[1]Mutual citations and related applications
[2]This application claims the benefit of priority based on the March 24 issue of Korea Patent Application No. 2016-0035560, and March 24, 2017 Date of Korea Patent Application No. 2017-0037748 years 2016, all described in the literature of the Korea Patent Application content of which is incorporated as a part hereof.
[3]Art
[4]The present invention relates to an excellent dispersibility and powder get a low resistance conductive material dispersion useful in the preparation of an electrode for high power, the method for producing a conductive material dispersion, and a secondary battery produced by using the dispersion of the conductive material.
BACKGROUND
[5]
There is demand for secondary batteries as an energy source is rapidly increasing as the development of technology and the demand for mobile devices increases. The secondary battery has a high energy density and voltage, long cycle life, self-discharge rate are commercially available and widely used low-lithium secondary battery. Further, as a high-capacity lithium secondary cell electrode as this, there has been actively conducted research on methods for the preparation of a unit to a higher energy density per unit electrode volume increase the electrode density.
[6]
In general, a high-density electrode since the electrode active material particles having a size of several to several tens can ㎛ ㎛ formed by molding with a high-pressure press, the particles are deformed, the space is reduced between the particles, the electrolyte tends to decrease permeability.
[7]
To address this problem, it uses a conductive material having excellent electrical conductivity and strength in the manufacture of electrodes. When using a conductive material, the conductive material in electrode production is easy penetration of the electrolyte to maintain the fine pores in between being distributed between the compressed particles of active material and the electrode active material, it is possible to reduce the electrode resistance in a good conductivity. In particular, such a conductive material and the use of fiber-like carbon-based conductive recognition carbon nanotubes that can further reduce the electrode resistance is increased by forming the electrically conductive paths within the electrode.
[8]
A type of carbon nanotube in the fine carbon fiber is a carbon tube having a diameter of 1μm or less diameter, due to the specific structure in which a high electric conductivity, tensile strength and heat resistance, etc. has been expected due to the application and practical use to various fields. However, this in spite of the availability of carbon nanotubes, and carbon nanotubes, there is a limit to their use due to their low solubility and dispersibility. In the composition for forming an electrode was prepared using line was dispersed in a dispersion medium, a carbon nanotube electrode manufacturing carbon nanotubes using. However, the carbon nanotubes have a problem, agglomeration does not form a stable dispersion state in the dispersion medium by strong van der Waals attraction between each other phenomena.
[9]
To solve these problems, there have been various attempts. Specifically, there is a method of dispersing a dispersion medium has been proposed in the carbon nanotubes through a mechanical dispersing treatment such as sonication. However, while investigating the case of the ultrasonic dispersion method is excellent, but if the ultrasonic irradiation is terminated is the aggregation of the carbon nanotubes start to have a problem that the concentration of carbon nanotubes As aggregation increases. In addition, there is a method of stabilizing a dispersion of carbon nanotubes have been proposed using a variety of dispersants. However, when these methods also be distributed at high concentrations in the fine carbon fiber dispersion medium, there is a problem that the viscosity is difficult to treat due to the rise.
[10]
Accordingly, there is a need for a way to improve the dispersibility of the carbon nano-tube electrodes without lowering the conductivity and the development of methods to use them for producing a carbon nanotube dispersion useful for electrode production.
Detailed Description of the Invention
SUMMARY
[11]
The first object of the present invention is to provide excellent dispersibility and dispersion useful conductive material and a method of manufacturing the powder get a low resistance characteristic in the manufacture of electrodes for high output.
[12]
The second object of the present invention to provide a composition for forming an electrode of a secondary battery including the conductive agent dispersion.
[13]
Further, a third object of the present invention, there is provided a secondary battery, the conductive material produced by using the dispersion of electrode, lithium secondary batteries, battery modules and a battery pack.
