CN102795618B - Vapor growth graphite fiber composition, its mixture and application - Google Patents
Vapor growth graphite fiber composition, its mixture and application Download PDFInfo
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- CN102795618B CN102795618B CN201210287234.XA CN201210287234A CN102795618B CN 102795618 B CN102795618 B CN 102795618B CN 201210287234 A CN201210287234 A CN 201210287234A CN 102795618 B CN102795618 B CN 102795618B
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Abstract
The invention relates to a vapor growth graphite fiber composition, its mixture and an application. The VGGF composition comprises a carbon component with content of at least 99.9 weight percentage, the graphitization degree of the carbon component is at least 75%, the carbon component comprises non fibrous carbon and fibrous VGGF, wherein the area ratio of the non fibrous carbon to the fibrous VGGF measured by a scanning electron microscope is less than or equal to 5%. The fibrous VGGF also comprises the graphite fiber in a three-dimensional crosslinked structure, wherein the content of the graphite fiber which is measured by the scanning electron microscope in the three-dimensional crosslinked structure is between 5 area percentages and 50 area percentages in the fibrous VGGF. The VGGF composition and its mixture can be used in the composite materials for increasing the strength, conductive property, heat conduction property and the like of the composite material.
Description
Technical field
The invention relates to a kind of graphite fibre (Graphite Fibers) constituent and its mixture, and relate to especially a kind of vapor phase growth graphite fibre (Vapor-Grown Graphite Fibers; VGGF) constituent and its mixture.
Background technology
In recent years, along with the evolution step of the industries such as information, communication, computer, the energy, the direction progress of electronic equipment past more small volume, higher function, therefore have higher demand for the performance of electronic material.Known technology often adds non-fibrous carbon black in the material such as plastics, rubber, to improve the performances such as the heat conduction, conduction, intensity of material.Because non-fibrous carbon black is particulate state, thereby lack continuity, therefore often must add in a large number slightly effect.But a large amount of results of adding can make the physical property of multiple material decline and easily decarburization, cause dust free chamber that the problem of processing degree of cleaning occurs.
Another known technology changes into and adopts polyacrylonitrile (PAN) base carbon fibre and pitch (Pitch) base carbon fibre.Although these carbon fibers have continuity, but its diameter too large (approximately 10 microns (μ m) more than), the network Limited Number that can form in Yu Fucai, thus still in a large number interpolation just can produce effect, also cause its physical property decline and have the problem of easy decarburization.
For solving the above problems, then a known technology utilizes the gas-phase growth of carbon fibre that diameter is less (Vapor-Grown Carbon Fiber; VGCF) replace non-fibrous carbon black and carbon fiber.Due to the diameter quite little (about 50 to 200 nanometers (nm)) of VGCF, therefore can form on a small quantity many contiguous networks as long as add in multiple material, thereby can not cause multiple material physical property to decline and the problem of decarburization, can maintain the degree of cleaning of dust free chamber.Add, VGCF has the characteristics such as excellent thermal conductivity, electroconductibility, high strength, can significantly promote the performance of multiple material.But known VGCF contains too many non-fibrous carbon, thus reduce its in multiple material can construction the number of contiguous network, thereby the performance of the multiple material of impact.Moreover, because known VGCF is not by high-graphitized, therefore the raising of its performance such as conduction, heat conduction to multiple material is not as expected.In addition, the metal catalyst that known VGCF processing procedure uses is not removed to a proper range, thereby metal content is too high, makes it in energy and material application, has detrimentally affect in the time of electrochemical reaction, ineffective to the raising of the power of battery and cycle life.
Therefore, need to propose a kind of VGGF constituent and its mixture, use and improve known VGCF not by high-graphitized and problem that contain the impurity such as too many non-fibrous carbon and metal ingredient.
summary of the invention
One aspect of the present invention is to provide a kind of vapor phase growth graphite fibre (VGGF) constituent, uses and improves known VGCF not by high-graphitized and substantive issue that contain the impurity such as too many non-fibrous carbon and metal ingredient.
