CN1305150C - Modified graphite and its preparing method - Google Patents
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- CN1305150C CN1305150C CNB031401996A CN03140199A CN1305150C CN 1305150 C CN1305150 C CN 1305150C CN B031401996 A CNB031401996 A CN B031401996A CN 03140199 A CN03140199 A CN 03140199A CN 1305150 C CN1305150 C CN 1305150C
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Abstract
The present invention relates to modified graphite which comprises graphite core material particles and an amorphous carbon film coated on the surface of the graphite core material particles, wherein the interval d002 of every two microcrystal levels of the graphite core material particles is 0.335 to 0.340 nm; the specific surface area of the modified graphite is 1.3 to 4.2m<2>/g, and the average particle diameter of the modified graphite is 8 to 35 mu m. The preparation method of the modified graphite comprises: graphite core material particles are soaked in a polymer surface modifier solution, stirred, separated, screened, solidified and carbonized. The modified graphite of the present invention has the advantages of favorable heavy current performance, high reversible specific capacity and long cycle life, and can safety the requirement of practical application; the preparation method of the modified graphite has the advantages of simple technique, low cost and easy realization of industrialized production.
Description
[technical field]
The present invention relates to a kind of modified graphite and preparation method thereof, relate to modified graphite of a kind of high-rate performance excellence and preparation method thereof or rather.
[background technology]
Along with developing rapidly of electronics industry, information industry, people are also more and more higher to the requirement of all kinds of electric product power supplys, and lithium rechargeable battery is developing over past ten years rapidly, is being extensive use of with its superior combination property.
Because the especially portable electric product function of electric product is increasingly sophisticated, and volume is small and exquisite day by day, thereby to the wherein also raising day by day of requirement of power supply, this is embodied in: sufficiently high volume energy density, superior high-rate performance, suitable cycle life and reliable security performance, wherein with to the requirement of volume energy density and high-rate performance for very.
In some occasion, electric products such as modern portable product, electric tool, electric bicycle, electric automobile require very high to the time per electric weight, for example, functions such as the mobile Internet access of modern colour screen handset, multimedia, the requirement that the notebook computer electricity consumption time is long, the starting process of power vehicle, or the like.This situation as for the lithium rechargeable battery of power supply, belongs to the heavy-current discharge process for wherein.That is to say that under many circumstances, people have relatively high expectations to the high-rate performance of lithium rechargeable battery in recent years.
The high-rate performance of lithium rechargeable battery depends primarily on positive and negative pole material wherein, and wherein negative active core-shell material is having significance aspect the raising high-rate performance, and this is mainly reflected on the conductivity and structural stability thereof of material itself.
At present the most frequently used negative active core-shell material of lithium rechargeable battery is a graphite type material, mainly is because lower discharge platform of graphite and cyclical stability preferably.Wherein, the higher native graphite of degree of graphitization has higher specific capacity, but because at embedding lithium/take off in the lithium process, and microstructure is lax easily even destroy, and its cycle performance and high-rate performance are relatively poor.
Patent CN1230159 " graphite granule and use graphite granule are as the lithium secondary battery of negative pole " has invented a kind of graphite granule, the fast charging and discharging performance and the cycle performance that have excellence with the lithium secondary battery of this graphite granule.The characteristics of this graphite granule are, the combination of the particle of a plurality of writing board shapes or combine, make that the crystal face that aligns of particle of each writing board shape is not parallel each other, promptly reduce the orientation of graphite granule.Like this, Li
+Embedding with take off embedding and can carry out more fully with higher speed, therefore the lithium secondary battery made of the graphite that obtains has excellent high-rate performance.But in fact a kind of Delanium process of the preparation method of this graphite need be up to carrying out graphitization processing under 2800 ℃ the temperature, the cost height, and technology difficulty is big, is difficult to suitability for industrialized production.
[summary of the invention]
An object of the present invention is: a kind of have excellent high-rate performance, higher reversible specific capacity and the modified graphite of long cycle life are provided;
Another object of the present invention is: provide that a kind of technology is simple, cost is low, be easy to the method for the above-mentioned modified graphite of preparation of suitability for industrialized production.
