CN102050437A - Carbon composite material, and preparation method and application thereof - Google Patents
Carbon composite material, and preparation method and application thereof Download PDFInfo
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- CN102050437A CN102050437A CN200910109962XA CN200910109962A CN102050437A CN 102050437 A CN102050437 A CN 102050437A CN 200910109962X A CN200910109962X A CN 200910109962XA CN 200910109962 A CN200910109962 A CN 200910109962A CN 102050437 A CN102050437 A CN 102050437A
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Abstract
The invention provides a carbon composite material. The carbon composite material comprises a core part and a shell part, wherein the core part comprises graphite; the shell part comprises amorphous carbon; the average grain diameter is 8 to 20 mu m; and the interlamellar spacing specific surface area is 0.3 to 2.5 m<2>/g. The invention also provides a preparation method of the carbon composite material. The preparation method comprises the following steps of: a, adding the graphite into aqueous solution of a carbon-coated precursor and mixing pulp uniformly; b, performing hydro-thermal treatment on the pulp obtained in the step a and the drying; and c, performing heat treatment on a product obtained in the step b under an inert atmosphere or a vacuum condition, wherein the heat treatment comprises carbonizing treatment and graphitizing treatment. In the carbon composite material prepared by the method, the appearance is more perfect; a coating layer is coated more uniformly; the grain diameter is controlled more easily; and the big current property is higher. The invention further provides application of the carbon composite material to a lithium battery as a cathode.
Description
Technical field
The present invention relates to a kind of carbon composite and its preparation method and application.
Background technology
Graphite type material has lower discharge platform, theoretical capacity height (372mAh.g-1) and efficiency for charge-discharge advantages of higher, extensively is used as the active material of energy storage device.But, make its easy generation solvent molecule in the process of charging be inserted into graphite layers altogether and cause peeling off of graphite linings, thereby cause the reduction of the cycle performance of lithium ion battery with lithium ion because graphite type material has the crystallization and the orientation degree of height; Reach the graphite surface carbon atom and have a large amount of unsaturated link(age)s, electrolytic solution can be decomposed to form SEI (solid electrolyte interface) film at graphite surface when initial charge, makes that irreversible capacity is bigger first, reduces the cycle efficiency of battery.And amorphous carbon material has the embedding lithium current potential of broad and good lithium ion spread coefficient, and is good with the electrolytic solution consistency, but its inefficiency and sparking voltage hysteresis first.The prior art broad research is come coating graphite class material with decolorizing carbon, avoid organic solvent to contact with the direct of graphite flake layer, avoid solvent molecule and lithium ion to insert altogether, reduce the specific surface area of graphite simultaneously, and the reason of the turbostratic of decolorizing carbon own, can remedy the problem that graphite type material lithium ion when discharging and recharging embeds difficulty, improve the performance of material.
The method of prior art widespread use is to coat one deck organism (as polyacrylonitrile, polyvinylidene difluoride (PVDF), resol, furfuryl alcohol resin, Resins, epoxy, coal-tar pitch, refinery coke etc.) by the surface in graphite type material earlier, obtains the carbon composite that the surface coats the nucleocapsid structure of one deck decolorizing carbon through high temperature cabonization then.But it is inhomogeneous that the graphite surface that these class methods obtain coats, carbon composite is easy to reunite together simultaneously, need through subsequent disposal such as fragmentation, classifications, fragmentation easily damages coating layer etc., covered effect is unsatisfactory, batch poor stability etc., Zhi Bei carbon composite pattern is also imperfect simultaneously, can not satisfy the demand of existing development.
Summary of the invention
The present invention coats inhomogeneous for the coating layer of the carbon composite that overcomes prior art for preparing, covered effect is undesirable, and the also faulty shortcoming of pattern of the carbon composite of preparation provides a kind of pattern more perfect, and coating layer coats more uniform carbon composite.
Carbon composite comprises nuclear part and shell part, and the nuclear part comprises graphite, and shell partly comprises decolorizing carbon; Wherein the median size of carbon composite be 8～20 μ m (, interlamellar spacing is
Specific surface area is 0.3～2.5m
2/ g.
