CN103214245A - Carbon/carbon composite microsphere material, production method and lithium ion battery - Google Patents
Carbon/carbon composite microsphere material, production method and lithium ion battery Download PDFInfo
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Abstract
The invention relates to a carbon/carbon composite microsphere material, a production method and a lithium ion battery. The carbon/carbon composite microsphere material is prepared through the following steps of: grinding petroleum coke, needle coke or other soft carbon materials into particles which are less than 2 microns in granularity, and mixing the particles with a binding agent, carbon black and a solvent by a certain proportion to obtain a slurry; carrying out spray-balling and drying to obtain an initial composite microsphere, and implementing heat treatment in the atmosphere of an inert gas to obtain the carbon/carbon composite microsphere material. The carbon/carbon composite microsphere material disclosed by the invention has a good sphericity degree and a proper microporous channel, the microsphere material, serving as a negative electrode material of a lithium ion battery, is well compatible with an electrolyte solution, and simultaneously, the microsphere material has a relatively high specific capacity and an excellent circulating performance. The preparation process is environmental-friendly, simple in process, low in cost and easy for industrial promotion.
Description
Technical field
The present invention relates to a kind of lithium cell cathode material and preparation method thereof, more particularly, the present invention relates to a kind of carbon/carbon composite microsphere material, production method and, belong to the lithium ion battery negative material technical field the lithium ion battery of described carbon/carbon composite microsphere material as negative material.
Background technology
Lithium ion battery is a kind of chemical power source that can satisfy the widely-used and high speed development needs of various portable electric appts, power tool and New-energy electric vehicle.It has that voltage height, specific energy are big, discharging voltage balance, low-temperature performance is good, safety performance is excellent and easily store and advantages such as long working life.The preparation of negative material is one of gordian technique of lithium ion battery.The graphitized carbon material good conductivity, the degree of crystallinity height has good laminate structure, and the embedding that is fit to lithium ion is deviate from, and becomes the lithium ion battery negative material of having realized commercial applications at present.Because the common embedding of organic solvent molecule in graphite linings, there is the phenomenon of solvolysis, cause phenomenons such as the peeling off of graphite electrode material, efflorescence; And because the existence of graphite surface active sites and defective forms unsettled solid electrolyte interface film at material surface, electrode enclosed pasture efficient reduces, and capacity attenuation is serious, and then influences the cycle performance of battery.
Hard carbon generally is through pyrogenically prepared decolorizing carbon by the lower organism of aromaticity, it is through 2000 ℃ of high temperature (〉) the higher degree of graphitization of the also very difficult acquisition of thermal treatment, common hard carbon mainly contains resol, glucose, inclined to one side fluorinated ethylene propylene, Resins, epoxy, polyvinyl chloride, glycan alcohol etc.
Soft carbon be by heavy oil component or coal-tar pitch and cut thereof 1000 ℃ of left and right sides thermal treatments, its deoxidation, dehydrogenation are formed.Soft carbon is a kind of decolorizing carbon, but its 2500 ℃ of greyings at high temperature, i.e. easy graphitized carbon.Have certain impurity in this class carbon material, be difficult to prepare high-purity charcoal, but its aboundresources is cheap.Common soft carbon has refinery coke, needle coke, carbon fiber bundle etc.The difference of refinery coke and needle coke is that the former contains more volatile matter, metal and ash content, and is difficult for greying.Soft carbon can reach 186mAh/g as the negative material specific storage, and the specific storage of the non-graphitized soft carbon of handling below 1000 ℃ usually is higher than the theoretical specific capacity of graphite.
It is low that soft carbon class negative material has degree of crystallinity, and grain-size is little, and spacing is big, with electrolytic solution consistency characteristics preferably, is used to gradually in energy-storage battery and the power cell.In commercial soft carbon material, carbosphere is considered to have most development potentiality.This is that carbosphere has more advantage because compare with other carbon material.For example, ball-like structure helps realizing tightly packed, thereby can improve the volume energy density of electrode; Globosity can make the lithium ion in the electrolytic solution embed and deviate from all directions of ball, has solved graphite type material because the graphite flake layer swelling that anisotropy causes, the multiplying power problem of subsiding and can not rapid large-current discharging and recharging.In addition, the hard carbon of random ordering has the characteristics of higher capacity, low cost and excellent cycle performance.It is good that synthetic graphite has with the electrolytic solution consistency, and its embedding, to take off speed bigger, and load character is preferably arranged.Therefore, in conjunction with the characteristics of differing materials, the negative material of exploitation excellent property also is one of emphasis of research.