The carbon composition that this VGGF constituent comprises content at least 99.9 weight percents (wt%), its degree of graphitization is at least more than 75%, be preferably more than 85%, this carbon composition comprises fibrous VGGF and non-fibrous carbon, wherein by sweep electron microscope (Scanning Electron Microscope; SEM) Area Ratio between measured non-fibrous carbon and fibrous VGGF is to be less than or equal to 5%.Fibrous VGGF more comprises the graphite fibre (being also referred to as " three-dimensional graphite fibre ") with 3 D cross-linked structure, and the content of this graphite fibre with 3 D cross-linked structure in fibrous VGGF is that essence is between 5 weight percent to 50 weight percents.
In one embodiment, the mean outside diameter of above-mentioned VGGF constituent be essence between 50 nanometer to 200 nanometers, its average aspect ratio essence is between 10 to 5000.When utilizing thermogravimetric analyzer (Thermogravimeteric Analyzer; TGA) analyze, under the test condition of 10 DEG C/min of temperature rise rates (DEG C/min) and air flow quantity 10 to 20 ml/min (ml/min), the pyrolysis starting temperature of above-mentioned VGGF constituent is to be greater than approximately 700 DEG C.The water ratio of graphite fibre constituent is to be less than approximately 0.2 weight percent, and its metal content is less than about 200ppm.
According to one embodiment of the invention, above-mentioned non-fibrous carbon with fibrous VGGF be connected, the state of overlapping or separation.
According to one embodiment of the invention, above-mentioned fibrous VGGF comprises by the carbon galvanized hexagonal wire mesh plane graphite elongate hollow multilayered structure forming of reeling.
Another aspect of the present invention is to provide a kind of mixture.This mixture comprises: resin or inorganics; And above-mentioned VGGF constituent.
According to one embodiment of the invention, above-mentioned fibrous VGGF constituent and N-Methyl pyrrolidone (N-Methyl-2-pyrrolidone; The unit volume resistance of mixture NMP) is to be less than 50 ohmcms (Ω-cm).Wherein the content of VGGF constituent in mixture is 30 weight percents.In one embodiment, this mixture also comprises resin or inorganics.
Another aspect of the present invention is to provide the various application of VGGF constituent, for example: electrode material of lithium battery, fuel cell material, conductive characteristic matrix material, thermal conduction characteristic matrix material, mechanical strength property matrix material etc., these materials all comprise above-mentioned mixture.
From above-described embodiment, the mixture of applying VGGF constituent of the present invention and containing this VGGF constituent, can promote significantly VGGF constituent in multiple material can construction the number of contiguous network, reduce the impact of impurity, and improve the performance of multiple material, and promote significantly the performance such as conduction, heat conduction, intensity of multiple material.
Brief description of the drawings
For above and other objects of the present invention, feature, advantage and embodiment can be become apparent, appended the description of the drawings is as follows:
The structural representation that Fig. 1 is the known VGCF reaction unit that illustrates embodiments of the invention and use;
The structural representation that Fig. 2 is the known VGCF reaction unit that illustrates comparative example and use;
Fig. 3 is the SEM figure that illustrates the VGGF constituent of embodiments of the invention;
Fig. 4 is another SEM figure that illustrates the VGGF constituent of embodiments of the invention;
Fig. 5 is the TEM figure that illustrates the VGGF constituent of the embodiment of the present invention;
Fig. 6 is the XRD figure spectrum that illustrates the VGGF constituent of the embodiment of the present invention;
Fig. 7 is the SEM figure that illustrates the VGCF constituent of comparative example;
Wherein, main element nomenclature:
10: air-intake duct 20: inlet mouth
40: reaction tubes 50: well heater
60: gathering system 100: rectilinear reaction tubes structure
110: outer tube 120: inner tube
120a, 120b: inner tube 122: dividing plate
130a, 130b: hole 140: thermal conducting material
150: well heater 160: preheater
170: air-intake duct 200: raw material and catalyst gas source
210: mixing tank 300: carrier gas source
310: pipeline 320,330: pipeline
400: carbon fiber gathering system 500: carrier gas recovery system
510: pipeline.
