CN103606681A - Preparation method of composite material of coating layer of lithium ion battery cathode - Google Patents
Preparation method of composite material of coating layer of lithium ion battery cathode Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a composite material of a coating layer of a lithium ion battery cathode. The preparation method specifically comprises the following steps of adding asphalt and resin in a kneading kettle with a heating and stirring device according to a weight ratio of 1:(1.5-4), heating to increase the temperature until the asphalt and the resin are melted into liquid, then stirring, uniformly mixing, and then stopping heating, cooling to obtain a composite coating material block body; and after coarsely crushing the composite coating material block body, carrying out ultrafine crushing by using an airflow crusher or a copious cooling crusher to obtain a composite ultrafine coating material powder body with an average particle diameter D50 being below 6 micrometers, namely, the composite coating layer material of the lithium ion battery cathode. The preparation method has the remarkable creation points that the composite material of the coating layer of the lithium ion battery cathode is obtained after melting, mixing, solidifying, coarsely crushing and finely crushing a precursor of the coating material; graphite can be coated, and a modified graphite cathode material is prepared; the uniformity of mixing precursors of multiple kinds of coating materials is ensured, and no any solvent is not needed, and the environmental friendliness is achieved; in addition, according to the preparation method, the process is simple, the cost is low and industrial production is easy.
Description
Technical field
The present invention relates to field of batteries, be specially a kind of preparation method of lithium ion battery negative pole coating layer composite material, coating layer composite material prepared by the method can be used for preparing modified graphite cathode material.
The application proposes application for a patent for invention " a kind of preparation method of modified graphite cathode material of lithium-ion power battery " according on December 14th, 2012 in China, and the patent No. is: 2012105410709, and quote its content at this.
Background technology
Along with the development of automobile industry, the exhaustion of the non-renewable fossil fuels such as oil, natural gas receives publicity day by day, and air pollution and room temperature effect also become global problem.For solving energy problem, realize low-carbon environment-friendly, the development level based on current energy technology, electric vehicle engineering becomes the emphasis direction of global economy development gradually, the countries such as the U.S., Japan, Germany, China in succession limit fuel vehicle and use, and greatly develop electric motor car.Core component as electric automobile---electrokinetic cell has also welcome large good opportunity to develop.Electrokinetic cell refers to the battery that is applied to electric motor car, comprise lithium ion battery, lead-acid battery, fuel cell etc., wherein, specific energy is high, specific power is large, self discharge is few because having for lithium ion battery, long service life and the advantage such as fail safe is good, has become the emphasis of current various countries development.
And have lower lithium as the graphite type material of lithium ion battery negative material, embedding/take off embedding current potential, suitable reversible capacity and aboundresources, the advantage such as cheap, is more satisfactory lithium ion battery negative material.But it also exists, and discharging efficiency is low first, cycle performance is poor, to shortcomings such as electrolyte selectivity height, graphite material application is restricted.In order to solve the above-mentioned shortcoming of graphite material, people carry out modification by the whole bag of tricks to graphite, and the method conventionally adopting is at present the coated method of carbon.Yang Ruizhi etc. are research > > (the < < Journal of Inorganic Materials > > as lithium ion battery negative electrode at < < resin carbon coated graphite, 2000,15(4): 712-718), with liquid impregnation method, on natural flake graphite surface, be coated phenolic resins, use constant current charge and discharge, powder microelectrode cyclic voltammetry has been investigated charge and discharge performance.Experimental result shows, through heat treated phenolic resins carbon coated graphite material to put a capacity higher, cycle life is longer, can be used as the negative material of high performance lithium ion battery.He Ming etc. are at preparation and chemical property > > (the < < battery > > thereof of < < resin carbon-coated graphite, 2003, 3(5): 281-284), at natural micro crystal graphite particle surface, be coated one deck resin carbon, coated processing can reduce the irreversible capacity first of natural micro crystal graphite, adopt and first mix the method coated graphite then disperseing, inside is natural micro crystal graphite, outside is the phenolic resins pyrolysis carbon-coating of 1～2 μ m.The irreversible capacity that lithium ion experimental cell records natural micro crystal graphite is 14%, and the irreversible capacity of coated graphite is 7%.Coated processing can reduce the irreversible capacity of natural micro crystal graphite to a great extent.Chen Meng etc. are at the preparation and property research > of < < pitch-coating native graphite > (< < battery industry > >, 2007,12(5): 298-302) adopt liquid phase coating method, pitch cracking carbon is coated on natural spherical plumbago, to improve its cycle performance.Experimental result shows, native graphite is after pitch-coating, irreversible capacity loss has reduced to 32.5mAh/g from 125.5mAh/g, specific capacity has been brought up to 365.3mAh/g from 290.8mAh/g, capability retention after 50 circulations has brought up to 93.66% from 55.4%, has effectively improved the cycle performance of native graphite.