Problem solving means
[14]
According to one embodiment of the present invention to solve the above problem, the conductive material comprising a bundle-type (bundle-type) carbon nanotubes; Hydrogenated nitrile-based dispersing agent comprising a rubber; And a dispersion medium, a rheometer measurement frequency 1Hz when the complex elastic modulus (Complex (shear) modulus, | G * | @ 1Hz) that provides a dispersion of a conductive material like a 20Pa to about 500Pa.
[15]
According to another embodiment of the invention, after mixing a dispersant and a dispersion medium containing a conductive material, a hydrogenated nitrile rubber comprising a bundle-type carbon nanotubes, rheometer measurement frequency 1Hz when the complex elastic modulus (| G * | @ 1Hz) that provides 20Pa to about 500Pa the milling step, the manufacturing method of the above-described conductive material, a dispersion containing such that.
[16]
In addition, according to another embodiment of the present invention to provide a composition for forming an electrode of a secondary battery including the above-described conductive material dispersion, the electrode active material and a binder.
[17]
According to another embodiment of the present invention, there is provided a secondary battery electrode and a lithium secondary battery produced by using the composition for forming the electrode.
[18]
More specific details of the embodiments of the invention are included in the following description.
Effects of the Invention
[19]
Conductive material dispersion according to the present invention is that the carbon nanotubes have excellent conductivity as the conductive material powder can reduce the resistance of the dispersion being optimal, composition for forming electrodes upon application to the electrode produced by improving the output characteristics of the electrode. Accordingly, the conductive material, the dispersion is useful for electrode production in a cell which requires high output characteristic, such as a car battery.
Brief Description of the Drawings
[20]
Following figures attached to this specification are intended to illustrate preferred embodiments of the present invention, the components which serve to further understand the teachings of the present invention with the content of the above-described invention, the invention is only to details set forth in those figures is limited shall not be interpreted.
[21]
1 is observed a change in shear viscosity of the Example 1, 2 and the comparative shear rate of a conductive material dispersion liquid prepared in Examples 1 to 4 in Experimental Example 1, the chart.
[22]
Figure 2 in Experimental Example 2, Examples 1, 2 and the Comparative Example 1 to observe the phase angle and the complex elastic modulus of the conductive material dispersion prepared in graph 4.
[23]
Figure 3 is a graph of observed changes in the powder resistance of the press density of Examples 1, 2 and Comparative Example 1 for the dispersion of conductive material, each forming an electrode prepared using the composition in to 3 in Experimental Example 3.
Best Mode for Carrying Out the Invention
[24]
Hereinafter, the present invention will be described in more detail to aid the understanding of the present invention.
[25]
Herein and in the terms or words used in the claims is general and not be construed as limited to the dictionary meanings are not, the inventor can adequately define terms to describe his own invention in the best way on the basis of the principle that the interpreted based on the meanings and concepts corresponding to technical aspects of the present invention.
[26]
[27]
The terms used in the present invention "bundled (bundle type)" is a plurality of carbon nanotube-units is 2 per unit length is substantially parallel to the array bundle (bundle) form in the same orientation axis in a direction unless otherwise stated It refers to a tea-like. Also refers to the form of "unbundled type (non-bundle type) or entangled (entangled type)" is a carbon nanotube unit intertwined without a certain shape, such as a bundle or rope form.
[28]
[29]
Usually after using a conductive material containing carbon nanotubes to prepare a dispersion by line dispersing the carbon nanotubes in the dispersion medium in order to improve the production, dispersibility of the secondary cell electrode, by using this, making the compositions and electrodes for forming an electrode and. Accordingly, electrodes and the characteristics of the battery, especially in order to improve the output characteristics of the battery must be used for the conductive material dispersion liquid having a suitable viscosity and dispersed in the composition for forming an electrode, the conductive member the dispersity of the conductive material, the dispersion easily For this evaluation and it must be measured.