CN1422235A adopts glucose, sucrose, fructose, Mierocrystalline cellulose or starch, or resol, polypropylene are fine, the mixture of Resins, epoxy and solidifying agent Tetra hydro Phthalic anhydride; Or the mixture of Resins, epoxy and polyoxymethylene and phenol and solvent be made into the homodisperse system, and, high temperature carbonization dry through liquid-phase dehydration, washing makes spheroid or spheroid hard carbon material, and this material can be used as the secondary lithium battery cathode active material.
CN102723469A is after the Graphite Powder 99 of fine grain size and macromolecule resin (resol, polyacrylonitrile (PAN), polyaniline (PA) etc.) are uniformly mixed, via spray-dired mode, make powder for drying and granulation, and then form the folded poly-matrix material of many coccoliths ink powder.
CN102522532A adopts natural graphite, the material that refinery coke, pitch are composited.Recombination process comprises mixing, mixes and pinch, roll processes such as sheet, pulverizing, moulding, carbonization, greying (more than 2800 ℃), ball-typeization, is prepared from negative material.
CN102569752A is to be raw material with acicular petroleum coke and/or coal tar and resin, in pressurized vessel, carry out the liquid-phase dehydration processing again after being dissolved in organic solvent, then by coating modification, low-temperature curing, charing, after make the carbon modified material of lithium ion secondary battery negative pole after the high-temperature heat treatment, cooling screening; The carbon modified material of making is sphere or elliposoidal.
It is raw material that CN102364727A adopts starch base hard carbon microballoon and expanded graphite, obtains product by preparation starch base hard carbon microballoon, mixing, cleaning concussion, separation, oven dry.This invention utilizes the expanded graphite its specific structure, carry out compound preparation with starch base hard carbon microballoon, utilize the conduction of building of solid spacial framework that good passage is provided, thereby improve the voltage delay effect of hard carbon material, and improve the efficient first of negative material to electronics.
CN102351163A is made by the steps such as a kind of process obtain solution, stirring and rectifying separation in the amphipathic raw material of wood-charcoal material of coal-tar pitch base, petroleum asphalt based amphipathic raw material of wood-charcoal material, the amphipathic raw material of wood-charcoal material of mesophase pitch base, the amphipathic raw material of wood-charcoal material of refinery coke base, the amphipathic raw material of wood-charcoal material of needle coke base and the amphipathic raw material of wood-charcoal material of pitch coke base, and nanometer carbon microspheres of this invention preparation is formed by the self-assembly under capillary constraint of amphipathic raw material of wood-charcoal material.
It is raw material that CN1461283A adopts resin, pitch and composition thereof, under hydrophobicity inorganic substance or silicone oil effect, obtain the charing mixture through thermal treatment under 700～1500 ℃ of inert environments, add acid then or the alkali solvent is removed inorganic substance, continue to obtain the ball-type charcoal 2000～3200 ℃ of following thermal treatments.
CN101800304A adopts natural flake graphite micro mist and cakingagent such as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyvinyl butyral acetal (PVB) to mix, after spray-dried, handle through 600～1000 ℃ of heat of carbonizations again, obtain 20～50 microns spherical graphite powder.
Above reported method ubiquity material ball-type degree is poor, raw materials cost height, complicated process of preparation, equipment requirements height, process condition harshness, seriously polluted, produce problem such as difficulty in batches.
Therefore, intend providing a kind of carbon in lithium ion battery/carbon complex microsphere negative material.This carbon/carbon complex microsphere negative material is made up of soft carbon and hard carbon material matrix, has good electronic conductance and ion transport passage.This negative material has good globosity, helps realizing close-packed, improves the volume energy density of electrode, simultaneously lithium ion is embedded from all directions, improves the structural stability and the high rate performance of material; Spheroidal particle inside has the pore passage structure of appropriate size, improves the charge/discharge capacity and the circulation volume conservation rate of material.When soft carbon material particle diameter is micron level, add an amount of nano level carbon black, can fill the accumulation hole of soft carbon material in the balling-up process, increase the slickness on spherical granules surface, increase the tap density and the intensity of material.
Carbon/carbon composite microsphere material production method that the present invention's plan provides, raw material sources are extensive, and preparation technology is simple, environmental friendliness, energy consumption and with low cost is easy to scale operation.
Summary of the invention
At the deficiencies in the prior art, one of purpose of the present invention is to provide the production method of a kind of carbon/carbon composite microsphere material.
Carbon/carbon composite microsphere material of providing the described production method of one of a kind of purpose to obtain is provided two of purpose of the present invention.
Three of purpose of the present invention is to provide the lithium ion battery of a kind of two described carbon/carbon composite microsphere materials of application target as negative material.
