CN103214245B - 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 the lithium ion battery using described carbon/carbon composite microsphere material as negative material, belong to lithium ion battery negative material technical field.
Background technology
Lithium ion battery is to meet being widely used and a kind of chemical power source of high speed development needs of various portable electric appts, power tool and New-energy electric vehicle.It has that voltage is high, specific energy is large, discharging voltage balance, low-temperature performance is good, safety performance is excellent and the easy advantage such as storage and long working life.The preparation of negative material is one of gordian technique of lithium ion battery.Graphitized carbon material good conductivity, degree of crystallinity is high, has good laminate structure, and the embedding that is applicable to lithium ion is deviate from, and becomes the lithium ion battery negative material of having realized commercial applications at present.Due to the common embedding of organic solvent molecule in graphite linings, there is the phenomenon of solvolysis, cause the phenomenons such as the peeling off of graphite electrode material, efflorescence; And due to the existence of graphite surface active sites and defect, form unsettled solid electrolyte interface film at material surface, electrode coulomb Efficiency Decreasing, capacity attenuation is serious, and then affects the cycle performance of battery.
Hard carbon is generally through pyrogenically prepared decolorizing carbon by the lower organism of aromaticity, it is also difficult to obtain higher degree of graphitization through high temperature (>2000 DEG C) thermal treatment, and common hard carbon mainly contains resol, glucose, segregation vinyl fluoride, epoxy resin, polyvinyl chloride, glycan alcohol etc.
Soft carbon be by heavy oil component or coal-tar pitch and cut thereof 1000 DEG C of left and right thermal treatments, its deoxidation, dehydrogenation are formed.Soft carbon is a kind of decolorizing carbon, its at high temperature 2500 DEG C can greying, i.e. easy graphitized carbon.In this class carbon material, have certain impurity, 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 negative material specific storage, and the specific storage of 1000 DEG C of following non-graphitized soft carbon of processing is usually 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 large, with the good feature of compatibility of electrolyte, is used to gradually in energy-storage battery and power cell.In commercial soft carbon material, carbosphere is considered to have most development potentiality.This is that carbosphere has more advantages because compared with other carbon material.For example, ball-like structure is conducive to realize tightly packed, thereby can improve the volume energy density of electrode; Globosity can make lithium ion in electrolytic solution embed and deviate from all directions of ball, solved graphite type material because the graphite flake layer that anisotropy causes is swelling, the multiplying power problem of subsiding and can not rapid large-current discharging and recharging.In addition, the hard carbon of random sequence has the feature of higher capacity, low cost and excellent cycle performance.It is good that synthetic graphite has with compatibility of electrolyte, and its embedding, de-speed are larger, have good load character.Therefore,, in conjunction with the feature of differing materials, the negative material of exploitation excellent property is also one of emphasis of research.
CN1422235A adopts glucose, sucrose, fructose, Mierocrystalline cellulose or starch, or resol, polypropylene are fine, the mixture of epoxy resin and solidifying agent Tetra hydro Phthalic anhydride; Or the mixture of epoxy resin and polyoxymethylene and phenol and solvent be made into homodisperse system,, high temperature carbonization dry through liquid-phase dehydration, washing makes spheroid or spheroid hard carbon material, and this material can be used as the negative active core-shell material of serondary lithium battery.
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, refinery coke, the material that pitch is composited.The processes such as recombination process comprises mixing, kneading, rolls sheet, pulverizing, moulding, carbonization, greying (more than 2800 DEG C), ball-type, are prepared from negative material.
CN102569752A is taking acicular petroleum coke and/or coal tar and resin as raw material, after being dissolved in organic solvent, in pressurized vessel, carry out again liquid-phase dehydration processing, then by coated modification, low-temperature curing, charing, finally by the carbon modified material of making lithium ion secondary battery negative pole after high-temperature heat treatment, cooling, screening; The carbon modified material of making is spherical 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 distinctive structure of expanded graphite, carry out compound preparation with starch base hard carbon microballoon, utilize building as the conduction of electronics provides good passage of solid spacial framework, thereby improve the voltage delay effect of hard carbon material, and improve the efficiency first of negative material.
