CN102050437B - Carbon composite material, preparation method and application thereof - Google Patents
Carbon composite material, preparation method and application thereof Download PDFInfo
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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 high (372mAh.g-1) and efficiency for charge-discharge advantages of higher, extensively is used as the active material of energy storage device.But because graphite type material has crystallization and the degree of orientation of height, make its easy generation solvent molecule in the process of charging be inserted into altogether graphite layers with lithium ion and cause peeling off of graphite linings, thereby cause the reduction of the cycle performance of lithium ion battery; Reach the graphite surface carbon atom and have a large amount of unsaturated bonds, electrolyte can be decomposed to form SEI (solid electrolyte interface) film at graphite surface when initial charge, so that irreversible capacity is larger first, reduces the cycle efficieny of battery.And amorphous carbon material has wider embedding lithium current potential and good lithium ion diffusion coefficient, and is good with compatibility of electrolyte, but its first inefficiency and discharge voltage hysteresis.The prior art broad research is come coated graphite class material with amorphous carbon, avoid organic solvent to contact with the direct of graphite flake layer, avoid solvent molecule and lithium ion to insert altogether, reduce simultaneously the specific area of graphite, and the reason of the Turbostratic of amorphous carbon own, can remedy graphite type material lithium ion when discharging and recharging and embed hard problem, improve the performance of material.
The method of prior art extensive use is to coat one deck organic substance (such as polyacrylonitrile, Kynoar, phenolic resins, furfuryl alcohol resin, epoxy resin, coal tar asphalt, petroleum coke etc.) by the surface in graphite type material first, then obtains the carbon composite that the surface coats the nucleocapsid structure of one deck amorphous carbon through high temperature cabonization.But the Graphite Coating that these class methods obtain is inhomogeneous, carbon composite is easy to reunite together simultaneously, need through subsequent treatment such as fragmentation, classifications, fragmentation easily damages coating layer etc., covered effect is unsatisfactory, batch poor stability etc., the carbon composite pattern of preparation 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 preparation, covered effect is undesirable, and the pattern of the carbon composite of preparation is faulty shortcoming also, 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 amorphous carbon; Wherein the average grain diameter of carbon composite be 8～20 μ m (, interlamellar spacing is
Specific 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, rear washing, drying;
C, with the heat treatment under inert atmosphere or vacuum condition of step b products therefrom, heat treatment comprises carbonization 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, rear washing, drying;
C, with step b products therefrom under inert atmosphere or vacuum condition through carbonization 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, rear drying;
F, with step e products therefrom under inert atmosphere or vacuum condition through carbonization 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 refers to operate identical, and material can be identical, also can be different.
The present inventor is unexpected to be found, when the carbon composite of preparation nucleocapsid structure, take water as solvent, graphite and carbon are coated the presoma mixing by hydrothermal treatment consists, the carbon composite of preparation not only pattern is perfect, uniform particle diameter, and specific area further reduces, and improved the irreversible capacity of material; The coating layer of the carbon composite of preparation is more even simultaneously, and the cycle performance of the carbon composite of preparation is more excellent; The granule-morphology of the carbon composite that particularly prepares after the process hydrothermal treatment consists is controlled, and particle has not only been saved broken classification flow process without reunion, has saved cost, and the material property of preparation is more excellent.The present invention further preferred the employing repeatedly 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 cryogenic property of battery.
Description of drawings
Fig. 1 is the scanning electron microscope (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 embodiment of the invention 1,5 and the multiplying power discharging figure of the battery of 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 amorphous carbon; Wherein, comprise hydrothermal treatment consists in the preparation process of carbon composite, the average grain diameter of carbon composite is 8～20 μ m, and interlamellar spacing is
Specific 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, rear drying;
C, with the heat treatment under inert atmosphere or vacuum condition of step b products therefrom, heat treatment comprises carbonization 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, rear drying;
C, with step b products therefrom under inert atmosphere or vacuum condition through carbonization 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, rear drying;
F, with step e products therefrom under inert atmosphere or vacuum condition through carbonization 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 refers to operate 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 treatment can adopt and well known to a person skilled in the art technological means, such as filter or centrifugal etc. after solid is washed rear 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 cellulose mixing granulation.Average grain diameter behind preferred graphite and the cellulose mixing granulation is 7～15 μ m.For example can by graphite and cellulose are blended in granulating and forming 10～40min in the trimmer, obtain spheric granules.The unexpected discovery of the present invention carried out granulation, Shape correction by 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 organic substance, further optimize the pattern of material, optimize covered effect, the cellulose RESEARCH OF PYROCARBON has also improved the conductivity of composite material simultaneously, has further improved the performance of the high current charge-discharge of material, and the cost of raw material 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, cellulose or their mixture, cellulose can be selected and well known to a person skilled in the art various celluloses, for example can be selected from methylcellulose, ethyl cellulose, hydroxypropyl methylcellulose or the cellulose acetate one or more; Carbohydrate can be selected one or more in sucrose, starch, glucose, fructose or the Arabic gum.The present inventor is unexpected find when graphite after through the cellulose granulation, coat precursor with carbohydrate carbon and be combined, the effect optimum can further improve the uniformity 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 carbohydrate etc.