The present inventor is through careful investigation authentication, and adopting soft carbon materials such as refinery coke or needle coke and carbon black is raw material, and preparation carbon/carbon complex microsphere is used as lithium ion battery negative material.Soft carbon material such as refinery coke or needle coke, carbon black and binding agent uniform distribution in the initial recombination microballoon, in heat treatment process, binder decomposed generates hard carbon and produces pore passage structure.Material of the present invention is made up of soft carbon and hard carbon material, and sphericity height, granule interior contain the controllable pore passage structure of 1～20nm.When soft carbon material particle diameter is micron level, add an amount of nano level carbon black, can fill the accumulation hole of soft carbon material in the balling-up process, the duct of regulating spheroidal particle inside distributes, increase the slickness on spherical granules surface, increase tap density, intensity and the conductivity of material, reduce the specific surface area of material, remedy the deficiency that soft carbon material particle diameter brings more greatly.Can improve the specific storage and the cycle performance of battery as lithium ion battery negative material, improve the consistency of negative material and electrolytic solution, the while has also solved problems such as carbon negative pole material production cost height, complex process, suitability for industrialized production difficulty.
For reaching this purpose, the present invention by the following technical solutions:
The production method of a kind of carbon/carbon composite microsphere material; at first soft carbon material is crushed to the particle of particle diameter less than 2 μ m; be mixed with slurry with binding agent, carbon black and solvent then; form the initial recombination microballoon by spraying balling-up drying process; under protection of inert gas, heat-treat again, obtain being applicable to the carbon/carbon composite microsphere material of lithium ion battery at last.
In the present invention, soft carbon material, carbon black and binding agent be uniform distribution in the initial recombination microballoon, and in heat treatment process, binder decomposed generates hard carbon and part pore passage structure, and the particulate globosity also is kept perfectly, and intensity increases.
The content of each raw material can be determined according to concrete needs by the prior art/new technology of one of ordinary skill in the art according to its grasp in described carbon/carbon complex microsphere negative material.
Soft carbon material of the present invention is that refinery coke, oil are the combination of any one or at least two kinds in needle coke or the coal-based needle coke.Soft carbon is easy graphitized carbon, and being meant can graphited decolorizing carbon under the high temperature more than 2500 ℃.The degree of crystallinity of soft carbon (being degree of graphitization) is low, and grain-size is little, and spacing is bigger, and is good with the consistency of electrolytic solution.
Further, the breaking method of described soft carbon material is selected from the combination of any one or at least two kinds in ball mill dry grinding, wet-milling or the crusher in crushing.
Binding agent of the present invention is the material with adhesive property of water soluble or organic solvent, preferably the combination of any one in sucrose, glucose, W-Gum, tapioca (flour), wheat starch, Mierocrystalline cellulose, polyvinyl alcohol, polyoxyethylene glycol, polyethylene wax, resol, Polyvinylpyrolidone (PVP), Resins, epoxy, polyvinyl chloride, glycan alcohol, furane resin, urea-formaldehyde resin, polymethylmethacrylate, polyvinylidene difluoride (PVDF) or polyacrylonitrile or at least two kinds.Typical but non-limiting example comprises: sucrose, W-Gum, Polyvinylpyrolidone (PVP), polyvinylidene difluoride (PVDF), urea-formaldehyde resin, the combination of sucrose and glucose, the combination of W-Gum and tapioca (flour), the combination of wheat starch, carboxymethyl cellulose and polyoxyethylene glycol, the combination of polyoxyethylene glycol, polyvinyl alcohol and resol, the combination of glucose, polyethylene wax, Resins, epoxy and furane resin, the combination of wheat starch, Polyvinylpyrolidone (PVP), glycan alcohol, polymethylmethacrylate and polyvinylidene difluoride (PVDF) etc. all can be used for implementing the present invention.
Carbon black of the present invention is the nano level carbon black, preferably the combination of any one in dim, channel black, furnace black or channel black or at least two kinds.Typical but non-limiting example comprises: dim, and furnace black, channel black, the combination of dim and channel black, the combination of dim and channel black, the combination of channel black and channel black, the combination of dim, channel black and channel black, combination of dim, channel black, furnace black and channel black etc. all can be used for implementing the present invention.
Solvent of the present invention is the combination of any one or at least two kinds in water, ethanol, ether, acetone, tetrahydrofuran (THF), benzene,toluene,xylene or the dimethyl formamide.Typical but non-limiting example comprises: water, acetone, benzene, dimethyl formamide, water and alcoholic acid combination, the combination of ethanol and ether, the combination of tetrahydrofuran (THF) and dimethylbenzene, the combination of benzene, toluene and dimethylbenzene, the combination of ether, acetone, tetrahydrofuran (THF) and dimethyl formamide, the combinations of water, ether, toluene, benzene and dimethyl formamide etc. all can be used for implementing the present invention.