Embodiment
The invention provides the VGGF constituent of the high fiber fineness of a kind of tool, it is the product forming after high-graphitized, its carbon component content at least 99.9 weight percents (wt%), and its degree of graphitization is at least more than 75%, be preferably more than 85%, its metal content is below 200ppm.This carbon composition includes non-fibrous carbon and fibrous VGGF, is to be wherein approximately less than or equal to 5% by the Area Ratio between SEM measured non-fibrous carbon and fibrous VGGF.Fibrous VGGF more comprises the graphite fibre with 3 D cross-linked structure, and wherein by the measured graphite fibre with 3 D cross-linked structure of SEM, the content in fibrous VGGF is between approximately 50 area percentages between approximately 5 area percentages.Vapor phase growth graphite fibre of the present invention will more be attained perfection in application, and the material of interpolation vapor phase growth graphite fibre is more powerful in electronic equipment application, more meets the progressive demand of industry.
Please refer to Fig. 1, it illustrates the structural representation of the reaction unit of making VGCF required for the present invention.The present invention is the VGCF reaction unit (as shown in Figure 1) that uses the front case of United States Patent (USP) to disclose for No. 7374731B2, and its full content is incorporated to this case at this with way of reference, and before this United States Patent (USP), case has the transferee identical with this case.The present invention is that to maintain reactive flowfield smooth and easy in this device, cause reactor to block or produce interrupting to avoid catalyzer and carbon fiber etc. to be attached on device inwall, react with process conditions with suitable composition of raw materials again, reducing non-fibrous carbon particle produces, and produced carbon fiber constituent is carried out to high temperature graphitization processing, for example: 2800 ~ 3200 DEG C of high temperature graphitization processing, make its crystalline texture more complete and remove impurity, and develop a kind of high purity vapor phase growth graphite fibre (VGGF) constituent.In the time that industry is applied, also can be again through shearing etc. to improve its dispersiveness.For example: be applied on the interpolation material of lithium battery pole slice, often vapor phase growth graphite fibre length be trimmed to 5 ~ 10 μ m, to help its dispersion in pole piece active material, its effect is manifested more.The fibrous VGGF that the present invention produces is the high purity carbon galvanized hexagonal wire mesh plane graphite elongate hollow multilayered structure forming of reeling, and its external diameter is about 50nm-200nm; Length-to-diameter ratio is about 10-5000; Its carbon component content at least 99.9 weight percents (wt%), its degree of graphitization at least, more than 75%, is preferably more than 85%; Area Ratio by the measured non-fibrous carbon of SEM and fibrous VGGF is below 5%; Fibrous VGGF more comprises the graphite fibre with 3 D cross-linked structure, and the content of the graphite fibre that wherein has a 3 D cross-linked structure by measured this of sweep electron microscope in fibrous VGGF is between 5 area percentage to 50 area percentages; Water ratio is below 0.2wt%; Metal content is below 200ppm.VGGF constituent of the present invention has good electroconductibility and thermal conductivity and high strength, the unit volume resistance containing 30%VGGF creme that itself and pure N-Methyl pyrrolidone (NMP) evenly mix is below 50 Ω-cm, and there is good oxidation-resistance, at thermogravimetric analysis (the Thermogravimetric Analyzer of 10 DEG C/min of temperature rise rate and air flow quantity 10～20ml/min test condition; TGA), under, the pyrolysis of VGGF constituent of the present invention initial (Onset) temperature is more than approximately 700 DEG C.Therefore, VGGF constituent of the present invention is applicable to energy and material, for example: the interpolation material of lithium battery pole slice, or the matrix material of the purposes such as tool high thermal conductivity, high conductivity, high strength, to coordinate the demand of industrial progress.
