carbon nanotubes, a method of dispersing carbon nanotubes in acetone while applying ultrasonic waves (Patent Document 1) has been proposed. However, even though it can be dispersed during the irradiation of ultrasonic waves, the carbon nanotubes start to aggregate when the irradiation ends, and when the concentration of the carbon nanotubes increases, they aggregate.
また、様々な分散剤を用いてカーボンナノチューブを分散安定化する方法が提案されている。例えば、陰イオン性界面活性剤であるドデシルスルホン酸ナトリウムやドデシルベンゼンスルホン酸ナトリウム水溶液中で超音波処理する事により、カーボンナノチューブ表面の疎水性と界面活性剤の疎水部を吸着させ、外側に親水部を形成して水溶液中に分散することも報告されている（非特許文献１、２）。また、非イオン系界面活性剤であるＴｒｉｔｏｎ（登録商標）−Ｘ−１００を用いて水中やＮ−メチル−２−ピロリドン（以下、ＮＭＰ）中で超音波処理することが提案されている（非特許文献３、特許文献２）。また、界面活性剤の替わりに水溶性高分子ポリビニルピロリドン（以下、ＰＶＰ）等のポリマー系分散剤を用いた水及びＮＭＰへの分散が提案されている（非特許文献４、特許文献３）。しかしながら、一般的なＭＷＮＴを溶液に高濃度に分散させようとした場合、高粘度のチキソ性流体となり易く、高濃度の分散液を得ることは難しい。したがって、微細炭素繊維が分散媒に高濃度かつ均一に分散した微細炭素繊維分散液を得る事は、用途拡大に向けた重要な課題であった。 In addition, methods for dispersing and stabilizing carbon nanotubes using various dispersants have been proposed. For example, ultrasonic treatment in sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate, which are anionic surfactants, adsorbs the hydrophobicity of the surface of the carbon nanotubes and the hydrophobic part of the surfactant, making the outer surface hydrophilic. It is also reported that a part is formed and dispersed in an aqueous solution (Non-Patent Documents 1 and 2). In addition, ultrasonic treatment in water or N-methyl-2-pyrrolidone (hereinafter referred to as NMP) using Triton (registered trademark) -X-100, which is a nonionic surfactant, has been proposed (Non-Surfactant). Patent Document 3 and Patent Document 2). In addition, dispersion in water and NMP using a polymer-based dispersant such as a water-soluble polymer polyvinyl pyrrolidone (hereinafter referred to as PVP) instead of a surfactant has been proposed (Non-patent Document 4 and Patent Document 3). However, when a general MWNT is to be dispersed in a solution at a high concentration, it tends to be a high-viscosity thixotropic fluid, and it is difficult to obtain a high-concentration dispersion. Therefore, obtaining a fine carbon fiber dispersion in which fine carbon fibers are uniformly dispersed in a dispersion medium at a high concentration has been an important issue for expanding applications.
本発明の目的は、微細炭素繊維が分散媒に高濃度かつ均一に分散した微細炭素繊維分散液の提供を可能にし、さらに前記微細炭素繊維分散液より得られる電極ペースト及び微細炭素被覆活物質を得ることが可能な新しい技術を提供することにある。 It is an object of the present invention to provide a fine carbon fiber dispersion in which fine carbon fibers are uniformly dispersed in a dispersion medium, and to provide an electrode paste and a fine carbon-coated active material obtained from the fine carbon fiber dispersion. It is to provide new technologies that can be obtained.
本発明者らは、鋭意研究を重ねた結果、平均直径が２０ｎｍ以下かつＤＢＰ吸油量が３６０ｍｌ／１００ｇ以下である微細炭素繊維を用いることで、分散媒に高濃度かつ均一に分散した微細炭素繊維分散液が得られる事を見出し、本発明を完成するに至った。
即ち、本発明は、以下の事項に関する。
１．平均直径が５〜２０ｎｍかつＤＢＰ吸油量が２５０〜３６０ｍｌ／１００ｇである微細炭素繊維と、分散媒と、分散剤からなる微細炭素繊維分散液。
２．前記微細炭素繊維が、マグネシウムが置換固溶したコバルトのスピネル型酸化物を含む触媒上に、ＣＯ及びＨ２を含む混合ガスを供給して反応させることによって製造された微細炭素繊維であることを特徴とする上記１に記載の微細炭素繊維分散液。
３．前記微細炭素繊維が、炭素原子のみから構成されるグラファイト網面が、閉じた頭頂部と下部が開いた胴部とを有する釣鐘状構造単位を形成し、前記胴部の母線と繊維軸とのなす角θが１５°より小さく、前記釣鐘状構造単位が、中心軸を共有して２〜３０個積み重なって集合体を形成し、前記集合体が、Ｈｅａｄ−ｔｏ−Ｔａｉｌ様式で間隔をもって連結して繊維を形成している微細炭素繊維であることを特徴とする上記１または２に記載の微細炭素繊維分散液。
４．前記分散媒が、水、及びまたは、水溶性有機溶媒のいずれか一種、若しくは二種以上からなる混合溶媒であることを特徴とする上記１ないし３のいずれか１項に記載の微細炭素繊維分散液。
５．前記水溶性有機溶媒がアミド系有機溶媒であることを特徴とする上記４に記載の微細炭素繊維分散液。
６．前記アミド系有機溶媒がＮ−メチル−２−ピロリドン及び／又は、Ｎ−エチル−２−ピロリドンであることを特徴とする上記５に記載の微細炭素分散液。
７．前記分散剤が、非イオン性分散剤であることを特徴とする上記１ないし６のいずれか１項に記載の微細炭素繊維分散液。
８．前記非イオン性分散剤が、ポリマー系分散剤であることを特徴とする上記７に記載の微細炭素繊維分散液。
９．前記ポリマー系分散剤の重量平均分子量が８０００〜５００００の範囲であることを特徴とする上記８に記載の微細炭素繊維分散液。
１０．前記微細炭素繊維を０．１〜２０ｗｔ％含むことを特徴とする上記１ないし９のいずれか１項に記載の微細炭素繊維分散液。
１１．分散された微細炭素繊維のメジアン径が０．１μｍ〜３μｍであることを特徴とする上記１ないし１０のいずれか１項に記載の微細炭素繊維分散液。
１２．分散液の回転粘度が５０〜５００ｍＰａ・ｓであることを特徴とする上記１ないし１１のいずれか１項に記載の微細炭素繊維分散液。
１３．マグネシウムが置換固溶したコバルトのスピネル型酸化物を含む触媒上に、ＣＯ及びＨ２を含む混合ガスを供給して反応させて製造された平均直径が５〜２０ｎｍかつＤＢＰ吸油量が２５０〜３６０ｍｌ／１００ｇである微細炭素繊維と、分散媒と、分散剤とを混合し、超音波処理及び／又は撹拌・粉砕処理を行なうことを特徴とする微細炭素繊維分散液の製造方法。
１４．前記攪拌・分散処理が、メディア型湿式分散装置を用いた処理であることを特徴とする上記１３に記載の微細炭素繊維分散液の製造方法。
１５．上記１〜１１のいずれか１項に記載の前記微細炭素繊維分散液と、活物質及びバインダを含むことを特徴とする電極ペースト。
１６．上記１５に記載の前記電極ペーストを用いて作成されることを特徴とするリチウムイオン電池用電極。
As a result of intensive studies, the present inventors have used fine carbon fibers having an average diameter of 20 nm or less and a DBP oil absorption of 360 ml / 100 g or less, so that fine carbon fibers dispersed in a high concentration and uniformly in a dispersion medium. The inventors have found that a dispersion can be obtained, and have completed the present invention.
That is, the present invention relates to the following matters.
1. A fine carbon fiber dispersion comprising a fine carbon fiber having an average diameter of 5 to 20 nm and a DBP oil absorption of 250 to 360 ml / 100 g, a dispersion medium, and a dispersant.
2. The fine carbon fiber is a fine carbon fiber produced by supplying and reacting a mixed gas containing CO and H2 on a catalyst containing a cobalt spinel oxide in which magnesium is substituted and dissolved in solid solution. 2. The fine carbon fiber dispersion liquid according to 1 above.
3. The fine carbon fiber has a graphite net surface composed of only carbon atoms to form a bell-shaped structural unit having a closed top and a trunk that is open at the bottom, and the busbar of the trunk and the fiber axis. The angle θ formed is smaller than 15 °, the bell-shaped structural units are stacked by sharing 2 to 30 pieces sharing the central axis, and the aggregates are connected in a head-to-tail manner at intervals. 3. The fine carbon fiber dispersion according to 1 or 2 above, which is a fine carbon fiber forming a fiber.
4). 4. The fine carbon fiber dispersion according to any one of 1 to 3 above, wherein the dispersion medium is water, and / or a mixed solvent composed of at least one of water-soluble organic solvents, or two or more thereof. liquid.
5. 5. The fine carbon fiber dispersion liquid as described in 4 above, wherein the water-soluble organic solvent is an amide organic solvent.
6). 6. The fine carbon dispersion liquid as described in 5 above, wherein the amide organic solvent is N-methyl-2-pyrrolidone and / or N-ethyl-2-pyrrolidone.
7). 7. The fine carbon fiber dispersion according to any one of 1 to 6 above, wherein the dispersant is a nonionic dispersant.
8). 8. The fine carbon fiber dispersion liquid as described in 7 above, wherein the nonionic dispersant is a polymer-based dispersant.
9. 9. The fine carbon fiber dispersion liquid as described in 8 above, wherein the polymer dispersant has a weight average molecular weight in the range of 8000 to 50000.
10. 10. The fine carbon fiber dispersion liquid according to any one of 1 to 9 above, wherein the fine carbon fiber is contained in an amount of 0.1 to 20 wt%.
11 11. The fine carbon fiber dispersion liquid according to any one of 1 to 10 above, wherein a median diameter of the fine carbon fibers dispersed is 0.1 μm to 3 μm.
12 12. The fine carbon fiber dispersion according to any one of 1 to 11 above, wherein the dispersion has a rotational viscosity of 50 to 500 mPa · s.
13. An average diameter of 5 to 20 nm and a DBP oil absorption of 250 to 360 ml / min produced by supplying and reacting a mixed gas containing CO and H2 on a catalyst containing cobalt spinel oxide in which magnesium is substituted and dissolved. A method for producing a fine carbon fiber dispersion, comprising mixing 100 g of fine carbon fibers, a dispersion medium, and a dispersant, and performing ultrasonic treatment and / or stirring / pulverization treatment.
14 14. The method for producing a fine carbon fiber dispersion as described in 13 above, wherein the agitation / dispersion treatment is treatment using a media type wet dispersion apparatus.
15. 12. An electrode paste comprising the fine carbon fiber dispersion according to any one of 1 to 11, an active material and a binder.
16. 16. An electrode for a lithium ion battery, wherein the electrode paste is produced using the electrode paste as described in 15 above.
本発明によって、分散媒への分散が困難であった微細炭素繊維を、高濃度かつ均一に分散した微細炭素繊維分散液を得ることが可能となった。本発明の微細炭素繊維分散液は、高濃度かつ均一に微細炭素繊維が分散している為、高濃度添加が求められる分野や均一な分散性が求められる分野に好適に利用できる。また、分散液の高濃度化によって微細炭素繊維の固形分を多くする事が出来る為、分散媒のコストや分散液の輸送コストを低減することができる。さらに、本発明の微細炭素繊維分散液を導電助剤として用いることで、微細炭素繊維が均一に分散した電池用電極ペースト及び微細炭素によって均一に被覆された活物質を得ることできる。本発明で得られる電極ペーストや微細炭素被覆活物質は、導電性良好な微細炭素繊維が均一に分散・被覆しており、各種電池の電極等に好適に用いることができる。 According to the present invention, it is possible to obtain a fine carbon fiber dispersion in which fine carbon fibers that have been difficult to be dispersed in a dispersion medium are uniformly dispersed at a high concentration. The fine carbon fiber dispersion liquid of the present invention can be suitably used in fields requiring high concentration addition and fields requiring uniform dispersibility because fine carbon fibers are uniformly dispersed at a high concentration. Moreover, since the solid content of the fine carbon fiber can be increased by increasing the concentration of the dispersion liquid, the cost of the dispersion medium and the transportation cost of the dispersion liquid can be reduced. Furthermore, by using the fine carbon fiber dispersion of the present invention as a conductive additive, a battery electrode paste in which fine carbon fibers are uniformly dispersed and an active material uniformly coated with fine carbon can be obtained. The electrode paste and fine carbon-coated active material obtained in the present invention are uniformly dispersed and coated with fine carbon fibers having good conductivity, and can be suitably used for electrodes of various batteries.