At present in the coated modification of graphite, all only hard charcoal precursor of independent resin-coated class or pitch class soft charcoal precursor.Chinese patent CN101604743A and CN1224251A etc. adopt resinae as clad material, major advantage is resin good fluidity at low temperatures, can not only clad surface, and be easy to penetrate into graphite granule inside by the micropore in graphite, tap density and electronic conductivity to raising graphite granule are useful, can also be by heating, the methods such as catalyst or ultraviolet ray irradiation of introducing are solidified, in resin pyrolytic process, can not melt distortion, can not produce obvious expansion yet, but also there are some problems, mainly contain: the affinity of resinous material and graphite is poor, therefore the Carbon Materials that their pyrolysis obtains and graphite are in conjunction with insecure, the Carbon Materials yield being obtained by resin pyrolysis is on the low side, enbrittle, in resin pyrolytic process, fugitive constituent is many, specific area is higher, the cohesive force of resin is stronger, be easy to cause coated particle to bond together, while pulverizing after heat treatment, easily cause the destruction of coating layer.These problems above, have affected the compressibility of cycle efficieny, cyclical stability and the graphite electrode of resin-coating graphite material.
Chinese patent CN96198348.5 and CN03120199.6 etc., adopt pitch, petroleum tar, coal tar or their mixture coated graphite, asphalt pyrolysis charcoal is less than the specific area of From Resin Char coated graphite, will get well with the affinity of graphite, structure is more firm, but pitch-coating in heating process because fusing is out of shape, consumption too much also easily causes the mutually bonding of Coating Graphite Particles, consumption is very few easily to be caused coated inhomogeneously, and in heating process, is easy to expand, and affects the electrical property of graphite.
After Chinese patent CN101162775A adopts liquid phase method that pitch and resin are dissolved simultaneously, add again graphite to mix, then steam solvent, finally heat-treat, the mixture of pitch and the formation of one or more resins is coated on to graphite surface, improves cycle efficieny and cyclical stability and multiplying power property and the compressible performance of graphite.But the method also has some shortcomings in actual applications, adopt liquid phase method to need with an organic solvent, easily pollute, simultaneously also very high to the requirement of dissolved matter pitch---(quinoline insolubles content is not more than 12%), solvent is reclaimed in evaporation needs complicated equipment, easily cause investment excessive, these have caused being difficult to be applied in suitability for industrialized production.
Chinese patent CN102082272A adopts hard charcoal precursor, soft charcoal precursor and hetero-atom modifier, and after graphite mixes in proportion, first be cured processing, carry out once more relatively low heat treatment, finally carry out secondary high-temperature graphitization processing, obtain containing the coated lithium ion battery negative material of hard charcoal.But the method will reach the ways of four kinds of powders mixing owing to adopting under normal-temperature solid-phase condition, first be difficult to the uniformity that guarantees that multiple clad material presoma mixes, secondly due in two kinds of precursors, the proportion of soft charcoal precursor is too high, so also need secondary high temperature graphitization to process, otherwise can cause the specific capacity of final coated graphite material on the low side because the degree of graphitization of soft charcoal is on the low side.The final like this rising that can cause production cost, is difficult to meet the market requirement inexpensive to product.
Chinese patent CN102030326A adopt twice coated---first by the coated one deck pitch of graphite after 1300 ± 100 ℃ of carbonizations, more coated one deck resin is 900 ± 50 ℃ of carbonizations, finally at graphite cathode material that more than 2500 ℃ prepared by graphitizing method.Be about to resin carbon and be coated on bitumencarb, bitumencarb is coated on again on graphite granule, forms the gradient-structure of different carbon-coatings.But in fact outermost layer or coated resin carbon, the final like this specific area of clad material that can cause is bigger than normal, first Efficiency Decreasing.The production cost that simultaneously charing repeatedly and graphitizing process can increase material, affects the marketing of product.