When slurry of the present invention was prepared, the mass ratio of soft carbon material, binding agent, carbon black, solvent is soft carbon material: binding agent: carbon black: solvent was 1:(0.01～1): (0.01～2): (2～20).For example can select 1:0.01:0.1:5,1:0.1:2:7,1:1:0.01:5,1:0.08:0.5:11,1:0.12:0.7:17,1:0.3:0.2:16,1:0.8:0.8:19,1:0.04:0.02:16 etc.
Preparation temperature of the present invention is 20～100 ℃, for example 20.02～99.89 ℃, and 22～99 ℃, 24.8～95.6 ℃, 28.7～92.3 ℃, 30.2～88.7 ℃, 34～83.5 ℃, 38.9～76.8 ℃, 45～70 ℃, 48.9～63.2 ℃, 53～57 ℃ etc., churning time is 0.5～5h, for example can select 0.51～4.98h, 0.7～4.5h, 0.98～4.17h, 1.2～4.05h, 1.56～3.8h, 1.85～3.4h, 2～3.02h, 2.2～2.75h, 2.4h etc.; Further preferred preparation temperature is 25～90 ℃, and churning time is 0.5～4h.
Spraying balling-up drying process inlet temperature of the present invention is 200～500 ℃, for example can select 200.01～496.8 ℃, 212～480 ℃, 238～463 ℃, 250～421 ℃, 278～400 ℃, 294～376 ℃, 322～346 ℃, 330 ℃ etc., temperature out is 70～150 ℃, for example can select 70.02～149.8 ℃, 74～142.1 ℃, 78.9～136 ℃, 88～124 ℃, 95～120.5 ℃, 104～112 ℃, 108.6 ℃ etc.
Thermal treatment of the present invention is charing or greying.Charing claims destructive distillation again, is the reaction process of solid or organism thermal degradation under the secluding air condition.The required temperature difference of different substances destructive distillation is very big, can be from 100 ℃ (as wood distillation) to more than 1000 ℃ (as coal high temperature carbonizations); Pressure can be normal pressure, also can be decompression.Greying is the later process of preparation graphitized fibre, generally is to carry out in 2000～3300 ℃ argon gas or nitrogen atmosphere.
Described rare gas element is the combination of any one or at least two kinds in nitrogen, helium, neon, argon gas or the carbonic acid gas.Typical but non-limiting example comprises: nitrogen, neon, argon gas, carbonic acid gas, the combination of nitrogen and helium, the combination of nitrogen and neon, the combination of neon and carbonic acid gas, the combination of nitrogen, helium and argon gas, the combination of nitrogen, argon gas and carbonic acid gas, the combinations of helium, neon, argon gas and carbonic acid gas etc. all can be used for implementing the present invention.
Equipment for Heating Processing of the present invention is fixed bed, fluidized-bed, agitated bed or high temperature graphitization stove.
Thermal treatment temp of the present invention is 500～3000 ℃, for example can select 500.01～2989 ℃, 526～2850 ℃, and 556.5～2600 ℃, 589～2340 ℃, 642～2130 ℃, 780～1860 ℃, 989～1500 ℃, 1224～1380 ℃ etc., heat treatment time is 1～48h, 1.02～47.9h for example, 2.8～45h, 5～40.8h, 7.6～35.4h, 9～30h, 12.3～27.6h, 15～23h, 18.5～21.3h, 20h etc.
The production method of a kind of carbon/carbon composite microsphere material, the processing condition of described method may further comprise the steps through optimization:
(1) soft carbon material is crushed to the particle of particle diameter less than 2 μ m;
(2) with soft carbon material, binding agent, carbon black and solvent after the fragmentation according to 1:(0.01～1): (0.01～2): the mass ratio of (2～20) mixes, and stirs 0.5～5h down at 20～100 ℃ and is mixed with slurry;
(3) form the initial recombination microballoon by spraying balling-up drying process;
(4) under protection of inert gas, under 500～3000 ℃, heat-treat 1～48h, obtain being applicable to the carbon/carbon composite microsphere material of lithium ion battery at last.
When soft carbon material raw material particle size is micron order among the present invention, in the balling-up process, there is certain accumulation hole between the soft carbon granule, nano level therebetween carbon black filled, increased the tightness degree of granule interior structure, the smooth degree on ball-type surface and the electroconductibility and the intensity of spherical granules.In addition, the nano level carbon black also can be regulated the pore passage structure of material internal, reduces the specific surface area of material.Because the carbon black wide material sources need not fragmentation in the use, therefore comparing graphite material also has certain cost advantage.