以下本発明を詳細に説明する。
本発明の微細炭素繊維分散液は、平均直径が５〜２０ｎｍ以下かつＤＢＰ吸油量が２５０〜３６０ｍｌ／１００ｇ以下である微細炭素繊維と、分散媒と、分散剤からなる。
The present invention will be described in detail below.
The fine carbon fiber dispersion of the present invention comprises fine carbon fibers having an average diameter of 5 to 20 nm or less and a DBP oil absorption of 250 to 360 ml / 100 g or less, a dispersion medium, and a dispersant.
本発明に用いる微細炭素繊維は、マグネシウムが置換固溶したコバルトのスピネル型酸化物を含む触媒上に、ＣＯ及びＨ２を含む混合ガスを供給して反応させることによって製造された微細炭素繊維である事が好ましい。 The fine carbon fiber used in the present invention is a fine carbon fiber produced by supplying and reacting a mixed gas containing CO and H2 on a catalyst containing a cobalt spinel oxide in which magnesium is substituted and dissolved. Things are preferable.
また、本発明に用いる微細炭素繊維は、炭素原子のみから構成されるグラファイト網面が、閉じた頭頂部と下部が開いた胴部とを有する釣鐘状構造単位を形成し、前記胴部の母線と繊維軸とのなす角θが１５°より小さく、前記釣鐘状構造単位が、中心軸を共有して２〜３０個積み重なって集合体を形成し、前記集合体が、Ｈｅａｄ−ｔｏ−Ｔａｉｌ様式で間隔をもって連結して繊維を形成している事が好ましい。 Further, in the fine carbon fiber used in the present invention, the graphite mesh surface composed only of carbon atoms forms a bell-shaped structural unit having a closed top and an open trunk, and the bus bar of the trunk The angle θ formed between the fiber axis and the fiber axis is smaller than 15 °, and the bell-shaped structural units are stacked by sharing 2 to 30 pieces sharing the central axis, and the aggregate is a head-to-tail style. It is preferable that the fibers are formed by connecting at intervals.
以上のような微細炭素繊維を用いる事で、分散媒に高濃度に分散した際も比較的粘度が低く、かつ均一に分散した微細炭素繊維分散液を得ることが可能となる。高濃度に分散した際に比較的粘度が低く、かつ均一に分散できる理由は定かではないが、下記の３点が影響しているものと推測される。第一に、本発明で用いられる微細炭素繊維は、ＤＢＰ吸油量が低い為に分散媒への分散時に微細炭素繊維に取り込まれる分散媒量が少なく、結果として高濃度でも粘度の上昇が小さいことが挙げられる。なお、平均直径が２０ｎｍ以上の場合、微細炭素繊維が太く、分散液中の微細炭素繊維の本数が少なくなる為、結果として分散液の粘度は低く抑える事が出来るが、平均直径２０ｎｍ以下の微細炭素繊維を用いた場合のような高い導電性との両立を図ることは難しい。第二に、本発明に用いられる微細炭素繊維は、ＣＯ及びＨ２を含む混合ガスを供給して反応させることによって製造することで、エチレンガスやメタン等の炭化水素を炭素源として用いて製造される従来のＭＷＮＴ等の微細炭素繊維と比較して、微細炭素繊維の成長が緩やかである為に微細炭素繊維同士の絡まりが弱く、均一に分散しやすいことが挙げられる。第三に、本発明で用いられる微細炭素繊維は、前記釣鐘状構造単位がＨｅａｄ−ｔｏ−Ｔａｉｌ様式で間隔をもって連結している為に、分散処理を施した際に適度に連結部分が外れることによって分散性が高く、かつ高濃度分散時の粘度上昇が小さいことが挙げられる。 By using the fine carbon fibers as described above, it is possible to obtain a fine carbon fiber dispersion liquid having a relatively low viscosity and uniformly dispersed even when dispersed in a dispersion medium at a high concentration. The reason why the viscosity is relatively low and can be uniformly dispersed when dispersed at a high concentration is not clear, but is presumed to be influenced by the following three points. First, since the fine carbon fiber used in the present invention has a low DBP oil absorption amount, the amount of the dispersion medium taken into the fine carbon fiber when dispersed in the dispersion medium is small, and as a result, the increase in viscosity is small even at a high concentration. Is mentioned. When the average diameter is 20 nm or more, the fine carbon fibers are thick and the number of fine carbon fibers in the dispersion is reduced. As a result, the viscosity of the dispersion can be kept low, but the average diameter is 20 nm or less. It is difficult to achieve both high conductivity as in the case of using carbon fiber. Secondly, the fine carbon fiber used in the present invention is produced by supplying a mixed gas containing CO and H2 and reacting it, and is produced using a hydrocarbon such as ethylene gas or methane as a carbon source. Compared with the conventional fine carbon fibers such as MWNT, the growth of the fine carbon fibers is gentle, so that the entanglement between the fine carbon fibers is weak and easily dispersed uniformly. Thirdly, the fine carbon fiber used in the present invention has the bell-shaped structural units connected at intervals in the head-to-tail manner, so that the connecting portion is appropriately disengaged when subjected to dispersion treatment. Therefore, the dispersibility is high, and the viscosity increase at high concentration dispersion is small.
以下、本発明で用いられる微細炭素繊維について、詳細に説明する。本発明に用いられる微細炭素繊維およびその製造方法は、再公表特許ＷＯ２００９／１１０５７０に記載のものと同様である。 Hereinafter, the fine carbon fiber used in the present invention will be described in detail. The fine carbon fiber used in the present invention and the production method thereof are the same as those described in the republished patent WO2009 / 110570.
本発明に用いられる微細炭素繊維は、図１（ａ）に示すような釣鐘状構造を最小構造単位として有する。釣鐘（ｔｅｍｐｌｅ ｂｅｌｌ）は、日本の寺院で見られ、比較的円筒形に近い胴部を有しており、円錐形に近いクリスマスベルとは形状が異なる。図１（ａ）に示すように、構造単位１１は、釣鐘のように、頭頂部１２と、開放端を備える胴部１３とを有し、概ね中心軸の周囲に回転させた回転体形状となっている。構造単位１１は、炭素原子のみからなるグラファイト網面により形成され、胴部開放端の円周状部分はグラファイト網面の開放端となる。なお、図１（ａ）において、中心軸および胴部１３は、便宜上直線で示されているが、必ずしも直線でなくともよい。 The fine carbon fiber used in the present invention has a bell-shaped structure as shown in FIG. The temple bell is found in Japanese temples, has a relatively cylindrical body, and is different in shape from a conical Christmas bell. As shown in FIG. 1 (a), the structural unit 11 has a top portion 12 and a trunk portion 13 having an open end, like a bell, and has a rotating body shape rotated about the central axis. It has become. The structural unit 11 is formed of a graphite network surface made of only carbon atoms, and the circumferential portion of the body portion open end is the open end of the graphite network surface. In FIG. 1A, the central axis and the body portion 13 are shown as straight lines for convenience, but may not necessarily be straight lines.
胴部１３は、開放端側に緩やかに広がっており、その結果、胴部１３の母線は釣鐘状構造単位の中心軸に対してわずかに傾斜し、両者のなす角θは、１５°より小さく、より好ましくは１°＜θ＜１５°、更に好ましくは２°＜θ＜１０°である。θが大きくなりすぎると、該構造単位から構成される微細繊維が魚骨状炭素繊維様の構造を呈してしまい、繊維軸方向の導電性が損なわれてしまう。一方θが小さいと、円筒チューブ状に近い構造となり、構造単位の胴部を構成するグラファイト網面の開放端が繊維外周面に露出する頻度が低くなるため、隣接繊維間の導電性が悪化する。 The trunk portion 13 gently spreads toward the open end. As a result, the bus bar of the trunk portion 13 is slightly inclined with respect to the central axis of the bell-shaped structural unit, and the angle θ formed by both is smaller than 15 °. More preferably, 1 ° <θ <15 °, and further preferably 2 ° <θ <10 °. If θ is too large, fine fibers composed of the structural unit exhibit a fishbone-like carbon fiber-like structure, and the conductivity in the fiber axis direction is impaired. On the other hand, when θ is small, the structure is close to a cylindrical tube shape, and the frequency at which the open end of the graphite mesh surface constituting the body of the structural unit is exposed to the outer peripheral surface of the fiber becomes low, so the conductivity between adjacent fibers deteriorates. .
本発明に用いられる微細炭素繊維には、欠陥、不規則な乱れが存在するが、このような不規則性を排除して、全体としての形状を捉えると、胴部１３が開放端側に緩やかに広がった釣鐘状構造を有していると言える。この微細炭素繊維は、すべての部分においてθが上記範囲を示すことを意味しているのではなく、欠陥部分や不規則な部分を排除しつつ、構造単位１１を全体的に捉えたときに、総合的にθが上記範囲を満たしていることを意味している。そこで、θの測定では、胴部の太さが不規則に変化していることもある頭頂部１２付近を除くことが好ましい。より具体的には、例えば、図１（ｂ）に示すように釣鐘状構造単位集合体２１の長さをＬとすると、頭頂側から（１／４）Ｌ、（１／２）Ｌおよび（３／４）Ｌの３点においてθを測定してその平均を求め、その値を、構造単位１１についての全体的なθとしてもよい。また、Ｌについては、直線で測定することが理想であるが、実際は胴部１３が曲線であることも多いため、胴部１３の曲線に沿って測定した方が実際の値に近い場合もある。 The fine carbon fiber used in the present invention has defects and irregular turbulence. However, if such irregularity is eliminated and the shape of the whole is captured, the body portion 13 gradually moves toward the open end side. It can be said that it has a bell-shaped structure spread out. This fine carbon fiber does not mean that θ indicates the above range in all portions, but excludes defective portions and irregular portions while capturing the structural unit 11 as a whole, Overall, it means that θ satisfies the above range. Therefore, in the measurement of θ, it is preferable to exclude the vicinity of the crown 12 where the thickness of the trunk may be irregularly changed. More specifically, for example, when the length of the bell-shaped structural unit aggregate 21 is L as shown in FIG. 1B, (1/4) L, (1/2) L and ( 3/4) θ may be measured at three points of L to obtain an average, and the value may be used as the overall θ for the structural unit 11. In addition, it is ideal to measure L with a straight line. However, since the body part 13 is often a curved line in practice, it may be closer to the actual value when measured along the curve of the body part 13. .
頭頂部の形状は、胴部と滑らかに連続し、上側（図において）に凸の曲面となっている。頭頂部の長さは、典型的には、釣鐘状構造単位集合体について説明するＤ（図１（ｂ））以下程度であり、ｄ（図１（ｂ））以下程度であるときもある。 The shape of the top of the head is smoothly continuous with the torso and has a curved surface that protrudes upward (in the drawing). The length of the top of the head is typically about D (FIG. 1 (b)) or less and about d (FIG. 1 (b)) for explaining the bell-shaped structural unit aggregate.
さらに、後述するように活性な窒素を原料として使用しないため、窒素等の他の原子は、釣鐘状構造単位のグラファイト網面中に含まれない。このため繊維の結晶性が良好である。 Furthermore, since active nitrogen is not used as a raw material as will be described later, other atoms such as nitrogen are not included in the graphite network surface of the bell-shaped structural unit. For this reason, the crystallinity of the fiber is good.