The weight ratio of the 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 preferred 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 uniformity of coating layer, improve high-rate performance and the cryogenic property of material.Wherein the reactor of hydrothermal treatment consists generally can be selected autoclave etc.
The fixed carbon content of the further preferred graphite of the present invention is greater than 90%, and average grain diameter is 6～13 μ m.Graphite can be selected 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, Delanium.
The temperature of the preferred carbonization treatment of the present invention is 600～1400 ℃, and the time is 0.5～48 hour.Wherein, the heating rate of temperature is 30～600 ℃/H in the further preferred reactor of the present invention, and the product after the processing can cool off naturally, also can adopt to well known to a person skilled in the art other annealing in process.
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, electrolyte, battery container and collector etc. are not particularly limited, and can adopt to well known to a person skilled in the art various anodes, electrolyte, battery container and collector.For example positive pole can adopt LiFePO4.
The below comes detailed the present invention with specific embodiment.
(1) carbon composite
250g sucrose is soluble in water, fully stirred 1 hour, make the aqueous sucrose solution that mass concentration is 5wt%.Be that 12.3 μ m, interlamellar spacing (d002) are with average grain diameter
Particle size distribution slowly add in the sucrose solution of 5wt% at the domestic natural flake graphite 1000g of 3.1～35.2 μ m (fixed carbon content 99.5%), then fully stirred 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.
Black powder obtained above has been put into N
2In the high temperature furnace of protection, be elevated to 1000 ℃ with the speed of 120 ℃/h, and be incubated 6 hours, the room temperature that then naturally cools obtains black powder.
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 composite material that the surface coats amorphous carbon.
The JSM-5610LV type scanning electron microscopy that adopts Japanese JEOL to produce is carried out the SEM test to product, test result such as Fig. 1, and the average grain diameter that records the carbon composite of preparation is 12.7 μ m.
The D/MAX2200PC type x-ray powder diffraction instrument that adopts Rigaku company to produce carries out the test of crystallization parameters to product, the K α of Cu target is radiation source, operating voltage is 40KV, operating current is 20mA, sweep limits 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 area that records the carbon composite of preparation with the BET method is 1.12m
2/ g.
(2) preparation of simulated battery
Take the carbon composite of above-mentioned preparation as negative active core-shell material, take water as solvent, according to active material: polystyrene fourth rubber: sodium carboxymethylcellulose is that 100: 8: 6 (weight ratio) mix and blends are uniformly dispersed it, then in baking oven 120 ℃ the baking 24 hours, the oven dry after take nickel foam as collector at 1ton/cm
2Pressure it is pressed into diameter is that the cake of 15mm is as Electrode; Take onesize lithium sheet as to electrode, electrolyte 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.
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 with embodiment 1 to test to such an extent that the average grain diameter of the carbon composite for preparing is 12.5 μ m.Interlamellar spacing (d002) is
Specific area is 2.31m
2/ g.
Adopt the method identical with embodiment 1 to prepare carbon composite and simulated battery, different is before graphite adds aqueous sucrose solution with graphite and 30g ethyl cellulose mix and blend 3 hours in blender, then put into and carry out granulating and forming processing 25min in the graphite trimmer, obtain spherical graphite and the ethyl cellulose compound particles of average grain diameter 13.4 μ m.Again compound particles is slowly joined in the aqueous sucrose solution.
Adopt the method identical with embodiment 1 to test to such an extent that the average grain diameter of the carbon composite for preparing is 13.3 μ m.Interlamellar spacing (d002) is
Specific area is 0.95m
2/ g.
Embodiment 4
(1) carbon composite
Be that 12.3 μ m, interlamellar spacing (d002) are with average grain diameter
Particle size distribution at the domestic natural flake graphite 5000g of 3.1～35.2 μ m (fixed carbon content 99.5%), with 150g ethyl cellulose mix and blend 3 hours in blender, then put into and carry out granulating and forming processing 25min in the graphite trimmer, obtain the spherical graphite particle of average grain diameter 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 average grain diameter 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, then fully stirred 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.
Black powder obtained above has been put into N
2Carry out carbonization treatment in the high temperature furnace of protection, be elevated to 1000 ℃ with the speed of 120 ℃/h, and be incubated 6 hours, the room temperature that then naturally cools obtains black powder.