Another object of the present invention provides a kind of preparation method of above-mentioned carbon composite, and step comprises:
A, graphite is added carbon coat in the precursor water solution, mixing makes slurry;
B, with step a gained slurry through hydrothermal treatment consists, after scouring, drying;
C, with the thermal treatment under inert atmosphere or vacuum condition of step b products therefrom, thermal treatment comprises carbonizing treatment and graphitization processing.
Further preferred steps comprises
A, graphite is added carbon coat in the precursor water solution, mixing makes slurry;
B, with step a gained slurry through hydrothermal treatment consists, after scouring, drying;
C, with step b products therefrom under inert atmosphere or vacuum condition through carbonizing treatment;
D, step c products therefrom is added carbon coat in the precursor water solution mixing;
E, with steps d gained material through hydrothermal treatment consists, after drying;
F, with step e products therefrom under inert atmosphere or vacuum condition through carbonizing treatment;
G, repeating step d～f, 0～20 time;
H, with products therefrom under inert atmosphere or vacuum condition through graphitization processing.
Wherein, the carbon in per step coats precursor can be identical, also can be different.Repeating step, the present invention is meant that operation is identical, material can be identical, also can be different.
The present inventor is unexpected to be found, when the carbon composite of preparation nucleocapsid structure, with water is solvent, graphite and carbon are coated the presoma mixing after hydrothermal treatment consists, the not only pattern perfection of carbon composite of preparation, uniform particle diameter, and specific surface area further reduces, and improved the irreversible capacity of material; The coating layer of Zhi Bei carbon composite is more even simultaneously, and the cycle performance of the carbon composite of preparation is more excellent; Particularly the granule-morphology of the carbon composite for preparing after the process hydrothermal treatment consists is controlled, and particle does not have reunion, has not only saved broken classification flow process, has saved cost, and the material property of preparation is more excellent.Further preferred the employing repeatedly of the present invention coats on a small quantity, makes the covered effect of carbon composite better, and pattern is more perfect, the easier control of the particle diameter of material, and high-rate performance is better.
The carbon composite of the present invention's preparation not only can obviously improve the heavy-current discharge performance of battery as the negative active core-shell material of lithium ion battery, and can improve the low-temperature performance of battery.
Description of drawings
Fig. 1 is the sem photograph of the carbon composite of the embodiment of the invention 5 preparations;
Fig. 2 is the X crystallogram of the carbon composite of the embodiment of the invention 5 preparations;
Fig. 3 is the battery of the embodiment of the invention 5 and the comparative example 1 preparation cycle performance figure with 0.5C in-10 ℃ of environment;
Fig. 4 is the multiplying power discharging figure of the battery of the embodiment of the invention 1,5 and comparative example 1 preparation.
Embodiment
The invention provides a kind of carbon composite, comprise nuclear part and shell part, the nuclear part comprises graphite, and shell partly comprises decolorizing carbon; Wherein, comprise hydrothermal treatment consists in the preparation process of carbon composite, the median size of carbon composite is 8～20 μ m, and interlamellar spacing is
Specific surface area is 0.3～2.5m
2/ g.
The present invention further provides the preparation method of above-mentioned carbon composite, step comprises:
A, graphite is added carbon coat in the precursor water solution mixing slurry;
B, with step a gained slurry through hydrothermal treatment consists, after drying;
C, with the thermal treatment under inert atmosphere or vacuum condition of step b products therefrom, thermal treatment comprises carbonizing treatment and graphitization processing.The material pattern of preparation is more perfect, and coating layer coats more even, the easier control of the particle diameter of material, and the material high-rate performance is better.Further preferred steps comprises
A, graphite is added carbon coat in the precursor water solution mixing slurry;
B, with step a gained slurry through hydrothermal treatment consists, after drying;
C, with step b products therefrom under inert atmosphere or vacuum condition through carbonizing treatment;
D, step c products therefrom is added carbon coat in the precursor water solution mixing slurry;
E, with steps d gained slurry through hydrothermal treatment consists, after drying;
F, with step e products therefrom under inert atmosphere or vacuum condition through carbonizing treatment;
Repeating step d～f, 0～20 time;
C, with products therefrom under inert atmosphere or vacuum condition through graphitization processing.Wherein, the carbon in per step coats precursor can be identical, also can be different.In the repeating step, the present invention is meant that operation is identical, and material can be identical, also can be different.The present invention preferably repeatedly coats on a small quantity, makes coating layer more even etc., further optimizes the performance of material.