Modified graphite of the present invention is achieved through the following technical solutions:
A kind of modified graphite comprises graphite core material granule and surface coated amorphous carbon rete thereof, wherein, and the microcrystalline coating interplanar distance d of graphite core material granule
002Be 0.335～0.340nm, the specific area of described modified graphite is 1.3～4.2m
2/ g, average grain diameter is 8～35 μ m.
Technique scheme can also further be improved to:
The microcrystalline coating interplanar distance d of described modified graphite
002Be 0.335～0.338nm, specific area is 1.8～3.5m
2/ g, average grain diameter is 10～20 μ m.
The thickness of described amorphous carbon rete is 0.05 μ m～1 μ m.
The present invention prepares that the method for above-mentioned modified graphite is achieved through the following technical solutions:
The preparation method of above-mentioned modified graphite comprises the steps:
(1), the polymer surfaces dressing agent is dissolved in the corresponding organic solvent, obtain polymer surfaces dressing agent solution, described polymer surfaces dressing agent solution concentration is 90.9%～100% of this polymer surfaces dressing agent saturated solution concentration;
(2), the graphite core material granule is immersed in the above-mentioned polymer surfaces dressing agent solution that obtains, ratio according to graphite 1kg, polymer surfaces dressing agent solution 1.5L～3L is carried out, speed with 100～2000rpm stirs, mixing time is 0.5～10h, coating material is fully contacted with the graphite core material granule and sticks thereon;
(3), the graphite core material granule is separated from polymer surfaces dressing agent solution, and the residual solvent on the oven dry graphite core material granule, sieve;
(4), the dry graphite that will obtain under protective atmosphere is cured respectively and carbonization treatment, obtains surface modified graphite;
Wherein, the graphite core material granule can be native graphite or Delanium, and average grain diameter is 7～35 μ m;
The polymer surfaces dressing agent can be coal tar pitch, coal tar, petroleum asphalt, petroleum tar, benzene, naphthalene, benzene naphthalene copolymer, pertroleum wax, one or more in the Petropols;
Organic solvent can be a kind of in acetone, absolute ethyl alcohol, N-methyl pyrrolidone, chloroform, oxolane, carbon tetrachloride, the cyclohexane;
Curing is to carry out under 200～600 ℃, and heating rate is 0.5～35 ℃/minute, and temperature retention time is 0.2～12 hour;
Carbonization is to carry out under 750～1300 ℃, and heating rate is 0.1～30 ℃/minute, and temperature retention time is 1～24 hour.
Technique scheme can also further be improved to:
Described curing is to carry out under 300～500 ℃, and temperature retention time is 0.5～3 hour.
In the described solidification process, heating rate is 5～20 ℃/minute.
Described carbonization is to carry out under 800～1200 ℃, and temperature retention time is 2～10 hours.
In the described carbonisation, heating rate is 3～20 ℃/minute.
In described step (4) carbonisation, rate of temperature fall is 5～15 ℃/minute.
The advantage of modified graphite of the present invention is: have excellent high-rate performance, higher reversible specific capacity and long cycle life.
The preparation method's of modified graphite of the present invention advantage is: technology is simple, cost is low, be easy to suitability for industrialized production.
The present invention is further illustrated below in conjunction with example.
[description of drawings]
Fig. 1 is the SEM figure of the raw material graphite of embodiment 1 employing
The SEM figure of the modified graphite that Fig. 2 makes for embodiment 1
The DSC figure of the modified graphite that Fig. 3 makes for embodiment 1
[embodiment]
A kind of modified graphite provided by the invention comprises graphite core material granule and surface coated amorphous carbon rete thereof, wherein, and microcrystalline coating interplanar distance d
002Be 0.335～0.340nm, specific area is 1.3～4.2m
2/ g, average grain diameter is 8～30 μ m.
Wherein, average grain diameter is: the D that measures with the laser light scattering particle size analyzer
50
Microcrystalline coating interplanar distance d
002: record by the X-ray diffraction analysis instrument;
Specific area is measured by the BET spot measurement method of N2 displacement method.
By coating the amorphous carbon rete on graphite core material granule surface, can improve the configuration of surface of graphite granule on the one hand, reduce specific area, improve the compatibility of graphite and electrolyte, thereby improve first charge-discharge efficiency; On the other hand, can also remedy the fault of construction of graphite core material granule microstructure limit end parts, reduce crystallite orientation, stablize graphite microcrystal, further improve the uniformity of its conductivity and electron distributions, thereby made it in charge and discharge process Li
+Electromigration speed and the stability of negative pole structure be improved, thereby improve high-rate performance.