CN102351163A is made up through steps such as obtain solution, stirring and rectifying separation of the one in the amphipathic Carbon Materials of coal-tar pitch base, petroleum asphalt based amphipathic Carbon Materials, the amphipathic Carbon Materials of intermediate phase pitch-based, the amphipathic Carbon Materials of refinery coke base, the amphipathic Carbon Materials of needle coke base and the amphipathic Carbon Materials of pitch coke base, and Nano carbon microballoon prepared by this invention is formed by the self-assembly under capillary constraint of amphipathic Carbon Materials.
It is raw material that CN1461283A adopts resin, pitch and composition thereof, under hydrophobicity inorganic substance or silicone oil effect, obtain charing mixture through thermal treatment under 700～1500 DEG C of inert environments, then add acid or alkali solvent is removed inorganic substance, continue thermal treatment at 2000～3200 DEG C and obtain ball-type charcoal.
CN101800304A adopts natural flake graphite micro mist and cakingagent to mix as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyvinyl butyral acetal (PVB), after spray-dried, through 600～1000 DEG C of heat of carbonization processing, obtain the spherical graphite powder of 20～50 microns again.
The problems such as more than the method ubiquity material ball-type degree of report is poor, raw materials cost is high, complicated process of preparation, equipment requirements is high, process condition is harsh, seriously polluted, batch production is difficult.
Therefore, intend providing a kind of carbon in lithium ion battery/carbon complex microsphere negative material.This carbon/carbon complex microsphere negative material, by soft carbon and hard carbon material matrix composition, has good electronic conductance and ion transport passage.This negative material has good globosity, is conducive to realize close-packed, improves the volume energy density of electrode, can make lithium ion embed from all directions simultaneously, improves structural stability and the high rate performance of material; Spheroidal particle inside has the pore passage structure of appropriate size, improves charge/discharge capacity and the circulation volume conservation rate of material.In the time that soft carbon material particle diameter is micron level, add appropriate nano level carbon black, can fill the accumulation hole of soft carbon material in balling-up process, increase the slickness on spherical granules surface, increase tap density and the intensity of material.
Carbon/carbon composite microsphere material the production method providing is provided in the present invention, and raw material sources are extensive, and preparation technology is simple, environmental friendliness, and energy consumption and with low cost, is easy to scale operation.
Summary of the invention
For the deficiencies in the prior art, one of object of the present invention is to provide a kind of production method of carbon/carbon composite microsphere material.
Carbon/carbon the composite microsphere material that provides the described production method of one of a kind of object to obtain is provided two of object of the present invention.
Three of object of the present invention be to provide a kind of application target two described in carbon/carbon composite microsphere material as the lithium ion battery of negative material.
The present inventor is through carefully investigation certification, and adopting the soft carbon materials such as refinery coke or needle coke and carbon black is raw material, prepares carbon/carbon complex microsphere as lithium ion battery negative material.The soft carbon material such as refinery coke or needle coke, carbon black and binding agent are uniformly distributed in initial recombination microballoon, and 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, the controllable pore passage structure that sphericity is high, granule interior contains 1～20nm.In the time that soft carbon material particle diameter is micron level, add appropriate nano level carbon black, can fill the accumulation hole of soft carbon material in balling-up process, regulate the pore distribution of spheroidal particle inside, increase the slickness on spherical granules surface, increase tap density, intensity and the conductivity of material, reduce the specific surface area of material, make up the deficiency that soft carbon material particle diameter brings more greatly.Can improve specific storage and the cycle performance of battery as lithium ion battery negative material, improve the consistency of negative material and electrolytic solution, also solve the problems such as carbon negative pole material production cost is high, complex process, suitability for industrialized production difficulty simultaneously.
For reaching this object, the present invention by the following technical solutions:
A kind of production method of carbon/carbon composite microsphere material; first soft carbon material is crushed to the particle that particle diameter is less than 2 μ m; then be mixed with slurry with binding agent, carbon black and solvent; form initial recombination microballoon by spraying balling-up drying process; under protection of inert gas, heat-treat again, finally obtain being applicable to carbon/carbon composite microsphere material of lithium ion battery.
In the present invention, soft carbon material, carbon black and binding agent are uniformly distributed in initial recombination microballoon, and in heat treatment process, binder decomposed generates hard carbon and part pore passage structure, and that the globosity of particle also keeps is complete, strength increase.
In described carbon/carbon complex microsphere negative material, the content of each raw material can, by one of ordinary skill in the art according to the prior art/new technology of its grasp, be determined according to specific needs.