本発明に用いられる微細炭素繊維は、図１（ｂ）に示すように、このような釣鐘状構造単位が中心軸を共有して２〜３０個積み重なって釣鐘状構造単位集合体２１（以下、単に集合体という場合がある。）を形成している。積層数は、好ましくは２〜２５個であり、より好ましくは２〜１５個である。 As shown in FIG. 1 (b), the fine carbon fiber used in the present invention has a bell-shaped structural unit assembly 21 (hereinafter referred to as “bell-shaped structural unit assembly”) in which 2 to 30 such bell-shaped structural units share a central axis. It may be simply called an aggregate.) The number of stacked layers is preferably 2 to 25, and more preferably 2 to 15.
集合体２１の胴部の外径Ｄは、５〜４０ｎｍ、好ましくは５〜３０ｎｍ、更に好ましくは５〜２０ｎｍである。Ｄが大きくなると形成される微細繊維の径が太くなるため、例えばポリマーとのコンポジットにおいて導電性能等の機能を付与するためには、多くの添加量が必要となってしまう。一方、Ｄが小さくなると形成される微細繊維の径が細くなって繊維同士の凝集が強くなり、例えばポリマーとのコンポジット調製において、分散させることが困難になる。胴部外径Ｄの測定は、集合体の頭頂側から、（１／４）Ｌ、（１／２）Ｌおよび（３／４）Ｌの３点で測定して平均することが好ましい。なお、図１（ｂ）に胴部外径Ｄを便宜上示しているが、実際のＤの値は、上記３点の平均値が好ましい。 The outer diameter D of the trunk | drum of the aggregate 21 is 5-40 nm, Preferably it is 5-30 nm, More preferably, it is 5-20 nm. Since the diameter of the fine fiber formed increases as D increases, for example, in order to impart functions such as conductive performance in a composite with a polymer, a large amount of addition is required. On the other hand, when D becomes small, the diameter of the fine fibers formed becomes thin and the aggregation of the fibers becomes strong. For example, in preparing a composite with a polymer, it becomes difficult to disperse. The measurement of the trunk outer diameter D is preferably performed by measuring at three points (1/4) L, (1/2) L, and (3/4) L from the top of the aggregate. In addition, although the trunk | drum outer diameter D is shown for convenience in FIG.1 (b), the value of actual D has the preferable average value of the said 3 points | pieces.
また、集合体胴部の内径ｄは、３〜３０ｎｍ、好ましくは３〜２０ｎｍ、更に好ましくは３〜１０ｎｍである。胴部内径ｄの測定についても、釣鐘状構造単位集合体の頭頂側から、（１／４）Ｌ、（１／２）Ｌおよび（３／４）Ｌの３点で測定して平均することが好ましい。なお、図１（ｂ）に胴部内径ｄを便宜上示しているが、実際のｄの値は、上記３点の平均値が好ましい。 The inner diameter d of the aggregate body is 3 to 30 nm, preferably 3 to 20 nm, more preferably 3 to 10 nm. The inner diameter d of the trunk is also measured and averaged at three points (1/4) L, (1/2) L, and (3/4) L from the top of the bell-shaped structural unit assembly. Is preferred. In addition, although the trunk | drum internal diameter d is shown in FIG.1 (b) for convenience, the actual value of d has the preferable average value of the said 3 points | pieces.
集合体２１の長さＬと胴部外径Ｄから算出されるアスペクト比（Ｌ／Ｄ）は、２〜１５０、好ましくは２〜３０、より好ましくは２〜２０、更に好ましくは２〜１０である。アスペクト比が大きいと、形成される繊維の構造が円筒チューブ状に近づき、１本の繊維における繊維軸方向の導電性は向上するが、構造単位胴部を構成するグラファイト網面の開放端が繊維外周面に露出する頻度が低くなるため、隣接繊維間の導電性が悪化する。一方、アスペクト比が小さいと構造単位胴部を構成するグラファイト網面の開放端が繊維外周面に露出する頻度が高くなるため、隣接繊維間の導電性は向上するが、繊維外周面が、繊維軸方向に短いグラファイト網面が多数連結して構成されるため、１本の繊維における繊維軸方向の導電性が損なわれる。 The aspect ratio (L / D) calculated from the length L of the aggregate 21 and the body outer diameter D is 2 to 150, preferably 2 to 30, more preferably 2 to 20, and further preferably 2 to 10. is there. When the aspect ratio is large, the structure of the formed fiber approaches a cylindrical tube shape, and the conductivity in the fiber axis direction of one fiber is improved. However, the open end of the graphite network surface constituting the structural unit body is a fiber. Since the frequency of exposure to the outer peripheral surface is reduced, the conductivity between adjacent fibers is deteriorated. On the other hand, when the aspect ratio is small, the open end of the graphite mesh surface constituting the structural unit body portion is more frequently exposed to the outer peripheral surface of the fiber, so that the conductivity between adjacent fibers is improved. Since many short graphite mesh surfaces are connected in the axial direction, conductivity in the fiber axial direction of one fiber is impaired.
本発明に用いられる微細炭素繊維における、釣鐘状構造単位および釣鐘状構造単位集合体については、本質的に同じ構成を有しているが、以下ように繊維長が異なる。 The bell-shaped structural unit and the bell-shaped structural unit aggregate in the fine carbon fiber used in the present invention have essentially the same configuration, but have different fiber lengths as follows.
本発明に用いられる微細炭素繊維は、図２（ａ）に示すように、前記集合体がさらにＨｅａｄ−ｔｏ−Ｔａｉｌの様式で連結することにより形成される。Ｈｅａｄ−ｔｏ−Ｔａｉｌの様式とは、微細炭素繊維の構成において、隣り合った前記集合体どうしの接合部位が、一方の集合体の頭頂部（Ｈｅａｄ）と他方の集合体の下端部（Ｔａｉｌ）の組合せで形成されていることを意味する。具体的な接合部分の形態は、第一の集合体２１ａの下端開口部において、最内層の釣鐘状構造単位の更に内側に、第二の集合体２１ｂの最外層の釣鐘状構造単位の頭頂部が挿入され、さらに、第二の集合体２１ｂの下端開口部に、第三の集合体２１ｃの頭頂部が挿入され、これがさらに連続することによって繊維が構成される。 As shown in FIG. 2A, the fine carbon fiber used in the present invention is formed by further connecting the aggregates in a head-to-tail manner. The head-to-tail style means that in the configuration of fine carbon fiber, the joining portions of the adjacent aggregates are the top (Head) of one aggregate and the lower end (Tail) of the other aggregate. It means that it is formed by the combination of. Specifically, the shape of the joint portion is the top of the bell-shaped structural unit of the outermost layer of the second aggregate 21b, further inside the bell-shaped structural unit of the innermost layer, at the lower end opening of the first aggregate 21a. Is inserted, and the top of the third assembly 21c is inserted into the lower end opening of the second assembly 21b, and this is further continued to form a fiber.
本発明に用いられる微細炭素繊維の１本の微細繊維を形成する各々の接合部分は、構造的な規則性を有しておらず、例えば第一の集合体と第二の集合体の接合部分の繊維軸方向の長さは、第二の集合体と第三の集合体の接合部分の長さと必ずしも同じではない。また、図２（ａ）のように、接合される二つの集合体が中心軸を共有して直線状に連結することもあるが、図２（ｂ）の釣鐘状構造単位集合体２１ｂと２１ｃのように、中心軸が共有されずに接合して、結果として接合部分において屈曲構造を生じることもある。前記釣鐘状構造単位集合体の長さＬは繊維ごとにおおむね一定である。しかしながら、気相成長法では、原料及び副生のガス成分と触媒及び生成物の固体成分が混在するため、発熱的な炭素析出反応の実施においては、前記気体及び固体からなる不均一な反応混合物の流動状態によって一時的に温度の高い局所が形成されるなど、反応器内に温度分布が生じ、その結果、長さＬにある程度のばらつきが生じることもある。 Each joining part which forms one fine fiber of the fine carbon fiber used for this invention does not have structural regularity, for example, the joined part of a 1st aggregate and a 2nd aggregate The length in the fiber axis direction is not necessarily the same as the length of the joint portion of the second assembly and the third assembly. Further, as shown in FIG. 2A, the two assemblies to be joined may be connected linearly sharing the central axis, but the bell-shaped structural unit assemblies 21b and 21c in FIG. As described above, the central axis may be joined without being shared, resulting in a bent structure at the joint. The length L of the bell-shaped structural unit assembly is generally constant for each fiber. However, in the vapor phase growth method, since raw material and by-product gas components and catalyst and product solid components are mixed, in the exothermic carbon deposition reaction, a heterogeneous reaction mixture composed of the gas and solids. A temperature distribution is generated in the reactor, for example, a locally high temperature is formed depending on the flow state, and as a result, some variation in the length L may occur.
このようにして構成される微細炭素繊維は、前記釣鐘状構造単位下端のグラファイト網面の開放端の少なくとも一部が、前記集合体の連結間隔に応じて、繊維外周面に露出する。この結果、１本の繊維における繊維軸方向の導電性を損なうことなく、前記π電子の飛び出しによるジャンピング効果（トンネル効果）によって隣接する繊維間の導電性を向上させることができる。以上のような微細炭素繊維の構造は、ＴＥＭ画像によって観察できる。また、本発明の微細炭素繊維の効果は、集合体自体の曲がり、集合体の連結部分における屈曲が存在しても、ほとんど影響がないと考えられる。従って、ＴＥＭ画像の中で、比較的直線に近い形状を有する集合体を観察して、構造に関する各パラメータを求め、その繊維についての構造パラメータ（θ、Ｄ、ｄ、Ｌ）としてよい。 In the fine carbon fiber configured as described above, at least a part of the open end of the graphite mesh surface at the lower end of the bell-shaped structural unit is exposed on the outer peripheral surface of the fiber according to the connection interval of the aggregate. As a result, the conductivity between adjacent fibers can be improved by the jumping effect (tunnel effect) caused by the jumping out of the π electrons without impairing the conductivity in the fiber axis direction of one fiber. The structure of the fine carbon fiber as described above can be observed by a TEM image. In addition, the effect of the fine carbon fiber of the present invention is considered to have almost no influence even when the aggregate itself is bent or there is a bend in the connecting portion of the aggregate. Therefore, in the TEM image, an assembly having a shape that is relatively close to a straight line is observed to obtain each parameter relating to the structure, and the structure parameter (θ, D, d, L) for the fiber may be obtained.
本発明に用いられる微細炭素繊維の学振法によるＸＲＤにおいて、測定される００２面のピーク半価幅Ｗ（単位：ｄｅｇｒｅｅ）は、２〜４の範囲である。Ｗが４を超えると、グラファイト結晶性が低く導電性も低い。一方、Ｗが２未満ではグラファイト結晶性は良いが、同時に繊維径が太くなり、ポリマーに導電性等の機能を付与するためには多くの添加量が必要となってしまう。 In XRD based on the Gakushin method of fine carbon fibers used in the present invention, the peak half width W (unit: degree) of the 002 plane measured is in the range of 2-4. When W exceeds 4, the graphite crystallinity is low and the conductivity is low. On the other hand, when W is less than 2, the graphite crystallinity is good, but at the same time, the fiber diameter becomes large, and a large amount of addition is required to impart a function such as conductivity to the polymer.
本発明に用いられる微細炭素繊維の学振法によるＸＲＤ測定によって求められるグラファイト面間隔ｄ００２は、０．３５０ｎｍ以下、好ましくは０．３４１〜０．３４８ｎｍである。ｄ００２が０．３５０ｎｍを超えるとグラファイト結晶性が低くなり、導電性が低下する。一方、０．３４１ｎｍ未満の繊維は、製造の際に収率が低い。 The graphite plane distance d002 obtained by XRD measurement by the Gakushin method of fine carbon fibers used in the present invention is 0.350 nm or less, preferably 0.341 to 0.348 nm. If d002 exceeds 0.350 nm, the graphite crystallinity is lowered and the conductivity is lowered. On the other hand, the fiber of less than 0.341 nm has a low yield in production.
