CN101209837B - Modification method of graphite and modified graphite - Google Patents
Modification method of graphite and modified graphite Download PDFInfo
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Abstract
The invention discloses a modification method of graphite material and modified graphite prepared by the method. A macromolecule polymer is dissolved in corresponding organic solvent, the boiling point of which is not exceeding the softening point of the macromolecule polymer, and fully mixed with graphite. The mixture is stirred and heated to fully dip the graphite, then is distilled and granulated and kept on heating to solidify the macromolecule polymer. Therefore, graphite composite material, surface of which is coated with macromolecule polymer, is obtained, which is treated with normal carbonization after cooled to room temperature. The invention adopts a method combining liquid-phase and solid-phase to result in even coating. A crushing treatment is unnecessary, for the prepared modified graphite is not agglomerated, which simplifies the process and reduces equipment investment, thus the invention is beneficial to mass production. The modified graphite of the invention, especially the modified natural graphite used as carbon cathode material has longer cycle service life and better discharge performance at high current.
Description
Technical field
The present invention relates to the carbon cathode material field, particularly a kind of method of modifying of graphite and the modified graphite that makes.
Background technology
In recent years, lithium ion battery makes lithium ion battery obtain large-scale application in many industries with the excellent properties of aspects such as its high-energy-density, high-voltage, pollution-free, long circulation life, fast charging and discharging and the cost of manufacture that reduces day by day.The develop rapidly of lithium ion battery mainly is the contribution that has benefited from electrode materials; The particularly progress of carbon cathode material; And from now in a very long time, the raising of capacity of lithium ion battery and heavy-current discharge performance will depend on the development of carbon cathode material and perfect.
Graphite type material; Particularly natural graphite has lower discharge platform; It is high to insert the lithium capacity, and first charge-discharge efficiency is higher, yet because the height crystallization and the orientation degree of graphite material; Make it in process of charging, can take place solvent molecule and get into graphite layers and cause the phenomenon that graphite linings is peeled off, cause cycle performance of battery to reduce thus.And the consistency of amorphous carbon that obtains after the high molecular polymer pyrolysis and organic electrolyte is better, has cyclical stability preferably, but its irreversible capacity is bigger, and discharge platform is also desirable not as graphite.Take all factors into consideration the relative merits of graphite type material and high molecular polymer pyrolyzed carbon materials; Coat one deck high molecular polymer and the processing of charing at a certain temperature at graphite surface; Obtain the composite graphite of nucleocapsid structure; The characteristic that both can keep the high and better charge and discharge platform of graphite reversible specific capacity has absorbed the polymkeric substance RESEARCH OF PYROCARBON again and the organic electrolyte compatibility is good, has prevented that the caused graphite linings of inserting altogether of lithium ion and electrolytic solution from peeling off and efflorescence; Reduce the capacity attenuation that is caused thus, prolonged the cycle life of electrode.
In existing high molecular polymer pyrolytic carbon and the graphite compound method for coating, employing be organic polymer such as resol, epoxy resin, furfuryl alcohol resin or the like, be mostly polymkeric substance through overcuring, form coating layer after the charing.As:
Chinese invention patent (lithium ion battery negative pole carbon material and preparation method thereof; CN1282115A) with epoxy resin natural graphite is coated; Adopt the epoxy resin solution and the natural graphite powder that will be dissolved in earlier in the solvent to mix; Treat that solvent evaporates makes epoxy resin be coated on the skin of natural graphite after intact, and then add solidifying agent curing, carry out the charing processing at last again and obtain composite graphite.This method for coating lumps easily, just can obtain the negative material that suitable particle size distributes after must matrix material being pulverized, and this just can destroy shell inevitably, is difficult to accomplish coat all even maintenance shape, also can make the electrode performance variation.Pulverize simultaneously, can sneak into impurity when sieving again thereby make production process become more complicated.Owing to used organic solvent, be prone to cause environmental pollution in addition.