As shown in Figure 1, reaction unit of the present invention includes rectilinear reaction tubes structure 100 and well heater 150, and rectilinear reaction tubes structure 100 is mainly made up of inner tube 120 and outer tube 110, its material can be aluminum oxide, silicon carbide, quartz, mullite (mullite) or silicon nitride etc., the principal character of this reaction unit is, at the bottom of inner tube 120a tube wall, multiple hole 130a are set, and at the top of inner tube 120b tube wall, multiple hole 130b are set, use carrier gas is diverted to inner tube 120 center, to increase the mixed effect of carrier gas and unstripped gas, more can prevent catalyzer, carbon fiber adheres on the tube wall of inner tube, cause flow field to have some setbacks, and non-fibrous carbon particle is produced, even cause reactor to block or produce and interrupt.Between inner tube 120 and outer tube 110, be filled with thermal conducting material, to improve heat conduction efficiency.The present invention adopts the flowing-type catalyst method that swims, manufacture continuously gas-phase growth of carbon fibre (VGCF), it is generally taking low-molecular-weight hydrocarbon as raw material, for example: aliphatics or aromatic series hydrocarbons, wherein aliphatic carbon hydride can be for example methane, ethane, ethene, acetylene, propane, liquefied petroleum gas (LPG), butane, butylene, divinyl etc., and aromatic series hydrocarbons is for example benzene,toluene,xylene etc.The flowing-type catalyst method that swims is taking reducing gas as carrier gas, for example hydrogen (H2), and under the promotor such as catalysis and the sulfide effect of the ultrafine particulate nucleus of the transition metal such as iron, nickel or cobalt, high temperature pyrolysis generates VGCF, wherein the source of the ultrafine particulate nucleus of transition metal can be the compound of the transition metal such as iron, nickel or cobalt, for example: ferrocene (Ferrocene; Fe (C
5h
5)
2) or nickelocene etc., and sulfide can be for example thiophene (Thiophene; C
4h
4s), its temperature of reaction is between 800 DEG C～1300 DEG C, and the efficiency of reaction and quality product are relevant with composition of raw materials and process conditions.Following examples are to illustrate formula and the condition of manufacturing high purity VGGF constituent, but the present invention is not limit by this.
Below coordinate Fig. 1 that the manufacture method of the VGGF constituent of one embodiment of the invention is described.
Embodiment
First the gas source 200 transferring raw material gases that, are made up of hydrocarbon polymer, catalyzer and promotor are to mixing tank 210.After mixing with part carrier gas, the reactant gases of transferring raw material gas and carrier gas to preheater 160 is preheated to 300 DEG C.Then, the reactant gases after preheating imports reacting furnace-e/or by air-intake duct 170 and reacts.Remain carrier gas is delivered between inner tube 120a and 120b and outer tube 110 by pipeline 320, pipeline 330 respectively simultaneously, between inner tube 120 and outer tube 110, fill thermal conducting material 140, well heater 150 is in pipe external heat reacting furnace-e/or (outer tube 110) and thermal conducting material 140, carrier gas is sent into inner tube 120a and 120b by hole 130a, hole 130b ejection after heating via thermal conducting material 140.Products therefrom (VGCF) is collected in carbon fiber gathering system 400, and remainder of exhaust gas is by 500 recycling uses of carrier gas recovery system.
Specification and the operational condition of the rectilinear reaction tubes structure 100 of the present embodiment are:
(1) inner tube 120: the alumina tube of internal diameter 20 centimetres of (cm), 24 centimetres of external diameters, 200 centimetres of length.
(2) outer tube 110: the alumina tube of 30 centimetres of internal diameters, 34 centimetres of external diameters, 200 centimetres of length.
(3) hole 130a:
Position: started the scope of downward 15 centimetres by reaction tubes top distance 35 centimeters; Aperture: 2 millimeters of (mm) apertures of diameter, every small pitch is from 1 centimetre.
(4) hole 130b:
Position: started the scope of downward 30 centimetres by reaction tubes top distance 51 centimeters; Aperture: 2 millimeters of apertures of diameter, every small pitch is from 1 centimetre
(5) dividing plate 122: the aluminum oxide plectane of 20 centimetres of internal diameters, 30 centimetres, thick 1 centimetre of external diameter; Position: by reaction tubes top distance 50 ~ 51 centimeters.
(6) thermal conducting material 140: the hollow circular cylinder (0.8 centimetre of internal diameter, 1.0 centimetres of external diameters, 0.8 centimetre of length) of aluminum oxide material.
(7) the control temperature of well heater 150: 1150 DEG C.