Soft carbon material of the present invention is the combination of any one or at least two kinds in refinery coke, petroleum needle coke or coal-based needle coke.Soft carbon is easy graphitized carbon, and referring to can graphited decolorizing carbon under the high temperature more than 2500 DEG C.The degree of crystallinity (being degree of graphitization) of soft carbon is low, and grain-size is little, and spacing is larger, 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 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), epoxy resin, 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, epoxy resin 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 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 dimethyl formamide.Typical but non-limiting example comprises: water, acetone, benzene, dimethyl formamide, the combination of water and ethanol, 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 preparation of the present invention, the mass ratio of soft carbon material, binding agent, carbon black, solvent is soft carbon material: binding agent: carbon black: solvent is 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 DEG C, for example 20.02～99.89 DEG C, and 22～99 DEG C, 24.8～95.6 DEG C, 28.7～92.3 DEG C, 30.2～88.7 DEG C, 34～83.5 DEG C, 38.9～76.8 DEG C, 45～70 DEG C, 48.9～63.2 DEG C, 53～57 DEG C 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 preferably preparation temperature is 25～90 DEG C, and churning time is 0.5～4h.
Spraying balling-up drying process inlet temperature of the present invention is 200～500 DEG C, for example, can select 200.01～496.8 DEG C, 212～480 DEG C, 238～463 DEG C, 250～421 DEG C, 278～400 DEG C, 294～376 DEG C, 322～346 DEG C, 330 DEG C etc., temperature out is 70～150 DEG C, for example, can select 70.02～149.8 DEG C, 74～142.1 DEG C, 78.9～136 DEG C, 88～124 DEG C, 95～120.5 DEG C, 104～112 DEG C, 108.6 DEG C etc.
Thermal treatment of the present invention is charing or greying.Charing claims again destructive distillation, is the reaction process of solid or organism thermal degradation under isolated air conditions.The required temperature difference of different substances destructive distillation is very large, can be from 100 DEG C (as wood distillation) to more than 1000 DEG C (as High T-emperature Carbonizations); Pressure can be normal pressure, can be also decompression.Greying is to prepare the later process of graphitized fibre, is generally to carry out in the argon gas of 2000～3300 DEG C 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 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 DEG C, for example, can select 500.01～2989 DEG C, 526～2850 DEG C, and 556.5～2600 DEG C, 589～2340 DEG C, 642～2130 DEG C, 780～1860 DEG C, 989～1500 DEG C, 1224～1380 DEG C etc., heat treatment time is 1～48h, for example 1.02～47.9h, 2.8～45h, 5～40.8h, 7.6～35.4h, 9～30h, 12.3～27.6h, 15～23h, 18.5～21.3h, 20h etc.
A production method for carbon/carbon composite microsphere material, the processing condition of described method comprise the following steps through optimizing:
(1) soft carbon material is crushed to the particle that particle diameter is less than 2 μ m;
(2) by soft carbon material, binding agent, carbon black and solvent after fragmentation according to 1:(0.01～1): (0.01～2): the mass ratio of (2～20) mixes, and stirs 0.5～5h and be mixed with slurry at 20～100 DEG C;
(3) form initial recombination microballoon by spraying balling-up drying process;
(4) under protection of inert gas, at 500～3000 DEG C, heat-treat 1～48h, finally obtain being applicable to carbon/carbon composite microsphere material of lithium ion battery.
When in the present invention, soft carbon material raw material particle size is micron order, in balling-up process, between soft carbon granule, there is certain accumulation hole, nano level therebetween carbon black filled, increase tightness degree, the smooth degree on ball-type surface and the electroconductibility of spherical granules and the intensity of granule interior structure.In addition, nano level carbon black also can regulate the pore passage structure of material internal, reduces the specific surface area of material.Due to carbon black wide material sources, in use procedure, without fragmentation, therefore compare graphite material and also there is certain cost advantage.
The present invention adopts soft carbon material through broken, be mixed with slurry with carbon black, binding agent, solvent, prepare initial recombination microballoon by spraying balling-up drying process, in this structure, binding agent, carbon black and soft carbon material are evenly bonded as ball-type, and the specific surface area of material has had significantly and reduced than simple hard carbon material.In addition, initial carbon complex microsphere is in high-temperature process, and binder decomposed generates hard carbon and forms pore passage structure, and the globosity of particle also keeps complete, strength increase simultaneously.Carbon/carbon complex microsphere of the present invention contains soft carbon and hard carbon material simultaneously, have the ball-type structure of height, suitable pore distribution, combines the advantage of soft carbon and hard carbon material, realize the close-packed of material and the excellent compatibility of electrolytic solution, and there is suitable ion transport passage.