本発明に用いられる微細炭素繊維に含有される灰分は、４質量％以下であり、通常の用途では、精製を必要としない。通常、０．３質量％以上４質量％以下であり、より好ましくは０．３質量％以上３質量％以下である。尚、灰分は、繊維を０．１グラム以上燃焼して残った酸化物の重量から決定される。 The ash contained in the fine carbon fiber used in the present invention is 4% by mass or less, and purification is not necessary for normal use. Usually, it is 0.3 mass% or more and 4 mass% or less, More preferably, it is 0.3 mass% or more and 3 mass% or less. The ash content is determined from the weight of the oxide remaining after burning 0.1 g or more of the fiber.
次に、本発明に用いられる微細炭素繊維の製造方法について説明する。 Next, the manufacturing method of the fine carbon fiber used for this invention is demonstrated.
コバルトのスピネル型結晶構造を有する酸化物に、マグネシウムが固溶置換した触媒を用いて、ＣＯ及びＨ２を含む混合ガスを触媒粒子に供給して気相成長法により、微細炭素繊維を製造する。 Using a catalyst in which magnesium is replaced by solid solution with an oxide having a spinel crystal structure of cobalt, a mixed gas containing CO and H 2 is supplied to catalyst particles, and fine carbon fibers are produced by a vapor phase growth method.
Ｍｇが置換固溶したコバルトのスピネル型結晶構造は、ＭｇｘＣｏ３−ｘＯｙで表される。ここで、ｘは、ＭｇによるＣｏの置換を示す数であり、形式的には０＜ｘ＜３である。また、ｙはこの式全体が電荷的に中性になるように選ばれる数で、形式的には４以下の数を表す。即ち、コバルトのスピネル型酸化物Ｃｏ３Ｏ４では、２価と３価のＣｏイオンが存在しており、ここで、２価および３価のコバルトイオンをそれぞれＣｏＩＩおよびＣｏＩＩＩで表すと、スピネル型結晶構造を有するコバルト酸化物はＣｏＩＩＣｏＩＩＩ２Ｏ４で表される。Ｍｇは、ＣｏＩＩとＣｏＩＩＩのサイトの両方を置換して固溶する。ＭｇがＣｏＩＩＩを置換固溶すると、電荷的中性を保つためにｙの値は４より小さくなる。但し、ｘ、ｙ共に、スピネル型結晶構造を維持できる範囲の値をとる。 The spinel crystal structure of cobalt in which Mg is substituted and dissolved is represented by MgxCo3-xOy. Here, x is a number indicating the replacement of Co by Mg, and formally 0 <x <3. In addition, y is a number selected so that the entire expression is neutral in terms of charge, and formally represents a number of 4 or less. That is, in the spinel type oxide Co3O4 of cobalt, divalent and trivalent Co ions exist, and when the divalent and trivalent cobalt ions are represented by CoII and CoIII, respectively, the spinel type crystal structure is obtained. The cobalt oxide is represented by CoIICoIII2O4. Mg displaces both CoII and CoIII sites and forms a solid solution. When Mg substitutes and dissolves CoIII, the value of y becomes smaller than 4 in order to maintain charge neutrality. However, both x and y take values in a range where the spinel crystal structure can be maintained.
触媒として使用できる好ましい範囲として、Ｍｇの固溶範囲は、ｘの値が０．５〜１．５であり、より好ましくは０．７〜１．５である。ｘの値が０．５未満の固溶量では、触媒の活性は低く、生成する微細炭素繊維の量は少ない。ｘの値が１．５を超える範囲では、スピネル型結晶構造を調製することが困難である。 As a preferable range that can be used as a catalyst, the solid solution range of Mg has a value x of 0.5 to 1.5, and more preferably 0.7 to 1.5. When the value of x is less than 0.5, the catalyst activity is low and the amount of fine carbon fibers produced is small. When the value of x exceeds 1.5, it is difficult to prepare a spinel crystal structure.
触媒のスピネル型酸化物結晶構造は、ＸＲＤ測定により確認することが可能であり、結晶格子定数ａ（立方晶系）は、０．８１１〜０．８１８ｎｍの範囲であり、より好ましくは０．８１２〜０．８１８ｎｍである。ａが小さいとＭｇの固溶置換が充分でなく、触媒活性が低い。また、０．８１８ｎｍを超える格子定数を有する前記スピネル型酸化物結晶は調製困難である。 The spinel oxide crystal structure of the catalyst can be confirmed by XRD measurement, and the crystal lattice constant a (cubic system) is in the range of 0.811 to 0.818 nm, more preferably 0.812. ~ 0.818 nm. If “a” is small, the solid solution substitution of Mg is not sufficient, and the catalytic activity is low. Also, the spinel oxide crystal having a lattice constant exceeding 0.818 nm is difficult to prepare.
このような触媒が好適である理由として、コバルトのスピネル構造酸化物にマグネシウムが置換固溶した結果、あたかもマグネシウムのマトリックス中にコバルトが分散配置された結晶構造が形成されることにより、反応条件下においてコバルトの凝集が抑制されていると推定される。 The reason why such a catalyst is suitable is that as a result of substitutional solid solution of magnesium in the cobalt spinel structure oxide, a crystal structure in which cobalt is dispersed in a magnesium matrix is formed. It is presumed that the aggregation of cobalt is suppressed.
また、触媒の粒子サイズは、適宜選ぶことができるが、例えばメジアン径として、０．１〜１００μｍ、好ましくは、０．１〜１０μｍである。 The particle size of the catalyst can be selected as appropriate. For example, the median diameter is 0.1 to 100 μm, preferably 0.1 to 10 μm.
触媒粒子は、一般に基板または触媒床等の適当な支持体に、散布するなどの方法により載せて使用する。基板または触媒床への触媒粒子の散布は、触媒粒子を直接散布して良いが、エタノール等の分散媒に懸濁させて散布し、乾燥させることにより所望の量を散布しても良い。 The catalyst particles are generally used by being applied to a suitable support such as a substrate or a catalyst bed by a method such as spraying. The catalyst particles may be sprayed directly onto the substrate or the catalyst bed, but the catalyst particles may be sprayed directly, but a desired amount may be sprayed by suspending and dispersing in a dispersion medium such as ethanol.
触媒粒子は、原料ガスと反応させる前に、活性化させることも好ましい。活性化は通常、Ｈ２またはＣＯを含むガス雰囲気下で加熱することにより行われる。これらの活性化操作は、必要に応じて、ＨｅやＮ２などの不活性ガスで希釈することにより実施することができる。活性化を実施する温度は、好ましくは４００〜６００℃、より好ましくは４５０〜５５０℃である。 The catalyst particles are preferably activated before reacting with the raw material gas. Activation is usually performed by heating in a gas atmosphere containing H 2 or CO. These activation operations can be performed by diluting with an inert gas such as He or N 2 as necessary. The temperature at which the activation is performed is preferably 400 to 600 ° C, more preferably 450 to 550 ° C.
気相成長法の反応装置に特に制限はなく、固定床反応装置や流動床反応装置といった反応装置により実施することができる。 There is no particular limitation on the reactor for the vapor phase growth method, and the reaction can be performed by a reactor such as a fixed bed reactor or a fluidized bed reactor.
気相成長の炭素源となる原料ガスは、ＣＯ及びＨ２を含む混合ガスが利用される。 A mixed gas containing CO and H2 is used as a source gas that becomes a carbon source for vapor phase growth.
Ｈ２ガスの添加濃度｛Ｈ２／（Ｈ２＋ＣＯ）｝は、好ましくは０．１〜３０ｖｏｌ％、より好ましくは２〜２０ｖｏｌ％である。添加濃度が低すぎると円筒状のグラファイト質網面が繊維軸に平行したカーボンナノチューブ様の構造を形成してしまう。一方、３０ｖｏｌ％を超えると釣鐘状構造体の炭素側周面の繊維軸に対する傾斜角が大きくなり、魚骨形状を呈するため繊維方向の導電性の低下を招く。 The addition concentration of H2 gas {H2 / (H2 + CO)} is preferably 0.1 to 30 vol%, more preferably 2 to 20 vol%. If the addition concentration is too low, a cylindrical graphitic network surface forms a carbon nanotube-like structure parallel to the fiber axis. On the other hand, if it exceeds 30 vol%, the inclination angle of the carbon-side peripheral surface of the bell-shaped structure with respect to the fiber axis becomes large, and the fish-bone shape is exhibited, leading to a decrease in conductivity in the fiber direction.
また、原料ガスは不活性ガスを含有していてもよい。不活性ガスとしては、ＣＯ２、Ｎ２、Ｈｅ、Ａｒ等が挙げられる。不活性ガスの含有量は、反応速度を著しく低下させない程度が好ましく、例えば８０ｖｏｌ％以下、好ましくは５０ｖｏｌ％以下の量である。また、Ｈ２およびＣＯを含有する合成ガスまたは転炉排出ガス等の廃棄ガスを、必要により適宜処理して使用することもできる。 Further, the raw material gas may contain an inert gas. Examples of the inert gas include CO2, N2, He, Ar, and the like. The content of the inert gas is preferably such that the reaction rate is not significantly reduced, for example, 80 vol% or less, preferably 50 vol% or less. Further, waste gas such as synthesis gas or converter exhaust gas containing H2 and CO can be appropriately treated and used as necessary.
気相成長を実施する反応温度は、好ましくは４００〜６５０℃、より好ましくは５００〜６００℃である。反応温度が低すぎると繊維の成長が進行しない。一方、反応温度が高すぎると収量が低下してしまう。反応時間は、特に限定されないが、例えば２時間以上であり、また１２時間程度以下である。 The reaction temperature for carrying out the vapor phase growth is preferably 400 to 650 ° C, more preferably 500 to 600 ° C. If the reaction temperature is too low, fiber growth does not proceed. On the other hand, if the reaction temperature is too high, the yield decreases. Although reaction time is not specifically limited, For example, it is 2 hours or more, and is about 12 hours or less.
気相成長を実施する反応圧力は、反応装置や操作の簡便化の観点から常圧で行うことが好ましいが、Ｂｏｕｄｏｕａｒｄ平衡の炭素析出が進行する範囲であれば、加圧または減圧の条件で実施しても差し支えない。 The reaction pressure for carrying out the vapor phase growth is preferably normal pressure from the viewpoint of simplifying the reaction apparatus and operation, but it is carried out under pressure or reduced pressure as long as Boudard equilibrium carbon deposition proceeds. It doesn't matter.
本発明に用いられる微細炭素繊維の製造方法によれば、触媒単位重量あたりの微細炭素繊維の生成量は、従来の製造方法、例えば非特許文献（Ｃａｒｂｏｎ ２００３（４１）２９４９−２９５９（Ｇａｄｅｌｌｅ Ｐ．ら））記載の方法に比べて格段に大きいことが示された。この微細炭素繊維の製造方法による微細炭素繊維の生成量は、触媒単位重量あたり４０倍以上であり、例えば４０〜２００倍である。その結果、前述のような不純物、灰分の少ない微細炭素繊維の製造が可能である。 According to the method for producing fine carbon fibers used in the present invention, the amount of fine carbon fibers produced per unit weight of the catalyst is determined according to conventional production methods such as Non-Patent Document (Carbon 2003 (41) 2949-2959 (Gadelle P. Et al.) It was shown to be significantly larger than the method described. The amount of fine carbon fiber produced by this fine carbon fiber production method is 40 times or more per unit weight of the catalyst, for example, 40 to 200 times. As a result, it is possible to produce fine carbon fibers with less impurities and ash as described above.
