CN103201026A

CN103201026A - Carbon microfiber dispersion liquid

Info

Publication number: CN103201026A
Application number: CN2011800440059A
Authority: CN
Inventors: 樽本直浩; 塚田高行
Original assignee: Hodogaya Chemical Co Ltd
Current assignee: Hodogaya Chemical Co Ltd
Priority date: 2010-09-13
Filing date: 2011-09-13
Publication date: 2013-07-10
Also published as: JPWO2012036172A1; KR20130099030A; WO2012036172A1

Abstract

Carbon microfibers having an extremely high cohesive force and forming aggregates are uniformly dispersed and defibrated in an organic solvent, resulting in the disclosed stable dispersion state carbon microfiber dispersion liquid. The carbon microfiber dispersion liquid in which carbon microfibers are dispersed in an organic solvent contains a polymer dispersant represented by formula (1), and the size of aggregates of the carbon microfibers contained in said dispersion liquid is 5[mu]m or less.

Description

The fine carbon fiber dispersion liquid

Technical field

The present invention relates to a kind of fine carbon fiber dispersion liquid, it can make fine carbon fiber disperse, separate fibre well in organic solvent, and should disperse, separate fibre and keep in stable conditionly.

Background technology

The fine carbon fiber of having confirmed its existence before about 20 years is the tubular material below the diameter 1 μ m, in desirable fine carbon fiber, parallel with respect to tubular axis by the formed pipe of sheet material (carbon plate material) that 6 yuan of looped network shape structures of carbon atom constitute, and then, the fine carbon fiber that also exists this pipe to be formed by the carbon plate material of bilayer or multilayer.

This fine carbon fiber has various character according to 6 yuan of cancellated numbers of ring that are made of carbon atom, the thickness difference of pipe, utilizes its character, can expect various application.For example, utilize rerum naturas such as chemical characteristic, electrical characteristics, mechanical property, thermal conduction characteristic, architectural characteristic, can expect the application of fine carbon fiber in anti-static part, secondary battery electrode material, fortified resin composite, electric wave absorbing materials, electric heating coversion material, flat-panel monitor Field Emission Cathode Materials, nesa coating, thermoelectric conversion element material, capacitance electrode, hydrogen storage material, electric wiring, heat sink material, solar cell material and catalyst cupport material.

As the anti-static part of having used fine carbon fiber, the known pallet that in thermoplastic resin or thermosetting resin, has added fine carbon fiber, carrier band etc.They are for preventing at the static of carrying, producing when carrying semiconductor device, goods.That is, fine carbon fiber is compared with employed spherical carbon material as carbon black in the past, shows higher electric conductivity, and be shaped as fibrous, therefore add just can prevent the generation of static on a small quantity, and have from the few advantage of coming off of matrix resin, be widely used in the antistatic purposes.

In the field of secondary battery electrode material, propose to use fine carbon fiber as the additive of electrode film.

For example, confirmed by in the graphite as negative electrode active material, mixing fine carbon fiber, thereby conduction auxiliaring effect and recirculation characteristic improve, and as the additive of the electrode film of the lithium ion battery of use in mobile phone, the PC etc., are adopting fine carbon fiber.

Consider from above-mentioned viewpoint, cathode film additive as the secondary cell of the high power that uses in hybrid vehicle and the electric automobile, high power capacity, by mixing with fine carbon fiber with the cobalt of active material acid lithium, LiFePO4 etc. as positive pole, thereby can expect to conduct electricity impregnability raising of auxiliaring effect and anodal film strength raising, densification, electrode solution etc., its research is carried out.

In the field of fortified resin composite, carrying out following research: the mixture of fine carbon fiber with carbon and glass fibre is added in the resin, further improves rigidity.In addition, studying to having used carbon, glass cloth or mat (mat) thus the FRP article shaped in add the purpose that characteristic improves, mechanical characteristic improves that fine carbon fiber reaches the surface.And then, in synthetic fibers, add fine carbon fiber and to improve the research of intensity etc. of fiber in vogue.

In the field that electronic equipment is made, studied fine carbon fiber is applicable to the fine distribution that utilizes ink-jetting style to make integrated circuit (LSI, super LSI etc.), utilizes serigraphy or spraying method manufacturing homogeneous field-emissive cathode source, also studied the application in flat-panel monitor, electric conductivity pottery, it is big that fine carbon fiber and metal wiring are compared conducting capacity, therefore also expects carrying out in power-supply device etc.

Make the field at conductive material, research fine carbon fiber just in vogue is utilizing compression, cast molding, is injecting, extrudes or the anti-charged plates of stretching mode making; Use conductive coating paint to make the anti-charged membrane of micron order, anti-electrolemma or electrostatic spraying electric conductivity underlying membrane; Utilize spraying method, spin coating or rod to be coated with being suitable for of aspects such as translucent or transparent conducting film that mode is made secondary micron order.

As mentioned above, after deliberation fine carbon fiber as the material that has electricity, function, machinery and composite effect concurrently being suitable in various uses, in order to bring into play additive effect to greatest extent, fine carbon fiber is evenly dispersed in the decentralized media such as water, organic solvent, resin solution, thermosetting resin and thermoplastic resin.

Yet for fine carbon fiber, the following tubular fiber of diameter 1 μ m twines the formation aggregation mutually or exists to have cancellated state, and is directly commercially available with such form.In addition, such aggregation or network structure are further assembled, commercially available after the raising bulk density.Therefore, with the fine fiber that becomes one one of the aggregation of this fine carbon fiber or network structure solution, or separate that fine to become the state of the little aggregation of number nm～tens of nm sizes be very difficult.

In addition, between the fine carbon fiber of separating one one of fine one-tenth or between the aggregation of number nm～tens of nm, acting on very strong aggregation force (Van der Waals force).Therefore, on one side in decentralized media such as water, organic solvent, resin solution, thermosetting resin and thermoplastic resin, will separate on one side fibre become one one fine carbon fiber or its aggregation keeping the former state form to make its dispersion be very difficult.That is, because temporary transient the solution between fine fine carbon fiber or its aggregation also reassociates easily.

Like this, present situation be difficult to obtain in solvent, fully to disperse between the fine carbon fiber and do not assemble, the dispersion liquid of fine carbon fiber that its dispersity is stable.

For the problem of the dispersiveness that solves above-mentioned fine carbon fiber, up to now, following various schemes have been proposed.

Patent documentation 1 discloses following method, with 5～120s ^-1Vibration frequency with CNT (CNT) and ring type organic compound vibration pulverization process and obtain the CNT mixture, then, in the CNT mixture, add organic solvent, obtain containing the dispersion liquid of CNT.In the method, as the ring type organic compound, use the compound of solubility in organic solvent, for example, polyvinylpyrrolidone, poly styrene sulfonate and polythiophene.

Disclose in the patent documentation 2, material with carbon element has been dispersed in the hydrocarbon system solvent that has added alkaline macromolecule dispersing agent, by dipping anode and apply voltage in this solvent, thereby formed the material with carbon element film at this anode surface.As alkaline macromolecule dispersing agent, can use the polyesteramide amine salt.

It is the CNT dispersion soln that polar organic solvent and polyvinylpyrrolidone are formed that patent documentation 3 discloses by CNT, acid amides.Be polar organic solvent as acid amides, can use N-N-methyl-2-2-pyrrolidone N-(NMP).

Disclose in the patent documentation 4, in the organic solvent solution of organic solvent soluble resin, during the dispersed carbon fiber, added the carbon fiber dispersion liquid that the compound shown in the following general formula prepares to improve dispersiveness with dispersant as carbon fiber.

Put down in writing in the table 1 of patent documentation 4, in the above-mentioned formula, R ¹～R ⁴Be hydrogen atom, R ⁵Be propyl group or hydrogen atom, R ⁶Be hydrogen atom, R ⁷Be acetyl group, x is 75～80 value, and y is 16～20 value, and z is 0～2 value.

Patent documentation 5 discloses, and adheres to amphiphatic molecule in a plurality of at least a portion that constitute the CNT of CNT bundle, by electric attraction between the amphiphatic molecule that is attached to adjacent C NT, makes the isolated dispersion of a plurality of CNT of formation CNT bundle and makes CNT dispersion paste.

Patent documentation 6 discloses a kind of fine carbon fiber aqueous dispersions, it is characterized in that, is containing two kinds of anionic surfactants (A) and (C) and in the aqueous solution of nonionic surfactant (B), fine carbon fiber is scattered here and there.

In the patent documentation 1～3, use the anionic surfactant for polar organic solvent, use nonionic surfactant for non-polar organic solvent, thereby can modulate good carbon fiber dispersion liquid, but must use different dispersants according to the kind of organic solvent.That is the situation of dispersed carbon fiber and in non-polar organic solvent, under the situation of dispersed carbon fiber, must use different dispersants (anionic surfactant or nonionic surfactant) in polar organic solvent.

The disclosed method that carbon fiber is dispersed in the organic solvent is to utilize the method for viscosity of resin solution in the patent documentation 4, and the scope of application of dispersion liquid is restricted.In addition, owing to be the dispersion in the viscosity solution, even want degree of scatter is brought up to certain more than level, this viscosity becomes main hindering factor, the aggregate size minimum of the carbon fiber that finally obtains is only about 20 μ m, be difficult to be dispersed to aggregation and be of a size of the following degree of 20 μ m, and the long-term stability of dispersion liquid also has problems.And then, also exist must be with an organic solvent in the problem of soluble resin.