[30]
Conductive material, the degree of dispersion of a conventional conductive material dispersion liquid was evaluated by the particle size distribution measured by a particle size analyzer (particle size analysis, PSA). However, in the case of the linear carbon nanotube, such as bundle-type carbon nanotubes because the particle size is dependent on the measured angle, it is difficult to evaluate dispersibility of the dispersion. In addition, there is, a fear that the contact resistance is increased, the output characteristics of a battery significantly reduced if the linear carbon nanotube and dispersing.
[31]
[32]
Thus, in the present invention for bundled (bundle-type) electrode production using a conductive material containing carbon nanotubes, the complex elastic modulus of the conductive material dispersion liquid (Complex (shear) modulus, | @ 1Hz | G *) for the control of through the conductive material provides a dispersion having a favorable conductive material dispersibility and viscosity characteristics to the electrodes formed in the high-output characteristics.
[33]
[34]
That is, the conductive material dispersion liquid in accordance with one embodiment of the present invention,
[35]
Conductive material comprising a bundle-type carbon nanotubes;
[36]
Hydrogenated nitrile rubber-based dispersing agent; And
[37]
Comprising a dispersion medium,
[38]
Rheometer (rheometer) measured at 1Hz frequency when the complex elastic modulus (| G * | @ 1Hz) is a 20Pa to about 500Pa.
[39]
[40]
In the present invention, the complex elastic modulus or the complex shear modulus of the conductive material dispersion liquid is a quantity representing the dynamic viscoelasticity, it means the size of the elastic energy accumulated in the material becomes smaller gradually changed from a solid to a liquid state. The complex elastic modulus of the conductive material in the dispersion of the invention is a viscosity meter, specifically, can be measured by using a rheometer. More specifically, after a set constant distance between the rheometer of the circular rotary plate, the conductive material into the dispersion for the volume are filled in the interval, the frequency is 1Hz when the shear rate in 1 / s every 10 -3 eseo 10 3 a force that generates dolrineunde set on the spindle to the extent can be determined by measuring the viscosity shear rate (shear viscosity) value.
[41]
[42]
Specifically, the conductive material dispersion liquid in accordance with one embodiment of the present invention, the complex modulus of elasticity when the rheometer measurement frequency 1Hz a (| @ 1Hz | G *) is 20Pa to about 500Pa. If the complex elastic modulus of the conductive material dispersion liquid is less than 20Pa low viscosity of the dispersion too, is not easy to form the electrodes because the dispersibility is reduced, and if the complex modulus exceeds 500Pa the viscosity of the dispersion liquid by a pressure increase in the manufacturing process since not only difficult to handle has high viscoelasticity in the manufacture of a composition for forming an electrode there is a fear that the productivity decreases due to the reduced solids content. Minutes improve dispersibility of the conductive material, the dispersion according to the complex elastic modulus of the control of the conductive material dispersion, and further considering the hereinafter a remarkable improvement effect of the powder resistance decreases and the battery output characteristics of the electrode produced by using a complex of the conductive material dispersion modulus may be 50Pa to about 350Pa in detail.
[43]
[44]
In addition, the conductive material dispersion liquid in accordance with one embodiment of the present invention is a shear rate when measured using a rheometer (shear rate) is a 1 / 6.3s days when shear rate viscosity (shear viscosity) is 2Pa · s to 20Pa · s It may be. By having a low shear rate viscosity as compared to prior art as described above, it can exhibit an excellent dispersing property when applied than for the electrode manufacture. More specifically, the conductive material, the dispersion may be a shear rate viscosity 3.0Pa · s to 15Pa · s.
[45]
[46]
Grade water dispersion characteristics of the conductive material as described above may be implemented via control of the conductive material, the dispersant and the type of the dispersion medium, the physical properties and the mixing ratio to configure it.
[47]
In addition, carbon nanotubes can have physical properties vary depending on the structure and shape of the secondary particles made of a crystal and structure and form of the unit of the unit of the carbon nanotubes. Accordingly, by controlling which of the above factors, one or two or more in combination, it is possible to have the physical properties required according to the application of carbon nanotubes.
[48]
[49]
Specifically, according to the conductive material dispersion liquid in accordance with one embodiment of the present invention, a type conductive material comprising the carbon nanotube bundles.