(8) gas source plenum system: raw material is by the toluene (Toluene) of 95 weight percents, the ferrocene (Ferrocene) of 2 weight percents, the ethyl ketone (Ethyl 3-oxobutanoate) of 2 weight percents, the sulfuration (methyl-sulfide amide group) (Bis (dimethylthiocarbamyl) sulfide) of 0.5 weight percent, the triethylenediamine (Triethylenediamine) of 0.5 weight percent forms, (25 DEG C of liquid raw material flow 50 ml/min (ml/min), under one normal atmosphere), after changing into gas source, heat air imports reactive system.
(9) carrier gas kind: hydrogen; Carrier gas flux: 20 liters/min (L/min) (being imported by air-intake duct 170), 30 liters/min (130a imports by hole), 100 liters/min (130b imports by hole).
(10) reaction times: can successive reaction until stop supplies raw material, in reaction tube, dirt settling is little.
(11) product: by above-mentioned reaction, collect VGCF in gathering system 400.
Then, this VGCF, under the atmospheric condition of argon gas (Ar), is carried out to high-temperature heat treatment at 3000 DEG C, to form high-graphitized VGGF constituent of the present invention.
Below analyze the characteristic of VGGF constituent of the present invention.
Please refer to Fig. 3, the SEM figure of the VGGF constituent that it is the embodiment of the present invention.As shown in Figure 3, the VGGF constituent major part of the present embodiment is elongated vapor phase growth graphite fibre, the wherein Area Ratio of non-fibrous carbon and fibrous VGGF approximately 1.2%, the external diameter of the VGGF constituent of the present embodiment is about 50nm-200nm, mean outside diameter is about 110nm, and average aspect ratio is approximately 180.In addition, fibrous vapor phase growth graphite fibre VGGF is outside linear, more comprises Y-shaped or has the elongated graphite fibre of 3 D cross-linked structure.Please refer to Fig. 4, another SEM figure of the VGGF constituent that it is embodiments of the invention, wherein demonstrates the graphite fibre with 3 D cross-linked structure.As shown in Figure 3, the content of the graphite fibre that has a 3 D cross-linked structure in fibrous VGGF is about 22 area percentages.
Please refer to Fig. 5, it illustrates transmission electron microscope (the Transmission Electron Microscope of the VGGF constituent of the embodiment of the present invention; TEM) figure.As shown in Figure 5, the fibrous VGGF in the VGGF constituent of the present embodiment gained is elongate hollow multilayered structure.
Please refer to Fig. 6, X-ray diffraction (the X-ray Diffraction of the VGGF constituent that it is the embodiment of the present invention; XRD) collection of illustrative plates.By Bragg's equation (Bragg's Law), the degree of graphitization that can result as shown in Figure 6 calculates VGGF constituent of the present invention is 95.4%.
In addition, learnt by ultimate analysis, the carbon content of the VGGF constituent of the present embodiment is 99.99%.Close plasma atomic emission spectrum (ICP-AES) analysis by induction lotus root and learn, the iron level of the VGGF constituent of the present embodiment is 35.9ppm, and other metal content is atomic and detect and do not measure.Learnt by moisture analysis, the water ratio of the VGGF constituent of the present embodiment is 0.05%.Under the thermogravimetric analysis of 10 DEG C/min of temperature rise rate and air flow quantity 10～20ml/min test condition, pyrolysis initial (onset) temperature of the VGGF constituent of the present embodiment is 752 DEG C.In addition, taking the VGGF constituent of the present embodiment of 30 weight percents and the unit volume resistance of the creme that pure N-Methyl pyrrolidone (NMP) evenly mixes as 15 ohmcms (Ω-cm).
The advantage of VGGF constituent of the present invention is described with a comparative example below.
Comparative example
Please refer to Fig. 2, it illustrates the structural representation of the reaction unit of the known VGCF that comparative example uses.The equipment that this comparative example uses for currently known methods, its specification and operational condition are:
(1) reaction tubes 40: the alumina tube of 20 centimetres of internal diameters, 24 centimetres of external diameters, 200 centimetres of length,
(2) the control temperature of well heater 50: 1150 DEG C.
(3) reaction raw materials composition: raw material is made up of the dimethylbenzene (Xylene) of 96 weight percents, the ferrocene (Ferrocene) of 4 weight percents, liquid raw material flow 50 ml/min (25 DEG C, a normal atmosphere under) import reactive system after heating and gasifying.