The present invention adopts soft carbon material through broken, be mixed with slurry with carbon black, binding agent, solvent, prepare the initial recombination microballoon by spraying balling-up drying process, binding agent, carbon black and soft carbon material evenly are bonded as ball-type in this structure, and the specific surface area of material has had significantly reduction than simple hard carbon material.In addition, the initial carbon complex microsphere is in high-temperature process, and binder decomposed generates hard carbon and forms pore passage structure, and the particulate globosity also is kept perfectly simultaneously, and intensity increases.Carbon of the present invention/carbon complex microsphere contains soft carbon and hard carbon material simultaneously, ball-type structure with height, suitable duct distributes, and combines the advantage of soft carbon and hard carbon material, realize the close-packed of material and the excellent compatibility of electrolytic solution, and had suitable ion transport passage.
A kind of carbon that obtains by aforesaid method production/carbon composite microsphere material, the particle diameter of described carbon/carbon composite microsphere material is controlled, and its particle diameter is preferably 2～100 μ m; The granule interior duct controllable size of described carbon/carbon composite microsphere material, it is preferably dimensioned to be 1～20nm.
The particle diameter of carbon of the present invention/carbon composite microsphere material is controlled to be to realize by the particle diameter and the spray-dired processing condition of control as raw material.
The controllable size in the granule interior duct of carbon of the present invention/carbon composite microsphere material by control heat treated temperature, time and binding agent, the sooty addition is realized.
A kind of lithium ion battery, described lithium ion battery use the negative material of aforesaid carbon/carbon composite microsphere material as battery.
Compare with the prior art scheme, the present invention has following beneficial effect:
1, carbon of the present invention/carbon composite microsphere material combines the high reversible capacity characteristics of hard carbon, and soft carbon material and the good advantage of electrolytic solution consistency, and it has higher specific storage and excellent cycle performance as lithium ion battery negative material.
2, carbon of the present invention/carbon composite microsphere material increases the strength of materials through heat treatment process, has strengthened the anti-pressure ability of electrode.
3, adopt nano level carbon black auxiliary adjustment material pore passage structure, specific surface area, intensity and conductivity, the carbon black wide material sources need not fragmentation, and employed method is simple.
4, carbon/carbon composite microsphere material involved in the present invention has higher sphericity, and the preparation method is simple, environmental protection, and energy consumption and with low cost is easy to suitability for industrialized production.
Description of drawings
Fig. 1 is the SEM figure (* 1000 times) of embodiment 1 carbon/carbon composite microsphere material;
Fig. 2 is the particle size distribution figure of embodiment 1 carbon/carbon composite microsphere material;
Fig. 3 is the SEM figure (* 1000 times) of embodiment 2 carbon/carbon composite microsphere material;
Fig. 4 is the SEM figure (* 1000 times) of Comparative Examples 2 carbon/carbon composite microsphere material.
Below the present invention is described in more detail.But following example only is a simple and easy example of the present invention, does not represent or limit the scope of the present invention, and protection scope of the present invention is as the criterion with claims.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
Refinery coke after the 5 gram fragmentations, 10 gram channel blacks, 5 gram glucose and 150 gram water are mixed, stir 4h down at 50 ℃ and be mixed with slurry.Adopt spray-drier that slurry is carried out drying and granulation, its spraying drying inlet temperature is 230 ℃, and temperature out is 70 ℃; Can obtain initial carbon/carbon complex microsphere after the drying.Then with the gained material under argon gas atmosphere protection, obtain carbon/carbon composite microsphere material at 900 ℃ of following fixed bed thermal treatment 2h.
The JSM-7001F type field emission scanning electron microscope observing samples pattern that the carbon/carbon composite microsphere material of above-mentioned preparation is produced in NEC Oxford instrument company.
The SEM figure of the carbon that Fig. 1 obtains for embodiment 1/carbon composite microsphere material.This material ball-type degree is higher.
Carbon/carbon complex microsphere employing Dandong Bai Te BT-9300Z laser particle size distribution instrument of above-mentioned preparation is carried out particle size analysis and seen Fig. 2, and particle size is between 2～40 μ m.
The battery that assembles is carried out the charge-discharge performance test on the 2001A type charge-discharge test instrument that the blue electric company in Wuhan produces, test result sees Table 1.
The SEM of other embodiment scans, the testing method of sreen analysis is identical with embodiment 1.