本発明に用いられる微細炭素繊維の製造方法により製造される微細炭素繊維に特有な接合部の形成過程は明らかではないが、発熱的なＢｏｕｄｏｕａｒｄ平衡と原料ガスの流通による除熱とのバランスから、前記触媒から形成されたコバルト微粒子近傍の温度が上下に振幅するため、炭素析出が断続的に進行することにより形成されるものと考えられる。即ち、［１］釣鐘状構造体頭頂部形成、［２］釣鐘状構造体の胴部成長、［３］前記［１］、［２］過程の発熱による温度上昇のため成長停止、［４］流通ガスによる冷却、の４過程が触媒微粒子上で繰り返されることにより、微細炭素繊維構造特有の接合部が形成されると推定される。 Although the formation process of the joint specific to the fine carbon fiber produced by the method for producing fine carbon fiber used in the present invention is not clear, from the balance between exothermic Boudouard equilibrium and heat removal by circulation of the raw material gas, Since the temperature in the vicinity of the cobalt fine particles formed from the catalyst fluctuates up and down, it is considered that carbon deposition is formed by intermittent progress. That is, [1] formation of the top of the bell-shaped structure, [2] growth of the trunk of the bell-shaped structure, [3] growth stop due to temperature rise due to heat generated in the processes [1] and [2], [4] It is presumed that the joint part peculiar to the fine carbon fiber structure is formed by repeating the four processes of cooling by the circulating gas on the catalyst fine particles.
本発明における分散媒は、微細炭素繊維が分散可能な範囲で特に限定されないが、水、及びまたは、水溶性有機溶媒のいずれか一種、若しくは二種以上からなる混合溶媒であることが好ましい。 Although the dispersion medium in this invention is not specifically limited in the range which can disperse | distribute a fine carbon fiber, It is preferable that it is a mixed solvent which consists of any 1 type or 2 types or more of water and / or a water-soluble organic solvent.
水溶性有機溶媒としては、アルコール系（メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、セカンダリーブタノール、ターシャリーブタノール、ベンジルアルコールなど）、多価アルコール系（エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、ブチレングリコール、ヘキサンジオール、ペンタンジオール、グリセリン、ヘキサントリオール、チオジグリコールなど）、多価アルコールエーテル系（エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、プロピレングリコールモノフェニルエーテルなど）、アミン系（エタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−エチルジエタノールアミン、モルホリン、Ｎ−エチルモルホリン、エチレンジアミン、ジエチレンジアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ポリエチレンイミン、ペンタメチルジエチレントリアミン、テトラメチルプロピレンジアミンなど）、アミド系（Ｎ−メチル−２−ピロリドン（ＮＭＰ）、Ｎ−エチル−２−ピロリドン（ＮＥＰ）、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ−メチルカプロラクタムなど）、複素環系（シクロヘキシルピロリドン、２−オキサゾリドン、１，３−ジメチル−２−イミダゾリジノン、γ−ブチロラクトンなど）、スルホキシド系（ジメチルスルホキシドなど）、スルホン系（ヘキサメチルホスホロトリアミド、スルホランなど）、低級ケトン系（アセトン、メチルエチルケトンなど）、その他、テトラヒドロフラン、尿素、アセトニトリルなどを使用することができる。この中でも電池用電極ペーストへの応用の観点から水及びまたはアミド系有機溶媒であることがより好ましく、アミド系溶媒の中でもＮ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドンが特に好ましい。 Water-soluble organic solvents include alcohols (methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, benzyl alcohol, etc.), polyhydric alcohols (ethylene glycol, diethylene glycol, triethylene glycol, polyethylene) Glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene) Glycol monobutyl ether, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, Ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amine-based (ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, Reethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), N, N -Dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methylcaprolactam, etc.), heterocyclic system (cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, γ- Butyrolactone, etc.), sulfoxides (dimethylsulfoxide, etc.), sulfones (hexamethylphosphorotriamide, sulfolane, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), tetrahydrofuran, urea, aceto It can be used, such as tolyl. Among these, water and / or an amide organic solvent are more preferable from the viewpoint of application to battery electrode paste, and N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone are particularly preferable among the amide solvents.
本発明における分散剤は、微細炭素繊維を分散安定化できる範囲で特に限定されず、アニオン性界面活性剤、カチオン性分散剤、両性分散剤、非イオン性分散剤などの公知の分散剤を使用できる。 The dispersant in the present invention is not particularly limited as long as the fine carbon fibers can be dispersed and stabilized, and a known dispersant such as an anionic surfactant, a cationic dispersant, an amphoteric dispersant, and a nonionic dispersant is used. it can.
アニオン性分散剤の例としては、芳香族スルホン酸系界面活性剤（ドデシルベンゼンスルホン酸等のアルキルベンゼンスルホン酸塩、ドデシルフェニルエーテルスルホン酸塩等）、モノソープ系アニオン性界面活性剤、エーテルサルフェート系界面活性剤、フォスフェート系界面活性剤、カルボン酸系界面活性剤などが挙げられる。また、コール酸、オレイン酸などや、アニオン性官能基を有する糖類であるカルボキシメチルセルロースのナトリウム塩及びアンモニウム塩、アルギン酸、コンドロイチン硫酸、ヒアルロン酸なども好適に使用できる。シクロデキストリンなどはアニオン性官能基で修飾することによって使用することが可能である。エステル基を有するポリマー、オリゴマーのエステル部分を加水分解してアニオン性官能基に変換して使用することも可能である。 Examples of anionic dispersants include aromatic sulfonic acid surfactants (alkyl benzene sulfonates such as dodecylbenzene sulfonic acid, dodecyl phenyl ether sulfonate, etc.), monosoap anionic surfactants, ether sulfates Surfactants, phosphate surfactants, carboxylic acid surfactants and the like can be mentioned. In addition, cholic acid, oleic acid, and the like, sodium salts and ammonium salts of carboxymethyl cellulose, which is a saccharide having an anionic functional group, alginic acid, chondroitin sulfate, hyaluronic acid, and the like can also be suitably used. Cyclodextrins and the like can be used by modification with an anionic functional group. It is also possible to use the ester part of a polymer or oligomer having an ester group by hydrolyzing it into an anionic functional group.
カチオン性分散剤の例としては、第４級アルキルアンモニウム塩、アルキルピリジニウム塩、アルキルアミン塩等のカチオン性界面活性剤、ポリエチレンイミン、ポリビニルアミン、ポリアリルアミン、ポリビニルピリジン、ポリアクリルアミド等のカチオン性基を有する化合物が挙げられる。 Examples of cationic dispersants include cationic surfactants such as quaternary alkylammonium salts, alkylpyridinium salts, and alkylamine salts, and cationic groups such as polyethyleneimine, polyvinylamine, polyallylamine, polyvinylpyridine, and polyacrylamide. The compound which has is mentioned.
両性分散剤の例としては、アルキルベタイン系界面活性剤（ラウリルジメチルアミノ酢酸ベタイン、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン、プロピルジメチルアミノ酢酸ベタイン）、スルホベタイン系界面活性剤、アミンオキサイド系界面活性剤などが挙げられる。 Examples of amphoteric dispersants include alkylbetaine surfactants (lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, propyldimethylaminoacetic acid betaine), sulfobetaine-based interfaces An activator, an amine oxide type surfactant, etc. are mentioned.
非イオン性分散剤としては、エーテル系（ポリオキシエチレン、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシアルキレンアルキルエーテル等）およびエステル系（ポリオキシエチレンオレエート、ポリオキシエチレンジステアレート、ソルビタンラウレート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタンセスキオレエート、ポリオキシエチレンモノオレエート、ポリオキシエチレンステアレート等）、ソルビトールおよびグリセリン等の多価アルコール脂肪酸のアルキルエーテルおよびアルキルエステル、アミノアルコール脂肪酸アミド等の界面活性剤が挙げられる。また、セルロース誘導体（セルロースアセテート、セルロースアセテートブチレート、セルロースブチレート、シアノエチルセルロース、エチルヒドロキシエチルセルロース、ニトロセルロース、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロースなど）、ポリビニルアルコール、ポリビニルブチラール、ポリビニルピロリドンなどのポリマー系分散剤も挙げられる。 Nonionic dispersants include ethers (polyoxyethylene, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene oleyl ether, Oxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, etc.) and ester type (polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan Sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc.), sorbitol, glycerin, etc. Alkyl ethers and alkyl esters of polyhydric alcohols fatty acids, surfactants such as amino alcohol fatty acid amide. In addition, cellulose derivatives (cellulose acetate, cellulose acetate butyrate, cellulose butyrate, cyanoethyl cellulose, ethyl hydroxyethyl cellulose, nitrocellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, etc.), polyvinyl alcohol, polyvinyl butyral, Polymeric dispersants such as polyvinyl pyrrolidone are also included.
電池用電極ペーストへの応用の観点からは、イオン成分は電池特性に影響を及ぼす懸念があるため、非イオン性分散剤である事が特に好ましい。また、高濃度で分散安定性の高い均一な分散液を得る場合、ポリマー系分散剤が特に好ましい。ポリマー系分散剤の分子量は、微細炭素繊維を分散安定化できる範囲で特に限定されず、分散剤の種類によっても異なるが、通常重量平均分子量が５０００〜１０００００程度であれば好適に分散できる。高濃度で粘度の低い分散液を得る場合は、重量平均分子量が８０００〜５００００であることが特に好ましい。 From the viewpoint of application to a battery electrode paste, a nonionic dispersant is particularly preferable because the ionic component may affect battery characteristics. Further, when obtaining a uniform dispersion having a high concentration and high dispersion stability, a polymer dispersant is particularly preferable. The molecular weight of the polymer-based dispersant is not particularly limited as long as the fine carbon fibers can be dispersed and stabilized, and varies depending on the type of the dispersant, but can be suitably dispersed if the weight average molecular weight is usually about 5000 to 100,000. When obtaining a dispersion having a high concentration and a low viscosity, the weight average molecular weight is particularly preferably 8000 to 50,000.
本発明において、微細炭素繊維と分散媒と分散剤を分散混合する方法は、特に限定されない。例えば、分散媒に分散剤を溶解した分散剤溶液に、微細炭素繊維を投入し、超音波処理や、攪拌方法といった分散処理を行うことによって分散混合することができる。また、微細炭素繊維と分散剤を混合後、分散媒を加えて希釈し、分散処理をすることもできる。超音波処理としてはバス型やプローブ型のソニケータを用いることができる。攪拌方法としては、ホモミキサー、ホモジナイザーのような高速攪拌やアトライター、ビーズミル、サンドミル、遊星ミル等のメディア型湿式分散装置や、ジェットミル等の攪拌方法を使用することができる。微細炭素繊維を１重量％以下の低濃度に分散させる場合は、特に超音波処理が好適である。超音波処理の処理時間は、微細炭素繊維の添加量、用いる微細カーボン分散剤の種類及び添加量によって適宜決められるが、概ね１０分〜５時間の処理が好ましく、１０分〜３時間の処理がより好ましい。また、微細炭素繊維を１重量％以上の高濃度に分散させる場合は、アトライター、ビーズミル、サンドミル、遊星ミル等のメディア型湿式分散装置による処理が特に好適である。メディア型湿式分散装置による処理時間は処理方法、微細炭素繊維の添加量、微細カーボン分散剤の種類及び添加量によって適宜決められるが、概ね３０分〜５０時間の処理が好ましい。処理時間が短すぎると微細カーボンの分散が不十分となる恐れがある。また処理時間が長すぎると過度のエネルギーにより微細カーボンを傷付ける恐れがある。 In the present invention, the method for dispersing and mixing the fine carbon fibers, the dispersion medium, and the dispersant is not particularly limited. For example, it is possible to disperse and mix by introducing fine carbon fibers into a dispersant solution in which a dispersant is dissolved in a dispersion medium and performing a dispersion treatment such as ultrasonic treatment or a stirring method. Further, after mixing the fine carbon fibers and the dispersant, a dispersion medium can be added and diluted to carry out a dispersion treatment. As the ultrasonic treatment, a bus type or probe type sonicator can be used. As a stirring method, high-speed stirring such as a homomixer or a homogenizer, a media-type wet dispersion apparatus such as an attritor, a bead mill, a sand mill, or a planetary mill, or a stirring method such as a jet mill can be used. When fine carbon fibers are dispersed at a low concentration of 1% by weight or less, ultrasonic treatment is particularly suitable. The treatment time of the ultrasonic treatment is appropriately determined depending on the addition amount of the fine carbon fiber, the type and addition amount of the fine carbon dispersant to be used, and is preferably about 10 minutes to 5 hours, and preferably 10 minutes to 3 hours. More preferred. When fine carbon fibers are dispersed at a high concentration of 1% by weight or more, treatment with a media-type wet dispersion device such as an attritor, a bead mill, a sand mill, or a planetary mill is particularly suitable. The treatment time by the media-type wet dispersion apparatus is appropriately determined depending on the treatment method, the amount of fine carbon fiber added, the type and amount of fine carbon dispersant, and a treatment of about 30 minutes to 50 hours is preferable. If the treatment time is too short, the fine carbon dispersion may be insufficient. If the treatment time is too long, fine carbon may be damaged by excessive energy.