On the other hand, the fine carbon fiber aqueous dispersions that patent documentation 5 and 6 is put down in writing shows good dispersity and completeness height, therefore begin to be applicable to various purposes, but because solvent is water, use in the dispersion liquid that therefore can not cause performance to reduce in the influence because of moisture.In addition, can not be applicable to organic solvent.

Like this, though present situation is to have carried out fine carbon fiber is dispersed in various trials in the organic solvent, might not obtain effect of sufficient.

The prior art document

Patent documentation

Patent documentation 1:WO2007/004652

Patent documentation 2: TOHKEMY 2006-63436

Patent documentation 3: TOHKEMY 2005-162877

Patent documentation 4: TOHKEMY 2008-248412

Patent documentation 5: TOHKEMY 2007-39623

Patent documentation 6:WO2010/041750

Summary of the invention

The problem that invention will solve

Therefore, the objective of the invention is to obtain following fine carbon fiber dispersion liquid: it makes the fine carbon fiber that has high aggregation force and formed aggregation can disperse, separate fine in organic solvent equably, suppress the size of aggregation less, and can stably keep dispersity.

For the scheme of dealing with problems

In order to solve above-mentioned problem, inventors etc. further investigate, found that, for the aggregation that makes fine carbon fiber is separated fine, dispersion equably in organic solvent, polymer with the chemical constitution shown in the following general formula (1) becomes outstanding fine carbon fiber dispersant, thereby has finished the present invention.

The invention provides a kind of fine carbon fiber dispersion liquid, it is for being dispersed with the fine carbon fiber dispersion liquid of fine carbon fiber in organic solvent, it is characterized in that, contain the macromolecule dispersing agent that is constituted by the polymer shown in the following general formula (1), and the aggregation of contained fine carbon fiber is of a size of below the 5 μ m in this dispersion liquid:

In the formula (1),

R ¹～R ⁴Alkyl, hydroxy alkyl, alkoxyl, acyloxy, carboxyl, acyl group, amino, aryl, aryloxy group or the heterocyclic radical of representing hydrogen atom, carbon number 1～30 respectively independently,

R ⁵And R ⁶Alkyl, aryl or the heterocyclic radical of representing hydrogen atom, carbon number 1～30 respectively independently, R ⁵And R ⁶Also bonding forms ring mutually,

R ⁷Alkyl, hydroxy alkyl, alkoxyl, acyloxy, carbonyl, carboxyl, primary amino radical, secondary amino group, uncle's amino, aryl, aryloxy group or the heterocyclic radical of expression hydrogen atom, carbon number 1～30,

X, y and z all are not 0, with the expression main chain carbon number (4x+2y+2z) value average out to 400～6000 as condition, x, y and z are the number that satisfies following formula:

(x＋z)/y＝60/40～90/10。

Among the present invention preferably,

(1) be that the amount of 1～200 mass parts contains aforementioned macromolecule dispersing agent to be equivalent to 100 mass parts fine carbon fibers;

(2) aforementioned macromolecule dispersing agent is shown in following general formula (2):

In the formula (2),

R ⁵～R ⁷And x～z is with identical shown in the aforementioned formula (1);

(3) aforementioned macromolecule dispersing agent is shown in following general formula (3):

In the formula (3),

R ⁸Alkyl, aryl or the heterocyclic radical of expression hydrogen atom, carbon number 1～30,

R ⁹Be alkyl, alkyl-carbonyl, aryl, heterocyclic radical, pyrans glycosyl or the furyl glycosyl of carbon number 1～30,

X, y and z are with identical shown in the general formula (1);

(4) also contain anionic surfactant or nonionic surfactant;

(5) as aforementioned anionic surfactant, contain the compound shown in the following general formula (4):

In the formula (4),

A is sodium ion, potassium ion or ammonium ion,

The number of B average out to 1～100,

C is 1～3 number;

(6) as aforementioned nonionic surfactant, contain the compound shown in any one of following general formula (5), general formula (6) or general formula (7),

In aforementioned formula (5)～(7),

R ¹⁰～R ¹⁴Alkyl, hydroxyl, hydroxy alkyl, 1-phenyl-ethyl or the benzyl of representing hydrogen atom, carbon number 1～30 respectively independently,

R ¹⁰～R ¹⁴At least one be not hydrogen atom,

The number of D average out to 1～100,

The number of E average out to 1～100,

F is 1～3 number,

R ¹⁵～R ¹⁸Alkyl, hydroxyl, hydroxy alkyl, the 1-phenyl-ethyl of representing hydrogen atom, carbon number 1～30 respectively independently, R ¹⁵～R ¹⁸At least one be not hydrogen atom,

The number of G average out to 10～50;

(7) aforementioned fine carbon fiber has the mean outside diameter of 0.5～200nm.

In addition, fine carbon fiber dispersion liquid of the present invention is according to purposes, and the paste that for example can be used as viscosity height to 0.2～100Pas (20 ℃) uses.

For example high viscosity fine carbon fiber dispersion liquid as described above (paste) can be used as lithium ion cell electrode and uses with paste.

Such lithium ion cell electrode with paste preferably,

(8) be added with negative pole with electrode active material or the anodal electrode active material of using;

(9) aforementioned negative pole electrode active material is that to be selected from by charcoal be that active material, silicon are at least a in the group formed of active material and lithium titanate;

(10) aforementioned anodal be to be selected from least a in the group of being formed by bedded rock salt compound and derivative, spinel-type compound and derivative, polyanionic compound and derivative thereof with electrode active material.

By above-mentioned lithium ion cell electrode is applied on the metallic film with paste, can obtain lithium ion battery electrode conducting film, use this electrodes conduct film can form lithium ion battery.

In addition, among the present invention, the size of the aggregation of fine carbon fiber is to use grind meter (particle size measuring instrument) to measure according to ASTM D-1210.

The effect of invention

Fine carbon fiber dispersion liquid of the present invention is using the polymer shown in the general formula (1) as having notable feature for the dispersant this point that fine carbon fiber is scattered in organic solvent.

Described polymer (macromolecule dispersing agent) contains the construction unit with acetal skeleton and the construction unit with hydroxyl in the main chain as to understand by general formula (1).In this construction unit, have the construction unit of acetal skeleton to the compatibility height of organic solvent, have the construction unit of hydroxyl to the compatibility height of fine carbon fiber.That is, such construction unit and other construction units (have radicals R ⁷Construction unit) in the main chain (carbon number average 400～6000) of certain-length, enroll with certain balance together.Its result, in the fine carbon fiber dispersion liquid of the present invention, the state that selectively is attached to the surface of fine carbon fiber with above-mentioned dispersant is scattered in the organic solvent, dispersion treatment by machinery makes the aggregation of fine carbon fiber easily separate fibre, dispersion, make the little fine size to 5 μ m of its aggregate size, and can stably keep fine carbon fiber homodisperse state in organic solvent.

Fine carbon fiber dispersion liquid of the present invention like this because fine carbon fiber stably disperses with reduced size, therefore can utilize it to be applied to various uses and brings into play the excellent specific property of fine carbon fiber.For example, this dispersion liquid in this dispersion liquid, add to mix the pigment of organic or inorganic or binding agent with or the resin person of forming of dilution usefulness can be used as be used to form conductive coating coating with additive or the coating fluid that forms usefulness of filming use.And then, in this dispersion liquid, add the electrode film formation material that the mixed electrode active material person of forming can be used as lithium ion battery etc. and use effectively.

Description of drawings

Fig. 1 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 1

Fig. 2 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 1

Fig. 3 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 2

Fig. 4 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 2

Fig. 5 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 3

Fig. 6 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 3

Fig. 7 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 4

Fig. 8 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 4

Fig. 9 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 5

Figure 10 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 5

Figure 11 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 6

Figure 12 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 6

Figure 13 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 7

Figure 14 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 7

Figure 15 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 8

Figure 16 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 8

Figure 17 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 9

Figure 18 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 9

Figure 19 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 10

Figure 20 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 10

Figure 21 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 11

Figure 22 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 11

Figure 23 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 12

Figure 24 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 12

Figure 25 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration embodiment 13

Figure 26 is the optical microscope photograph (35 times) of the dispersity of demonstration embodiment 13

Figure 27 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration comparative example 1

Figure 28 is the optical microscope photograph (35 times) of the dispersity of demonstration comparative example 1

Figure 29 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration comparative example 2

Figure 30 is the optical microscope photograph (35 times) of the dispersity of demonstration comparative example 2

Figure 31 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration comparative example 3

Figure 32 is the optical microscope photograph (35 times) of the dispersity of demonstration comparative example 3

Figure 33 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration comparative example 4

Figure 34 is the optical microscope photograph (35 times) of the dispersity of demonstration comparative example 4

Figure 35 is the stereomicroscope photo (2.8 times) of the dispersity of demonstration comparative example 5

Figure 36 is the optical microscope photograph (35 times) of the dispersity of demonstration comparative example 5

Figure 37 is the optical microscope photograph (35 times) of the dispersity after place 4 months of demonstration embodiment 2

Figure 38 is the optical microscope photograph (35 times) of the dispersity after place 4 months of demonstration embodiment 2

Figure 39 is the optical microscope photograph (35 times) of the dispersity after place 4 months of demonstration embodiment 4