Embodiment 2
With the oil after the 7 gram fragmentations is that needle coke, 3 gram channel blacks, 5 gram wheat starches and 120 gram water mix, and stirs 2h down at 40 ℃ and is mixed with slurry.Adopt spray-drier that slurry is carried out drying and granulation, its spraying drying inlet temperature is 230 ℃, and temperature out is 150 ℃; Can obtain initial carbon/carbon complex microsphere after the drying.Then with the gained material under nitrogen atmosphere protection, obtain carbon/carbon composite microsphere material at 1400 ℃ of following fluidized-bed thermal treatment 5h.Through sreen analysis, carbon/carbon complex microsphere particle diameter is between 2-60 μ m; Electrochemical property test the results are shown in Table 1.
Embodiment 3
Coal-based needle coke after the 15 gram fragmentations, 15 gram Mierocrystalline celluloses, 10 gram furnace blacks, 5 gram channel blacks and 300 gram water are mixed, stir 1.5h down at 30 ℃ and be mixed with slurry.Adopt spray-drier that slurry is carried out drying and granulation, its spraying drying inlet temperature is 200 ℃, and temperature out is 100 ℃; Can obtain initial carbon/carbon complex microsphere after the drying.Then with the gained material under nitrogen atmosphere protection, obtain carbon/carbon composite microsphere material at 800 ℃ of following agitated bed thermal treatment 3h.Through sreen analysis, carbon/carbon complex microsphere particle diameter is between 10～80 μ m; Electrochemical property test the results are shown in Table 1.
Embodiment 4
Restrain the refinery coke after the 20 gram fragmentations, 1.2 gram Polyvinylpyrolidone (PVP)s, 5 dim and 200 gram water mixing, stir 3h down at 50 ℃.Adopt spray-drier that slurry is carried out drying and granulation, its spraying drying inlet temperature is 500 ℃, and temperature out is 80 ℃; Can obtain initial carbon/carbon complex microsphere after the drying.Then with the gained material under nitrogen atmosphere protection, obtain carbon/carbon composite microsphere material at 2000 ℃ of following fixed bed thermal treatment 16h.Through sreen analysis, carbon/carbon complex microsphere particle diameter is between 2～50 μ m; Electrochemical property test the results are shown in Table 1.
Embodiment 5
3 gram resol being dissolved in 20 grams making solution in the ethanol, is that needle coke, 1 gram are dim, the mixed slurry of 80 gram water with the oil after the 10 gram fragmentations, and the two is blended in 20 ℃ and stirs 5h down and be mixed with slurry.Adopt spray-drier that slurry is carried out drying and granulation, its spraying drying inlet temperature is 280 ℃, and temperature out is 120 ℃; Can obtain initial carbon/carbon complex microsphere after the drying.Then with the gained material under nitrogen atmosphere protection, obtain carbon/carbon composite microsphere material at 2600 ℃ of following agitated bed thermal treatment 24h.Through sreen analysis, carbon/carbon complex microsphere particle diameter is between 3～40 μ m; Electrochemical property test the results are shown in Table 1.
Embodiment 6
Refinery coke after the 20 gram fragmentations, 18 gram W-Gums, 10 gram channel blacks and 350 gram water are mixed, stir 2h down at 25 ℃ and be mixed with slurry.Adopt spray-drier that slurry is carried out drying and granulation, its spraying drying inlet temperature is 230 ℃, and temperature out is 150 ℃; Can obtain initial carbon/carbon complex microsphere after the drying.Then with the gained material under helium atmosphere protection, obtain carbon/carbon composite microsphere material at 900 ℃ of following high temperature graphitization furnace treatments reason 2h.Through sreen analysis, carbon/carbon complex microsphere particle diameter is between 9～100 μ m; Electrochemical property test the results are shown in Table 1.
Embodiment 7
With the oil after the 20 gram fragmentations is that needle coke, 20 gram furnace blacks, 20 gram sucrose and 400 gram water mix, and stirs 1h down at 30 ℃ and is mixed with slurry.Adopt spray-drier that slurry is carried out drying and granulation, its spraying drying inlet temperature is 320 ℃, and temperature out is 70 ℃; Can obtain initial carbon/carbon complex microsphere after the drying.Then with the gained material under nitrogen atmosphere protection, obtain carbon/carbon composite microsphere material at 1300 ℃ of following fluidized-bed thermal treatment 5h.Through sreen analysis, carbon/carbon complex microsphere particle diameter is between 6～50 μ m; Electrochemical property test the results are shown in Table 1.
Embodiment 8
Coal-based needle coke after the 8 gram fragmentations, 2 gram channel blacks, 3 gram Mierocrystalline celluloses and 90 gram water are mixed, stir 0.5h down at 90 ℃ and be mixed with slurry.Adopt spray-drier that slurry is carried out drying and granulation, its spraying drying inlet temperature is 230 ℃, and temperature out is 104 ℃; Can obtain initial carbon/carbon complex microsphere after the drying.Then with the gained material under nitrogen atmosphere protection, obtain carbon/carbon composite microsphere material at 500 ℃ of following agitated bed thermal treatment 1h.Through sreen analysis, carbon/carbon complex microsphere particle diameter is between 8～70 μ m; Electrochemical property test the results are shown in Table 1.