Among the present invention, the average grain diameter of modified graphite is 8～30 μ m, is preferably 10～20 μ m.The average grain diameter of graphite is too little, and then graphite powder is too thin, and specific area is bigger than normal, diminishes the reversible discharge capacity of material; The average grain diameter of graphite is too big, and then graphite granule back gauge centre distance is remote, is unfavorable for Li
+Abundant embedding and take off embedding, be not suitable for doing negative electrode of lithium ionic secondary battery.
Among the present invention, the microcrystalline coating interplanar distance d of modified graphite
002Be 0.335～0.340nm, be preferably 0.335～0.338nm.The d of graphite
002Depend primarily on raw material---the Delanium that native graphite or degree of graphitization are higher, and the finishing process is to d
002Influence little.Generally speaking, d
002Near ideal graphite value 0.3354nm, then degree of graphitization is high more more, and the high more graphite of degree of graphitization, its reversible specific capacity is also high more.Therefore, in order to guarantee the discharge capacity of lithium rechargeable battery, should select for use higher native graphite of degree of graphitization or Delanium as raw material.
Among the present invention, the specific area of modified graphite is 1.3～4.2m
2/ g is preferably 1.8～3.5m
2/ g, the modified graphite of handling through finishing effectively reduce the specific area of raw material graphite, and (specific area of raw material graphite is 5m
2About/g), and the size of specific area directly influences the size of the irreversible capacity that forms the consumption of SEI film in the lithium rechargeable battery initial charge process, promptly is directly connected to the first charge-discharge efficiency of battery and the size of reversible discharge capacity.Therefore, on the angle of the reversible specific capacity of collateral security negative material, specific area is the smaller the better.
The thickness of described amorphous carbon rete is 0.05 μ m～1 μ m, and the thickness of amorphous carbon rete is to calculate at the covering amount on graphite core material granule surface and the average grain diameter of graphite core material granule according to the polymer surfaces dressing agent; Can obtain the DSC curve chart of modified graphite by thermal analysis system.
Among the present invention, modified graphite mainly is the higher native graphite of degree of graphitization or Delanium to be carried out finishing handle and obtain.The preparation method may further comprise the steps: prepare certain density polymer surfaces dressing agent organic solution (being generally saturated or approaching saturated degree) in advance; Will be as graphite core material soaking stir process therein, mixing speed is 100～2000rpm, mixing time is 0.5～10h; Separate (filtration or centrifugal) then and go out graphite wherein, and dry the solvent that wherein participates in, sieve; The dry graphite that will obtain at last is cured respectively and carbonization treatment under protective atmosphere, does not need crushing process can obtain modified graphite of the present invention.
Among the preparation method of modified graphite of the present invention, described coating material is the very high organic substance of a kind of phosphorus content, can be coal tar pitch, coal tar, petroleum asphalt, petroleum tar, benzene, naphthalene, benzene naphthalene copolymer, pertroleum wax, one or more in the Petropols; Corresponding organic solvent can be a kind of in acetone, absolute ethyl alcohol, N-methyl pyrrolidone, chloroform, oxolane, carbon tetrachloride, the cyclohexane.
Among the preparation method of modified graphite of the present invention, in the described stir process process, the finishing effect is relevant with mixing time.Mixing time is oversize, and the organic substance film thickness that then is attached on graphite core material granule surface is too thick, and then the performance to modified graphite has certain influence, as the first charge-discharge efficiency that reduces modified graphite etc.; Mixing time is too short, and the organic substance film thickness that then is attached on graphite core material granule surface is too thin, and the organic substance film is at the skewness on graphite core material granule surface, and the performance of modified graphite is had certain influence.
Among the preparation method of modified graphite of the present invention, described solidification process is to be warmed up to 0.5～35 ℃/minute heating rate to solidify temperature requiredly, and better is 5～20 ℃/minute; Curing temperature is 200～600 ℃, and more preferably 300～500 ℃, temperature retention time is 0.2～12 hour, more preferably 0.5～3 hour.Solidifying after finishing heating rate with 0.1～30 ℃/minute (better is 3～20 ℃/minute), to be warmed up to carbonization temperature required, and carburizing temperature is 750～1300 ℃, and better is 800～1200 ℃, and temperature retention time is 1～24 hour, and better is 2～10 hours.Can lower the temperature after the carbonization, rate of temperature fall is 1～20 ℃/minute, and better is 5～15 ℃/minute, also can lower the temperature naturally.