Produce the carbon/carbon composite microsphere material obtaining by method as above, 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 pore size of described carbon/carbon composite microsphere material is controlled, and it is preferably dimensioned to be 1～20nm.
The particle diameter of carbon/carbon composite microsphere material of the present invention is controlled is to realize by controlling as particle diameter and the spray-dired processing condition of raw material.
The size in the granule interior duct of carbon/carbon composite microsphere material of the present invention is controlled is that addition by controlling heat treated temperature, time and binding agent, carbon black is realized.
A kind of lithium ion battery, described lithium ion battery uses the negative material of carbon/carbon composite microsphere material as above as battery.
Compared with prior art scheme, the present invention has following beneficial effect:
1, carbon/carbon composite microsphere material of the present invention combines the high reversible capacity feature of hard carbon, and soft carbon material and the good advantage of compatibility of electrolyte, and it has higher specific storage and good cycle performance as lithium ion battery negative material.
2, carbon/carbon composite microsphere material of the present invention, through heat treatment process, increases the strength of materials, 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, carbon black wide material sources, without fragmentation, use that method is simple.
4, carbon/carbon composite microsphere material involved in the present invention has higher sphericity, and preparation method is simple, environmental protection, and energy consumption and with low cost, is easy to suitability for industrialized production.
Brief description of the 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 example 2 carbon/carbon composite microsphere material.
The present invention is described in more detail below.But following example is only 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 5 grams of fragmentations, 10 grams of channel blacks, 5 grams of glucose and 150 grams of water are mixed, at 50 DEG C, stir 4h and be mixed with slurry.Adopt spray-drier that slurry is dried and granulation, the dry inlet temperature of its spraying is 230 DEG C, and temperature out is 70 DEG C; After dry, can obtain initial carbon/carbon complex microsphere.Then by resulting materials under argon gas atmosphere protection, at 900 DEG C, fixed bed thermal treatment 2h obtains carbon/carbon composite microsphere material.
The JSM-7001F type field emission scanning electron microscope observing samples pattern that carbon/carbon composite microsphere material of above-mentioned preparation is produced in NEC Oxford instrument company.
Fig. 1 is the SEM figure of carbon/carbon composite microsphere material of obtaining of embodiment 1.This material ball-type degree is higher.
Adopt Dandong Bai Te BT-9300Z laser fineness gage to carry out particle size analysis carbon/carbon complex microsphere of above-mentioned preparation and see Fig. 2, particle size is between 2～40 μ m.
On the 2001A type charge-discharge test instrument that the battery assembling is produced in Wuhan Lan electricity company, carry out charge-discharge performance test, test result is in table 1.
The SEM of other embodiment scans, the testing method of sreen analysis is identical with embodiment 1.
Embodiment 2
Be that needle coke, 3 grams of channel blacks, 5 grams of wheat starches and 120 grams of water mix by the oil after 7 grams of fragmentations, at 40 DEG C, stir 2h and be mixed with slurry.Adopt spray-drier that slurry is dried and granulation, the dry inlet temperature of its spraying is 230 DEG C, and temperature out is 150 DEG C; After dry, can obtain initial carbon/carbon complex microsphere.Then by resulting materials under nitrogen atmosphere protection, obtain carbon/carbon composite microsphere material at 1400 DEG C of fluidized bed at elevated 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 15 grams of fragmentations, 15 grams of Mierocrystalline celluloses, 10 grams of furnace blacks, 5 grams of channel blacks and 300 grams of water are mixed, at 30 DEG C, stir 1.5h and be mixed with slurry.Adopt spray-drier that slurry is dried and granulation, the dry inlet temperature of its spraying is 200 DEG C, and temperature out is 100 DEG C; After dry, can obtain initial carbon/carbon complex microsphere.Then by resulting materials under nitrogen atmosphere protection, at 800 DEG C, agitated bed thermal treatment 3h obtains carbon/carbon composite microsphere material.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
By the refinery coke after 20 grams of fragmentations, 1.2 grams of Polyvinylpyrolidone (PVP)s, 5 grams of dim and 200 grams of water mixing, at 50 DEG C, stir 3h.Adopt spray-drier that slurry is dried and granulation, the dry inlet temperature of its spraying is 500 DEG C, and temperature out is 80 DEG C; After dry, can obtain initial carbon/carbon complex microsphere.Then by resulting materials under nitrogen atmosphere protection, at 2000 DEG C, fixed bed thermal treatment 16h obtains 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.