Take by weighing the 50g Arabic gum, the 50g hydroxypropyl methylcellulose is soluble in water and fully stirred 1 hour, makes concentration and be 5% Arabic gum, Gonak;
Black powder through carbonization obtained above added (quality of Arabic gum, hydroxypropyl methylcellulose accounts for black powder quality 1/10 in the solution) stirs in this Arabic gum of 5%, the Gonak, 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 composite material that the surface coats amorphous carbon.
Adopt the method identical with embodiment 1 to test to such an extent that the average grain diameter of the carbon composite for preparing is 13.9 μ m.Interlamellar spacing (d002) is
Specific area is 2.10m
2/ g.
Adopt the method identical with embodiment 1 to prepare simulated battery.
Embodiment 5
(1) carbon composite
Be that 12.3 μ m, interlamellar spacing (d002) are with average grain diameter
Particle size distribution at the domestic natural flake graphite 5000g of 3.1～35.2 μ m (fixed carbon content 99.5%), with 150g ethyl cellulose mix and blend 3 hours in blender, then put into and carry out granulating and forming processing 25min in the graphite trimmer, obtain the spherical graphite particle of average grain diameter 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 average grain diameter 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, then fully stirred 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.
Black powder obtained above has been put into N
2Carry out carbonization treatment in the high temperature furnace of protection, be elevated to 1000 ℃ with the speed of 120 ℃/h, and be incubated 6 hours, the room temperature that then naturally cools obtains black powder.
It is soluble in water and fully stirred 1 hour to take by weighing 100g sucrose, makes concentration and be 5% sucrose solution; Black powder through carbonization obtained above added (quality of sucrose accounts for black powder quality 1/10 in the solution) stirs in this sucrose solution of 5%, 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 composite material that the surface coats amorphous carbon.
Adopt the method identical with embodiment 1 to test to such an extent that the average grain diameter of the carbon composite for preparing is 13.7 μ m.Interlamellar spacing (d002) is
Specific area is 0.65m
2/ g.
Adopt the method identical with embodiment 1 to prepare simulated battery.
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 with embodiment 1 to test to such an extent that the average grain diameter of the carbon composite for preparing is 13.7 μ m.Interlamellar spacing (d002) is
Specific 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 with embodiment 1 to test to such an extent that the average grain diameter of the carbon composite for preparing is 14.1 μ m.Interlamellar spacing (d002) is
Specific area is 0.87m
2/ g.
Embodiment 8
Adopt the method identical with embodiment 5 to prepare carbon composite and simulated battery, temperature that hydro-thermal is hydrolyzed that different is is that 250 ℃, pressure are 20mPa.Adopt the method identical with embodiment 1 to test to such an extent that the average grain diameter of the carbon composite for preparing is 14.3 μ m.Interlamellar spacing (d002) is
Specific 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 number of repetition of high temperature cabonization is 20 times.
Adopt the method identical with embodiment 1 to test to such an extent that the average grain diameter of the carbon composite for preparing is 14.9 μ m.Interlamellar spacing (d002) is
Specific 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 with embodiment 1 to test to such an extent that the average grain diameter of the carbon composite for preparing is 12.5 μ m.Interlamellar spacing (d002) is
Specific area is 3.25m
2/ g.
Performance test
Take the carbon composite of embodiment 1～9 and Comparative Examples 1 preparation as negative active core-shell material, take domestic LiFePO4 as positive electrode active materials, electrolyte 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 cryogenic property and high rate performance.
Low-temperature circulating performance: the rectangular cell of embodiment 1-9 and Comparative Examples 1 preparation is put into-10 ℃ of environment left standstill 12 hours, then 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, voltage range is 3.8～2.0V, capacity after the discharge capacity of first circulation of record and 100 circulations, the recording capacity conservation rate, result such as table 1.Discharge capacity * 100% of capacity after capability retention=circulation/first.
Multiplying power discharging property: the rectangular cell of embodiment 1-9 and Comparative Examples 1 preparation is charged to 3.8V with the constant current of 0.2C with battery cashier's office in a shop in the strange BK-6016AR test of producing of Guangzhou indigo plant, and then the constant current with 0.2C is discharged to 0.005V; 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 recording each battery discharge to 0.005V, and the capacity when discharging take 0.2C is the basis, the calculated capacity conservation rate the results are shown in Table 2.Capability retention=discharge capacity/0.2C discharge capacity * 100%.
Specific capacity, 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 to 0.005V and the capacity (first discharge capacity) when discharging into 2.5V first.The quality of discharge capacity/carbon composite of specific capacity=first; Discharge capacity/initial charge capacity * 100% of first charge-discharge efficiency=first.