Figure 40 is the optical microscope photograph (35 times) of the dispersity after place 4 months of demonstration embodiment 4

Figure 41 is the optical microscope photograph (35 times) of the dispersity after place 4 months of demonstration embodiment 8

Figure 42 is the optical microscope photograph (35 times) of the dispersity after place 4 months of demonstration embodiment 8

Figure 43 is the optical microscope photograph (35 times) of the dispersity after place 4 months of demonstration embodiment 10

Figure 44 is the optical microscope photograph (35 times) of the dispersity after place 4 months of demonstration embodiment 10

Figure 45 is the optical microscope photograph (35 times) that is presented at the dispersity behind the interpolation resinous principle among the embodiment 4

Figure 46 is the optical microscope photograph (35 times) that is presented at the dispersity behind the interpolation resinous principle among the embodiment 6

Figure 47 is the electron micrograph (1000 times) of the dispersity of demonstration embodiment 14

Figure 48 is the electron micrograph (5000 times) of the dispersity of demonstration embodiment 14

Figure 49 is the electron micrograph (10000 times) of the dispersity of demonstration embodiment 14

Figure 50 is the electron micrograph (1000 times) of the dispersity of demonstration embodiment 15

Figure 51 is the electron micrograph (5000 times) of the dispersity of demonstration embodiment 15

Figure 52 is the electron micrograph (10000 times) of the dispersity of demonstration embodiment 15

Figure 53 is the electron micrograph (1000 times) of the dispersity of demonstration embodiment 16

Figure 54 is the electron micrograph (5000 times) of the dispersity of demonstration embodiment 16

Figure 55 is the electron micrograph (10000 times) of the dispersity of demonstration embodiment 16

Figure 56 is the electron micrograph (1000 times) of the dispersity of demonstration embodiment 17

Figure 57 is the electron micrograph (5000 times) of the dispersity of demonstration embodiment 17

Figure 58 is the electron micrograph (10000 times) of the dispersity of demonstration embodiment 17

Figure 59 is the electron micrograph (1000 times) of the dispersity of demonstration embodiment 18

Figure 60 is the electron micrograph (5000 times) of the dispersity of demonstration embodiment 18

Figure 61 is the electron micrograph (10000 times) of the dispersity of demonstration embodiment 18

Figure 62 is the electron micrograph (1000 times) of the dispersity of demonstration embodiment 19

Figure 63 is the electron micrograph (5000 times) of the dispersity of demonstration embodiment 19

Figure 64 is the electron micrograph (10000 times) of the dispersity of demonstration embodiment 19

Figure 65 is the electron micrograph (1000 times) of the dispersity of demonstration embodiment 20

Figure 66 is the electron micrograph (5000 times) of the dispersity of demonstration embodiment 20

Figure 67 is the electron micrograph (10000 times) of the dispersity of demonstration embodiment 20

Figure 68 is the electron micrograph (1000 times) of the dispersity of demonstration embodiment 21

Figure 69 is the electron micrograph (5000 times) of the dispersity of demonstration embodiment 21

Figure 70 is the electron micrograph (10000 times) of the dispersity of demonstration embodiment 21

Figure 71 is the stereomicroscope photo (1000 times) of the dispersity of demonstration comparative example 6

Figure 72 is the optical microscope photograph (5000 times) of the dispersity of demonstration comparative example 6

Figure 73 is the stereomicroscope photo (10000 times) of the dispersity of demonstration comparative example 6

Figure 74 is the optical microscope photograph (1000 times) of the dispersity of demonstration comparative example 7

Figure 75 is the stereomicroscope photo (5000 times) of the dispersity of demonstration comparative example 7

Figure 76 is the optical microscope photograph (10000 times) of the dispersity of demonstration comparative example 7

Figure 77 is the stereomicroscope photo (1000 times) of the dispersity of demonstration comparative example 8

Figure 78 is the optical microscope photograph (5000 times) of the dispersity of demonstration comparative example 8

Figure 79 is the stereomicroscope photo (10000 times) of the dispersity of demonstration comparative example 8

The specific embodiment

For fine carbon fiber dispersion liquid of the present invention, the aggregate size of the fine carbon fiber in the dispersion liquid is below the 5 μ m, obtains by add macromolecule dispersing agent with fine carbon fiber in organic solvent.In addition, in this dispersion liquid, can also the conduct of matching surface activating agent be used for improving dispersed dispersing aid, and then, can also cooperate various additives according to purposes.

＜macromolecule dispersing agent＞

Make an addition to the macromolecule dispersing agent in the fine carbon fiber dispersion liquid of the present invention, shown in following general formula (1) like that, be made of the polymer with following backbone structure, this backbone structure contains construction unit with acetal skeleton, has the construction unit of hydroxyl and have R with the number (all not being 0) of x, y and z respectively ⁷The construction unit of base.

In the above-mentioned general formula (1), R ¹～R ⁴Alkyl, hydroxy alkyl, alkoxyl, acyloxy, carboxyl, acyl group, amino, aryl, aryloxy group or the heterocyclic radical of representing hydrogen atom, carbon number 1～30 respectively independently.

Above-mentioned each group also can have substituting group respectively, and for example, above-mentioned amino also can be single substituted-amino or disubstituted amido.

R ⁵And R ⁶Alkyl, aryl or the heterocyclic radical of representing hydrogen atom, carbon number 1～30 respectively independently, R ⁵And R ⁶Also bonding forms ring mutually.In addition, above-mentioned group also can have substituting group.

R ⁷Alkyl, hydroxy alkyl, alkoxyl, acyloxy, carbonyl, carboxyl, amino, aryl, aryloxy group or the heterocyclic radical of expression hydrogen atom, carbon number 1～30.

In the above-mentioned general formula (1), x, y and z all are not 0, value (4x+2y+2z), that is, and the carbon number average out to 400～6000 of main chain.And then x, y and z must satisfy following formula:

(x＋z)/y＝60/40～90/10。

That is, in the main chain of above-mentioned length, aforementioned each construction unit exists with the balance of above-mentioned formula defined, thereby described polymer is scattered in fine carbon fiber the dispersant of organic solvent and brings into play function effectively as being used for.

In addition, in the above-mentioned general formula (1), preferred R ¹～R ⁴Be hydrogen atom.Particularly, among the present invention, preferably use the polymer shown in the following general formula (2) as macromolecule dispersing agent.

In the above-mentioned general formula (2), R ⁵～R ⁷With x～z with identical shown in the aforementioned formula (1).

And then in above-mentioned general formula (2), the polymer shown in the following general formula (3) is most preferably as macromolecule dispersing agent.

In the above-mentioned general formula (3), x～z is with identical shown in the aforementioned formula (1), R ⁸With the radicals R in general formula (1) or (2) ⁵(or R ⁶) identical.

In addition, R ⁹Alkyl, alkyl-carbonyl, aryl, heterocyclic radical, pyrans glycosyl or furyl glycosyl for carbon number 1～30.These groups also can have substituting group.

Polymer shown in above-mentioned general formula (1)～(3) for example can make reaction such as polyvinyl alcohol that polyvinyl acetate copolymers such as (or) plastic of poly vinyl acetate saponification is obtained copolymers such as (or) poly ethylene vinyl alcohols and aldehydes or ketones and obtain.That is, bonding has radicals R in the general formula (1) ⁷Construction unit come from the not saponified unit the when saponification of vinyl acetate ester units is converted into vinyl alcohol units or come from by the copolymerization to vinyl and import construction unit in the polyvinyl acetate.

In aforementioned formula (1)～(3), when the x value becomes big, perhaps, at R ⁷Or OR ⁹Base is that acetal radical or acetyl group increased when the z value became big under the situation of acetyl group, and therefore the dissolubility in non-polar organic solvent improves.On the other hand, when the y value became big, hydroxyl increased, and therefore mainly was that the dissolubility in polar organic solvent improves.Usually, the x value is under the situation of certain limit, and the dissolubility of the dispersant of y value in 10～25 scope in non-polar organic solvent improves, and the dissolubility of the above-mentioned dispersant of y value in 25～40 scope in polar organic solvent improves.

In addition, the rerum natura of the value of x, the y of aforementioned formula (1)～(3) and z and fine carbon fiber dispersion liquid, relevant at the characteristic of various base materials that use according to the purposes of this dispersion liquid etc.For example, the compatibility of the value of x and the property of softening, resistance to water, this dispersion liquid and other compositions of film (solid constituent) that formed by this dispersion liquid etc. has bigger relation, and the value of y and filming of being formed by this dispersion liquid are to the cementability of various base materials, hydrophily that this is filmed or relevant with the reactivity of thermosetting resin.In addition, the value of z is tended to relevant with the viscosity of glass transition temperature, fine carbon fiber dispersion liquid.

And then the average carbon atom number (4x+2y+2z) of the main chain of the chemical constitution of the above-mentioned dispersant shown in aforementioned formula (1)～(3) is 400～6000, is preferably 500～5000, more preferably 600～4000 scope.During the average carbon atom number less than 400 of this main chain, the dispersion stabilization of fine carbon fiber is poor, surpasses at 6000 o'clock, might the dissolubility in organic solvent lack.

Among the present invention, as the polymer that macromolecule dispersing agent most preferably uses, that is, the polymer shown in the general formula (3) is just commercially available.