If carburizing temperature is low excessively, as be lower than 750 ℃, then the organic layer carbonization on graphite core material granule surface is insufficient, is not enough to form stable fine and close carbon film layer, even forms microcellular structure, and specific area is bigger, is unfavorable for the improvement of configuration of surface; If carburizing temperature is too high, as be higher than 1200 ℃, it is not obvious to the improvement of effect then to increase temperature, and energy consumption increases, uneconomical; Temperature retention time should not be too short, otherwise carbonization is insufficient, can not form stable fine and close carbon film layer; Time is oversize, and then energy consumption increases, and is uneconomical.
Among the preparation method of modified graphite of the present invention; curing and carbonization can be adopted chamber type electric resistance furnace, tube furnace, plug-type continuous tunnel furnace, rotatable continuous tunnel furnace etc.; only need to reach temperature required and can airtightly protect gas to lead to, described protective atmosphere can be one or more mixing in argon gas, helium, the nitrogen.
In order to check the chemical property of modified graphite preparation method of the present invention and the modified graphite that utilizes this method preparation, add that in modified graphite of the present invention adhesive and deionized water and stirring, coating, oven dry make the negative plate of lithium rechargeable battery, with above-mentioned negative plate that makes and LiCoO
2The positive pole that makes with corresponding conductive agent, adhesive, and corresponding electrolyte makes lithium rechargeable battery by existing technology, carries out correlated performance and tests.
[embodiment 1]
Take by weighing petroleum tar 8g, be dissolved in the carbon tetrachloride, be mixed with 4% finishing agent solution 200ml, standby.Take by weighing the native graphite of 100g drying, be immersed in the coating material organic solution, stirred 1 hour, make the graphite granule surface form skim finishing film with the rotating speed of 300rpm.Filter then and obtain graphite, 300 mesh sieves are crossed in oven dry.Graphite after sieving is put into closed tube type high-temperature furnace, with the logical high-purity N of 10 liters/minute flows
2, 15 ℃/minute heating rate rises to 400 ℃, is incubated 1 hour, rises to 1000 ℃ with 10 ℃/minute heating rate again, is incubated 3 hours, is cooled to room temperature naturally, obtains surface modified graphite.This graphite is with D
50The average grain diameter that characterizes is 13.8 μ m, microcrystalline coating interplanar distance d
002Be 0.3365, specific area is 2.8m
2/ g.
Be assembled into lithium rechargeable battery with this graphite as negative active core-shell material, the employing active material is LiCoO
2Positive plate, electrolytic salt is LiPF
6, electrolyte solvent is the mixed organic solvents of ethylene carbonate, ethylene carbonate, diethyl carbonate, and concentration is 1 mol, and diaphragm paper is polyethylene, polypropylene composite diaphragm paper.
[embodiment 2]
The tetrahydrofuran solution of the coal tar pitch of coating material employing 5% in the present embodiment, in addition, other processes and embodiment 1 are consistent.The average grain diameter D of the modified graphite that present embodiment obtains
50With microcrystalline coating interplanar distance d
002With embodiment 1 basically identical.
[embodiment 3]
The chloroformic solution of the petroleum asphalt of coating material employing 3% in the present embodiment, in addition, other processes and embodiment 1 are consistent.The average grain diameter D of the modified graphite that present embodiment obtains
50With microcrystalline coating interplanar distance d
002With embodiment 1 basically identical.
[embodiment 4]
Carburizing temperature adopts 800 ℃ in the present embodiment, and in addition, other processes and embodiment 1 are consistent.The average grain diameter D of the modified graphite that present embodiment obtains
50With microcrystalline coating interplanar distance d
002With embodiment 1 basically identical.
[embodiment 5]
Carburizing temperature adopts 1200 ℃ in the present embodiment, and in addition, other processes and embodiment 1 are consistent.The average grain diameter D of the modified graphite that present embodiment obtains
50With microcrystalline coating interplanar distance d
002With embodiment 1 basically identical.