[50]
The carbon nanotube is a secondary structure of the carbon nanotubes per unit formed are set to fulfill the bundled in whole or in part, the CNT units has a cylindrical form of the graphite surface (graphite sheet) The nano-sized diameter, sp 2 It has a coupling structure. At this time, the angle and the structure in which the graphite surface to dry and thus can exhibit the characteristics of a conductor or semiconductor. CNT unit is single-walled carbon nanotube according to the number of bonding that make up the wall (SWCNT, single-walled carbon nanotube ), double-walled carbon nanotube (DWCNT, doublewalled carbon nanotube) and multi-walled carbon nanotube (MWCNT, multi- It can be classified as a walled carbon nanotube), and the lower the more the wall thickness thinner resistance.
[51]
[52]
The conductive material according to the dispersion according to one embodiment of the invention Accordingly, the carbon nanotube may include any of the carbon nanotubes per unit of single wall, double-wall and multi-wall one or more than one.
[53]
[54]
In addition, as a secondary battery, conductive material, the diameter of the CNT units is too large, it is also significantly increase the pore diameter of the electrode may be an electrode density decreases. Further, if the diameter of the CNT units is too small, dispersion is a dispersion prepared fairness decreases difficult, the dispersion of carbon nanotubes per unit or a carbon nanotube is buried in a space between the electrode active material particles, it is difficult to have sufficient porogen . Accordingly, the average strand diameter of a carbon nanotube unit in the carbon nanotubes can be used in the present invention can be less than 30nm, considering the conductive material dispersibility improves, and the electrode within the drag reduction effects of the diameter control of the unit, the the average strand diameter of the carbon nanotubes per unit may be a 10nm to 20nm.
[55]
[56]
Further, the longer the carbon nanotubes per unit electrical conductivity, strength and electrolytic solution retention of a storage electrode can be improved. If there since the length of carbon nanotubes per unit is difficult to form a conductive path short-effective is a fear that the electrical conductivity decreases. On the other hand, there is a fear that the length of the carbon nanotubes per unit is too long, the dispersibility decreases. Accordingly, the length of the unit in a carbon nanotube can be used in the present invention may be a 1㎛ to 200㎛. In addition, given the diameter of the carbon nanotubes per unit, the CNT units has went by the center of the carbon nanotube length (length of the long axis passing through the center of the unit) and the diameter of the unit (unit, perpendicular to the longitudinal axis the aspect ratio is defined as the ratio of the length of the minor axis) it may be from 5 to 50,000, and may be more specifically 10 to 20,000.
[57]
In the present invention, the strand diameter and the length of the carbon nanotubes per unit can be measured using a field emission scanning electron microscope.
[58]
[59]
On the other hand, carbon nanotubes including carbon nanotube units as described above may be one of the true density (TD) and the ratio (TD / BD ratio) is 70 to 120 of the bulk density (BD).
[60]
In the present invention, the true density (TD) and there from the ratio of the bulk density (BD) to predict the internal structure of the carbon nanotube, and capacity characteristics of the battery because of TD / BD ratio is too large, the carbon nanotube is low the content of the monomer this has a risk of degradation, if the addition ratio is too small, TD / BD there is a possibility that the dispersibility of the carbon nanotube decreases. When the bulk density and true to consider that the remarkable effect of improvement of the ratio control of the density, TD / BD ratio of the carbon nanotubes can be used in the present invention can be from 70 to 100 days in detail. Also, the true density of the carbon nanotubes can be used in the present invention under conditions that satisfy the above-described TD / BD ratio kg 1800 / m 3 to kg 2200 / m 3 may be.
[61]
[62]
Further, in the above-mentioned conductive material dispersion liquid in accordance with one embodiment of the present invention, the carbon nanotubes have a bulk density kg 10 / m 3 to kg 50 / m 3 may be the. The conductivity and the dispersibility of carbon nanotubes, by having a bulk density in the above range can be improved.