For example, from Sekisui Chemical Co., the S-LEC B (R of Ltd. system ⁸=C ₃H ₇, R ⁹=COCH ₃) and the denka butyral (R of DENKI KAGAKU KOGYO KABUSHIKI KAISHA system ⁸=CH ₃H ₇, R ⁹=COCH ₃) the commercially available product of trade name in preferably use following kind.

Sekisui Chemical Co., Ltd. S-LEC B processed:

DENKI KAGAKU KOGYO KABUSHIKI KAISHA denka butyral processed:

In the fine carbon fiber dispersion liquid of the present invention, with respect to per 100 mass parts fine carbon fibers, the addition of macromolecule dispersing agent is 1～200 mass parts, is preferably 4～150 mass parts, and more preferably the scope of 5～100 mass parts is preferable.If the addition of the macromolecule dispersing agent in the fine carbon fiber dispersion liquid is very few, then can't give full play to the divergent function of this macromolecule dispersing agent, may be difficult to size with the fine carbon fiber aggregation and be suppressed at size below the 5 μ m, in addition, the dispersion stabilization of the fine carbon fiber in the organic solvent tends to reduce.And then when adding macromolecule dispersing agent in a large number to surpass necessary amount, the peculiar characteristic of fine carbon fiber (for example electric conductivity) is impaired, and the purposes of this dispersion liquid is restricted.

＜fine carbon fiber＞

Among the present invention, as fine carbon fiber, can use himself known person.For example, can select any one use of the fine carbon fiber of individual layer, bilayer and multilayer according to the purposes of dispersion liquid.In a lot of purposes, preferably use the fine carbon fiber of multilayer.

The mean outside diameter of the fine carbon fiber of individual layer, bilayer or the multilayer that obtains with the whole bag of tricks is generally 0.5～200nm as described above, with the form of the aggregation of equivalent circle diameter with several cm degree and obtain, with its aggregation of separating fibre or being crushed to the round equivalent average diameter about 50～100 μ m, use aforementioned macromolecule dispersing agent that it is dispersed in the organic solvent, thereby modulate dispersion liquid of the present invention.

The concentration of the fine carbon fiber in the fine carbon fiber dispersion liquid of the present invention is 0.01～30 mass parts with respect to 100 mass parts organic solvent described later, is preferably 0.2～20 mass parts, and more preferably the scope of 0.5～15 mass parts is preferable.If the concentration of this fine carbon fiber is low excessively, then be difficult to give full play to the peculiar characteristic of fine carbon fiber (for example, electric conductivity).In addition, if the excessive concentration of this fine carbon fiber is then stably kept its dispersity and is become difficult.

＜organic solvent＞

Organic solvent as disperseing above-mentioned fine carbon fiber is not particularly limited, and can use himself known material, generally speaking, and the following material of preferred use.

The alcohol series solvent:

Methyl alcohol, ethanol, isopropyl alcohol, butanols, cyclohexanol, ethylene glycol, propane diols, diethylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, polypropylene glycol list ether, polyethylene glycol mono allyl ether, polypropylene glycol mono allyl ether, ethyl cellosolve, butyl cellosolve, carbitol, BC, methoxybutanol

The ketone series solvent:

Acetone, MEK, methylisobutylketone, cyclohexanone, isophorone

The ester series solvent:

Ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, oxytol acetate, butyl cellosolve acetate, acetic acid carbitol ester, acetic acid methoxyl group butyl ester, poly glycol monomethyl ether acetate, polyethyleneglycol ethyl ether acetate ester

The ether series solvent:

Oxolane, diox, dimethyl sulfoxide (DMSO)

The aliphatic hydrocarbon series solvent:

Mineral spirits (mineral spirit), clicyclic hydrocarbon series solvent are that turpentine oil, hydrocarbon mixture series solvent are HAWS, solvent100, solvent150

The aromatic hydrocarbon series solvent:

Toluene, dimethylbenzene, ethylbenzene, vinyl benzene

The halogenated hydrocarbons series solvent:

Chlorobenzene, dichloro-benzenes, chloroform, bromobenzene, fluoride class

The silicone oil series solvent:

Dimethyl silicone polymer, part octyl group substituted polydimethylsiloxanederivative, part phenyl substituted polydimethylsiloxanederivative

Amine is organic solvent:

N, dinethylformamide, N-N-methyl-2-2-pyrrolidone N-

＜surfactant＞

In fine carbon fiber dispersion liquid of the present invention, can use surfactant as dispersing aid, more stably keep the dispersity of fine carbon fiber thus, for example, suppress reassociating of fine carbon fiber effectively, and the size of the fine carbon fiber aggregation in the dispersion liquid is continued to remain on size below the 5 μ m, and in this, the use of such surfactant is more effective.

As such surfactant, preferred anionic surfacant or nonionic surfactant.

1. anion surfactant:

With the anion surfactant that uses in the dispersion liquid, can list following material as fine carbon fiber of the present invention.

Polyoxyethylene alkyl ether sulfate salt and derivative thereof

Polyoxyethylene phenyl ether sulfate and derivative thereof

Polycarboxylate and derivative thereof

Formalin condensation product and the derivative thereof of naphthalene sulfonate

Naphthyl sulfonate and derivative thereof

Polyoxyethylene alkyl ether phosphate

Alkyl sulfate salt and derivative thereof

Thio succinate and derivative thereof

Amide ether sulfate and derivative thereof

Taurine derivatives

Sarcosine derivative

Arylsulphonate and derivative thereof

Reactive surfactant

Soap

Alkenyl succinic salt and derivative thereof

Poly styrene sulfonate and derivative thereof

In addition, in the above-mentioned anionic surfactant who enumerates, preferred following material.

Polyoxyethylene alkyl ether sulfate salt and derivative thereof

Polyoxyethylene phenyl ether sulfate and derivative thereof

Polycarboxylate and derivative thereof

Naphthyl sulfonate and derivative thereof

And then, in the above-mentioned anionic surfactant who enumerates, most preferably polyoxyethylene phenyl ether sulfate and derivative thereof.

Among the present invention, represent with following general formula (4) as polyoxyethylene phenyl ether sulfate and derivative thereof that anion surfactant most preferably uses.

In the general formula (4), A is sodium ion, potassium ion or ammonium ion.

In addition, the molal quantity of B representative ring oxidative ethane (EO) base, average out to 1～100 is preferably 3～50, most preferably is 4～40.

And then C represents conjugate substituent number on the phenyl, is 1～3 number.

Among the present invention, commercially available with for example following trade name as polyoxyethylene phenyl ether sulfate and derivative thereof that anion surfactant most preferably uses.

Homogenol (Kao Corporation system):

L-18

L-1820

SORPOL (TOHO CHEMICAL INDUSTRY Co., Ltd. system):

T-10SPG (B＝9、C＝3)

T-15SPG (B＝14，C＝3)

7290P (B＝14、C＝3)

T-20SPG (B＝19，C＝3)

7953 (B＝14，C＝3)

7917B (B＝19，C＝3)

7948 (B＝33，C＝3)

7556 (B＝12，C＝2)

HITENOL (Dai-Ichi Kogyo Seiyaku Co., Ltd. system):

NF-08 (B＝8、C＝1～3)

NF-0825 (B＝8、C＝1～3)

NF-13 (B＝13、C＝1～3)

NF-17 (B＝25，C＝1～3)

2. non-ionic surface active agent:

With the nonionic surfactant that uses in the dispersion liquid, can list following material as fine carbon fiber of the present invention.

Polyoxyethylene alkyl ether and derivative thereof

Polyoxyethylene phenyl ether and derivative thereof

Formalin condensation product and the derivative thereof of polyoxyethylene phenyl ether

Polyoxyalkylene derivative

The alkanolamide type

Cithrol

Glyceride

P.O.E. glyceride

Polyoxyethylene sorbitan fatty acid ester

Sorbitan fatty acid ester

The polyoxyethylene sorbitol fatty acid ester

Fatty acid glyceride

Polyoxyethylene fatty acid ester

Crodaret

Polyoxyethylene alkyl amine

The alkyl alkanolamide

Polyethylene glycol

In the above-mentioned nonionic surfactant of enumerating, the material below preferred the use.

Polyoxyethylene phenyl ether and derivative thereof

In addition, in above-mentioned nonionic surfactant, the material that the polyoxyethylene chain in the preferred molecule is long.

Among the present invention, be surfactant and particularly preferred polyoxyethylene phenyl ether and derivative thereof as nonionic, can the material shown in following general formula (5) and (6) be shown example, as formalin condensation product and the derivative thereof of polyoxyethylene phenyl ether, can list the material shown in the following general formula (7).

Polyoxyethylene phenyl ether and derivative thereof:

In aforementioned formula (5) and (6),

R ¹⁰～R ¹⁴At least one be not hydrogen atom,

D and E respectively average out to 1～100 number, be preferably 3～50, more preferably 4～40.

F is 1～3 number.

Polyoxyethylene phenyl ether shown in above-mentioned general formula (5) or (6) and derivative thereof are commercially available with for example following trade name.