[embodiment 6]
Adopt the less native graphite of average grain diameter as raw material in the present embodiment, in addition, other processes and embodiment 1 are consistent.The average grain diameter D of the modified graphite that present embodiment obtains
50Be 8.2 μ m, microcrystalline coating interplanar distance d
002With embodiment 1 basically identical.
[embodiment 7]
Adopt the bigger native graphite of average grain diameter as raw material in the present embodiment, in addition, other processes and embodiment 1 are consistent.The average grain diameter D of the modified graphite that present embodiment obtains
50Be 35.0 μ m, microcrystalline coating interplanar distance d
002With embodiment 1 basically identical.
[comparative example 1]
Directly use the native graphite raw material among the embodiment 1 to make battery as negative active core-shell material, in addition, other processes and embodiment 1 are consistent.
[comparative example 2]
Carburizing temperature adopts 700 ℃ in the present embodiment, and temperature retention time is 5 hours, and in addition other processes and embodiment 1 are consistent.
[performance test]
Specific area: the BET spot measurement method by the N2 displacement method is measured.
The condition of thermal analysis test is as follows:
Instrument model: NETSCH STA449C
Mode: simultaneous thermal analysis, i.e. DSC-TG
Example weight: graphite 6.824mg
Crucible material: AL
2O
3
Furnace atmosphere: air, flow velocity are 25Nml/min
Temperature-rise period: begin to heat up under room temperature, programming rate is 10 ℃/min, is warming up to 1000 ℃.
Battery to embodiment and comparative example carries out performance test, and is as follows:
In the high-rate performance, C
3C/ C
0.5C: the electric current with 3C is discharged to the discharge capacity of 3.0V and the ratio that is discharged to the discharge capacity of 3.0V with the electric current of 0.5C from 4.2V from 4.2V.
In the high-rate performance, C
2C/ C
0.5C: the electric current with 2C is discharged to the discharge capacity of 3.0V and the ratio that is discharged to the discharge capacity of 3.0V with the electric current of 0.5C from 4.2V from 4.2V.
Reversible specific capacity: to 4.2V, be discharged to discharge capacity/negative active core-shell material quality of 3.0V then first from 4.2V with the electric current of 0.1C with the electric current initial charge of 0.1C.
Cycle life: be called once circulation at the current discharge with 1C to 3.0V with the 1C current charges then to 4.2V, so repeatedly, the discharge capacity of acquisition is the capacity of this circulation.Among the present invention, the cycle-index when cycle life refers to that discharge capacity reaches discharge capacity 80% first.
Above The performance test results sees the following form:
| Sequence number | Specific area/m 2/g | High-rate performance | Reversible specific capacity/mAh/g | Cycle life | |
| C 3C/C 0.5C | C 2C/C 0.5C | ||||
| Embodiment 1 | 2.8 | 86.2 | 96.4 | 340 | 280 |
| Embodiment 2 | 1.8 | 86.1 | 96.9 | 351 | 312 |
| Embodiment 3 | 2.6 | 82.6 | 96.4 | 338 | 264 |
| Embodiment 4 | 3.5 | 80.5 | 95.8 | 330 | 320 |
| Embodiment 5 | 2.3 | 88.4 | 96.7 | 350 | 277 |
| Embodiment 6 | 4.2 | 82.8 | 95.1 | 332 | 320 |
| Embodiment 7 | 1.5 | 80.2 | 94.6 | 340 | 245 |
| Comparative example 1 | 5.7 | 57.4 | 88.1 | 337 | 76 |
| Comparative example 2 | 4.8 | 72.2 | 94.5 | 332 | 253 |
As seen from the above table, the specific area of modified graphite is little than the specific area of comparative example 1～2 graphite among the embodiment 1～7; The battery of making among the embodiment 1～7 has the high-rate performance of excellence, higher reversible specific capacity and long cycle life.
Fig. 1 and Fig. 2 are respectively the SEM figure of embodiment 1 Central Plains work stone China ink and modified graphite, by scanning electron microscopy acquisition (employing equipment is the JSM-5160 model of JEOL company), as can be seen from Figure, modified graphite be shaped as potato shape or sphere.
Fig. 3 is for implementing the hot analysis result of 1 modified graphite that obtains, wherein, 592.1 ℃ peak correspondence be the amorphous carbon rete; 821.2 ℃ the peak correspondence be the graphite core material; Generally speaking, 500-650 ℃ peak correspondence be the amorphous carbon rete, 750-850 ℃ of correspondence be the graphite core material.