本発明の微細炭素繊維分散液において、微細炭素繊維の配合量は、微細炭素繊維が均一に分散している限り特に限定されるものではないが、一般的に０．１ｗｔ％〜２０ｗｔ％までの範囲で分散性や用途に応じて適宜選択される。本発明の微細炭素繊維分散液は分散性が非常に高い為、２ｗｔ％以上、より好ましくは５ｗｔ％以上の高濃度での分散が可能である。微細炭素繊維の濃度が２０ｗｔ％を超える場合は分散液の粘度が高すぎるため、分散処理が困難となる。 In the fine carbon fiber dispersion of the present invention, the amount of fine carbon fibers is not particularly limited as long as the fine carbon fibers are uniformly dispersed, but generally 0.1 wt% to 20 wt%. It is appropriately selected depending on the dispersibility and application within the range. Since the fine carbon fiber dispersion of the present invention has very high dispersibility, it can be dispersed at a high concentration of 2 wt% or more, more preferably 5 wt% or more. When the concentration of the fine carbon fiber exceeds 20 wt%, the dispersion treatment becomes difficult because the viscosity of the dispersion is too high.
本発明の微細炭素繊維分散液において、分散剤の添加量は、微細炭素繊維の配合量、分散剤の種類、及び用途に応じて適宜定めることができるが、一般には微細炭素繊維の重量に対して１０％以上、分散媒の重量に対して２０％以下であれば、微細炭素繊維を十分に分散させることができる。微細炭素繊維の重量に対して１０％以下であると、微細炭素繊維表面に吸着し、分散剤として働く分散剤の量が不足するために、一部の微細炭素繊維は凝集して多くの沈殿物が生じたり、分散液の粘度が高くなったりする危険性がある。また、分散媒の重量に対して２０％以上であると、分散剤の分散媒中での分子運動が困難になるために、微細炭素繊維表面に十分な量の分散剤が吸着することが困難となり、分散剤溶液の粘度が高すぎて機械的分散が困難となる。導電性を付与する為の分散液として塗膜、導電助剤、他のポリマーに添加する場合は分散性を保つ範囲で分散剤の添加量を少なくする事が好ましい。 In the fine carbon fiber dispersion of the present invention, the addition amount of the dispersant can be appropriately determined according to the blending amount of the fine carbon fiber, the kind of the dispersant, and the use, but in general, with respect to the weight of the fine carbon fiber. If it is 10% or more and 20% or less with respect to the weight of the dispersion medium, fine carbon fibers can be sufficiently dispersed. When the amount is 10% or less with respect to the weight of the fine carbon fiber, the amount of the dispersant adsorbed on the fine carbon fiber surface and acting as a dispersant is insufficient, so that some of the fine carbon fibers are aggregated and a lot of precipitates are formed. There is a risk that a product is formed or the viscosity of the dispersion is increased. Further, if it is 20% or more with respect to the weight of the dispersion medium, it becomes difficult for a sufficient amount of the dispersant to be adsorbed on the surface of the fine carbon fiber because the molecular motion of the dispersant in the dispersion medium becomes difficult. Thus, the viscosity of the dispersant solution is too high, making mechanical dispersion difficult. When added to a coating film, a conductive assistant or other polymer as a dispersion for imparting conductivity, it is preferable to reduce the amount of the dispersant added within a range that maintains dispersibility.
本発明の微細炭素繊維分散液の粘度は特に限定されるものではないが、分散性を保つ範囲でなるべく低い方が応用の観点から好ましく、後述する測定方法での回転粘度が５０〜５００ｍＰａ・ｓであることが特に好ましい。分散液の粘度が高すぎる場合、塗膜にする際の塗布や、他の樹脂との混合が困難になる場合がある。また、電池用電極ペーストを得る為に他の樹脂や活物質へ混合する際に分散が不十分になる可能性や、電池用電極ペーストの粘度が高く、成形時に悪影響を及ぼす懸念がある。 The viscosity of the fine carbon fiber dispersion of the present invention is not particularly limited, but it is preferably as low as possible within the range of maintaining dispersibility, and the rotational viscosity in the measurement method described later is 50 to 500 mPa · s. It is particularly preferred that If the viscosity of the dispersion is too high, it may be difficult to apply the coating film or mix with another resin. In addition, there is a possibility that dispersion may be insufficient when mixed with another resin or active material in order to obtain a battery electrode paste, and there is a concern that the battery electrode paste has a high viscosity and adversely affects molding.
本発明の微細炭素繊維分散液中の分散された微細炭素繊維のサイズは特に限定されるものではないが、微細炭素繊維一本一本が凝集する事なく孤立分散している事が好ましく、
後述する測定方法でのメジアン径が０．１〜３μｍである事が好ましく、０．１〜２μｍであることが特に好ましい。メジアン径が３μｍ以下であると塗布した際に光沢を示しやすく、分散性良好な塗膜が得られる。メジアン径が大きすぎる場合は微細炭素繊維の凝集が多く、孤立分散出来ていない為、高い光沢を示す塗膜は得られない。
The size of the fine carbon fiber dispersed in the fine carbon fiber dispersion liquid of the present invention is not particularly limited, but it is preferable that each fine carbon fiber is isolated and dispersed without agglomeration,
The median diameter in the measurement method described later is preferably 0.1 to 3 μm, and particularly preferably 0.1 to 2 μm. When the median diameter is 3 μm or less, it is easy to show gloss when applied, and a coating film with good dispersibility can be obtained. When the median diameter is too large, the fine carbon fibers are agglomerated and cannot be isolated and dispersed, so that a coating film showing high gloss cannot be obtained.
本発明の微細炭素繊維分散液は、電池の電極への導電性を付与するための導電助剤として好適に利用する事ができる。導電助剤として利用する際は、微細炭素繊維分散液、活物質、バインダを直接混合して電極ペーストを作成しても良いし、微細炭素繊維分散液と活物質を配合後、常圧または減圧下で乾燥・熱処理させることにより、前記活物質が微細炭素繊維によって被覆された微細炭素繊維被覆活物質を作成し、バインダ樹脂及び分散媒と混合して電極ペーストを作成しても良い。微細炭素繊維被覆活物質を作成する場合、電気特性の向上を図る為に分散剤を焼失させることが好ましく、これによって活物質が微細炭素繊維に被覆された微細炭素繊維被覆活物質が得られる。 The fine carbon fiber dispersion liquid of the present invention can be suitably used as a conductive aid for imparting conductivity to the battery electrode. When used as a conductive aid, an electrode paste may be prepared by directly mixing a fine carbon fiber dispersion, an active material, and a binder, or after mixing the fine carbon fiber dispersion and the active material, normal pressure or reduced pressure A fine carbon fiber-covered active material in which the active material is coated with fine carbon fibers is prepared by drying and heat-treating the mixture, and an electrode paste may be prepared by mixing with a binder resin and a dispersion medium. When producing a fine carbon fiber-covered active material, it is preferable to burn off the dispersant in order to improve the electrical characteristics, thereby obtaining a fine carbon fiber-covered active material in which the active material is coated with fine carbon fibers.
本発明の電極ペーストに用いる事が出来る電極活物質は特に限定されるものではないが、好ましくは１０℃〜６０℃の温度範囲で混合することにより、電極ペーストを好適に調製することができる。電極活物質は公知のものを好適に用いることができるが、リチウム含有金属複合酸化物、炭素粉末、ケイ素粉末、スズ粉末、またはケイ素若しくはスズを含む合金粉末が好ましい。電極ペースト中への微細炭素繊維分散液の配合量は、特に限定されないが、通常、電極活物質の固形分に対して微細炭素繊維の固形分で、０．３〜１０ｗｔ％添加する事が好ましい。微細炭素繊維が少なすぎると、集電体に形成された活物質同士の導電性が発現できず、不活性な部分が多くなり、電極としての機能が不十分になることがある。また、微細炭素繊維の量が多すぎると、相対的に活物質量が減る為、結果として電池の容量が低下する。 Although the electrode active material which can be used for the electrode paste of this invention is not specifically limited, Preferably an electrode paste can be suitably prepared by mixing in the temperature range of 10 to 60 degreeC. Known electrode active materials can be preferably used, but lithium-containing metal composite oxides, carbon powders, silicon powders, tin powders, or alloy powders containing silicon or tin are preferable. The blending amount of the fine carbon fiber dispersion in the electrode paste is not particularly limited, but it is usually preferable to add 0.3 to 10 wt% of the solid carbon fiber content relative to the solid content of the electrode active material. . When there are too few fine carbon fibers, the electroconductivity of the active materials formed in the electrical power collector cannot be expressed, an inactive part increases, and the function as an electrode may become inadequate. On the other hand, if the amount of fine carbon fibers is too large, the amount of active material is relatively reduced, resulting in a decrease in battery capacity.
本発明の電極ペーストに用いる事ができるバインダは特に限定されるものではないが、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリヘキサフルオロプロピレン、ポリエチレン、ポリプロピレン、ポリメタクリル酸メチル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ酢酸ビニル、ポリアクリル酸、ポリビニルブチラール、ポリアクリルアミド、ポリウレタン、ポリジメチルシロキサン、エポキシ樹脂、アクリル樹脂、ポリエステル樹脂、メラミン樹脂、フェノール樹脂、スチレンブタジエンゴムなどの各種ゴム、リグニン、ペクチン、ゼラチン、キサンタンガム、ウェランガム、サクシノグリカン、ポリビニルアルコール、ポリビニルアセタール、セルロース系樹脂、ポリアルキレンオキサイド、ポリビニルエーテル、ポリビニルピロリドン、キチン類、キトサン類、デンプンなどが挙げられる。これらバインダは、単独使用または２種以上併用することもできる。 The binder that can be used for the electrode paste of the present invention is not particularly limited. For example, polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene, polypropylene, polymethyl methacrylate, polyvinyl chloride, Various types of rubber such as polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, polyvinyl butyral, polyacrylamide, polyurethane, polydimethylsiloxane, epoxy resin, acrylic resin, polyester resin, melamine resin, phenol resin, styrene butadiene rubber, lignin, pectin , Gelatin, xanthan gum, welan gum, succinoglycan, polyvinyl alcohol, polyvinyl acetal, cellulose resin, polyalkylene oxide, polyvinyl ether Polyvinylpyrrolidone, chitins, chitosans, starch and the like. These binders can be used alone or in combination of two or more.
バインダの配合量は特に限定されないが、通常、電極活物質の固形分に対して０．３ｗｔ％〜２５ｗｔ％、より好ましくは１ｗｔ％〜１０ｗｔ％以下である。バインダが少なすぎると塗工特性が不十分であったり、電極組成物の結着が弱く、集電体から剥がれてしまったりする場合があり、バインダが多すぎると電池特性が低下する場合がある。なお、電極ペースト中には、必要に応じて界面活性剤や粘度調整剤などの添加剤を加えることができる。 Although the compounding quantity of a binder is not specifically limited, Usually, 0.3 wt%-25 wt% with respect to solid content of an electrode active material, More preferably, it is 1 wt%-10 wt% or less. If the binder is too small, the coating characteristics may be insufficient, the electrode composition may be weakly bonded, and may be peeled off from the current collector. If the binder is excessive, the battery characteristics may be deteriorated. . In the electrode paste, additives such as a surfactant and a viscosity modifier can be added as necessary.