Table 1
Table 2
| Battery | 0.2C | 0.5 | | |
10C | |
20C | |
| Embodiment | ||||||||
| 1 | 100 | 99.3 | 98.7 | 96.5 | 91.3 | 83.1 | 73.5 | |
| |
100 | 98.9 | 98.1 | 94.3 | 89.6 | 76.3 | 65.3 | |
| |
100 | 99.9 | 99.0 | 97.4 | 94.5 | 87.7 | 75.1 | |
| Embodiment 4 | 100 | 99.0 | 98.5 | 95.1 | 89.9 | 77.5 | 66.7 | |
| Embodiment 5 | 100 | 100 | 99.8 | 99.1 | 98.6 | 97.2 | 86.4 | |
| Embodiment 6 | 100 | 99.4 | 98.2 | 94.9 | 88.7 | 75.8 | 64.2 | |
| Embodiment 7 | 100 | 99.5 | 98.3 | 94.5 | 87.3 | 72.9 | 60.9 |
| Embodiment 8 | 100 | 99.3 | 97.8 | 93.1 | 85.9 | 70.6 | 58.3 |
| Embodiment 9 | 100 | 100 | 98.7 | 98.1 | 96.2 | 93.4 | 80.1 |
| Comparative example 1 | 100 | 98.9 | 94.1 | 87.7 | 78.4 | 60.2 | 40.6 |
Not only pattern is perfect for the carbon composite of the present invention preparation as can be seen from above, uniform particle diameter, and also specific area further reduces, and improved the irreversible capacity of material; The cycle performance of the carbon composite of preparation 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 cryogenic property of battery.
Claims (5)
1. 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 after hydrothermal treatment consists, wash, drying;
C, with the heat treatment under inert atmosphere or vacuum condition of step b products therefrom, described heat treatment comprises carbonization treatment and graphitization processing,
Wherein, described step a also is included in and graphite is added carbon coats before the precursor water solution graphite and cellulose mixing granulation, and described carbon coating presoma is carbohydrate,
The weight ratio that described carbon coats presoma and graphite is: 0.05: 1～2.0: 1,
The temperature of described hydrothermal treatment consists is 140～300 ℃, and pressure is 0.1～25MPa, and the time is 1～72 hour, and stir speed (S.S.) is 150～750 rev/mins,
The temperature of described carbonization 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.
2. the preparation method of carbon composite according to claim 1 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 after hydrothermal treatment consists, wash, drying;
C, with step b products therefrom under inert atmosphere or vacuum condition through carbonization treatment;
D, step c products therefrom is added carbon coat in the precursor water solution mixing;
E, the steps d products therefrom is dry after hydrothermal treatment consists;
F, with step e products therefrom under inert atmosphere or vacuum condition through carbonization treatment;
G, repeating step d～f, 0～20 time, wherein said repeating step operation is identical, and material is identical or different;
H, with products therefrom under inert atmosphere or vacuum condition through graphitization processing.
3. the preparation method of carbon composite according to claim 1 is characterized in that, the average grain diameter behind described graphite and the cellulose mixing granulation is 7～15 μ m.
4. each method of the system of carbon composite according to claim 1 is characterized in that, described carbohydrate is selected from one or more in sucrose, starch, glucose, fructose or the Arabic gum.
5. the preparation method of carbon composite according to claim 1 and 2 is characterized in that, described graphite is spherical graphite, and average grain diameter is 5～14 μ m; Described graphite is selected from one or more of natural flake graphite, graphite microcrystal, Delanium.
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| CN103008653B (en) * | 2012-12-31 | 2015-05-27 | 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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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1581544A (en) * | 2003-08-16 | 2005-02-16 | 比亚迪股份有限公司 | Modified graphite and its preparing method |
| CN1681145A (en) * | 2004-04-05 | 2005-10-12 | 中国科学院物理研究所 | Negative electrode active material and use of secondary lithium battery |
| CN1702894A (en) * | 2005-04-20 | 2005-11-30 | 深圳市贝特瑞电子材料有限公司 | Cathode material of lithium ion cell and preparation method thereof |
| CN1796334A (en) * | 2004-12-27 | 2006-07-05 | 陈瑾惠 | Carbon/Carbon Composite material and mfg. method thereof |
-
2009
- 2009-10-29 CN CN200910109962XA patent/CN102050437B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1581544A (en) * | 2003-08-16 | 2005-02-16 | 比亚迪股份有限公司 | Modified graphite and its preparing method |
| CN1681145A (en) * | 2004-04-05 | 2005-10-12 | 中国科学院物理研究所 | Negative electrode active material and use of secondary lithium battery |
| CN1796334A (en) * | 2004-12-27 | 2006-07-05 | 陈瑾惠 | Carbon/Carbon Composite material and mfg. method thereof |
| CN1702894A (en) * | 2005-04-20 | 2005-11-30 | 深圳市贝特瑞电子材料有限公司 | Cathode material of lithium ion cell and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP特许第3605133号B2 2004.12.22 |
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