[63]
In the present invention, the bulk density of the carbon nanotubes can be determined according to the following equation (1).
[64]
Equation 1
[65]
Bulk density (kg / m 3 ) = CNT weight (kg) / CNT volume (m 3 )
[66]
[67]
Further, in the above-mentioned conductive material dispersion liquid in accordance with one embodiment of the present invention, the carbon nanotubes exhibit excellent dispersibility gatjyeo a high BET specific surface area, because as described above the diameter of the unit is small, TD / BD ratio Size can. Specifically, the BET specific surface area of the carbon nanotube can be used in the present invention is 180 m 2 / g to 300 m 2 may be a / g, more specifically 230 m 2 / g to 300 m 2 may be / g. In the present invention, the specific surface area of the carbon nanotubes as measured by the BET method, specifically, can be calculated using the BEL Japan Inc. BELSORP-mino II from the nitrogen gas adsorption amount at the liquid nitrogen temperature, and (77K) have.
[68]
[69]
In the present embodiment the conductive material, the dispersion according to the invention, the carbon nanotube is 1580 ± 50 cm obtained by the Raman spectroscopic analysis using a laser of 514nm wavelength -1 up to the peak intensity of G-band of the (IG ) 1360 ± 50 cm about -1 may be a non-(ID / IG) is an average value of 0.7 to 1.2 of the maximum peak intensity (ID) of the D band at.
[70]
[71]
Raman spectrometry is a useful method in a method for analyzing the structure of the carbon nanotubes, the surface state analysis of the carbon nanotubes. Raman spectrum of a wave number of 1570cm CNT -1 ~ 1580cm -1 , and that the peak present in the region in the vicinity of the G band, which is a peak showing the sp2 bonding of carbon nanotubes, indicates the carbon crystal structure with no defect. On the other hand, the Raman spectrum of a wave number 1350cm -1 ~ 1360cm -1 to a peak present in the region in the vicinity of the called D band, which is a peak showing the sp3 bonding of the carbon nanotubes, the atom consisting of sp2 bond broken can be combined with sp3 It increases when. Such a D band is up to the peak intensity of D-band of the disorder (disorder) to the defect (defect), or because the increase when the amorphous is generated, a maximum peak intensity (IG) of G-band present in the carbon nanotubes ( by calculating the ratio (ID / IG) of the ID) it can be evaluated to generate the degree of disorder (disorder) to the defect (defect) quantitatively.
[72]
[73]
G band in Raman spectrum for the carbon nanotubes in the present invention is a wave number 50 cm ± 1580 -1 region, more specifically from 1575 cm -1 to 1600 cm -1 may be a peak in an area, the frequency band D 50 cm ± 1360 -1 region, and more specifically to 1340 cm -1 to 1360 cm -1 may be a peak in an area. Wave number range with respect to the G-band and D band is within the scope that can be shifted in accordance with the laser light source used for the Raman spectrometry. Raman value to be used in the present invention is not particularly limited, it is possible using the DXR Raman Microscope (Thermo Electron Scientific Instruments LLC) measured at a laser wavelength of 514nm.
[74]
[75]
Usually The G band is large, the peak integration value and the D band ratio value peak integration short of either the amorphous carbon is large amount means that the crystallinity is poor in the CNT, the present invention is increased and the secondary of the bundle-like structure a BET specific surface area the crystallinity of the CNT while preferably will have an average value of ID / IG as described above has a shape according to the.
[76]
[77]
In addition, the carbon nanotube is a main catalyst or a promoter derived from the metal elements such as Co, Mo, V, or Cr is used in the manufacturing process, less than 50ppm, and more particularly may comprise an amount up to 5ppm. Thus, by significantly reducing the metal content as the residual impurities from the carbon nanotube it can exhibit a more excellent conductivity without concern about side reactions within the electrodes. In the present invention, the content of the residual metal to carbon nanotube impurities may be analyzed with a high-frequency inductively coupled plasma (inductively coupled plasma, ICP). In addition, the carbon nanotubes may or may not contain Fe.