Embodiment 5
3 grams of resol are dissolved in 20 grams of ethanol and make solution, are needle coke, 1 gram of dim, 80 grams of water mixed pulp material by the oil after 10 grams of fragmentations, and the two is blended in and at 20 DEG C, stirs 5h and be mixed with slurry.Adopt spray-drier that slurry is dried and granulation, the dry inlet temperature of its spraying is 280 DEG C, and temperature out is 120 DEG C; After dry, can obtain initial carbon/carbon complex microsphere.Then by resulting materials under nitrogen atmosphere protection, at 2600 DEG C, agitated bed thermal treatment 24h obtains carbon/carbon composite microsphere material.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 20 grams of fragmentations, 18 grams of W-Gums, 10 grams of channel blacks and 350 grams of water are mixed, at 25 DEG C, stir 2h and be mixed with slurry.Adopt spray-drier that slurry is dried and granulation, the dry inlet temperature of its spraying is 230 DEG C, and temperature out is 150 DEG C; After dry, can obtain initial carbon/carbon complex microsphere.Then by resulting materials under helium atmosphere protection, at 900 DEG C, high temperature graphitization furnace treatment reason 2h obtains carbon/carbon composite microsphere material.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
Be that needle coke, 20 grams of furnace blacks, 20 grams of sucrose and 400 grams of water mix by the oil after 20 grams of fragmentations, at 30 DEG C, stir 1h and be mixed with slurry.Adopt spray-drier that slurry is dried and granulation, the dry inlet temperature of its spraying is 320 DEG C, and temperature out is 70 DEG C; After dry, can obtain initial carbon/carbon complex microsphere.Then by resulting materials under nitrogen atmosphere protection, obtain carbon/carbon composite microsphere material at 1300 DEG C of fluidized bed at elevated 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 8 grams of fragmentations, 2 grams of channel blacks, 3 grams of Mierocrystalline celluloses and 90 grams of water are mixed, at 90 DEG C, stir 0.5h and be mixed with slurry.Adopt spray-drier that slurry is dried and granulation, the dry inlet temperature of its spraying is 230 DEG C, and temperature out is 104 DEG C; After dry, can obtain initial carbon/carbon complex microsphere.Then by resulting materials under nitrogen atmosphere protection, at 500 DEG C, agitated bed thermal treatment 1h obtains carbon/carbon composite microsphere material.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 10 grams of fragmentations, 0.1 gram of channel black, 0.1 gram of Polyvinylpyrolidone (PVP) and 20 grams of water are mixed, at 100 DEG C, stir 1h and be mixed with slurry.Adopt spray-drier that slurry is dried and granulation, the dry inlet temperature of its spraying is 230 DEG C, and temperature out is 150 DEG C; After dry, can obtain initial carbon/carbon complex microsphere.Then by resulting materials under nitrogen atmosphere protection, at 3000 DEG C, fixed bed thermal treatment 48h obtains carbon/carbon composite microsphere material.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 grams of resol are dissolved in 30 grams of acetone and make solution, are that needle coke, 10 grams of broken refinery cokes, 4 grams of furnace blacks, 200 grams of water are mixed and made into slurry by the oil after 10 grams of fragmentations, and the two is blended in and at 30 DEG C, stirs 1h and be mixed with slurry.Adopt spray-drier that slurry is dried and granulation, the dry inlet temperature of its spraying is 250 DEG C, and temperature out is 70 DEG C; After dry, can obtain initial carbon/carbon complex microsphere.Then by resulting materials under nitrogen atmosphere protection, process 24h at 2600 DEG C 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 example 1
Choose the HAG2 graphite pebbles of Chang Sha Xing Cheng Graphite Co., Ltd.'s production as a comparison case;
The HAG2 graphite pebbles that Chang Sha Xing Cheng Graphite Co., Ltd. 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 example 2
Be that the refinery coke of 2 μ m, 5 grams of wheat starches and 150 grams of water mix by D90 after 5 grams of fragmentations, at 40 DEG C, stir 2h and be mixed with slurry.Adopt spray-drier that slurry is dried and granulation, the dry inlet temperature of its spraying is 230 DEG C, and temperature out is 130 DEG C; After dry, can obtain initial carbon/carbon complex microsphere.Then by resulting materials under nitrogen atmosphere protection, at 900 DEG C, thermal treatment 4h obtains carbon/carbon composite microsphere material.Its SEM figure is shown in Fig. 4.Comparison diagram 4 and Fig. 1 are visible, and in the time that soft carbon material particle diameter is larger, if do not add carbon black, particle surface is comparatively coarse, and hole is more, and 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 present invention 1～10 and comparative example are provided is made electrode, and carries out electrochemical property test, and concrete steps are as follows:
Carbosphere material that one of comparative example and/or embodiment 1～10 provide (or comparative example 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, then add PVDF(polyvinylidene difluoride (PVDF)) (PVDF is the PVDF/NMP solution of the 0.02g/mL for preparing, NMP is N-Methyl pyrrolidone) solution, be coated on Copper Foil, in vacuum drying oven, in 120 DEG C of vacuum-drying 24h, the disk that cut-off footpath is 14mm is as working electrode; Metallic lithium is to electrode; Electrolytic solution is LiPF6/EC-DMC-EMC(volume ratio 1:1:1); In Ar glove box, be assembled into two electrode simulated batteries being full of;
Charging/discharging voltage scope is 1.0～0.01V, and charging and discharging currents density is 50mA/g; High rate performance test is used current density to be respectively 200mA/g(0.5C), 500mA/g(1C).
Carbon/carbon complex microsphere and commercial graphite material that described embodiment obtains are as shown in table 1 as the chemical property of lithium ion battery negative material, the head of commercial graphite material week loading capacity is 320mAh/g as can be seen from the table, the capability retention after 20 times that circulates is 90%, first all coulomb efficiency and capability retention are poor, and under 200mA/g and 500mA/g current density, reversible capability of charging and discharging is for being respectively 250mAh/g and 150mAh/g.And in the time using carbon/carbon composite microsphere material of preparing of the inventive method as lithium ion battery negative material, first all loading capacities be 250mAh/g to 330mAh/g not etc., the capability retention that circulates after 20 times be under 99%, 200mA/g and 500mA/g current density reversible capability of charging and discharging respectively between 250～330mA/g and 210～270mA/g.
The chemical property evaluation result of table 1 embodiment of the present invention and comparative example
Applicant's statement, the present invention illustrates production method of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned production stage, does not mean that the present invention must rely on above-mentioned production stage and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the selected raw material of the present invention and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (16)
1. the production method of carbon/carbon composite microsphere material, it is characterized in that, first soft carbon material is crushed to the particle that particle diameter is less than 2 μ m, then be mixed with slurry with binding agent, carbon black and solvent, form initial recombination microballoon by spraying balling-up drying process, under protection of inert gas, heat-treat again, finally obtain being applicable to carbon/carbon composite microsphere material of lithium ion battery;
Described binding agent is the material with adhesive property of water soluble or organic solvent, is selected from the combination of any one or at least two kinds in sucrose, glucose, W-Gum, tapioca (flour), wheat starch, Mierocrystalline cellulose, polyvinyl alcohol, polyoxyethylene glycol, polyethylene wax, resol, Polyvinylpyrolidone (PVP), polyvinyl chloride, glycan alcohol, furane resin, polymethylmethacrylate, polyvinylidene difluoride (PVDF) or polyacrylonitrile;
When described slurry preparation, the mass ratio of soft carbon material, binding agent, carbon black, solvent is 1:(0.01～1): (0.01～2): (2～20);
Described spraying balling-up drying process inlet temperature is 200～500 DEG C, and temperature out is 70～150 DEG C;
Described thermal treatment temp is 500～3000 DEG C, and heat treatment time is 1～48h.
2. the method for claim 1, is characterized in that, described soft carbon material is petroleum needle coke and/or coal-based needle coke.
3. the method for claim 1, is characterized in that, 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 crusher in crushing.
4. the method as described in one of claim 1-3, is characterized in that, described carbon black is nano level carbon black.
5. method as claimed in claim 4, is characterized in that, that described carbon black is selected from is dim, the combination of any one or at least two kinds in channel black, furnace black or channel black.
6. the method for claim 1, is characterized in that, described solvent is the combination of any one or at least two kinds in water, ethanol, ether, acetone, tetrahydrofuran (THF), benzene,toluene,xylene or dimethyl formamide.
7. the method as described in one of claim 1-3, is characterized in that, described preparation temperature is 20～100 DEG C, and churning time is 0.5～5h.