Summary of the invention
The object of the invention is to make up the deficiencies in the prior art, a kind of preparation method of lithium ion battery negative pole coating layer composite material is provided, coating layer composite material prepared by the method is compounded to form jointly by pitch and resin; Together with after composite material carbonization, formed asphalt carbon is pinned at mutually with resin carbon, complementation is not enough, can improve the comprehensive electrochemical properties of coated graphite.
The present invention for solving the technical scheme of its technical problem employing is:
A preparation method for lithium ion battery negative pole coating layer composite material, concrete steps are as follows:
(1) by softening point, at the pitch between 100 ℃～300 ℃ and softening point, the resin between 50 ℃～150 ℃ joins by the weight ratio of 1:1.5～4 in the kneading still with heating and agitating device;
(2) with the speed of 10～40 ℃/min, be heated to pitch and resin is all fused into liquid;
(3) then under inert gas shielding, stir, stop heating after mixing, the final temperature of heating is higher 20～50 ℃ than the high softening-point of component medium pitch and resin; The cooling compound coating material block that obtains;
(4) compound coating material block is carried out after coarse crushing, then carry out ultra-fine grinding by airslide disintegrating mill or deep cooling crush machine, obtain the compound coating material superfine powder of average grain diameter D50 below 6 μ m, be lithium ion battery negative pole coating layer composite material.
The mixture of one or more in the condensation polycyclic polynuclear aromatic hydrocarbon that the pitch described in step of the present invention (1) comprises coal tar pitch, petroleum asphalt, modified coal tar pitch, mesophase pitch, obtained by asphalt modifier, its softening point is between 150 ℃～250 ℃.
Resin described in step of the present invention (1) is thermoplastic resin, comprise one or more the mixture in furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin and polyformaldehyde methyl acrylate resin, its softening point is between 80 ℃～120 ℃.
The speed of the heat temperature raising described in step of the present invention (2) is 20～30 ℃/min.
The time of the stirring described in step of the present invention (3) is 80～130min, and the final temperature of heating is higher 30～40 ℃ than the high softening-point of component medium pitch and resin.
In the process of resin charing, the chemical reaction at initial stage is the dehydration 300 ℃ of beginnings below, and at 400 ℃, reaction speed reaches the highest, and later slow decreasing is continued until more than 900 ℃.At 450 ℃, start to emit gas, there is contracting and react in hydroxyl simultaneously with methylene, mainly forms the crosslinked bonding of typical on-plane surface.500 ℃ of above carbonization reaction that occur, discharge H
2, CO and CH
4deng micro-molecular gas, H wherein
2at the formation speeds of 650 ℃, reach maximum, CO and CH
4it is maximum that formation speed 550 ℃ of left and right reaches; About 700 ℃ weightlessness, be mainly because further charing dehydrogenation reaction; At more than 800 ℃ little molecule, deviate from substantially to finish, finally form amorphous carbon.
And the Carbonization mechanism of pitch and resin have very large similar part, so, the temperature that both mix needs strict control, prevents excess Temperature and occurs thermal polycondensation phenomenon, prevents that Yin Wendu is too low simultaneously and occurs both thoroughly not melt and reduce the situations such as performance of composite material.
The particle diameter of the compound coating material superfine powder described in step of the present invention (4) is at 3 μ m.
Graphite during as negative material, forms one deck solid electrolyte film (Solid Electrolyte Interphase is SEI) on its surface in first charge-discharge process.Solid electrolyte film is the formation that react to each other such as electrolyte, negative material and lithium ion, irreversibly consumes lithium ion, is a main factor that forms irreversible capacity; It two is in the process that lithium ion embeds, electrolyte easily and its be embedded in altogether in the process of moving out, electrolyte is reduced, the gaseous product generating causes graphite flake layer to peel off, especially in containing the electrolyte of PC, graphite flake layer comes off the new interface of formation, causes further SEI to form, irreversible capacity increases, and cyclical stability declines simultaneously.And the degree of order of the amorphous carbon forming after phenolic resins pyrolysis is low, structure is more open, lithium ion can relatively freely embed therein and deviate from and impact that can be not large on its structure generation, therefore be not easy to occur efflorescence, RESEARCH OF PYROCARBON is coated on graphite periphery as one deck barrier simultaneously, can effectively stop the effect of organic solvent and graphite body, thereby prevent that the caused graphite linings of inserting altogether of lithium ion and electrolyte from peeling off and efflorescence.But because resin is in heat treatment process, the little molecule in resin is too much, in overflow process, can cause coated after the surface of material produce too much space, the specific area that causes the graphite after coated is excessive and cause that irreversible capacity is excessive first.The compound coating material that adopts pitch and mixed with resin to form, at graphite surface, form Pyrolytic carbon coating, not only utilized the advantage of pitch and resin simultaneously, both uniformity, operability have also been guaranteed, after Overheating Treatment, together with asphalt carbon is pinned at mutually with resin carbon, complementary not enough, improved the comprehensive electrochemical properties of coated graphite, simultaneously can also be by regulating the ratio of pitch and resin to prepare different compound coating materials, thereby control the specific area of Coating Graphite Particles, meet cyclicity and doubly forthright different requirements.