(4) carrier gas kind: hydrogen, carrier gas flux 20 liters/min of (being imported by air-intake duct 10), 100 liters/min (being imported by inlet mouth 20).
(5) reaction times: approximately caused reactor to block through 2 hours and produce interruption, adhering to many products on tube wall.
(6) product: by above-mentioned reaction, collect carbon fiber in gathering system 60, this carbon fiber, in argon gas atmosphere condition, is heat-treated at 2750 DEG C, and acquire the VGCF constituent of comparative example.
Please refer to Fig. 7, the SEM figure of the VGCF constituent that it is comparative example.As shown in Figure 7, in the VGCF constituent of comparative example, non-fibrous impurity is many, the Area Ratio of its non-fibrous carbon and fibrous VGCF approximately 19.2%, and the area in fibrous VGCF with 3 D cross-linked structure accounts for 3%.The mean outside diameter of the VGCF constituent of comparative example is 89nm, and carbon content is 99.62%, and degree of graphitization is 65.3%.Under the thermogravimetric analysis of 10 DEG C/min of temperature rise rate and air flow quantity 10～20ml/min test condition, pyrolysis initial (onset) temperature of the VGCF constituent of comparative example is 652 DEG C.The water ratio 0.21% of the VGCF constituent of comparative example, iron level is 2010ppm.The unit volume resistance of the creme that its VGCF constituent taking the comparative example of 30 weight percents and pure NMP evenly mix is as 138 Ω-cm.
Compared to comparative example, embodiments of the invention have higher purity, lower foreign matter content, more high-graphitized fibrous VGGF, more 3 D cross-linked structural fibers.The high-graphitized fibrous VGGF of high-content and 3 D cross-linked structural fibers will contribute to construct conduction, heat conduction, the physical strength network of multiple material, and the foreign matter contents such as lower iron and water-content are by the application function of the multiple material that can not detract.In addition, VGGF constituent of the present invention has higher pyrolysis starting temperature, has higher resistance of oxidation in air, therefore there is preferably application characteristic.
Below lift two application examples the advantage of the VGGF constituent of the embodiment of the present invention is described.
Application examples 1: lithium cell
Using the VGGF constituent of the embodiment of the present invention, VGCF constituent, the conductive carbon black etc. of comparative example is positive electrode active materials additive, makes anode pole piece.Then, be assembled into Coin-shaped battery (Coin Cell), then the cycle life of more each sample (Cycle Life Test) and high-rate discharge ability (High C Rate Test).
Taking the VGGF constituent of the embodiment of the present invention as positive electrode active materials additive, make Coin-shaped battery, wherein anode pole piece is made and is described below:
Formula:
Solids ratio: LiFePO4 (Taiwan Su Chang garden label) 89wt%
PVDF (U.S. Solvay Solexis label) 8wt%
VGGF constituent (embodiment of the present invention) 3wt%
Solid/liquid (NMP) ratio: 1/1.5
Slurry making step:
PVDF is pressed to above-mentioned ratio, under vertical type stirrer 200rpm stirs, first be dissolved in NMP, rotating speed is brought up to 1500rpm, slowly adds VGGF in stirring, continues to stir until confirm to have disperseed completely, slowly add again LiFePO4, continue to stir after 2 hours, rotating speed is cut to 70rpm, maintains the slurry that obtains stirring after 3 hours.
Pole piece is made:
By the above-mentioned slurry stirring,, on aluminium foil, dry and remove solvent in 1 hour with 120 DEG C with 200 μ m scraper for coatings, then use roller press roll extrusion to the about 2.2g/cm of density
3obtain anode pole piece.
Coin-shaped battery is made:
By above-mentioned anode pole piece, the disk that cuts into 1.33cm size with tablet machine is as positive pole, and lithium metal disk is as negative pole, and PP is barrier film, 1M LiPF6/EC-DEC (1:1) is electrolytic solution, assembles capping and obtain Coin-shaped battery (sample A) in glove box.
Taking the VGCF constituent of comparative example as positive electrode active materials additive, make Coin-shaped battery, wherein replace the VGGF constituent of the embodiment of the present invention with the VGCF constituent of comparative example, all the other formulas and making step be (sample A) as mentioned above, obtains Coin-shaped battery (sample B).