8. method as claimed in claim 7, is characterized in that, preparation temperature is 25～90 DEG C, and churning time is 0.5～4h.
9. the method as described in one of claim 1-3, is characterized in that, described thermal treatment is charing or greying.
10. the method as described in one of claim 1-3, is characterized in that, described rare gas element is the combination of any one or at least two kinds in nitrogen, helium, neon, argon gas or carbonic acid gas.
11. methods as described in one of claim 1-3, is characterized in that, described equipment for Heating Processing is fixed bed, fluidized-bed, agitated bed or high temperature graphitization stove.
12. methods as described in one of claim 1-3, is characterized in that, said method comprising the steps of:
(1) soft carbon material is crushed to the particle that particle diameter is less than 2 μ m;
(2) by soft carbon material, binding agent, carbon black and solvent after fragmentation according to 1:(0.01～1): (0.01～2): the mass ratio of (2～20) mixes, and stirs 0.5～5h and be mixed with slurry at 20～100 DEG C;
(3) form initial recombination microballoon by spraying balling-up drying process;
(4) under protection of inert gas, at 500～3000 DEG C, heat-treat 1～48h, finally obtain being applicable to carbon/carbon composite microsphere material of lithium ion battery.
Produce the carbon/carbon composite microsphere material obtaining by the method as described in one of claim 1-12 for 13. 1 kinds, it is characterized in that, the particle diameter of described carbon/carbon composite microsphere material is controlled; The granule interior pore size of described carbon/carbon composite microsphere material is controlled.
14. carbon/carbon composite microsphere materials as claimed in claim 13, is characterized in that, the particle diameter of described carbon/carbon composite microsphere material is 2～100 μ m.
15. carbon/carbon composite microsphere materials as claimed in claim 13, is characterized in that, the granule interior pore size of described carbon/carbon composite microsphere material is 1～20nm.
16. 1 kinds of lithium ion batteries, is characterized in that, described lithium ion battery uses the negative material of carbon/carbon composite microsphere material as claimed in claim 13 as battery.
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| CN103551200B (en) * | 2013-11-20 | 2015-06-03 | 河南城建学院 | Porous graphite carbon composite material as well as preparation method and application thereof |
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| CN104925778B (en) * | 2014-03-21 | 2017-05-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube microsphere and preparation method and application thereof |
| JP6445585B2 (en) | 2014-03-21 | 2018-12-26 | 中国科学院蘇州納米技術与納米倣生研究所Ｓｕｚｈｏｕ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｎａｎｏ−Ｔｅｃｈ Ａｎｄ Ｎａｎｏ−Ｂｉｏｎｉｃｓ（Ｓｉｎａｎｏ），Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Porous carbon nanotube microspheres and production method and use thereof, metallic lithium-skeleton carbon composite material and production method thereof, negative electrode, and battery |
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| CN107993853B (en) * | 2017-11-30 | 2019-09-17 | 上海奥威科技开发有限公司 | A kind of negative electrode material that soft or hard carbon is compound, preparation method and the capacitor comprising the negative electrode material |
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| CN109841826B (en) * | 2019-04-04 | 2020-12-25 | 浙江大学 | Preparation method and application of mesocarbon microbead/nano-silicon composite sphere |
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| CN111048749B (en) * | 2019-10-30 | 2022-01-14 | 深圳市卓能新能源股份有限公司 | Negative pole piece, lithium ion battery and manufacturing method thereof |
| CN112174670B (en) * | 2020-09-30 | 2022-09-13 | 中国科学院上海应用物理研究所 | Preparation method for densification modification of graphite material, densified graphite material obtained by preparation method and application of densified graphite material |
| CN112310392B (en) * | 2020-11-03 | 2023-08-08 | 中国人民解放军军事科学院防化研究院 | Preparation method of porous carbon/lead composite material with high bulk density |
| CN112588201B (en) * | 2020-12-30 | 2022-11-15 | 重庆长江造型材料（集团）股份有限公司 | Consolidation granulation method of slurry |
| CN113003559A (en) * | 2021-02-06 | 2021-06-22 | 常德速碳新能源科技有限公司 | Preparation method of carbon negative electrode material for lithium ion battery |
| CN114122393A (en) * | 2021-11-11 | 2022-03-01 | 深圳市翔丰华科技股份有限公司 | Preparation method of high-power-density negative electrode material for lithium ion battery |
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