With prior art, the invention has the beneficial effects as follows:
1. the modified graphite cathode material that adopts lithium ion battery negative pole coating layer composite material of the present invention to prepare, compare with the graphite cathode material of the hard charcoal precursor of independent resin-coated class or pitch class soft charcoal precursor and Chinese patent CN102030326A etc., there is obvious superiority, together with asphalt carbon is pinned at mutually with resin carbon, complementation is not enough, has improved the comprehensive electrochemical properties of coated graphite.
2. the most outstanding innovative point of the present invention is after clad material presoma Combined Processing (melt, mix, solidify, coarse crushing, ultra-fine attritioning), to obtain lithium ion battery negative pole coating layer composite material; It can coated graphite, prepares modified graphite cathode material; Guaranteed the uniformity that multiple clad material presoma mixes, simultaneously without any need for solvent, environmentally friendly; In addition, technique is simple, and cost is low, easily suitability for industrialized production; Other adopt the technology of liquid phase methods and Chinese patent CN102082272A etc. other adopt and solidify the technology of processing and compare with Chinese patent CN101162775A etc., have outstanding creativeness and superiority.
Accompanying drawing explanation
The electromicroscopic photograph (1000 times) that Fig. 1 is the modified graphite cathode material that adopts lithium ion battery negative pole coating layer composite material of the present invention and prepare.
The electromicroscopic photograph (5000 times) that Fig. 2 is the modified graphite cathode material that adopts lithium ion battery negative pole coating layer composite material of the present invention and prepare.
The electromicroscopic photograph (10000 times) that Fig. 3 is the modified graphite cathode material that adopts lithium ion battery negative pole coating layer composite material of the present invention and prepare.
The first charge-discharge curve chart that Fig. 4 is the modified graphite cathode material that adopts lithium ion battery negative pole coating layer composite material of the present invention and prepare.
The multiplying power discharging curve chart that Fig. 5 is the modified graphite cathode material that adopts lithium ion battery negative pole coating layer composite material of the present invention and prepare.
Embodiment
In order to make technological means of the present invention, creation characteristic, workflow, using method reach object and effect is easy to understand, below further set forth the present invention.
Take natural spherical plumbago as raw material, adopt the made coating layer composite material of the present invention to come coated graphite to detect its performance, further illustrate, but these examples do not comprise or limit the full content of inventive concept.The average grain diameter D50 of natural spherical plumbago is 17.14 μ m, and tap density is 1.09g/cm
3, specific area is 6.5m
2/ g).
Embodiment 1
By mesophase pitch (250 ℃ of softening points) and phenolic resins (110 ℃ of softening points) according to 1:3(35Kg and 105Kg) ratio together with join in the kneading still of 200L, heating rate is 10 ℃/min, start to heat up and be heated to 300 ℃, at pitch and resin, be all fused into after liquid, start to stir, and after maintaining 2 hours, start cooling, after cooling, obtain compound coating material block; Compound coating material block is carried out after coarse crushing with Ordinary pulverization machine, then adopt airslide disintegrating mill to carry out ultra-fine grinding, obtaining average grain diameter D50 is the compound coating material superfine powder of 2.1 μ m.
During use, compound coating material superfine powder is mixed according to the ratio of 1:9 with natural spherical plumbago, the powder mixing is warming up to 1100 ℃ with the speed of 5 ℃/min, be incubated 1 hour, then be cooled to room temperature, through screening, obtain adopting composite material of the present invention as the prepared modified graphite cathode material of clad material.