Wherein, the hydrothermal treatment consists subsequent disposal can adopt and well known to a person skilled in the art technique means, the back such as for example filters or centrifugal solid is washed after drying.Inert atmosphere adopts and well known to a person skilled in the art various inert atmospheres, for example N
2, Ar etc.
Wherein, the present invention further preferred steps a also be included in and graphite is added carbon coat before the precursor water solution graphite and Mierocrystalline cellulose mixing granulation.Median size behind preferred graphite and the Mierocrystalline cellulose mixing granulation is 7～15 μ m.For example can obtain spheroidal particle by graphite and Mierocrystalline cellulose are blended in granulating and forming 10～40min in the trimmer.The unexpected discovery of the present invention carried out granulation, shaping processing by Mierocrystalline cellulose to graphite before coating, can further optimize the graphite granule pattern of nuclear part, and the carbon of shell part coats the easier graphite surface that is coated on of precursor organism, further optimize the pattern of material, optimize covered effect, the Mierocrystalline cellulose RESEARCH OF PYROCARBON has also improved the electroconductibility of matrix material simultaneously, has further improved the performance of the high current charge-discharge of material, and material cost is low, and environmental pollution is little.
Wherein, carbon coats presoma and can coat presoma, for example one or more in the organic polymer for well known to a person skilled in the art various carbon.Can comprise carbohydrate, Mierocrystalline cellulose or their mixture, Mierocrystalline cellulose can be selected for use and well known to a person skilled in the art various Mierocrystalline celluloses, for example can be selected from methylcellulose gum, ethyl cellulose, Vltra tears or the cellulose acetate one or more; Carbohydrate can be selected one or more in sucrose, starch, glucose, fructose or the gum arabic for use.The present inventor is unexpected find when graphite after through the Mierocrystalline cellulose granulation, combine with carbohydrate carbon coating precursor, the effect optimum can further improve the homogeneity of the coating layer of carbon encapsulated material.It can be carbohydrate that carbohydrate carbon coats precursor, also can be other organic polymers with the mixture of carbohydrate or different step in adopt different carbon to coat precursor, wherein certain step carbon coating precursor is a carbohydrate etc.
The weight ratio of preferred carbon coating presoma of the present invention and graphite 0.05: 1～1.0: 1 makes coating layer easier evenly.
Wherein, the heat treated temperature of preferably water of the present invention is 140～300 ℃, more preferably 140～220 ℃; Pressure is 0.1～25mPa, more preferably 0.1～15mPa; Time is 1～72 hour, more preferably 1～24 hour; Stir speed (S.S.) is 0～1500 rev/min, more preferably 150～750 rev/mins.To improve the homogeneity of coating layer, improve the high-rate performance and the low-temperature performance of material.Wherein the reactor of hydrothermal treatment consists generally can be selected autoclave etc. for use.
The fixed carbon content of the further preferred graphite of the present invention is greater than 90%, and median size is 6～13 μ m.Graphite can be selected for use and well known to a person skilled in the art various graphite, for example can be selected from one or more of natural flake graphite, graphite microcrystal, synthetic graphite.
The temperature of the preferred carbonizing treatment of the present invention is 600～1400 ℃, and the time is 0.5～48 hour.Wherein, the temperature rise rate of temperature is 30～600 ℃/H in the further preferred reactor of the present invention, and the product after the processing can naturally cooling, also can adopt to well known to a person skilled in the art other anneal.
The temperature of the preferred graphitization processing of the present invention is 2800 ℃; Time is 1～24 hour, more preferably 1～3 hour.
The carbon encapsulated material of the present invention's preparation can well be applied to lithium ion battery, as negative pole.When being applied to lithium ion battery, anode, electrolytic solution, battery container and collector etc. are not particularly limited, and can adopt to well known to a person skilled in the art various anodes, electrolytic solution, battery container and collector.For example positive pole can adopt iron lithium phosphate.
Come detailed the present invention with specific embodiment below.