[78]
[79]
In addition, the carbon nanotubes to have excellent electrical conductivity, specifically, may be in when the pressure is 62 MPa, the volume resistivity is 0.01Ω · cm or less, more specifically from 0.0001 Ω · cm to 0.009 Ω · cm .
[80]
In the present invention, the volume resistivity of the CNTs was the current and voltage of a surface-filled carbon nanotubes in an insulating mold having a diameter of 1mm and the pressure measured by the four probe, the pressure is 62 MPa to apply a correction coefficient days It was calculated by the volume resistivity values ​​at the time.
[81]
[82]
Carbon nanotubes as described above may be used to manufacture may be used either commercially available, or directly. When manufacturing, the arc discharge method, laser evaporation method, or may be prepared using conventional methods, such as chemical vapor deposition, the physical properties over the control, such as type, removing the heat treatment temperature and the impurities of the catalyst in manufacturing method a it can be implemented.
[83]
[84]
In particular, when prepared in accordance with the chemical vapor phase synthesis, the carbon nanotubes by contacting the supported catalyst with a metal catalyst on a spherical alumina support bearing α- under a carbon source to the heating step for producing a carbon nanotube, and optionally depending can be selectively prepared by the method comprising the step of removing the metal impurities in carbon nanotubes.
[85]
[86]
Producing a carbon nanotube according to the chemical vapor phase synthesis, the more the supported catalyst specifically in a horizontal fixed-bed reactor or a temperature below the melting point of the placed in a fluidized bed reactor and the gas phase above the thermal decomposition temperature of the carbon source to the said supported metal catalyst a carbon source; Or the carbon source and the reducing gas may be performed by (for example, hydrogen, etc.) and carrier gas (e.g., nitrogen) is injected into the gas mixture growing carbon nanotubes by chemical vapor phase synthesis over the carbon source decomposition of . Carbon nanotubes manufactured by chemical vapor phase synthesis as described above and the growth direction of the crystal substantially parallel to the tube axis, it is highly graphite crystalline structure as the tube longitudinal direction. As a result, the smaller the diameter of the unit, a high electrical conductivity and strength.
[87]
[88]
In addition, the production of the carbon nanotubes, specifically, a temperature of less than 500 ℃ 800 ℃, and more specifically may be carried out at 550 ℃ to 700 ℃. Within the reaction temperature range, because the weight is reduced while maintaining the bulk size of the carbon nanotube to be produced while minimizing the generation of non-crystalline carbon, and the dispersibility according to the reduced bulk density it can be further enhanced. As the heat source for the heat treatment inductive heating (induction heating), there is radiant heat, laser, IR, microwave, plasma, surface plasmon heating, can be used.
[89]
[90]
Further, as the carbon source is capable of supplying carbon, so long as it can be present in the gas phase at above 300 ℃ temperature can be used without particular limitations. More specifically, it may be a carbon based compound having a carbon number of 6 or less, more specifically coming from the carbon monoxide, methane, ethyl, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, and the like benzene or toluene, there is any one or a mixture of two or more of them may be used.
[91]
[92]
Then by a heat treatment, such as the growth of carbon nanotubes, cooling step for regularly aligned than the array of carbon nanotubes it can optionally be further performed. The cooling process may be specifically carried out using a self-cooling or the like according to the condenser of the heat source removed.
[93]
[94]
On the other hand, the catalyst used for the conductive material is prepared, the metal is a catalyst for the spherical α- alumina support bearing.
[95]
α- alumina has a very low utilization as a porous catalyst support is very low compared to the γ- alumina. However, by controlling the firing temperature at which the supported catalyst is formed by using this, while suppressing the carbon nanotubes during the generation of amorphous carbon to reduce the specific surface area it may increase the diameter. At the same time to reduce the bulk density of the carbon nanotubes may improve the dispersibility.