Modified graphite of the present invention has excellent high-rate performance, much the demanding occasion of fast charging and discharging had very big application potential and advantage, simultaneously, this negative active core-shell material has kept higher reversible specific capacity, and has long cycle life, reliable and stable, can satisfy application request.Preparation method's technology of modified graphite of the present invention is simple, cost is low, be easy to suitability for industrialized production.
Claims (9)
1, a kind of modified graphite is characterized in that: described modified graphite comprises graphite core material granule and surface coated amorphous carbon rete thereof, wherein, and the microcrystalline coating interplanar distance d of graphite core material granule
002Be 0.335～0.340nm, the specific area of described modified graphite is 1.3～4.2m
2/ g, average grain diameter is 8～35 μ m.
2, modified graphite as claimed in claim 1 is characterized in that: the microcrystalline coating interplanar distance d of described modified graphite
002Be 0.335～0.338nm, specific area is 1.8～3.5m
2/ g, average grain diameter is 10～20 μ m.
3, modified graphite as claimed in claim 1 is characterized in that: the thickness of described amorphous carbon rete is 0.05 μ m～1 μ m.
4, a kind of preparation method as claim 1 or 2 or 3 described modified graphites comprises the steps:
(1), the polymer surfaces dressing agent is dissolved in the corresponding organic solvent, obtain polymer surfaces dressing agent solution, described polymer surfaces dressing agent solution concentration is 90.9%～100% of this polymer surfaces dressing agent saturated solution concentration;
(2), the graphite core material granule is immersed in the above-mentioned polymer surfaces dressing agent solution that obtains, ratio according to graphite 1kg, polymer surfaces dressing agent solution 1.5L～3L is carried out, speed with 100～2000rpm stirs, mixing time is 0.5～10h, coating material is fully contacted with the graphite core material granule and sticks thereon;
(3), graphite is separated from polymer surfaces dressing agent solution, and the residual solvent on the oven dry graphite core material granule, sieve;
(4), under protective atmosphere, the above-mentioned dry graphite that obtains is cured respectively and carbonization treatment, obtain surface modified graphite;
Wherein, the graphite core material granule is native graphite or Delanium, and average grain diameter is 7～35 μ m;
The polymer surfaces dressing agent is coal tar pitch, coal tar, petroleum asphalt, petroleum tar, benzene, naphthalene, benzene naphthalene copolymer, pertroleum wax, one or more in the Petropols;
Organic solvent is a kind of in acetone, absolute ethyl alcohol, N-methyl pyrrolidone, chloroform, oxolane, carbon tetrachloride, the cyclohexane;
Curing is to carry out under 200～600 ℃, and heating rate is 0.5～35 ℃/minute, and temperature retention time is 0.2～12 hour;
Carbonization is to carry out under 750～1300 ℃, and heating rate is 0.1～30 ℃/minute, and temperature retention time is 1～24 hour.
5, the preparation method of modified graphite as claimed in claim 4 is characterized in that: described curing is to carry out under 300～500 ℃, and temperature retention time is 0.5～3 hour.
6, the preparation method of modified graphite as claimed in claim 4 is characterized in that: in the described solidification process, heating rate is 5～20 ℃/minute.
7, the preparation method of modified graphite as claimed in claim 4 is characterized in that: described carbonization is to carry out under 800～1200 ℃, and temperature retention time is 2～10 hours.
8, the preparation method of modified graphite as claimed in claim 4 is characterized in that: in the described carbonisation, heating rate is 3～20 ℃/minute.