Chinese invention patent (a kind of modified graphite and preparation method thereof; CN1581544) invented a kind of graphite granule, it has excellent high-rate performance and long cycle life, and this particulate characteristics are that the graphite core material granule is immersed in stir process in the polymer surfaces modifier solution; Separate; Sieve, be cured then and charing, but the separation of this method solvent employing is filtration or centrifugal; Can not guarantee that polymkeric substance is coated to graphite surface fully, be difficult to guarantee that each covering amount is all identical.
Summary of the invention
The technical problem that the present invention will solve promptly is the defective that overcomes above-mentioned prior art, provides a kind of and coats evenly, work simplification, is suitable for the method for modifying of the graphite of suitability for industrialized production; And coating obtained by this method evenly, is not lumpd and need not the modified graphite of break process.
In order to solve the problems of the technologies described above, the present invention adopts liquid phase and solid phase to coat the method that combines and makes graphite coated high molecular polymkeric substance.Specifically, be no more than in the organic solvent high molecular polymer softening temperature, corresponding, carry out thorough mixing with graphite again through Powdered high molecular polymer being dissolved into boiling point; Mixture is stirred intensification; Fully impregnated graphite distills then and removes organic solvent and stirring-granulating, and continuing to heat up makes polymer cure again; Obtain surperficial coated high molecular polymkeric substance graphite composite material; Then the product that obtains is carried out charing, obtaining inner is that graphite, skin are the modified graphite with nucleocapsid structure of polymer pyrolytic carbon, or claims composite graphite.For simplifying technology and shortening the PT, the present invention will be flooded, remove the organic solvent processing and will be incorporated in the temperature-rise period that is cured.Wherein dipping is different from conventional room temperature dipping, but in temperature-rise period, carries out, and therefore, the temperature that this moment, intensification was reached is in the scope that is lower than the organic solvent boiling point; Heat up to steam remove organic solvent then, the temperature that reached of heating up this moment at the organic solvent boiling point to the scope that is lower than the high molecular polymer softening temperature; Existing curing temperature-rise period was divided into for 3 stages, has not only removed solvent, and can make high molecular polymer evenly spread to graphite surface, and then can evenly be coated on graphite surface after making high molecular polymer softening.
Therefore, technical scheme of the present invention comprises: a kind of method of modifying of graphite, it can comprise the following steps:
1. high molecular polymer is dissolved in the corresponding organic solvent, the boiling point of this organic solvent is no more than the softening temperature of high molecular polymer;
2. with step 1. macromolecule polymer solution and graphite carry out thorough mixing, mixture is stirred heats up, temperature is lower than the boiling point of this organic solvent, fully impregnated graphite;
3. with the 2. mixture continuation intensification of gained of step; Temperature is lower than the softening temperature of high molecular polymer, steams except that heating up behind the organic solvent to make this high molecular polymer completely solidified abundant stirring-granulating in the temperature-rise period again; Obtain the graphite composite material of surperficial coated high molecular polymkeric substance, be cooled to room temperature;
4. the graphite composite material with the 3. cooled surperficial coated high molecular polymkeric substance of step carries out conventional charing processing.
Wherein, the graphite preferred potato shape natural graphite of step in 1., its median size D
50Be 5-45 μ m.
Step of the present invention 1. in said high molecular polymer for be usually used in the resin material that graphite coats, one or more in the thermoplastic resins such as preferred epoxy, polyvinyl acetal, resol, Polyurethane and furfuryl alcohol resin at present.
In order to make the graphite composite material prevented from caking after the coating; And then making final modified graphite product prevented from caking, the corresponding organic solvent of said each high molecular polymer of the present invention selects boiling point to be no more than the organic solvent of the softening temperature of high molecular polymer from the existing known solvent that can dissolve this high molecular polymer; For example the corresponding organic solvent of epoxy resin is selected organic solvents such as THF, toluene, ethanol, ether for use; Resol adopts ethanol, acetone and other organic solvent, and PVF adopts acetate, formic acid, phenols equal solvent, and Polyurethane adopts N; Organic solvent such as dinethylformamide, DMAC N,N.When solvent had steamed, polymkeric substance still was a solid owing to do not reach softening temperature like this, and polymkeric substance is difficult for sticking together.