Embodiment 9
Refinery coke after the 10 gram fragmentations, 0.1 gram channel black, 0.1 gram Polyvinylpyrolidone (PVP) and 20 gram water are mixed, stir 1h down at 100 ℃ and be mixed with slurry.Adopt spray-drier that slurry is carried out drying and granulation, its spraying drying inlet temperature is 230 ℃, and temperature out is 150 ℃; Can obtain initial carbon/carbon complex microsphere after the drying.Then with the gained material under nitrogen atmosphere protection, obtain carbon/carbon composite microsphere material at 3000 ℃ of following fixed bed thermal treatment 48h.Through sreen analysis, carbon/carbon complex microsphere particle diameter is between 5～65 μ m; Electrochemical property test the results are shown in Table 1.
Embodiment 10
6 gram resol being dissolved in 30 grams making solution in the acetone, is that the broken refinery coke of needle coke, 10 grams, 4 gram furnace blacks, 200 gram water are mixed and made into slurry with the oil after the 10 gram fragmentations, and the two is blended in 30 ℃ and stirs 1h down and be mixed with slurry.Adopt spray-drier that slurry is carried out drying and granulation, its spraying drying inlet temperature is 250 ℃, and temperature out is 70 ℃; Can obtain initial carbon/carbon complex microsphere after the drying.Then with the gained material under nitrogen atmosphere protection, handle 24h at 2600 ℃ of fluid bed heats and obtain carbon/carbon composite microsphere material.Through sreen analysis, carbon/carbon complex microsphere particle diameter is between 2～50 μ m; Electrochemical property test the results are shown in Table 1.
Comparative Examples 1
Choose HAG2 graphite pebbles that Changsha Xing Cheng micro crystal graphite company limited produces as a comparison case;
The HAG2 graphite pebbles that Changsha Xing Cheng micro crystal graphite company limited is produced is as lithium ion battery negative material, and wherein, electrode preparation is identical with embodiment 1 with the step of performance test.
Comparative Examples 2
Restrain refinery coke, the 5 gram wheat starches and 150 that fragmentation back D90 are 2 μ m with 5 and restrain the water mixing, under 40 ℃, stir 2h and be mixed with slurry.Adopt spray-drier that slurry is carried out drying and granulation, its spraying drying inlet temperature is 230 ℃, and temperature out is 130 ℃; Can obtain initial carbon/carbon complex microsphere after the drying.Then with the gained material under nitrogen atmosphere protection, obtain carbon/carbon composite microsphere material at 900 ℃ of following thermal treatment 4h.Its SEM figure sees Fig. 4.Comparison diagram 4 and Fig. 1 as seen, when soft carbon material particle diameter was big, if do not add carbon black, particle surface was comparatively coarse, hole is more, structure is more open, is difficult for balling-up.Therefore adding carbon black can regulate effectively to the structure of material.
Performance test:
The negative material that the embodiment of the invention 1～10 and Comparative Examples provide is made electrode, and carry out electrochemical property test, concrete steps are as follows:
The carbosphere material that one of Comparative Examples and/or embodiment 1～10 provide (or Comparative Examples provide graphite material), acetylene black and PVDF(polyvinylidene difluoride (PVDF)) mass ratio be 80:10:10; Carbosphere material (or graphite material) and acetylene black are mixed, add the PVDF(polyvinylidene difluoride (PVDF) then) (PVDF is the PVDF/NMP solution of the 0.02g/mL for preparing, NMP is a N-Methyl pyrrolidone) solution, be coated on the Copper Foil, in 120 ℃ of vacuum-drying 24h, cut-off directly is that the disk of 14mm is as working electrode in vacuum drying oven; Metallic lithium is a counter electrode; Electrolytic solution is LiPF6/EC-DMC-EMC(volume ratio 1:1:1); In being full of the Ar glove box, be assembled into two electrode simulated batteries;
The charging/discharging voltage scope is 1.0～0.01V, and charging and discharging currents density is 50mA/g; High rate performance test uses current density to be respectively 200mA/g(0.5C), 500mA/g(1C).