本発明の電極ペーストは、各成分を配合後、ビーズミルやボールミルなどの公知の分散混合装置によって混合させることで得られる。混合させる方法は特に限定されないが、アトライター、ビーズミル、サンドミル、遊星ミル等のメディア型湿式分散混合装置による処理や、プラネタリーミキサー、トリミックス（登録商標）、フィルミックス（登録商標）等のメディアレス分散混合装置を好適に用いる事が出来る。 The electrode paste of the present invention can be obtained by mixing each component with a known dispersion mixing device such as a bead mill or a ball mill. The mixing method is not particularly limited, but media such as attritors, bead mills, sand mills, planetary mills, and other media-type wet dispersion mixers, planetary mixers, Trimix (registered trademark) , and media such as Philmix (registered trademark) A less dispersion mixing apparatus can be suitably used.
本発明の電極ペーストは、アルミ箔や銅箔などの公知の集電体に塗布し、乾燥、圧密化させることでリチウムイオン電池用電極として好適に利用できる。塗布及び乾燥方法は特に限定されず、公知の方法を用いる事ができる。本発明のリチウムイオン電池用電極は、均一に分散した微細炭素繊維が活物質を均一に覆っている為、少量でも高い導電性の付与が期待できる。またそれぞれの活物質間を微細炭素繊維が繋いでいる為に活物質の高い利用効率が期待でき、充放電時の活物質の膨潤・収縮によっても活物質の孤立が起りにくい為にレート特性やサイクル特性の向上が期待される。 The electrode paste of the present invention can be suitably used as an electrode for a lithium ion battery by applying it to a known current collector such as an aluminum foil or a copper foil, followed by drying and consolidation. A coating and drying method is not particularly limited, and a known method can be used. The lithium ion battery electrode of the present invention can be expected to be imparted with high conductivity even in a small amount since the finely dispersed carbon fibers uniformly cover the active material. In addition, since the fine carbon fibers are connected between each active material, high utilization efficiency of the active material can be expected, and the isolation of the active material is less likely to occur due to the swelling / shrinking of the active material during charging / discharging. Improvement in cycle characteristics is expected.
以下、実施例により本発明をさらに詳細に説明する。なお、本発明はこれらの実施例に限定されるものではない。
実施例、および各比較例で用いた微細炭素繊維（多層カーボンナノチューブ）について、蛍光Ｘ線（ＸＲＦ）分析（Spectris PANalytical社製蛍光Ｘ線分析装置：型式PW2400 を用いて測定）による微量元素含有量およびＤＢＰ吸油量を表１に示す。表１における「−」は非検出を示す。微量元素の相違は微細炭素繊維の製造時に用いられる触媒の違いに基づくと推測される。なお、実施例１〜３および比較例７における微細炭素繊維は、宇部興産株式会社製ＡＭＣ（登録商標）を用いた。その他の微細炭素繊維は、市販のものを用いた。
Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.
Trace element content by X-ray fluorescence (XRF) analysis (measured using Spectris PANalytical X-ray fluorescence analyzer: model PW2400 ) for fine carbon fibers (multi-walled carbon nanotubes) used in Examples and Comparative Examples Table 1 shows the DBP oil absorption. “-” In Table 1 indicates non-detection. The difference in trace elements is presumed to be based on the difference in the catalyst used during the production of fine carbon fibers. The fine carbon fibers in Examples 1 to 3 and Comparative Example 7 were AMC (registered trademark) manufactured by Ube Industries, Ltd. Other fine carbon fibers were commercially available.
〔ＤＢＰ吸油量の測定〕
未分散の各微細炭素繊維のＤＢＰ吸油量を測定した。測定はＪＩＳ Ｋ ６２１７−４ ゴム用カーボンブラック−基本特性−第４部：オイル吸油量の求め方 を参考に、ブラベンダー社製 アブソープトメーターＣ型を用いて、回転翼１２５ｒｐｍ、ＤＢＰ滴下速度４．０ｍｌ／ｍｉｎ．の条件で実施し、ＤＢＰ吸油量の値は最大トルクの７０％値を指標とした。なお、試料重量は各微細炭素繊維でかさ密度が大きく異なっていたため、実施例１の微細炭素繊維５ｇの容積を標準に、混合室を十分に満たす重量で測定を行った。
[Measurement of DBP oil absorption]
The DBP oil absorption of each undispersed fine carbon fiber was measured. Measured using JIS K 6217-4 Carbon Black for Rubber-Basic Characteristics-Part 4: Determination of Oil Absorption, Using Brabender Absorbometer C Type, Rotor Blade 125rpm, DBP Drip Rate 4.0 ml / min. The DBP oil absorption value was set at 70% of the maximum torque as an index. In addition, since the bulk density differed greatly with each fine carbon fiber, the sample weight was measured by the weight which fully filled the mixing chamber with the volume of the fine carbon fiber 5g of Example 1 as a standard.
〔分散液中の微細炭素繊維の粒径測定〕
得られた微細炭素繊維分散液の微細炭素繊維の粒径をレーザー回折法により測定した。測定は堀場製作所製ＬＡ−９５０Ｖ２を用いて、体積基準５０％径（メジアン径（Ｄ５０））及び体積基準９０％径（Ｄ９０）を評価の指標とした。
[Measurement of particle size of fine carbon fiber in dispersion]
The particle size of the fine carbon fibers of the obtained fine carbon fiber dispersion was measured by a laser diffraction method. Measurement was carried out using LA-950V2 manufactured by HORIBA, Ltd., with a volume-based 50% diameter (median diameter (D50)) and a volume-based 90% diameter (D90) as evaluation indices.
〔微細炭素繊維分散液の粘度測定〕
得られた微細炭素繊維分散液の回転粘度を測定した。測定はＴＯＫＩＭＥＣ社製の回転粘度計でコーン角１．３４°、半径２４ｍｍのコーンプレートを用いて、１０ｒｐｍ（ずり速度４４．８ｓ−１）での測定値を粘度の指標とした。
[Measurement of viscosity of fine carbon fiber dispersion]
The rotational viscosity of the obtained fine carbon fiber dispersion was measured. The measurement was carried out using a rotational viscometer manufactured by TOKIMEC, using a cone plate with a cone angle of 1.34 ° and a radius of 24 mm, and the measured value at 10 rpm (shear speed 44.8 s −1 ) was used as an index of viscosity.
以下、実施例１〜３および比較例１〜８の微細炭素繊維を用いて得られた分散液の粒径および粘度等を表２に示す。 Hereinafter, Table 2 shows particle diameters, viscosities, and the like of dispersions obtained using the fine carbon fibers of Examples 1 to 3 and Comparative Examples 1 to 8.
〔実施例１〕
分散剤としてポリビニルピロリドン（ＰＶＰ）Ｌｕｖｉｔｅｃ（登録商標）Ｋ３０を１．２５ｗｔ％溶解したＮ−メチル−２−ピロリドン（ＮＭＰ）溶液２９．２５ｇと、実施例１の微細炭素繊維０．７５ｇとを１ｍｍのジルコニア（ＺｒＯ２）ビーズ５０ｇと共に遊星ミル（フリッチュ社製Ｐ−５）のジルコニア容器に投入し、室温、ポット回転数３５０ｒｐｍで８時間分散処理し、２．５ｗｔ％の微細炭素繊維分散液を得た。実施例１の微細炭素繊維を用いた分散液は、粒径も小さく分散性が良好で、粘度の低い分散液が得られることがわかった。
[Example 1]
1 mm of 29.25 g of an N-methyl-2-pyrrolidone (NMP) solution in which 1.25 wt% of polyvinylpyrrolidone (PVP) Luvitec (registered trademark) K30 was dissolved as a dispersant and 0.75 g of the fine carbon fiber of Example 1 Together with 50 g of zirconia (ZrO 2) beads in a planetary mill (Fritsch P-5) zirconia container and dispersed for 8 hours at room temperature at a pot rotation speed of 350 rpm to obtain a 2.5 wt% fine carbon fiber dispersion. It was. It was found that the dispersion using the fine carbon fiber of Example 1 has a small particle size, good dispersibility, and a low viscosity dispersion.
〔比較例１〜６〕
実施例１の微細炭素繊維に代えて比較例１〜６それぞれの微細炭素繊維を用いた以外は実施例１と同様の操作を行い微細炭素繊維分散液を得た。ＤＢＰ吸油量の大きい比較例１〜６の微細炭素繊維を用いた微細炭素繊維分散液は、粒径も大きく分散性は不良であり、分散液の粘度も高いことが示された。
[Comparative Examples 1-6]
A fine carbon fiber dispersion was obtained in the same manner as in Example 1 except that the fine carbon fibers of Comparative Examples 1 to 6 were used instead of the fine carbon fibers of Example 1. It was shown that the fine carbon fiber dispersion using the fine carbon fibers of Comparative Examples 1 to 6 having a large DBP oil absorption amount has a large particle size and poor dispersibility, and the dispersion has a high viscosity.
〔比較例７〕
分散剤を用いない以外は、実施例１と同様の操作を行い微細炭素繊維分散液を得た。分散剤を添加せずに分散媒中で微細炭素繊維を分散処理した微細炭素繊維分散液は、粒径も大きく分散性は不良であり、分散液の粘度も高いことが示された。
[Comparative Example 7]
Except not using a dispersing agent, operation similar to Example 1 was performed and the fine carbon fiber dispersion liquid was obtained. It was shown that a fine carbon fiber dispersion obtained by dispersing fine carbon fibers in a dispersion medium without adding a dispersant has a large particle size, poor dispersibility, and a high viscosity of the dispersion.
〔実施例２〕
分散剤としてポリビニルピロリドン（ＰＶＰ）Ｋｏｌｌｉｄｏｎ（登録商標）２５ を２．５ｗｔ％溶解したＮＭＰ溶液４７５ｇと、実施例１の微細炭素繊維２５ｇとを混合し、浅田鉄工株式会社製ビーズミルＰＣＭ−Ｌを用いて２時間分散処理し、５ｗｔ％の微細炭素繊維分散液を得た。メディアは０．３ｍｍのジルコニア（ＺｒＯ２）ビーズを用い、周速１０ｍ／ｓで分散処理を行った。ＤＢＰ吸油量の低い実施例１の微細炭素繊維を用いた分散液は、粒径も小さく分散性が良好で、粘度の低い分散液が得られることがわかった。また、得られた微細炭素繊維分散液をバーコーターでＰＥＴフィルム上に塗布して８０℃で１時間乾燥させたところ、塗膜は光沢を示しており、微細炭素繊維の高い分散性が示された。
[Example 2]
As a dispersant, 475 g of an NMP solution in which 2.5 wt% of polyvinylpyrrolidone (PVP) Kollidon (registered trademark) 25 is dissolved and 25 g of fine carbon fiber of Example 1 are mixed, and a bead mill PCM-L manufactured by Asada Tekko Co., Ltd. is used. For 2 hours to obtain a 5 wt% fine carbon fiber dispersion. The media were 0.3 mm zirconia (ZrO2) beads and subjected to dispersion treatment at a peripheral speed of 10 m / s. It was found that the dispersion using the fine carbon fiber of Example 1 having a low DBP oil absorption has a small particle size, good dispersibility, and a low viscosity dispersion. Moreover, when the obtained fine carbon fiber dispersion was applied onto a PET film with a bar coater and dried at 80 ° C. for 1 hour, the coating film showed gloss and high dispersibility of the fine carbon fibers was shown. It was.