9, the preparation method of modified graphite as claimed in claim 4 is characterized in that: in the described carbonisation, rate of temperature fall is 5～15 ℃/minute.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031401996A CN1305150C (en) | 2003-08-16 | 2003-08-16 | Modified graphite and its preparing method |
| US10/771,010 US8133612B2 (en) | 2003-05-16 | 2004-02-02 | Negative electrodes for rechargeable batteries |
| US10/770,646 US20040229041A1 (en) | 2003-05-16 | 2004-02-02 | Graphite granules and their method of fabrication |
| US10/794,020 US20040227264A1 (en) | 2003-05-16 | 2004-03-04 | Methods for fabricating improved graphite granules |
| JP2006520651A JP2006528407A (en) | 2003-07-22 | 2004-07-20 | Improved graphite granules and method for producing the same |
| PCT/CN2004/000835 WO2005008811A1 (en) | 2003-07-22 | 2004-07-20 | Negative electrodes for rechargeable batteries |
| KR1020057019040A KR20060022230A (en) | 2003-07-22 | 2004-07-20 | Improved graphite granules and their method of fabrication |
| EP04761989A EP1647066B1 (en) | 2003-07-22 | 2004-07-20 | Negative electrodes for rechargeable batteries |
| KR1020067001456A KR100693397B1 (en) | 2003-07-22 | 2004-07-20 | Negative electrodes for rechargeable batteries |
| JP2006520652A JP2006528408A (en) | 2003-07-22 | 2004-07-20 | Rechargeable battery negative electrode |
| PCT/CN2004/000834 WO2005008810A1 (en) | 2003-07-22 | 2004-07-20 | Improved graphite granules and their method of fabrication |
| EP04761988A EP1652250B1 (en) | 2003-07-22 | 2004-07-20 | Method of fabrication of modified graphite granules |
| DE602004030799T DE602004030799D1 (en) | 2003-07-22 | 2004-07-20 | NEGATIVE ELECTRODES FOR RECHARGEABLE BATTERIES |
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| CNB031401996A CN1305150C (en) | 2003-08-16 | 2003-08-16 | Modified graphite and its preparing method |
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| US9904625B2 (en) | 2013-03-15 | 2018-02-27 | Intel Corporation | Methods, systems and apparatus for predicting the way of a set associative cache |
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| CN101162775B (en) * | 2006-10-10 | 2010-05-12 | 中国电子科技集团公司第十八研究所 | High performance lithium ionic cell cathode material producing method |
| CN101224882B (en) * | 2007-01-16 | 2011-12-07 | 深圳市比克电池有限公司 | Artificial graphite surface modifying method and lithium battery anode material produced thereby |
| CN101087021B (en) * | 2007-07-18 | 2014-04-30 | 深圳市贝特瑞新能源材料股份有限公司 | Man-made graphite cathode material for lithium ion battery and its making method |
| KR100936571B1 (en) * | 2008-04-10 | 2010-01-13 | 엘에스엠트론 주식회사 | Negative active material used for secondary battery, electrode of secondary battery and secondary battery including the same |
| CN101740764B (en) * | 2008-11-24 | 2013-10-23 | 上海杉杉科技有限公司 | Tin-graphite composite cathode material for lithium ion battery and preparation method thereof |
| CN102050437B (en) * | 2009-10-29 | 2013-01-30 | 上海比亚迪有限公司 | Carbon composite material, preparation method and application thereof |
| JP6003648B2 (en) * | 2010-09-24 | 2016-10-05 | 日立化成株式会社 | Negative electrode active material, lithium ion battery, and battery module using the same |
| KR101552763B1 (en) * | 2012-05-31 | 2015-09-11 | 주식회사 엘지화학 | Anode comprising silicon based material and carbon material, and lithium secondary battery comprising the same |
| CN103647083B (en) * | 2013-11-15 | 2015-12-02 | 成都兴能新材料有限公司 | The preparation method of composite plumbago-carbon negative pole material |
| CN104201388B (en) * | 2014-07-31 | 2016-06-29 | 湖南德天新能源科技有限公司 | The application in preparation method of the preparation method of composite lithium ion battery cathode material and Petropols |
| CN106887593B (en) * | 2017-03-23 | 2022-07-29 | 广东天劲新能源科技股份有限公司 | Preparation method of high-capacity lithium ion battery cathode material |
| CN108598478A (en) * | 2018-04-25 | 2018-09-28 | 北方奥钛纳米技术有限公司 | Modified graphite preparation method and modified graphite |
| CN112201776B (en) * | 2019-07-08 | 2022-02-08 | 宁波杉杉新材料科技有限公司 | Natural graphite negative electrode material, preparation method thereof and lithium ion battery |
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| JPH09203502A (en) * | 1996-01-30 | 1997-08-05 | Ishikawajima Harima Heavy Ind Co Ltd | Method for arranging vibrationproof board for pipe group |
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| CN1581544A (en) | 2005-02-16 |
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