Embodiment 1
(1) carbon composite
250g sucrose is soluble in water, fully stirred 1 hour, make the aqueous sucrose solution that mass concentration is 5wt%.With median size is that 12.3 μ m, interlamellar spacing (d002) are
Size-grade distribution slowly add in the sucrose solution of 5wt% at the homemade natural flake graphite 1000g of 3.1～35.2 μ m (fixed carbon content 99.5%), fully stirred then 5 hours, obtain uniform sizing material.
Slurry is transferred in the autoclave, under the pressure of 15mPa, 190 ℃, 500 rev/mins hydro-thermal processed 5 hours, washing, drying obtain black powder.
The above-mentioned black powder that obtains has been put into N
2In the High Temperature Furnaces Heating Apparatus of protection, be elevated to 1000 ℃ with the speed of 120 ℃/h, and be incubated 6 hours, naturally cooling cools to room temperature and obtains black powder then.
The black powder that obtains is put into Ar
22800 ℃ are carried out graphitization processing in the graphitizing furnace of atmosphere, obtain the spherical graphite matrix material that the surface coats decolorizing carbon.
The JSM-5610LV type scanning electronic microscope that adopts Japanese JEOL to produce is carried out the SEM test to product, test result such as Fig. 1, and the median size that records the carbon composite of preparation is 12.7 μ m.
The D/MAX2200PC type x-ray powder diffraction instrument that adopts Japanese company of science to produce carries out the test of crystallization parameters to product, the K α of Cu target is a source of radiation, operating voltage is 40KV, working current is 20mA, sweep limit 2 θ=10～80 °, test result such as Fig. 2, the interlamellar spacing (d002) that records the carbon composite of preparation is
Adopt the full-automatic nitrogen absorption of JW-004 type specific surface instrument, the specific surface area that records the carbon composite of preparation with the BET method is 1.12m
2/ g.
(2) preparation of simulated battery
Carbon composite with above-mentioned preparation is a negative active core-shell material, with water is solvent, according to active substance: polystyrene fourth rubber: Xylo-Mucine is that 100: 8: 6 (weight ratio) mixed to stir it is uniformly dispersed, 120 ℃ of bakings 24 hours in baking oven then, oven dry back is that collector is at 1ton/cm with the nickel foam
2Pressure with its be pressed into diameter be 15mm cake as research electrode; With onesize lithium sheet is counter electrode, and electrolytic solution is 1M LiPF
6/ EC+DEC+EMC (volume ratio is 2: 1: 3), barrier film is Celgard 2400 porous polypropylene films, (MBRAUN) is assembled into simulated battery in being full of the glove box of argon gas atmosphere.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare carbon composite and simulated battery, different is that precursor solution is 5% carboxymethyl cellulose aqueous solution.
Adopt the method identical to test to such an extent that the median size of the carbon composite for preparing is 12.5 μ m with embodiment 1.Interlamellar spacing (d002) is
Specific surface area is 2.31m
2/ g.
Embodiment 3
Adopt the method identical to prepare carbon composite and simulated battery with embodiment 1, different is before graphite adding aqueous sucrose solution graphite and 30g ethyl cellulose to be mixed stirring 3 hours in agitator, put into then and carry out granulating and forming processing 25min in the graphite trimmer, obtain spherical graphite and the ethyl cellulose compound particles of median size 13.4 μ m.Again compound particles is slowly joined in the aqueous sucrose solution.
Adopt the method identical to test to such an extent that the median size of the carbon composite for preparing is 13.3 μ m with embodiment 1.Interlamellar spacing (d002) is
Specific surface area is 0.95m
2/ g.
Embodiment 4
(1) carbon composite
With median size is that 12.3 μ m, interlamellar spacing (d002) are
Size-grade distribution at the homemade natural flake graphite 5000g of 3.1～35.2 μ m (fixed carbon content 99.5%), in agitator, mix stirring 3 hours with the 150g ethyl cellulose, put into then and carry out granulating and forming processing 25min in the graphite trimmer, obtain the spherical graphite particle of median size 13.4 μ m.