SORPOL (TOHO CHEMICAL INDUSTRY Co., Ltd. system):

T-10 (F＝3、E＝9)

T-15 (F＝3、E＝14)

T-20 (F＝3、E＝19)

T-26 (F＝3、E＝24)

T-32 (F＝3、E＝30)

T-18D (F＝2，E＝12)

EMULGEN (Kao Corporation system):

A-60 (F＝2，E＝15)

A-90 (F＝2，E＝20)

A-500 (F＝2，E＝50)

B-66 (F＝3)

NOIGEN (Dai-Ichi Kogyo Seiyaku Co., Ltd. system):

EA-87 (F＝1～3，E＝8)

EA-137 (F＝1～3，E＝13)

EA-157 (F＝1～3，E＝15)

EA-167 (F＝1～3，E＝17)

EA-177 (F＝1～3，E＝20)

EA-197D (F＝1～3，E＝50)

EA-207D (F＝1～3，E＝100)

The formalin condensation product of polyoxyethylene phenyl ether:

In aforementioned logical (7) formula,

R ¹⁵～R ¹⁸Alkyl, hydroxyl, hydroxy alkyl, the 1-phenyl-ethyl (most preferably being the 1-phenylethyl) of representing hydrogen atom, carbon number 1～30 respectively independently,

R ¹⁵～R ¹⁸At least one be not hydrogen atom,

G average out to 10～50 is preferably 15～45, more preferably 20～40 number.

Formalin condensation product and derivative thereof with the polyoxyethylene phenyl ether shown in the general formula (7) are commercially available with for example following trade name.

SORPOL (TOHO CHEMICAL INDUSTRY Co., Ltd. system):

F-15 (G=21, R ¹⁵～R ¹⁸=1-phenyl-ethyl)

F-19 (G=26, R ¹⁵～R ¹⁸=1-phenyl-ethyl)

F-24 (G=34, R ¹⁵～R ¹⁸=1-phenyl-ethyl)

F-27 (G=38, R ¹⁵～R ¹⁸=1-phenyl-ethyl)

Among the present invention, above-mentioned anion is surfactant or nonionic surfactant, usually with respect to 100 mass parts fine carbon fibers, preferably with 5～100 mass parts, particularly 10～60 mass parts, most preferably the amount of 20～50 mass parts is used preferable.If the use amount of these surfactants is few, then can't give full play to the dispersion auxiliaring effect that surfactant brings, in addition, if excessively use more than the necessary amount, then form micellar structure between the surfactant, therefore the dispersion effect that conforms to its amount can't be expected, economically unfavorable can only be caused.

＜other additive＞

Only otherwise dispersiveness and the dispersion stabilization of infringement fine carbon fiber, can be according to purposes etc., in fine carbon fiber dispersion liquid of the present invention, suitably cooperate various additives.

As the example of such additive, can list inorganic pigment, organic pigment, whisker as filler, sodium carboxymethylcellulose as thickener, sagging inhibitor, ultraviolet ray prevents agent, wetting agent, emulsifying agent, antiskinning agent, anti-polymerizer, anti-sagging agent, defoamer, anti-flooding agent, levelling agent, drier, curing agent, curing accelerator, plasticizer, fire-resistantly prevent agent, the algae agent is prevented in mildew-resistant, antiseptic, pesticide, marine antifoulant, metal conditioner, take off the rust agent, degreasing agent, the chemical conversion film agent, bleaching agent, colouring agent, timber sealant (wood sealer), filler (filler), sanding sealer (sanding sealer), sealer, the cement paste of cement filler (cement filler) or adding resin etc.

Particularly, fine carbon fiber dispersion liquid of the present invention is being used, when giving electric conductivity to filming of being formed by coating, for example also can add inorganic pigment, organic pigment etc. in advance in this dispersion liquid with additive as coating.In addition, can add as binding agent (or for diluent of adjusting resistance) and the resin of use etc.As the example of such resin, can following material be shown example, these also can add with the form of the resin solution that dissolves in the organic solvent.

Grease class (soybean oil, linseed oil, safflower oil, castor oil) or derivatives thereof

Natural resin (rosin, copal, shellac) or derivatives thereof

Processing resin (chroman resin, Petropols) or derivatives thereof

Synthetic resin (alkyd resins (single oil alkyd resin, medium oil alkyd resin, long oil alkyd resin, phthalic alkyd resin) or derivatives thereof

Modified alkyd resin (phenol-formaldehyde resin modified, styrene resin) or derivatives thereof

The amino-alkyd resin or derivatives thereof

The oil-free alkyd resin or derivatives thereof

Acrylic resin (printing with, the usefulness of spraying paint, acrylic polyol, emulsion) or derivatives thereof

The polystyrene resin or derivatives thereof

The mylar or derivatives thereof

Urea melamine resin (butylation melamine resin, melamine resin methylates) or derivatives thereof

The melamine resin or derivatives thereof

Phenolic resins (phenol aldehyde modified maleic acid resin, natural resin modification, phenol aldehyde modified pentaerythritol resin) or derivatives thereof

The polyurethane resin or derivatives thereof,

The polyamide or derivatives thereof

Polyimide resin precursor (polyamic acid) or derivatives thereof

Polyetherimide resin precursor or derivatives thereof

Alcohol resol resin or derivatives thereof

The epoxy resin or derivatives thereof

Fluororesin (Kynoar) or derivatives thereof

Chlorinated polyolefin resin (chlorinated polyethylene resin, chlorinated polypropylene, ethlyene dichloride-propylene copolymer, ethylene chloride-ethylene acetate ester copolymer) or derivatives thereof

The silicone resin or derivatives thereof

Rubber derivative (chlorinated rubber, thermoprene) or derivatives thereof

Cellulose derivative (nitrocotton, acetyl group cellulose) or derivatives thereof

In addition, fine carbon fiber dispersion liquid of the present invention is preferred for the formation of lithium ion cell electrode, the such a material that is used for electrode formation, usually, viewpoint from coating etc., forming its viscosity (20 ℃) is the paste of 0.2～100Pas scope, usually, can add electrode active material (negative pole with active material or the anodal active material of using) as additive.

As such negative pole active material, for example, can list carbon-based negative electrode with active material, tin be negative pole with active material, silicon be negative pole with active material and lithium titanate, as its concrete example, can following material be shown example.

The carbon-based negative electrode active material:

Delanium, easy graphite voltinism charcoal, difficult graphite voltinism charcoal etc.

Tin is the negative pole active material:

Ashbury metal based material: copper-Xi, iron-Xi, silver-ashbury metal etc.

Tin is oxide: SnMxOy (M=B, P, Al,

Sn:B:P:Al＝1.0:0.6:0.4:0.4)

Tin is amorphous: with a plurality of elements such as tin-cobalt-carbon on atomic level, evenly mix, amorphousization and the material that obtains.

Silicon is the negative pole active material:

The Si system alloy of Li44Si etc.

Lithium titanate:

LiTiO ₂(112 phase), LiTi ₂O ₄(124 phase),

Li ₄TiO ₄(414 phase), Li ₂TiO ₃(213 phase),

Li ₄Ti ₅O ₁₂(4512 phase), Li ₂Ti ₃O ₇(237 phase) etc.

Positive pole for example can list bedded rock salt compound and derivative thereof, spinel-type compound and derivative, polyanionic compound and derivative thereof etc. with active material, as its concrete example, can following material be shown example.

Bedded rock salt compound and derivative thereof:

LiCoO ₂、LiNiO ₂、LiCrO ₂、LiMnO ₂、

LiFeO ₂、LiTiO ₂、LiNi _0.5Mn _0.5O ₂、

LiNi _1/3Co _1/3O ₂

Spinel-type compound and derivative thereof:

LiMn ₂O ₄、LiNi _0.5Mn _1.5O ₄、LiNiVO ₄、

LiCoVO ₄、LiCoVO ₄、LiMnVO ₄

Polyanionic compound and derivative thereof:

LiFePO ₄、LiMnPO ₄、LiCoPO ₄、

LiNiPO ₄、Li ₂FeSiO ₄

And then, in the aforesaid paste, as the conduction auxiliary material, for example can also add carbon black, acetylene black, Ketjen black etc., and then, as the binding agent composition, can also cooperate for example fluororesin (Kynoar (PVDF), PTFE, FKM) or derivatives thereof, polyimide resin precursor (polyamic acid) or derivatives thereof, SBR, NBR, BR, PAN, EVOH, EPDM, polyurethane, polyacrylic acid, polyamide, polyacrylate, polyvingl ether or derivatives thereof.

The electrolyte layers of using during as the making lithium ion battery for example can list organic electrolyte (electrolyte: LiPF ₆, LiClO ₄, LiBF ₄, LiN (CF ₂SO ₂) ₂, LiN (C ₂F ₄SO ₂) ₂, PC-LiBOB etc., electrolyte: ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) be solvent or mixed liquor separately), solid electrolyte (composite, the gel-form solid polymer electrolyte that comprise macromolecules such as PEO or PPOX and electrolytic salt), ionic liquid (ethyl-methyl glyoxaline cation (EMI) salt etc.) etc.

The barrier film that uses when making lithium ion battery for example has the micro-porous film of polyethylene system, according to manufacture method and the porous difference can list the single composition of dry type system, wet type binary system, wet type three component system etc.

The shape of lithium ion battery can list coin cell, semihard coin battery, layer-built battery, cylinder type, box type etc.

The modulation of＜fine carbon fiber dispersion liquid＞

Fine carbon fiber dispersion liquid of the present invention can be modulated by adding aforesaid macromolecule dispersing agent, fine carbon fiber and the surfactant that adds as required or other additives.In this case, the order of each agent of adding in organic solvent is not particularly limited, in order to obtain the fine carbon fiber dispersion liquid of good dispersity reliably, the preferred method of after adding to macromolecule dispersing agent and the surfactant that adds as required in the organic solvent, adding fine carbon fiber again.Particularly, in order to reach the good dispersion of fine carbon fiber, most preferably in organic solvent, add and add fine carbon fiber again after macromolecule dispersing agent makes its dissolving.