Accompanying drawing 1～3 is the electromicroscopic photograph of this modified graphite cathode material of lithium-ion power battery under different amplification, from electromicroscopic photograph, can find out, graphite has the coated skin that one deck mutual intersection is clearly superimposed outward.
Embodiment 2
By mesophase pitch (250 ℃ of softening points) and phenolic resins (110 ℃ of softening points) according to 1:4(30Kg and 120Kg) ratio together with join in the kneading still of 200L, heating rate is 20 ℃/min, start to heat up and be heated to 280 ℃, at pitch and resin, be all fused into after liquid, start to stir, and after maintaining 2 hours, start cooling, after cooling, obtain compound coating material block; Compound coating material block is carried out after coarse crushing with Ordinary pulverization machine, then adopt airslide disintegrating mill to carry out ultra-fine grinding, obtaining average grain diameter D50 is the compound coating material superfine powder of 2.1 μ m.
During use, compound coating material superfine powder is mixed according to the ratio of 1:10 with natural spherical plumbago, the powder mixing is warming up to 1100 ℃ with the speed of 5 ℃/min, be incubated 1 hour, then be cooled to room temperature, through screening, obtain adopting composite material of the present invention as the prepared modified graphite cathode material of clad material.
Embodiment 3
By coal tar pitch (120 ℃ of softening points) and phenolic resins (110 ℃ of softening points) according to 1:3(35Kg and 105Kg) ratio together with join in the kneading still of 200L, heating rate is 15 ℃/min, start to heat up and be heated to 150 ℃, at pitch and resin, be all fused into after liquid, start to stir, and after maintaining 2 hours, start cooling, after cooling, obtain compound coating material block; Compound coating material block is carried out after coarse crushing with Ordinary pulverization machine, then adopt deep cooling crush machine to carry out ultra-fine grinding, obtaining average grain diameter D50 is the compound coating material superfine powder of 2.1 μ m.
During use, compound coating material superfine powder is mixed according to the ratio of 1:9 with natural spherical plumbago, the powder mixing is warming up to 1100 ℃ with the speed of 5 ℃/min, be incubated 1 hour, then be cooled to room temperature, through screening, obtain adopting composite material of the present invention as the prepared modified graphite cathode material of clad material.
Comparative example 1
Adopt airslide disintegrating mill to carry out ultra-fine grinding mesophase pitch (250 ℃ of softening points), obtaining average grain diameter D50 is the pitch-coating material superfine powder of 2.1 μ m; Again pitch-coating material superfine powder is mixed according to the ratio of 1:9 with natural spherical plumbago, the powder mixing is warming up to 1100 ℃ with the speed of 10 ℃/min, be incubated 1 hour, then be cooled to room temperature, through screening, obtain adopting single pitch as the modified graphite cathode material of clad material.
Comparative example 2
Adopt deep cooling crush machine to carry out ultra-fine grinding in phenolic resins (110 ℃ of softening points), obtaining average grain diameter D50 is the resin-coating material superfine powder of 2.1 μ m.Again resin-coating material superfine powder is mixed according to the ratio of 1:9 with natural spherical plumbago, the powder mixing is warming up to 1100 ℃ with the speed of 5 ℃/min, be incubated 1 hour, then be cooled to room temperature, through screening, obtain adopting single resin as the modified graphite cathode material of clad material.
Comparative example 3
Not coated natural spherical plumbago directly carries out electric performance test.
Electrochemical property test
For check adopts composite material of the present invention as the performance of the prepared modified graphite cathode material of clad material, by half-cell method of testing, test, negative material with above embodiment and comparative example: acetylene black: PVDF(Kynoar)=93:3:4(weight ratio), add appropriate NMP(N-methyl pyrrolidone) furnishing pulpous state, coat on Copper Foil, through 110 ℃ of dry negative plates of making for 8 hours of vacuum; Take metal lithium sheet as to electrode, and electrolyte is 1mol/L LiPF
6/ EC+DEC+DMC=1:1:1, microporous polypropylene membrane is barrier film, is assembled into battery.Charging/discharging voltage is 0～2.0V, and charge-discharge velocity is 0.2C, and battery performance is carried out testing, and test result is in Table 1.
Table 1 be negative material in different embodiment and comparative example Performance Ratio
For detect adopt composite material of the present invention as the prepared modified graphite cathode material of clad material at the high rate performance aspect electrokinetic cell, adopt to be prepared into 18650 type cylinder finished product batteries and to carry out the detection of rate charge-discharge.