Taking Super-P (conductive carbon black) as positive electrode active materials additive, make Coin-shaped battery, wherein does not add the VGGF constituent of the embodiment of the present invention or the VGCF constituent of comparative example, and use Super-P for positive electrode active materials additive completely, that is formula is:
Solids ratio: LiFePO4 (Taiwan Su Chang garden label) 89wt%
PVDF (U.S. Solvay Solexis label) 8wt%
Super-P (Switzerland Timcal label) 3wt%
Solid/liquid (NMP) ratio: 1/1.5
All the other making steps as above-mentioned 1. Coin-shaped battery (sample C).
The battery performance of following comparative sample A, sample B, sample C.
Cycle life test:
Charge cutoff voltage is 4.2V, and discharge cut-off voltage is 2.5V, and sets 1C and discharge and recharge, after 500 circulations (cycles) following result:
Table 1
| Coin-shaped battery | Initial cells capacity (mAh) | Capability retention (%) after 500 circulations |
| Sample A | 135 | 92 |
| Sample B | 135 | 88 |
| Sample C | 132 | 76 |
High-multiplying power discharge test:
Charge cutoff voltage is 4.2V, and discharge cut-off voltage is 2.5V, and sets 0.2C charging, and 5C, 15C electric discharge, obtains following result:
Table 2
Please refer to table 1, it is the result of cycle life test, and its test condition is: charge cutoff voltage is 4.2V; Discharge cut-off voltage is 2.5V; And set 1C and discharge and recharge: through 500 circulations (cycles), wherein sample A is that to add the VGGF constituent of the embodiment of the present invention made; Sample B is that the VGCF constituent of interpolation comparative example is made; Sample C is that interpolation conductive carbon black is made.
As shown in Table 1, the cycle life of sample A is better than sample B, C.
Please refer to table 2, it is the result of high-multiplying power discharge test, and its test condition is: charge cutoff voltage is 4.2V, and discharge cut-off voltage is 2.5V, and sets 0.2C charging, 5C, 15C electric discharge.
As shown in Table 2, after the circulation of sample A, capability retention is better than sample B, C.
Application examples 2: fuel cell double polar plate
Using respectively VGGF constituent, the VGCF constituent of comparative example, the Graphite Powder 99 of the embodiment of the present invention is additive and electro-conductive material, form matrix material with epoxy resin etc., to make fuel cell double polar plate, then the electroconductibility of more each sample, thermal conductivity, intensity etc.
Taking the VGGF constituent of the embodiment of the present invention as additive, make fuel cell double polar plate and make and be described below:
Formula:
Making step:
By above-mentioned formula mixture, at 85 DEG C of kneaders, to mediate after mixing one hour, taking-up pulverizes and sieves, and then after 1 minute, obtains the fuel cell double polar plate (sample D) of thickness 3mm in 180 DEG C of hot pressing with hot compacting machine.
Taking the VGCF constituent of comparative example as additive, make fuel cell double polar plate, wherein replace the VGGF constituent of the embodiment of the present invention with the VGCF constituent of comparative example, all the other formulas and making step be (sample D) as mentioned above, and obtains fuel cell double polar plate (sample E).
Taking KS-150 Graphite Powder 99 as electro-conductive material, make fuel cell double polar plate, wherein do not add the VGGF constituent of the embodiment of the present invention or the VGCF constituent of comparative example, use KS-150 Graphite Powder 99 for electro-conductive material completely, that is formula is:
All the other making steps are (sample D) as mentioned above, and obtains fuel cell double polar plate (sample F).
The thermal conductivity of above-mentioned sample D, sample E, sample F, electroconductibility, intensity etc., obtain following result:
Table 3
| Performance | Sample D | Sample E | Sample F |
| Thermal conductivity (W/mK) | 61 | 46 | 31 |
| Conductance (S/cm) | 156 | 125 | 103 |
| Flexural strength (psi) | 7660 | 6105 | 4077 |
Please refer to table 3, the comparative result of its thermal conductivity that is each sample, electroconductibility, intensity, wherein sample D is that to add the VGGF constituent of the embodiment of the present invention made; Sample E is that the VGCF constituent of interpolation comparative example is made; Sample F is that interpolation Graphite Powder 99 is made.