The carbon that described embodiment obtains/carbon complex microsphere and commercial graphite material are as shown in table 1 as the chemical property of lithium ion battery negative material, first all loading capacities of commercial graphite material are 320mAh/g as can be seen from the table, circulating, capability retention is 90% after 20 times, first all enclosed pasture efficient and capability retention are relatively poor, and reversible capability of charging and discharging is for being respectively 250mAh/g and 150mAh/g under 200mA/g and the 500mA/g current density.And when the carbon/carbon composite microsphere material that uses the inventive method preparation during as lithium ion battery negative material, first all loading capacities are that 250mAh/g does not wait to 330mAh/g, circulating, capability retention is 99% after 20 times, and reversible capability of charging and discharging is respectively between 250～330mA/g and 210～270mA/g under 200mA/g and the 500mA/g current density.
The chemical property evaluation result of table 1 embodiment of the invention and Comparative Examples
Applicant's statement, the present invention illustrates production method of the present invention by the foregoing description, but the present invention is not limited to above-mentioned production stage, does not mean that promptly the present invention must rely on above-mentioned production stage and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of the selected raw material of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (9)
1. the production method of carbon/carbon composite microsphere material; it is characterized in that; at first soft carbon material is crushed to the particle of particle diameter less than 2 μ m; be mixed with slurry with binding agent, carbon black and solvent then; form the initial recombination microballoon by spraying balling-up drying process; under protection of inert gas, heat-treat again, obtain being applicable to the carbon/carbon composite microsphere material of lithium ion battery at last.
2. the method for claim 1 is characterized in that, described soft carbon material is that refinery coke, oil are the combination of any one or at least two kinds in needle coke or the coal-based needle coke;
Preferably, the breaking method of described soft carbon material is selected from the combination of any one or at least two kinds in ball mill dry grinding, wet-milling or the crusher in crushing.
3. method as claimed in claim 1 or 2, it is characterized in that, described binding agent is the material with adhesive property of water soluble or organic solvent, preferably the combination of any one in sucrose, glucose, W-Gum, tapioca (flour), wheat starch, Mierocrystalline cellulose, polyvinyl alcohol, polyoxyethylene glycol, polyethylene wax, resol, Polyvinylpyrolidone (PVP), Resins, epoxy, polyvinyl chloride, glycan alcohol, furane resin, urea-formaldehyde resin, polymethylmethacrylate, polyvinylidene difluoride (PVDF) or polyacrylonitrile or at least two kinds.
4. as the described method of one of claim 1-3, it is characterized in that described carbon black is the nano level carbon black, preferably the combination of any one in dim, channel black, furnace black or channel black or at least two kinds;
Preferably, described solvent is the combination of any one or at least two kinds in water, ethanol, ether, acetone, tetrahydrofuran (THF), benzene,toluene,xylene or the dimethyl formamide.
5. as the described method of one of claim 1-4, it is characterized in that when described slurry was prepared, the mass ratio of soft carbon material, binding agent, carbon black, solvent was 1:(0.01～1): (0.01～2): (2～20);
Preferably, described preparation temperature is 20～100 ℃, and churning time is 0.5～5h; Further preferred preparation temperature is 25～90 ℃, and churning time is 0.5～4h.
6. as the described method of one of claim 1-5, it is characterized in that described spraying balling-up drying process inlet temperature is 200～500 ℃, temperature out is 70～150 ℃;
Preferably, described thermal treatment is charing or greying;
Preferably, described rare gas element is the combination of any one or at least two kinds in nitrogen, helium, neon, argon gas or the carbonic acid gas;
Preferably, described Equipment for Heating Processing is fixed bed, fluidized-bed, agitated bed or high temperature graphitization stove;
Preferably, described thermal treatment temp is 500～3000 ℃, and heat treatment time is 1～48h.
7. as the described method of one of claim 1-6, it is characterized in that, said method comprising the steps of:
(1) soft carbon material is crushed to the particle of particle diameter less than 2 μ m;
(2) with soft carbon material, binding agent, carbon black and solvent after the fragmentation according to 1:(0.01～1): (0.01～2): the mass ratio of (2～20) mixes, and stirs 0.5～5h down at 20～100 ℃ and is mixed with slurry;
(3) form the initial recombination microballoon by spraying balling-up drying process;
(4) under protection of inert gas, under 500～3000 ℃, heat-treat 1～48h, obtain being applicable to the carbon/carbon composite microsphere material of lithium ion battery at last.
8. carbon/carbon the composite microsphere material that obtains by the described method production as one of claim 1-7 is characterized in that the particle diameter of described carbon/carbon composite microsphere material is controlled, and its particle diameter is preferably 2～100 μ m; The granule interior duct controllable size of described carbon/carbon composite microsphere material, it is preferably dimensioned to be 1～20nm.
9. a lithium ion battery is characterized in that, described lithium ion battery uses the negative material of carbon as claimed in claim 8/carbon composite microsphere material as battery.
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