Use the negative material of embodiment and comparative example: SP:SBR(solid content 50%): CMC=94:2.5:1.5:2(weight ratio), add appropriate amount of deionized water and mix furnishing pulpous state, be applied on Copper Foil, at 90 ℃, vacuumize dry; By LiFePO
4powder: SP:KS-6:PVDF=92:3.5:2:2.5(weight ratio), after doing solvent and evenly size mixing with NMP, be applied on aluminium foil, vacuumize dry at 100 ℃; By the roll-in of dried positive and negative electrode pole piece process, cut-parts, coiling, fluid injection, sealing, formation process, make LiFePO4 power type 18650 cylindrical batteries, barrier film is Celgard2400, electrolyte is 1M LiPF6 ∕ DMC:EC:DEC, use powered cell detection device to carry out the detection of high rate performance, test result is in Table 2.
Table 2 is the high rate performance comparison of negative material in different embodiment and comparative example
More than show and described basic principle of the present invention, principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (6)
1. a preparation method for lithium ion battery negative pole coating layer composite material, is characterized in that: concrete steps are as follows:
(1) by softening point, at the pitch between 100 ℃～300 ℃ and softening point, the resin between 50 ℃～150 ℃ joins by the weight ratio of 1:1.5～4 in the kneading still with heating and agitating device;
(2) with the speed of 10～40 ℃/min, be heated to pitch and resin is all fused into liquid;
(3) then under inert gas shielding, stir, stop heating after mixing, the final temperature of heating is higher 20～50 ℃ than the high softening-point of component medium pitch and resin; The cooling compound coating material block that obtains;
(4) compound coating material block is carried out after coarse crushing, then carry out ultra-fine grinding by airslide disintegrating mill or deep cooling crush machine, obtain the compound coating material superfine powder of average grain diameter D50 below 6 μ m, be lithium ion battery negative pole coating layer composite material.
2. the preparation method of lithium ion battery negative pole coating layer composite material according to claim 1, it is characterized in that: the mixture of one or more in the condensation polycyclic polynuclear aromatic hydrocarbon that the pitch described in step (1) comprises coal tar pitch, petroleum asphalt, modified coal tar pitch, mesophase pitch, obtained by asphalt modifier, its softening point is between 150 ℃～250 ℃.
3. the preparation method of lithium ion battery negative pole coating layer composite material according to claim 1, it is characterized in that: the resin described in step (1) is thermoplastic resin, comprise one or more the mixture in furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin and polyformaldehyde methyl acrylate resin, its softening point is between 80 ℃～120 ℃.
4. the preparation method of lithium ion battery negative pole coating layer composite material according to claim 1, is characterized in that: the speed of the heat temperature raising described in step (2) is 20～30 ℃/min.
5. the preparation method of lithium ion battery negative pole coating layer composite material according to claim 1, it is characterized in that: the time of the stirring described in step (3) is 80～130min, the final temperature of heating is higher 30～40 ℃ than the high softening-point of component medium pitch and resin.
6. the preparation method of lithium ion battery negative pole coating layer composite material according to claim 1, is characterized in that: the particle diameter of the compound coating material superfine powder described in step (4) is below 3 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310661597.XA CN103606681A (en) | 2012-12-14 | 2013-12-10 | Preparation method of composite material of coating layer of lithium ion battery cathode |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210541070.9 | 2012-12-14 | ||
| CN2012105410709A CN103035919A (en) | 2012-12-14 | 2012-12-14 | Method for preparing modified graphite negative electrode material of lithium ion power battery |
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| CN105070899A (en) * | 2015-08-07 | 2015-11-18 | 田东 | Preparation method of lithium-ion power battery anode material |
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| CN110323426A (en) * | 2019-06-27 | 2019-10-11 | 桑顿新能源科技(长沙)有限公司 | Covering material and preparation method, negative electrode material and preparation method, lithium ion battery |
| CN111500077A (en) * | 2020-04-23 | 2020-08-07 | 湖南中科星城石墨有限公司 | Low-temperature plastic asphalt for lithium battery negative electrode composite granulation and preparation method thereof |
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Also Published As
| Publication number | Publication date |
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| CN103594691A (en) | 2014-02-19 |
| CN103626170A (en) | 2014-03-12 |
| CN103618073A (en) | 2014-03-05 |
| CN103035919A (en) | 2013-04-10 |
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