As shown in Table 3, the electroconductibility of sample D, thermal conductivity, intensity are better than sample E, F.
Therefore, the present invention has the fibrous high-graphitized VGGF of high level, more foreign matter content and the water content such as 3 D cross-linked structural fibers, lower iron, therefore can promote significantly VGGF constituent in multiple material can construction the number of contiguous network, reduce the impact of impurity, and the performance of the multiple material of improvement, and promote significantly the characteristic such as conduction, heat conduction, intensity of multiple material and the application function of the multiple material that can not detract.In addition, utilize the prepared energy purposes material of VGGF constituent of the present invention to have preferably cycle life, good capability retention, and preferably heat conductivity, electroconductibility, with performances such as flexural strengths.
Although the present invention discloses as above with embodiment; so it is not in order to limit the present invention; any those having an ordinary knowledge in this technical field; without departing from the spirit and scope of the present invention; when being used for a variety of modifications and variations, the scope that therefore protection scope of the present invention ought define depending on accompanying claims is as the criterion.
Claims (10)
1. a vapor phase growth graphite fibre constituent, comprises:
One carbon composition, the carbon content that wherein said carbon composition comprises at least 99.9 weight percents, the degree of graphitization of described carbon composition is at least 75%, described carbon composition comprises:
One fibrous vapor phase growth graphite fibre, comprises:
One three-dimensional graphite fibre, wherein by measured this solid graphite fibre of one scan formula electron microscope, the content in this fibrous vapor phase growth graphite fibre is between 5 area percentage to 50 area percentages; And
One non-fibrous carbon is to be wherein less than or equal to 5% by the Area Ratio between the measured described non-fibrous carbon of sweep electron microscope and described fibrous vapor phase growth graphite fibre.
2. vapor phase growth graphite fibre constituent as claimed in claim 1, the mean outside diameter of wherein said vapor phase growth graphite fibre constituent is between 50 nanometer to 200 nanometers; The average aspect ratio of described vapor phase growth graphite fibre constituent is between 10 to 5000.
3. vapor phase growth graphite fibre constituent as claimed in claim 1, wherein in the time using thermogravimetric analyzer to analyze, being 10 DEG C/min at temperature rise rate is under the test condition of 10 to 20 ml/min with air flow quantity, and the pyrolysis starting temperature of described vapor phase growth graphite fibre constituent is to be greater than 700 DEG C.
4. vapor phase growth graphite fibre constituent as claimed in claim 1, the water ratio of wherein said vapor phase growth graphite fibre constituent is to be less than 0.2 weight percent.
5. vapor phase growth graphite fibre constituent as claimed in claim 1, the metal content of wherein said vapor phase growth graphite fibre constituent is to be less than 200ppm.
6. vapor phase growth graphite fibre constituent as claimed in claim 1, wherein said non-fibrous carbon be connected with described fibrous vapor phase growth graphite fibre, overlapping or separate.
7. vapor phase growth graphite fibre constituent as claimed in claim 1, wherein said fibrous vapor phase growth graphite fibre comprises by the carbon galvanized hexagonal wire mesh plane graphite elongate hollow multilayered structure forming of reeling.
8. vapor phase growth graphite fibre constituent as claimed in claim 1, the degree of graphitization of wherein said carbon composition is at least 85%.
9. a mixture, comprises:
Vapor phase growth graphite fibre constituent as described in any one in claim 1 to 8, wherein said vapor phase growth graphite fibre constituent is 30 weight percents in the content of described mixture; And
N-N-methyl 2-pyrrolidone N-;
The unit volume resistance of wherein said mixture is to be less than 50 ohmcms.
10. a mixture, comprises:
Resin or inorganics; And
Vapor phase growth graphite fibre constituent as described in any one in claim 1 to 8.
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| Purification and structural annealing of multiwalled carbon nanotubes at graphitization temperatures;R. Andrews et al.;《Carbon》;20011231;第39卷;1681-1687 * |
| R. Andrews et al..Purification and structural annealing of multiwalled carbon nanotubes at graphitization temperatures.《Carbon》.2001,第39卷1681-1687. * |
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