Take by weighing 100g sucrose, it is soluble in water and fully stirred 1 hour, make concentration and be 5% sucrose solution; To obtain median size through granulating and forming be that the graphite microparticles 1000g of 13.4 μ m slowly adds in the sucrose solution of 5wt% with above-mentioned, fully stirred then 5 hours, obtains uniform sizing material.
Slurry is transferred in the autoclave, under the pressure of 15mPa, 190 ℃, 500 rev/mins processed 5 hours, washing, drying obtain black powder.
The above-mentioned black powder that obtains has been put into N
2Carry out carbonizing treatment in the High Temperature Furnaces Heating Apparatus of protection, be elevated to 1000 ℃ with the speed of 120 ℃/h, and be incubated 6 hours, naturally cooling cools to room temperature and obtains black powder then.
Take by weighing the 50g gum arabic, the 50g Vltra tears is soluble in water and fully stirred 1 hour, makes concentration and be 5% gum arabic, Gonak;
(quality of gum arabic, Vltra tears accounts for black powder quality 1/10 in the solution) stirs in this gum arabic of 5%, the Gonak with above-mentioned adding through the black powder of carbonization of obtaining, then in autoclave with the dehydration of the identical condition of preceding step, carbonization, and repetitive operation 4 times.At last the black powder that obtains is put into Ar
22800 ℃ are carried out graphitization processing in the graphitizing furnace of atmosphere, obtain the spherical graphite matrix material that the surface coats decolorizing carbon.
Adopt the method identical to test to such an extent that the median size of the carbon composite for preparing is 13.9 μ m with embodiment 1.Interlamellar spacing (d002) is
Specific surface area is 2.10m
2/ g.
Adopt the method identical to prepare simulated battery with embodiment 1.
Embodiment 5
(1) carbon composite
With median size is that 12.3 μ m, interlamellar spacing (d002) are
Size-grade distribution at the homemade natural flake graphite 5000g of 3.1～35.2 μ m (fixed carbon content 99.5%), in agitator, mix stirring 3 hours with the 150g ethyl cellulose, put into then and carry out granulating and forming processing 25min in the graphite trimmer, obtain the spherical graphite particle of median size 13.4 μ m.
Take by weighing 100g sucrose, it is soluble in water and fully stirred 1 hour, make concentration and be 5% sucrose solution; To obtain median size through granulating and forming be that the graphite microparticles 1000g of 13.4 μ m slowly adds in the sucrose solution of 5wt% with above-mentioned, fully stirred then 5 hours, obtains uniform sizing material.
Slurry is transferred in the autoclave, under the pressure of 15mPa, 190 ℃, 500 rev/mins processed 5 hours, washing, drying obtain black powder.
The above-mentioned black powder that obtains has been put into N
2Carry out carbonizing treatment in the High Temperature Furnaces Heating Apparatus of protection, be elevated to 1000 ℃ with the speed of 120 ℃/h, and be incubated 6 hours, naturally cooling cools to room temperature and obtains black powder then.
It is soluble in water and fully stirred 1 hour to take by weighing 100g sucrose, makes concentration and be 5% sucrose solution; (quality of sucrose accounts for black powder quality 1/10 in the solution) stirs in this sucrose solution of 5% with above-mentioned adding through the black powder of carbonization of obtaining, then in autoclave with the dehydration of the identical condition of preceding step, high temperature cabonization, and repetitive operation 4 times.At last the black powder that obtains is put into Ar
22800 ℃ are carried out graphitization processing in the graphitizing furnace of atmosphere, obtain the spherical graphite matrix material that the surface coats decolorizing carbon.
Adopt the method identical to test to such an extent that the median size of the carbon composite for preparing is 13.7 μ m with embodiment 1.Interlamellar spacing (d002) is
Specific surface area is 0.65m
2/ g.
Adopt the method identical to prepare simulated battery with embodiment 1.
Embodiment 6
Adopt the method identical with embodiment 5 to prepare carbon composite and simulated battery, hydro-thermal is dewatered in reactor temperature that different is is that 160 ℃, pressure are 0.1mPa.Adopt the method identical to test to such an extent that the median size of the carbon composite for preparing is 13.7 μ m with embodiment 1.Interlamellar spacing (d002) is
Specific surface area is 1.34m
2/ g.