[96]
[97]
Specifically, the α- alumina is available as a support in the invention is the average particle diameter (D 50 is a) 20㎛ to 200㎛, 1 m 2 / g to 50 m 2 may be one having a BET specific surface area / g. In Fig it said α- alumina has a very low porosity smoother the surface, specifically, cm 0.001 3 / g to 0.1 cm 3 may be one having a porosity of / g.
[98]
[99]
On the other hand, the containing of the α- alumina spherical support with the supported catalyst may be prepared by firing after loading of the metal catalyst in the α- alumina support of the above-described spherical shape. Specifically, the supported catalyst is carried out by the one prepared by dissolving a precursor of the metal catalyst with water the metal catalyst precursor solution After adding and mixing the α- alumina support of the spherical, calcined at a temperature not higher than 700 ℃ It can be.
[100]
[101]
Metal catalyst to be supported on the support and serves to help the carbon components present in the gaseous carbon source to form a 6-membered ring structure are bonded to each other. In the metal catalyst is iron, nickel or may be a main catalyst of cobalt and the like used alone, or the main catalyst is a main catalyst with a cocatalyst, such as molybdenum, vanadium or chromium-may be used in the form of a co-catalyst complex catalyst . Specifically, the complex catalyst and the like FeCO, CoMo, CoV, FeCoMo, FeMoV, FeV, or FeCoMoV, there is any one or a mixture of two or more of them may be used. In addition, the co-catalyst is a catalyst with respect to 1 mol of the main 0.01 mol to 1 mol, more particularly, may be used in an amount of 0.05 mol to 0.5 mol.
[102]
[103]
In the production of a supported catalyst, which is the precursor to the metal catalyst and the like, soluble metal salt or metal oxide in water can be used, which is specifically, Fe, Ni, Co, Mo, V, Cr, and selected from one or more than one metal salt containing a metallic element, metal oxide, or metal halide can be a. More specifically, the Fe (NO 3 ) 2 · 9H 2 O, Co (NO 3 ) 2 · 6H 2 O, Co 2 (CO) 8 , [Co 2 (CO) 6 (t-BuC = CH)], Cu (OAc) 2 , Ni (NO 3 ) 2 · 6H 2 O, (NH 4 ) 6 Mo 7 O 24 · 4H 2 O, Mo (CO) 6 , (NH 4) MoS 4 and NH 4 VO 3 may be any one or a mixture of two or more selected from the group consisting of is used.
[104]
[105]
In addition, precursors of the metal catalyst may be used as an aqueous solution dissolved in water, at this time, and in consideration of the impregnation efficiency, the concentration of the metal catalyst precursor in the aqueous solution can be properly adjusted. Specifically, the metal concentration in the catalyst precursor in an aqueous solution may be a 0.1 g / ml to 0.6 g / ml.
[106]
[107]
Further, in consideration of the content of the support in the supported catalyst to be finally manufactured, the content of the metal catalyst precursor and the α- alumina support of the rectangle to be mixed may be determined as appropriate.

Claims

[Claim 1]Conductive material comprising a bundle-type carbon nanotubes; dispersing agent including a hydrogenated nitrile rubber; And a dispersion medium, a rheometer measurement frequency 1Hz when the complex elastic modulus (| G * | @ 1Hz) is 20Pa to about 500Pa in that the conductive material dispersion.
[Claim 2]
The method of claim 1, wherein, when measured using a rheometer shear rate is 1 / 6.3s one viscosity when shear rate is 2Pa · s to 20Pa · s in that the conductive material dispersion.
[Claim 3]
The method of claim 1, wherein the carbon nanotubes of the conductive material and having an average dispersion diameter of the strands comprising the carbon nanotubes per unit than 30nm.
[Claim 4]
The method of claim 1, wherein the carbon nanotube is 1580 ± 50 cm obtained by the Raman spectroscopic analysis using a laser of 514nm wavelength -1 1360 ± 50 cm on the maximum peak intensity of G-band at -1 of D band at the conductive material dispersion to the average value of the maximum peak intensity ratio of 0.7 to 1.2.