〔実施例３〕
分散剤としてポリビニルピロリドン（ＰＶＰ）Ｋｏｌｌｉｄｏｎ（登録商標）２５を１．２５ｗｔ％溶解したイオン交換水溶液４７５ｇと、実施例１の微細炭素繊維２５ｇとを混合し、浅田鉄工株式会社製循環型ビーズミルＰＣＭ−Ｌを用いて２時間分散処理し、５ｗｔ％の微細炭素繊維分散液を得た。メディアは０．３ｍｍのジルコニア（ＺｒＯ２）ビーズを用い、周速１０ｍ／ｓで分散処理を行った。得られた分散液の粒径、粘度を表１に示す。溶媒として水を用いた場合もＤＢＰ吸油量の低い実施例１の微細炭素繊維を用いた分散液は、粒径も小さく分散性が良好で、粘度の低い分散液が得られることがわかった。また、得られた微細炭素繊維分散液をバーコーターでＰＥＴフィルム上に塗布して８０℃で１時間乾燥させたところ、塗膜は光沢を示しており、微細炭素繊維の高い分散性が示された。
Example 3
As a dispersant, 475 g of an ion exchange aqueous solution in which 1.25 wt% of polyvinylpyrrolidone (PVP) Kollidon (registered trademark) 25 is dissolved and 25 g of fine carbon fiber of Example 1 are mixed, and a circulating bead mill PCM- manufactured by Asada Iron Works Co., Ltd. Dispersion treatment was performed using L for 2 hours to obtain a 5 wt% fine carbon fiber dispersion. The media were 0.3 mm zirconia (ZrO2) beads and subjected to dispersion treatment at a peripheral speed of 10 m / s. Table 1 shows the particle diameter and viscosity of the obtained dispersion. Even when water was used as the solvent, it was found that the dispersion using the fine carbon fiber of Example 1 having a low DBP oil absorption has a small particle size, good dispersibility, and a low viscosity dispersion. Moreover, when the obtained fine carbon fiber dispersion was applied onto a PET film with a bar coater and dried at 80 ° C. for 1 hour, the coating film showed gloss and high dispersibility of the fine carbon fibers was shown. It was.
〔比較例８、９〕
実施例２の微細炭素繊維に代えて比較例８，９それぞれの微細炭素繊維を用いた以外は実施例２と同様の操作を行った。しかし、分散処理中に粘度が急上昇してチキソ性のゲル状になり、送液不良が起こって分散処理を継続する事が出来なかった。そのため、体積基準５０％径（メジアン径（Ｄ５０））及び体積基準９０％径（Ｄ９０）の測定は行っていない。回収したゲル状物をバーコーターでＰＥＴフィルム上に塗布して８０℃で１時間乾燥させたところ、塗膜はザラザラで光沢を示さず、分散性が不良である事が示された。ＤＢＰ吸油量の大きい微細炭素繊維を用いて分散液を得る場合、高濃度では分散処理時の粘度上昇が非常に大きく、循環型ビーズミルで処理する事が困難である事が示された。
[Comparative Examples 8 and 9]
The same operation as in Example 2 was performed except that the fine carbon fibers of Comparative Examples 8 and 9 were used in place of the fine carbon fiber of Example 2. However, the viscosity rapidly increased during the dispersion treatment to form a thixotropic gel, and liquid feeding failure occurred and the dispersion treatment could not be continued. Therefore, the measurement of the volume-based 50% diameter (median diameter (D50)) and the volume-based 90% diameter (D90) is not performed. When the collected gel-like material was applied onto a PET film with a bar coater and dried at 80 ° C. for 1 hour, the coating film was not lustrous and glossy, indicating that the dispersibility was poor. In the case of obtaining a dispersion using fine carbon fibers having a large DBP oil absorption amount, it was shown that at a high concentration, the viscosity increase during the dispersion treatment is very large and it is difficult to treat with a circulation type bead mill.
〔実施例４〕
セルシード（登録商標）Ｃ−５Ｈ（コバルト酸リチウム、日本化学工業社製、平均粒径５μｍ）４．６５ｇ（固形分９３ｗｔ％）と、実施例３で得られた微細炭素繊維分散液２ｇ（固形分２ｗｔ％）と、ポリフッ化ビニリデンの１２ｗｔ％ＮＭＰ溶液を２．０８ｇ（固形分５ｗｔ％）を１０ｍｍのビーズ４個と共に遊星ミル（フリッチュ社製Ｐ−５）のジルコニア容器に投入し、室温、ポット回転数３５０ｒｐｍで１０分間混合し、リチウムイオン電池正極用電極ペーストを得た。得られた電極ペーストをアルミ箔上に塗布し、常圧、１２０℃で３０分間乾燥後、減圧下、１２０℃で２時間乾燥した。得られた塗膜を室温下、油圧プレス機を用いて５ＭＰａで５分間圧密化処理し、リチウムイオン電池用電極（正極）を得た。得られた電極の走査型電子顕微鏡（ＳＥＭ）像を図３に示す。本発明で得られた微細炭素繊維分散液を用いて作成した電極は、微細炭素繊維が活物質を均一に覆って活物質同士をつないでおり、電極全体にわたって高い導電性が示唆される。このことから、充放電時も活物質同士が孤立する事無く、活物質間の導電性の担保により容量低下の抑制効果が期待される。
Example 4
Cell seed (registered trademark) C-5H (lithium cobaltate, manufactured by Nippon Chemical Industry Co., Ltd., average particle size 5 μm) 4.65 g (solid content 93 wt%) and 2 g of fine carbon fiber dispersion obtained in Example 3 (solid 2 wt%) and 12 wt% NMP solution of polyvinylidene fluoride (2.08 g, solid content 5 wt%) together with four 10 mm beads into a zirconia container of a planetary mill (Fritsch P-5), The mixture was mixed at a pot rotation speed of 350 rpm for 10 minutes to obtain an electrode paste for a lithium ion battery positive electrode. The obtained electrode paste was applied onto an aluminum foil, dried at normal pressure and 120 ° C. for 30 minutes, and then dried under reduced pressure at 120 ° C. for 2 hours. The obtained coating film was consolidated at 5 MPa for 5 minutes at room temperature using a hydraulic press machine to obtain an electrode (positive electrode) for a lithium ion battery. A scanning electron microscope (SEM) image of the obtained electrode is shown in FIG. In the electrode prepared using the fine carbon fiber dispersion obtained in the present invention, the fine carbon fiber uniformly covers the active material and connects the active materials, suggesting high conductivity over the entire electrode. For this reason, the active material is not isolated even during charging and discharging, and the effect of suppressing the decrease in capacity is expected by ensuring the conductivity between the active materials.
本発明の微細炭素繊維分散液は、高濃度かつ均一に微細炭素繊維が分散した分散液である。本発明の微細炭素繊維分散液は、高濃度添加が求められる分野や均一な分散性が求められる分野に好適に利用できる。また、分散液の高濃度化によって微細炭素繊維の固形分を多くする事が出来る為、溶媒のコストや分散液の輸送コストを低減することができる。さらに、本発明の微細炭素繊維分散液を導電助剤として用いることで、微細炭素繊維が均一に分散した電池用電極ペースト及び微細炭素によって均一に被覆された活物質を得ることできる。本発明で得られる電極ペーストや微細炭素被覆活物質は、導電性良好な微細炭素繊維が均一に分散・被覆しており、高い導電性付与性能や、充放電サイクル時の活物質の孤立化による容量低下の抑制効果が期待されるため、各種電池の電極等に好適に用いることができる。本発明の微細炭素繊維分散液は、他の樹脂または金属と混練し、微細炭素繊維と樹脂または金属との複合体としても用いる事が可能である。本発明の微細炭素繊維分散液は、リチウムイオン電池、燃料電池、キャパシタ等の電極用途の他、水素吸蔵材料、ＬＳＩ配線、太陽電池、透明導電膜、帯電防止コーティング、機械的強度向上用途、熱伝導性向上用途等にも好適に利用できる。 The fine carbon fiber dispersion of the present invention is a dispersion in which fine carbon fibers are uniformly dispersed at a high concentration. The fine carbon fiber dispersion liquid of the present invention can be suitably used in fields requiring high concentration addition and fields requiring uniform dispersibility. Further, since the solid content of the fine carbon fiber can be increased by increasing the concentration of the dispersion liquid, the cost of the solvent and the transportation cost of the dispersion liquid can be reduced. Furthermore, by using the fine carbon fiber dispersion of the present invention as a conductive additive, a battery electrode paste in which fine carbon fibers are uniformly dispersed and an active material uniformly coated with fine carbon can be obtained. The electrode paste and fine carbon-coated active material obtained in the present invention are uniformly dispersed and coated with fine carbon fibers with good conductivity, and due to high conductivity imparting performance and isolation of the active material during charge / discharge cycles Since the effect of suppressing the decrease in capacity is expected, it can be suitably used for various battery electrodes and the like. The fine carbon fiber dispersion of the present invention can be used as a composite of fine carbon fiber and resin or metal by kneading with other resin or metal. The fine carbon fiber dispersion of the present invention is used for electrodes such as lithium ion batteries, fuel cells and capacitors, as well as hydrogen storage materials, LSI wiring, solar cells, transparent conductive films, antistatic coatings, applications for improving mechanical strength, heat It can also be suitably used for conductivity enhancement applications.
Claims (5)
前記微細炭素繊維が、炭素原子のみから構成されるグラファイト網面が、閉じた頭頂部と下部が開いた胴部とを有する釣鐘状構造単位を形成し、前記胴部の母線と繊維軸とのなす角θが１５°より小さく、前記釣鐘状構造単位が、中心軸を共有して２〜３０個積み重なって集合体を形成し、前記集合体が、Ｈｅａｄ−ｔｏ−Ｔａｉｌ様式で間隔をもって連結して繊維を形成し、
前記微細炭素繊維を０．１〜２０ｗｔ％含み、かつ回転粘度が５０〜５００ｍＰａ・ｓであって、
前記分散剤はポリビニルピロリドンであること
を特徴とする微細炭素分散液。 A fine carbon fiber dispersion comprising a fine carbon fiber having an average diameter of 5 to 20 nm and a DBP oil absorption of 250 to 360 ml / 100 g, a dispersion medium, and a dispersant,
The fine carbon fiber has a graphite net surface composed of only carbon atoms to form a bell-shaped structural unit having a closed top and a trunk that is open at the bottom, and the busbar of the trunk and the fiber axis. The angle θ formed is smaller than 15 °, the bell-shaped structural units are stacked by sharing 2 to 30 pieces sharing the central axis, and the aggregates are connected in a head-to-tail manner at intervals. Forming fibers,
Containing 0.1 to 20 wt% of the fine carbon fiber and having a rotational viscosity of 50 to 500 mPa · s ,
The fine carbon dispersion liquid, wherein the dispersant is polyvinylpyrrolidone .
を特徴とする請求項１または２に記載の微細炭素繊維分散液。 The fine carbon fiber dispersion liquid according to claim 1 or 2.
前記微細炭素繊維が、炭素原子のみから構成されるグラファイト網面が、閉じた頭頂部と下部が開いた胴部とを有する釣鐘状構造単位を形成し、前記胴部の母線と繊維軸とのなす角θが１５°より小さく、前記釣鐘状構造単位が、中心軸を共有して２〜３０個積み重なって集合体を形成し、前記集合体が、Ｈｅａｄ−ｔｏ−Ｔａｉｌ様式で間隔をもって連結して繊維を形成し、 The fine carbon fiber has a graphite net surface composed of only carbon atoms to form a bell-shaped structural unit having a closed top and a trunk that is open at the bottom, and the busbar of the trunk and the fiber axis. The angle θ formed is smaller than 15 °, the bell-shaped structural units are stacked by sharing 2 to 30 pieces sharing the central axis, and the aggregates are connected in a head-to-tail manner at intervals. Forming fibers,
前記微細炭素繊維を０．１〜２０ｗｔ％含み、かつ回転粘度が５０〜５００ｍＰａ・ｓであって、 Containing 0.1 to 20 wt% of the fine carbon fiber and having a rotational viscosity of 50 to 500 mPa · s,
前記分散剤はポリビニルピロリドンであること The dispersant is polyvinylpyrrolidone
を特徴とする微細炭素繊維分散液の製造方法。 A method for producing a fine carbon fiber dispersion characterized by the above.
を特徴とする電極ペースト。 An electrode paste characterized by.
を特徴とするリチウムイオン電池用電極。 An electrode for a lithium ion battery.
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