In addition, for the various additives that add as required, preferably then add fine carbon fiber in the organic solvent and carry out dispersion treatment and add above-mentioned additive after modulating the fine carbon fiber dispersion liquid in that macromolecule dispersing agent, surfactant are added to.Preferably in advance the aggregation of fine carbon fiber fully separated fibre, disperseed to add afterwards desired various additives, if before solution fibre, the dispersion of aggregation are fully carried out, add various additives, then the solution fibre of aggregation, dispersion become insufficient, might the residual aggregation that surpasses 5 μ m.

In addition, the dispersion treatment after macromolecule dispersing agent, the surfactant that adds as required and fine carbon fiber are added into organic solvent can use common dispersion machine to carry out.For example, can list pearl mill dispersion machine (Dinomill, Shimaru Enterprises Corporation system), TK LABO DISPER, TK FILMICS, TK PIPELINE MIXER, TK HOMOMIC LINE MILL, TK HOMO JETTER, TK UNI MIXER, TK HOMOMIC LINE FLOW, TK AGI HOMO DISPER (above Tokushu Kika Kogyo K.K system), Homogenizer POLYTRON (center science trade Co., Ltd. system), Homogenizer HISTRON (a day sound medical knowledge section machine is made Co., Ltd. of institute system), BIO MIXER (NISSEI Corporation. system), Scroll-type mixer (Kodaira Seisakusho Co., Ltd. make), Ul Tra Disperser (Asada Iron Works Co., Ltd. make), Ebara Milder (EBARA Corporation system), ultrasonic unit or sonic washing machine (AS ONE Corporation system) etc.

The condition of this machine when using these machines to carry out dispersion treatment of the present invention etc. is as long as suitably set according to the dispersity of desired fine carbon fiber.

In addition, after temporarily fine carbon fiber being disperseed, interpolation organic solvent in back dilutes aptly.

The modulation of＜fine carbon fiber paste＞

In above-mentioned fine carbon fiber dispersion liquid, especially for the paste of formation of the electrode film of lithium ion battery etc., as already described, its viscosity (20 ℃) is necessary in the scope of 0.2～100Pas.

The modulator approach of such fine carbon fiber paste is shown in following, but is not limited to these.

Modulator approach as fine carbon fiber paste of the present invention, for example electrode is mixed with active material, conduction auxiliary material, fine carbon fiber dispersion liquid of the present invention, binder solution and stir, and then in order to adjust solid component concentration and to add organic solvent (N-N-methyl-2-2-pyrrolidone N-) with 20～90% scope.Can list the method that the dispersion machine FILMICS of these mixtures by PRIMIX Corporation system modulated.

In addition, by fine carbon fiber, macromolecule dispersing agent, add the electrode active material in the fine carbon fiber dispersion liquid that organic solvent and surfactant are formed, conduction auxiliary material and a spot of binder solution, use planetary mixer (planetary mixer), after PD mixer (PD mixer) or three arm planetary mixers (TRIMIX) etc. carry out the dispersion machine mixing of planetary motion (planetary motion), again according to the mode of the solid component concentration that reaches regulation, the binder solution and the organic solvent (N-N-methyl-2-2-pyrrolidone N-) that add surplus finally mix, thereby can modulate the fine carbon fiber paste.

The formation of＜conductive coating＞

As already described, for fine carbon fiber dispersion liquid of the present invention, fine carbon fiber is stablized and is scattered here and there imperceptibly, so the composition that can be used as for modulation coating and paste uses, for example, can add pigment, the electrode active material of organic or inorganic and become the resinous principle of binding agent, modulation is used to form coating and the fine carbon fiber paste of conductive film.

As the method for using such coating and fine carbon fiber paste formation conducting film or lithium ion battery with the electrode conducting film, for example can by air-atomizing application, airless spraying application, the application of low pressure atomizing spraying, utilize rod be coated with method application, use spin coating instrument, dip coater application, in the conducting film that lithium ion battery is used forms, be by usual ways such as applicators, carry out continuously or discontinuously.

The kind of the resin that the drying after the coating is used according to organic solvent, as binding agent and difference, generally speaking, as long as with 10～300 ℃, preferably with 60～250 ℃, more preferably carry out reasonable time with about 70～200 ℃ temperature.If temperature is low excessively, then may drying can not fully carry out, if temperature is too high, then might cause the reduction of the distortion that is formed with the base material of filming, the xanthochromia of filming, film rerum natura etc.In the situation as the strictness control moisture of lithium ion battery with electrode film, behind drying process, further in 150～250 ℃ scope, carry out drying under reduced pressure sometimes.

In addition, the thickness of filming is not particularly limited, and generally speaking, is 0.01～5mm, particularly 0.1～4mm, is preferably the thickness (dry film thickness) of 1～3mm especially.

Form above-mentioned base material of filming and can list metals such as glass, resin, Copper Foil and aluminium foil, shape can list different shapes such as film, sheet material, plate, solid forming thing.

Embodiment

In following experiment, with following method evaluation or dispersity, the viscosity of mensuration fine carbon fiber dispersion liquid and the sheet resistance of filming of using this dispersion liquid to form.

Fine carbon fiber dispersity observation in the＜fine carbon fiber dispersion liquid＞

In 2 of the fine carbon fiber dispersion liquids of embodiment 1～13 and comparative example 1～5, add organic solvent 20g, after dilution is stirred, use stereomicroscope to carry out macroscopic observation (2.8 times of multiplying powers; 1 times on object lens, 4 times of zoom ratios, digital camera variable power 0.7), use light microscope to carry out microscopic observation (35 times of multiplying powers; 50 times on object lens, digital camera variable power 0.7) estimate.

In addition, use grind meter (Grind Meter) (big flat physics and chemistry Industrial Co., Ltd system) to carry out the mensuration of aggregate size, aggregate size is 5 μ m when following, and dispersity is evaluated as zero, aggregate size is during greater than 5 μ m, dispersity is evaluated as *.

Fine carbon fiber dispersity observation in the＜fine carbon fiber paste＞

5g is added drop-wise on the metallic film with the fine carbon fiber paste, after the applicator coating, carries out 10 minutes dryings under 120 ℃.Carry out the electron microscope observation (1000 times, 5000 times and 10000 times of multiplying powers) of resulting conducting film, estimate the dispersity of fine carbon fiber.

The viscosimetric analysis of＜fine carbon fiber dispersion liquid＞

Use rotation viscometer (MODEL RE100L, Toki Sangyo Co., Ltd. system) under 20 ℃, the fine carbon fiber dispersion liquid to be carried out viscosimetric analysis.

The viscosimetric analysis of＜fine carbon fiber paste＞

Use SV type viscosimeter (A﹠amp; D Company SV-10 processed) under 25 ℃, the fine carbon fiber paste is carried out viscosimetric analysis.

The sheet resistance value of＜fine carbon fiber film＞

Fine carbon dispersion liquid is put into culture dish (diameter 5cm), in 120 ℃ drying machine, make the organic solvent volatilization.Afterwards, further culture dish was placed 5 hours in 120 ℃ drying machine, thereby made the fine carbon fiber film.The sheet resistance value of the fine carbon fiber film that use four point probe resistrivity meter (Loresta-GP, MCP-T610, Mitsubishi chemical Co., Ltd's system) mensuration is made (Ω/sq).

In addition, in following experiment, as macromolecule dispersing agent, organic solvent and surfactant, prepare following material.

Macromolecule dispersing agent:

Sekisui Chemical Co., Ltd. S-LEC B processed BL-1

Sekisui Chemical Co., Ltd. S-LEC B processed BL-S

Organic solvent:

Ethanol (EtOH)

MEK (MEK)

Toluene (Toluene)

N-N-methyl-2-2-pyrrolidone N-(NMP)

Isopropyl alcohol (IPA)

Anion surfactant:

Kao Corporation Homogenol L-1820 processed

Non-ionic surface active agent:

SORPOL T-18D

SORPOL7290P

The volume resistance value of the conducting film that＜use fine carbon fiber paste is made＞

By applicator the fine carbon fiber paste is applied to lithium ion battery with on the electrode (copper film, aluminium film), carries out 120 ℃ of 10 minutes dryings with drying machine.Desciccator diaphragm is carried out compression process with roll squeezer and make the mensuration conducting film.The volume resistance value of thickness direction is measured with YOKOGAWA (Programmable DC source7651) and YOKOGAWA (Digital multimeter7555).

＜embodiment 1～13＞

As fine carbon fiber, prepare Baotugu Chemical Industrial Co., Ltd's multilayer carbon nanotube processed (NT-7K, average fiber footpath 40～80nm) and (CT-12K, average fiber footpath 100～120nm).

Macromolecule dispersing agent B (g) in the organic solvent A shown in the table 1 (g) shown in the mixture table 1 and surfactant C (g), after the uniform dissolution, the above-mentioned fine carbon fiber that mixes the amount of Table 1 D (g) utilizes pearl mill dispersion machine to carry out dispersion treatment, obtains the fine carbon fiber dispersion liquid.

In addition, as pearl mill dispersion machine, use Dinomill MULTI LAB type (SHINMARU ENTERPRISES Corporation system).