Embodiment 7
Adopt the method identical with embodiment 5 to prepare carbon composite and simulated battery, different dehydration temperaturres in reactor is that 220 ℃, pressure are that 15mPa, dewatering time are 24 hours.Adopt the method identical to test to such an extent that the median size of the carbon composite for preparing is 14.1 μ m with embodiment 1.Interlamellar spacing (d002) is
Specific surface area is 0.87m
2/ g.
Embodiment 8
Adopt the method identical with embodiment 5 to prepare carbon composite and simulated battery, the temperature of hydro-thermal hydrolysis that different is is that 250 ℃, pressure are 20mPa.Adopt the method identical to test to such an extent that the median size of the carbon composite for preparing is 14.3 μ m with embodiment 1.Interlamellar spacing (d002) is
Specific surface area is 0.97m
2/ g.
Embodiment 9
Adopt the method identical with embodiment 8 to prepare carbon composite and simulated battery, hydro-thermal that different is in reactor is dewatered, the multiplicity of high temperature cabonization is 20 times.
Adopt the method identical to test to such an extent that the median size of the carbon composite for preparing is 14.9 μ m with embodiment 1.Interlamellar spacing (d002) is
Specific surface area is 0.59m
2/ g.
Comparative Examples 1
Adopt the method identical with embodiment 1 to prepare carbon composite and simulated battery, different is the mixing slurry not to be carried out hydrothermal treatment consists, directly carries out carbonization, graphitization processing.
Adopt the method identical to test to such an extent that the median size of the carbon composite for preparing is 12.5 μ m with embodiment 1.Interlamellar spacing (d002) is
Specific surface area is 3.25m
2/ g.
Performance test
Carbon composite with embodiment 1～9 and Comparative Examples 1 preparation is a negative active core-shell material, with homemade iron lithium phosphate is positive electrode active materials, electrolytic solution is 1M LiPF6/EC+DEC+EMC (volume ratio is 2: 1: 3), barrier film is the Celgard2400 porous polypropylene film, and the rectangular cell that is assembled into the 1C capacity and is 750mAh carries out the test of low-temperature performance and high rate performance.
Cold cycle performance: the rectangular cell of embodiment 1-9 and Comparative Examples 1 preparation is put into-10 ℃ of environment left standstill 12 hours, blue strange BK-6016AR test of producing is carried out the charge and discharge cycles test with the constant current of 0.5C to battery cashier's office in a shop in Guangzhou then, voltage range is 3.8～2.0V, write down round-robin loading capacity and 100 circulation back capacity first, the recording capacity conservation rate, result such as table 1.Loading capacity * 100% of capability retention=circulation back capacity/first.
Multiplying power discharging property: with the rectangular cell of embodiment 1-9 and Comparative Examples 1 preparation in Guangzhou blue strange BK-6016AR test of producing cashier's office in a shop with the constant current of 0.2C with battery charge to 3.8V, the constant current with 0.2C is discharged to 0.005V then; Then respectively with the 0.2C constant current charge to 3.8V, with set electric current (0.5C, 1C, 5C, 10C, 15C, 20C) constant current with battery discharge to 0.005V, capacity when writing down each battery discharge to 0.005V, and the capacity when discharging based on 0.2C, the rated capacity conservation rate the results are shown in Table 2.Capability retention=loading capacity/0.2C loading capacity * 100%.
Specific storage, first charge-discharge efficiency:
The simulated battery of embodiment 1～9 and Comparative Examples 1 preparation is placed on the blue strange BK-6016AR test of producing in Guangzhou with 0.5 milliampere constant current simulated battery is carried out charge-discharge test cashier's office in a shop, voltage range is 0.005V～2.5V.The capacity (initial charge capacity) of record initial charge during and the capacity (loading capacity first) when discharging into 2.5V first to 0.005V.The quality of loading capacity/carbon composite of specific storage=first; Loading capacity/initial charge capacity * 100% of first charge-discharge efficiency=first.