[Claim 5]
The method of claim 1, wherein the carbon nanotubes when the pressure is 62MPa, the volume resistance of 0.01Ω · cm or less dispersion of the conductive material.
[Claim 6]
The method of claim 1, wherein the carbon nanotubes have a BET specific surface area m 180 2 / g m to about 300 2 / g, and a bulk density of kg 10 / m 3 to kg 50 / m 3 a dispersion of a conductive material like a.
[Claim 7]
The method of claim 1, wherein the carbon nanotubes the dispersion of the conductive material is included as 1% to 5% by weight relative to the total weight of the conductive material dispersion.
[Claim 8]
The method of claim 1 wherein the hydrogenated nitrile rubber dispersion of the conductive material comprises a conjugated diene from 1 weight% to 15 weight% of repeating units derived from the structure for the hydrogenation rubber total weight.
[Claim 9]
The method of claim 1 wherein the hydrogenated nitrile rubber dispersion of the conductive material comprises a α, 10% to 60% by weight of repeating units of β- unsaturated nitrile-derived structure for the rubber total weight.
[Claim 10]
The method of claim 1 wherein the hydrogenated nitrile rubber, the rubber total, relative to the weight, of repeating units of acrylonitrile repeating units of hydrogenated butadiene-derived structure with 1% by weight to 15% by weight and an acrylic-derived structure 10% to 60 dispersion of a nitrile to a hydrogenated acrylonitrile butadiene rubber to the conductive material comprising in weight percent.
[Claim 11]
The method of claim 1 wherein the hydrogenated nitrile rubber has a weight average molecular weight of 10,000g / mol to about 700,000g / mol, and the dispersion of the conductive material will have a polydispersity index of 2.0 to 6.0.
[Claim 12]
The method of claim 1 wherein the dispersant is a dispersion of the conductive material will be an amount of 10 parts to 50 parts by weight based on 100 parts by weight of carbon nanotubes.
[Claim 13]
The method of claim 1, wherein the dispersing agent is introduced to the surface of the carbon nanotubes, carbon nanotubes form a complex dispersant, and the carbon nanotube-dispersant complex is the particle size distribution D 99 is less than the 50㎛, the dispersion total weight the conductive material dispersion liquid is included in an amount of 1% to 5% by weight based.
[Claim 14]
The method of claim 1, wherein the dispersion medium is the dispersion of the conductive material to the amide-based organic solvent.
[Claim 15]
After mixing, a dispersant and a dispersion medium containing a conductive material, a hydrogenated nitrile rubber comprising a bundle-type carbon nanotubes, rheometer measurement frequency 1Hz when the complex elastic modulus (| G * | @ 1Hz) is such that the 20Pa to about 500Pa method for producing a conductive material, the dispersion comprising the step of milling.
[Claim 16]
The method of claim 15 wherein the milling method of producing a conductive material, the dispersion is performed by a bead mill.
[Claim 17]
The method of claim 15, wherein the milling mean diameter of 0.5mm to 2mm by using a bead mill for 90 to 120 minutes The method of producing a conductive material, the dispersion is performed for.
[Claim 18]
The electrode active material; bookbinder; And any one of claims 1 to 14 for an electrode of a secondary battery formed of a conductive material dispersion according to any one of items composition.
[Claim 19]
It is manufactured using the composition for forming an electrode according to claim 18, wherein the secondary cell electrode.
[Claim 20]
20. The method of claim 19, wherein the secondary cell electrode to which the electrode is the anode.
[Claim 21]
21. The method of claim 20, wherein the positive electrode is the positive electrode active material 500 mg / 25cm 2 to about mg 1000 / 25cm 2 of the secondary cell electrode comprises a loading of.
[Claim 22]
anode; cathode; Comprising a separator and an electrolyte, wherein at least one of the positive electrode and the negative electrode is a lithium secondary battery to an electrode according to claim 19.