For resulting dispersion liquid, measure viscosity by described method just now, and then carry out dispersed evaluation and the mensuration of the sheet resistance of filming that obtained by this dispersion liquid, it be the results are shown in table 1.

In addition, for dispersiveness, the microphotograph of 35 times of 2.8 times of each embodiment moderate multiplying factors and multiplying powers has been shown among Fig. 1～Figure 26.In addition, for embodiment 2,4,8 and 10, will show that the microphotograph (35 times of multiplying powers) through the dispersity of the dispersion liquid after 4 months is shown in Figure 37～44.

＜comparative example 1～5＞

Do not add macromolecule dispersing agent and surfactant, carry out dispersion treatment and modulate the fine carbon fiber dispersion liquid with the condition shown in the table 1 (with embodiment 1,3,5,7 or 9 the same terms), carry out the mensuration same with embodiment 1～13, it be the results are shown in table 1.The microphotograph that shows the dispersity of dispersion liquid is shown in Figure 27～36.[table 1]

By above-mentioned experimental result as can be known, use the fine carbon fiber dispersion liquid of the present invention (embodiment 1～13) of specific macromolecule dispersing agent modulation, separate aggregation fine, that be dispersed to fine carbon fiber and be of a size of the following less level of 5 μ m.

In addition, even be appreciated that fine carbon fiber dispersion liquid of the present invention through after 4 months by the microphotograph of Figure 37～44, fine carbon fiber can not reassociate yet, and keeps fine dimensionally stable ground to disperse yet.

And then clear, even under the many situations of the addition of fine carbon fiber, viscosity is also lower.

And then in addition, by the use of macromolecule dispersing agent, the electric conductivity of formed film can not reduce yet.

The fine carbon fiber dispersion liquid (comparative example 1～5) that does not use macromolecule dispersing agent and modulate, the aggregation of fine carbon fiber can't be separated fine to the little size below the 5 μ m.In addition, the viscosity of dispersion liquid is also than the present invention height.

＜added the dispersion stabilization of the fine carbon fiber dispersion liquid of resinous principle＞

In the fine carbon fiber dispersion liquid 7.5g of embodiment 4 and 6, add cinnamic acrylic ester acrylic copolymer resin solution (30 weight % resin solutions as additive, MARUAI Corporation system) behind the 30g, in the dispersion liquid of embodiment 4, add toluene 7.5g, in the dispersion liquid of embodiment 6, add MEK7.5g, mix, modulation contains the fine carbon fiber dispersion liquid of resin solution.

The dispersity of similarly observing the fine carbon fiber of resulting dispersion liquid with embodiment 1～13 is shown in Figure 45 (embodiment 4) and Figure 46 (embodiment 6) with the microphotograph of 35 times of multiplying powers.

Be appreciated that in the fine carbon fiber dispersion liquid of the present invention by this photo, even added under the situation of resinous principle, also do not exist size to surpass the aggregation of 5 μ m, reassociating of fine carbon fiber do not taken place.

＜embodiment 14＞

As the fine carbon fiber dispersion liquid, use the N-N-methyl-2-2-pyrrolidone N-dispersion liquid that contains 10wt%CT-12K of modulation among the embodiment 13.

Utilize three arm planet dispersion machines (dispersion machine that aboveground making is made) to mix with cobalt acid lithium (NIPPON CHEMICAL INDUSTRIAL Co., the Cellseed C-5H of the Ltd. system) 150g of active material, acetylene black (the DENKA BLACK HS-100 of the DENKI KAGAKU KOGYO KABUSHIKI KAISHA system) 3.3g of conduct conduction auxiliary material as positive pole.32.5g carries out mixing to the N-N-methyl-2-2-pyrrolidone N-solution that wherein adds 12wt%PVDF (the KF Polymer W#1700 of KUREHA Corporation system).

Afterwards, the fine carbon fiber dispersion liquid 33g that adds embodiment 13 mixes, at last, in order to adjust solid component concentration, the N-N-methyl-2-2-pyrrolidone N-solution 9.5g, the N-N-methyl-2-2-pyrrolidone N-3.3g that add 12wt%PVDF, mix, thus modulation fine carbon fiber paste (solid component concentration 70%).

The viscosity of this fine carbon fiber paste is 3.0Pas, and the electron micrograph that shows the fine carbon fiber dispersity in the conducting film that uses it and make is shown in Figure 47～49 (1000 times, 5000 times, 10000 times of multiplying powers).In addition, this lithium ion battery shows 1.97 * 10 with the volume resistance value of conducting film ³Ω cm.

＜embodiment 15＞

As fine carbon fiber liquid, use the N-N-methyl-2-2-pyrrolidone N-dispersion liquid that contains 10wt%NT-7K of modulation among the embodiment 12, in addition, modulate based on embodiment 14.

The viscosity of this fine carbon fiber paste is 8.5Pas, and the fine carbon fiber dispersity observed result in the conducting film that uses it and make is shown in Figure 50～52 (1000 times, 5000 times, 10000 times of multiplying powers).In addition, this lithium ion battery shows 4.25 * 10 with the volume resistance value of conducting film ²Ω cm.

＜embodiment 16＞

As fine carbon fiber liquid, use the N-N-methyl-2-2-pyrrolidone N-dispersion liquid that contains 10wt%CT-12K of modulation among the embodiment 13.

Add acetylene black (the DENKI KAGAKU KOGYO KABUSHIKI KAISHA DENKA BLACK processed HS-100) 4.4g as anodal LiFePO4 (Tianjin STL SLFP-PD60 processed) 400g with active material, conduct conduction auxiliary material, utilize three arm planet dispersion machines (dispersion machine that aboveground making is made) to mix, afterwards, add N-N-methyl-2-2-pyrrolidone N-solution 30g, mix.

The fine carbon fiber dispersion liquid 44g, the N-N-methyl-2-2-pyrrolidone N-193.3g that add embodiment 13 in this solution, mix, at last, in order to adjust solid component concentration, the N-N-methyl-2-2-pyrrolidone N-solution 296.4g that adds 12wt%PVDF, mix modulation fine carbon fiber paste (solid component concentration 46%).

The viscosity of this fine carbon fiber paste is 1.2Pas, and the fine carbon fiber dispersity observed result in the conducting film that uses it and make is shown in Figure 53～55 (1000 times, 5000 times, 10000 times of multiplying powers).

＜embodiment 17＞

As fine carbon fiber liquid, use the N-N-methyl-2-2-pyrrolidone N-dispersion liquid that contains 10wt%NT-7K of modulation among the embodiment 12, in addition, modulate based on embodiment 16.

The viscosity of this fine carbon fiber paste is 3.0Pas, and the fine carbon fiber dispersity observed result in the conducting film that uses it and make is shown in Figure 56～58 (1000 times, 5000 times, 10000 times of multiplying powers).In addition, this lithium ion battery shows 2.23 * 10 with the volume resistance value of conducting film ²Ω cm.

＜embodiment 18＞

Adding utilizes three arm planet dispersion machines (dispersion machine that aboveground making is made) to carry out mixing as N-N-methyl-2-2-pyrrolidone N-solution (the KF PolymerW#9200 of the KUREHA Corporation system) 12.7g of negative pole with Delanium (JFE CHEMICAL Corporation HKG-P1 processed) 100g, the 12wt%PVDF of active material.Afterwards, add the N-N-methyl-2-2-pyrrolidone N-solution 32g of N-N-methyl-2-2-pyrrolidone N-solution 7.7g, 12wt%PVDF, mix.Add the fine carbon fiber dispersion liquid 22g of embodiment 13 in this solution, mix, modulation fine carbon fiber paste (solid component concentration 61%).

The viscosity of this fine carbon fiber paste is 0.47Pas, and the fine carbon fiber dispersity observed result in the conducting film that uses it and make is shown in Figure 59～61 (1000 times, 5000 times, 10000 times of multiplying powers).

＜embodiment 19＞

As fine carbon fiber liquid, use the N-N-methyl-2-2-pyrrolidone N-dispersion liquid that contains 10wt%NT-7K of modulation among the embodiment 12, in addition, modulate based on embodiment 18.

The viscosity of this fine carbon fiber paste is 0.5Pas, and the fine carbon fiber dispersity observed result in the conducting film that uses it and make is shown in Figure 62～64 (1000 times, 5000 times, 10000 times of multiplying powers).In addition, this lithium ion battery shows 3.90 * 10 with the volume resistance value of conducting film ¹Ω cm.

＜embodiment 20＞

Adding is as lithium titanate (the TOHO TITANIUM Co. of negative pole with active material, Ltd. the system) 110g, as the conduction auxiliary material Ketjen black (Lion Corporation Ketjen Black processed EC-300J) 2.4g, utilize three arm planet dispersion machines (dispersion machine that aboveground making is made) to mix.N-N-methyl-2-2-pyrrolidone N-solution (the KUREHA Corporation KFpolymerW#1100 processed) 38g that adds fine carbon fiber dispersion liquid 12g, the 12wt%PVDF of embodiment 13 in this solution mixes.

Afterwards, the N-N-methyl-2-2-pyrrolidone N-solution 11.8g of adding N-N-methyl-2-2-pyrrolidone N-solution 9.8g, 12wt%PVDF mixes.At last, in order to adjust solid component concentration, add N-N-methyl-2-2-pyrrolidone N-solution 64g, mix modulation fine carbon fiber paste (solid component concentration 50%).