Table 1
Table 2
From the not only pattern perfection of carbon composite of last the present invention as can be seen preparation, uniform particle diameter, and also specific surface area further reduces, and improved the irreversible capacity of material; The cycle performance of Zhi Bei carbon composite is more excellent simultaneously, and the carbon composite of the present invention's preparation not only can obviously improve the heavy-current discharge performance of battery as the negative pole of lithium ion battery, and can improve the low-temperature performance of battery.
Claims (13)
1. a carbon composite is characterized in that, described carbon composite comprises nuclear part and shell part, and described nuclear partly comprises graphite, and described shell partly comprises decolorizing carbon; The median size of described carbon composite is 8～20 μ m, and interlamellar spacing is
Specific surface area is 0.3～2.5m
2/ g.
2. the preparation method of a carbon composite is characterized in that, step comprises:
A, graphite is added carbon coat in the precursor water solution, mixing makes slurry;
B, with step a gained slurry through hydrothermal treatment consists, after scouring, drying;
C, with the thermal treatment under inert atmosphere or vacuum condition of step b products therefrom, described thermal treatment comprises carbonizing treatment and graphitization processing.
3. the preparation method of carbon composite according to claim 2 is characterized in that, described step comprises:
A, graphite is added carbon coat in the precursor water solution, mixing makes slurry;
B, with step a gained slurry through hydrothermal treatment consists, after scouring, drying;
C, with step b products therefrom under inert atmosphere or vacuum condition through carbonizing treatment;
D, step c products therefrom is added carbon coat in the precursor water solution mixing;
E, with the steps d products therefrom through hydrothermal treatment consists, after drying;
F, with step e products therefrom under inert atmosphere or vacuum condition through carbonizing treatment;
G, repeating step d～f, 0～20 time;
H, with products therefrom under inert atmosphere or vacuum condition through graphitization processing.
4. according to the preparation method of claim 2 or 3 described carbon composites, it is characterized in that described step a also is included in and graphite is added carbon coats before the precursor water solution graphite and Mierocrystalline cellulose mixing granulation.
5. the preparation method of carbon composite according to claim 4 is characterized in that, the median size behind described graphite and the Mierocrystalline cellulose mixing granulation is 7～15 μ m.
6. the preparation method of carbon composite according to claim 4 is characterized in that, described carbon coats presoma and comprises carbohydrate or Mierocrystalline cellulose or its mixture.
7. the preparation method of carbon composite according to claim 6 is characterized in that, described carbohydrate is selected from one or more in sucrose, starch, glucose, fructose or the gum arabic.
8. the preparation method of carbon composite according to claim 6 is characterized in that, described Mierocrystalline cellulose is selected from one or more in methylcellulose gum, ethyl cellulose, Vltra tears or the cellulose acetate.
9. according to the preparation method of claim 2 or 3 described carbon composites, it is characterized in that the weight ratio that described carbon coats presoma and graphite is: 0.05: 1～2.0: 1.
10. according to the preparation method of claim 2 or 3 described carbon composites, it is characterized in that the temperature of described hydrothermal treatment consists is 140～300 ℃, pressure is 0.1～25mPa, and the time is 1～72 hour, and stir speed (S.S.) is 150～750 rev/mins.
11. the preparation method according to claim 2 or 3 described carbon composites is characterized in that, described graphite is spherical graphite, and median size is 5～14 μ m; Described graphite is selected from one or more of natural flake graphite, graphite microcrystal, synthetic graphite.
12. the preparation method according to claim 2 or 3 described carbon composites is characterized in that, the temperature of described carbonizing treatment is 600～1400 ℃, and the time is 0.5～48 hour; The temperature of described graphitization processing is 2800 ℃, and the time is 1～3 hour.
13. a carbon composite as claimed in claim 1 is as the application of lithium ion battery negative active material.
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| CN102569755A (en) * | 2011-11-03 | 2012-07-11 | 青岛瀚博电子科技有限公司 | Graphite carbon negative electrode material for lithium ion battery, and preparation method thereof |
| CN103008653A (en) * | 2012-12-31 | 2013-04-03 | 株洲冶炼集团股份有限公司 | Carbon coated lead composite material and preparation method thereof |
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| JP3605133B2 (en) * | 1993-12-29 | 2004-12-22 | 日本タングステン株式会社 | Carbide material coated with diamond-like carbon film functionally graded to substrate and method for producing the same |
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