The viscosity of this fine carbon fiber paste is 0.85Pas, and the fine carbon fiber dispersity observed result in the conducting film that uses it and make is shown in Figure 65～67 (1000 times, 5000 times, 10000 times of multiplying powers).In addition, this lithium ion battery shows 3.25 * 10 with the volume resistance value of conducting film ⁴Ω cm.

＜embodiment 21＞

As fine carbon fiber liquid, use the N-N-methyl-2-2-pyrrolidone N-dispersion liquid that contains 10wt%NT-7K of modulation among the embodiment 12, in addition, modulate based on embodiment 20.

The viscosity of this fine carbon fiber paste is 0.845Pas, and the fine carbon fiber dispersity observed result in the conducting film that uses it and make is shown in Figure 68～70 (1000 times, 5000 times, 10000 times of multiplying powers).In addition, this lithium ion battery shows 4.31 * 10 with the volume resistance value of conducting film ⁴Ω cm.

＜comparative example 6＞

As fine carbon fiber, use the multilayer carbon nanotube CT-12K processed of Baotugu Chemical Industrial Co., Ltd (average diameter 110nm) that uses among the embodiment 13.

Add as anodal cobalt acid lithium 150g, conduction auxiliary material (acetylene black) 3.3g, Baotugu Chemical Industrial Co., Ltd's multilayer carbon nanotube processed (CT-12K) 3.3g with active material, utilize three arm planet dispersion machines (dispersion machine that aboveground making is made) to mix.

The N-N-methyl-2-2-pyrrolidone N-solution 35.5g that adds 12wt%PVDF in the resulting solution carries out mixing, and then the N-N-methyl-2-2-pyrrolidone N-solution 6.5g, the N-N-methyl-2-2-pyrrolidone N-18.2g that add 12wt%PVDF mix.

At last, in order to adjust solid component concentration, add N-N-methyl-2-2-pyrrolidone N-solution 14.8g, mix modulation fine carbon fiber paste (solid component concentration 70%).

The viscosity of this fine carbon fiber paste is 1.41Pas, and the fine carbon fiber dispersity observed result in the conducting film that uses it and make is shown in Figure 71～73 (1000 times, 5000 times, 10000 times of multiplying powers).

＜comparative example 7＞

As fine carbon fiber, use Baotugu Chemical Industrial Co., Ltd's multilayer carbon nanotube processed (CT-12K, the average fiber footpath 100～120nm) of using among the embodiment 13.

Add as anodal LiFePO4 400g with active material, conduction auxiliary material (acetylene black) 4.4g, Baotugu Chemical Industrial Co., Ltd's multilayer carbon nanotube processed (CT-12K) 4.4g, utilize three arm planet dispersion machines (dispersion machine that aboveground making is made) to mix.Afterwards, adding N-N-methyl-2-2-pyrrolidone N-solution 30g carries out mixing.To wherein adding N-N-methyl-2-2-pyrrolidone N-206g, mix.And then the N-N-methyl-2-2-pyrrolidone N-solution 101.4g that adds 12wt%PVDF mixes.

At last, in order to adjust solid component concentration, add N-N-methyl-2-2-pyrrolidone N-solution 195.1g, the N-N-methyl-2-2-pyrrolidone N-33.3g of 12wt%PVDF, the fine carbon fiber paste of modulation solid component concentration 45.6%.

The viscosity of this fine carbon fiber paste is 1.22Pas, and the fine carbon fiber dispersity observed result in the conducting film that uses it and make is shown in Figure 74～76 (1000 times, 5000 times, 10000 times of multiplying powers).

＜comparative example 8＞

As fine carbon fiber, (in addition, example 7 obtains the fine carbon fiber paste based on the comparison for NT-7K, average fiber footpath 40～80nm) to use the Baotugu Chemical Industrial Co., Ltd's multilayer carbon nanotube processed that uses among the embodiment 12.

The viscosity of this fine carbon fiber paste is 1.18Pas, and the fine carbon fiber dispersity observed result in the conducting film that uses it and make is shown in Figure 77～79 (1000 times, 5000 times, 10000 times of multiplying powers).In addition, this lithium ion battery shows 3.59 * 10 with the volume resistance value of conducting film ²Ω cm.

Utilizability on the industry

According to the present invention, by using specific macromolecule dispersing agent, thereby can obtain to disperse, separate the fine carbon fiber dispersion liquid of fibre and the high and low viscosity of storage stability.In addition, even for the fine carbon fiber dispersion liquid that contains additives such as resinous principle, also can fully keep the dispersiveness of fine carbon fiber.And then, use this fine carbon fiber dispersion liquid and the fine carbon fiber film made, have good electrical conductivity.Therefore, they go for not wishing having in the e-machine field, cleaning shop of static etc. etc. in case charged membrane, low resistance film for the electrode of necessary thermal diffusivity resin molding, electromagnetic shielding film, lithium ion battery etc.

Claims

1. fine carbon fiber dispersion liquid, it is for being dispersed with the fine carbon fiber dispersion liquid of fine carbon fiber in organic solvent, it is characterized in that, contain the macromolecule dispersing agent that is constituted by the polymer shown in the following general formula (1), and the aggregation of contained fine carbon fiber is of a size of below the 5 μ m in this dispersion liquid

In the formula (1), R ¹～R ⁴Alkyl, hydroxy alkyl, alkoxyl, acyloxy, carboxyl, acyl group, amino, aryl, aryloxy group or the heterocyclic radical of representing hydrogen atom, carbon number 1～30 respectively independently,

(x＋z)/y＝60/40～90/10。

2. fine carbon fiber dispersion liquid according to claim 1 wherein, is that the amount of 1～200 mass parts contains aforementioned macromolecule dispersing agent to be equivalent to fine carbon fiber 100 mass parts.

3. fine carbon fiber dispersion liquid according to claim 1, wherein, aforementioned macromolecule dispersing agent is represented by following general formula (2):

In the formula (2), R ⁵～R ⁷And x～z is with identical shown in the aforementioned formula (1).

4. fine carbon fiber dispersion liquid according to claim 3, wherein, aforementioned macromolecule dispersing agent is represented by following general formula (3):

In the formula (3), R ⁸Alkyl, aryl or the heterocyclic radical of expression hydrogen atom, carbon number 1～30,

R ⁹Be alkyl, alkyl-carbonyl, aryl, heterocyclic radical, pyrans glycosyl or the furyl glycosyl of carbon number 1～30, x, y and z are with identical shown in the general formula (1).

5. fine carbon fiber dispersion liquid according to claim 1, it also contains anionic surfactant or nonionic surfactant.

6. fine carbon fiber dispersion liquid according to claim 5, it contains the compound shown in the following general formula (4) as aforementioned anionic surfactant:

In the formula (4), A is sodium ion, potassium ion or ammonium ion, and the number of B average out to 1～100, C are 1～3 number.

7. fine carbon fiber dispersion liquid according to claim 5, it contains the compound shown in any one of following general formula (5), general formula (6) or general formula (7) as aforementioned nonionic surfactant,

In aforementioned formula (5)～(7),

R ¹⁰～R ¹⁴Alkyl, hydroxyl, hydroxy alkyl, 1-phenyl-ethyl or the benzyl of representing hydrogen atom, carbon number 1～30 respectively independently, R ¹⁰～R ¹⁴At least one be not hydrogen atom,

The number of D average out to 1～100,

The number of E average out to 1～100,

F is 1～3 number,

The number of G average out to 10～50.

8. fine carbon fiber dispersion liquid according to claim 1, wherein, aforementioned fine carbon fiber has the mean outside diameter of 0.5～200nm.

9. fine carbon fiber dispersion liquid according to claim 1, it has the viscosity of 0.2～100Pas (20 ℃).

10. fine carbon fiber dispersion liquid according to claim 9, it is used for the formation of lithium ion cell electrode.

11. fine carbon fiber dispersion liquid according to claim 10 wherein, has added negative pole with electrode active material or positive pole electrode active material.

12. fine carbon fiber dispersion liquid according to claim 11, wherein, aforementioned negative pole electrode active material is that to be selected from by charcoal be that active material, silicon are at least a in the group formed of active material and lithium titanate.

13. fine carbon fiber dispersion liquid according to claim 11, wherein, aforementioned anodal be to be selected from least a in the group of being formed by bedded rock salt compound and derivative, spinel-type compound and derivative, polyanionic compound and derivative thereof with electrode active material.

14. a lithium ion cell electrode paste, it is added with negative pole and uses electrode active material with electrode active material or positive pole in fine carbon dispersion liquid, and has the viscosity of 0.2～100Pas (20 ℃).

15. lithium ion cell electrode paste according to claim 14, wherein, aforementioned negative pole electrode active material is that being selected from by native graphite, Delanium, silicon is at least a in the group formed of active material and lithium titanate.

16. lithium ion cell electrode paste according to claim 14, wherein, aforementioned anodal be to be selected from least a in the group of being formed by bedded rock salt compound and derivative, spinel-type compound and derivative, polyanionic compound and derivative thereof with electrode active material.

17. a lithium ion battery electrode conducting film, the described lithium ion cell electrode of its coating claim 14 obtains with paste.

18. a lithium ion battery conducting film, it is coated the described lithium ion cell electrode of claim 14 on the metallic film with paste and obtains.

19. a lithium ion battery, its right to use require 17 described lithium ion batteries to obtain with the electrode conducting film.