Certainly, according to routine, for making some high molecular polymers, be easy to solidify like resol, epoxy resin etc., step can also add the solidifying agent of high molecular polymer in 1., and the same prior art of the kind of solidifying agent and consumption is different according to different polymer.For example: per 100 parts of resol are with 5-15 part hexamethylenetetramine, per 100 parts of used for epoxy resin 14-16 part mphenylenediamines.The weight ratio of 2. middle macromolecule polymer solution of step of the present invention and graphite is 1: 1～2, wherein the ratio preferred 1: 0.03～0.50, preferred 1: 0.04～0.45, more preferably 1: 0.1～0.2 of the weight of graphite and high molecular polymer and solidifying agent total amount thereof; Ratio is too low, and resin makes graphite evenly not coat very little, otherwise then resin makes the graphite granule caking too much easily, and increases cost.
In like manner; Some high molecular polymer like polyvinyl acetal, Polyurethane etc., need not add solidifying agent; Then the weight ratio of 2. middle macromolecule polymer solution of step and graphite is 1: 1～2; Wherein the weight ratio of graphite and high molecular polymer is 1: 0.03～0.50, preferred 1: 0.04～0.45, more preferably 1: 0.1～0.2.
Heat up in 2. time of dipping of step of the present invention is 1～12 hour, though the more abundant impregnated graphite of time length can increase the reaction times, increases energy consumption, balance both, preferred about 2 hours of the present invention.
Be evaporate to dryness organic solvent as far as possible, and recycle, the 3. preferred distillating method of step of the present invention.
The softening temperature of said various high molecular polymers and solidification value are known, and different polymer has different softening temperatures and solidification value.For the high molecular polymer that makes coating fully solidifies, the 3. middle solidified time of step is 1-12 hour usually.Naturally cooling is cooled to room temperature and gets final product afterwards.
For preventing graphite oxidation, 3. step is under protection of inert gas, to carry out.
Step 2., the speed that heat up to stir in 3. is with conventional, is generally 50～200rpm.
The 4. said conventional charing of step is handled and is included in rare gas element, and as carrying out under the protections such as nitrogen, carbonization temperature is 800-1200 ℃, and soaking time is 1-24h.
And modified graphite of the present invention comprises that modified natural graphite is promptly made by above-mentioned method of modifying.
Compared with prior art, the invention has the beneficial effects as follows: the present invention adopts liquid phase and solid phase to coat the method that combines, and makes to coat evenly, and each covering amount is also consistent, promptly batch between the uniformity consistency of product better; In the intensification solidification process, combine dipping and steaming to desolventize processing, simplified technology; Prepared modified graphite can not lump, and does not need break process, has reduced facility investment, helps scale operation; And modified graphite of the present invention, particularly modified natural graphite have long cycle life and preferable heavy-current discharge performance as carbon cathode material.
Description of drawings
Fig. 1 is the Electronic Speculum figure of the modified natural graphite of the embodiment of the invention 1.
Fig. 2 is the Electronic Speculum figure of the modified natural graphite of comparative example 1.
The 1C cycle performance comparison diagram of the battery that Fig. 3 makes for the natural graphite of the modified natural graphite of the embodiment of the invention 1～3 and comparative example 2.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
Adopt D in the following example
50The potato shape natural graphite (Shandong Nan Shu product) that is 15.1 μ m illustrates as core material, and used organic solvent is the technical grade organic solvent.
The modified natural graphite that each embodiment makes is made negative pole, and cobalt acid lithium is done anodal, 1M-LiPF
6EC: DMC: EMC=1: 1: 1 (volume ratio) solution is done the electrolytic solution assembling and is helped battery, measures the capacity of 3C discharge and the percent value (C of 0.5C loading capacity
3C/ C
0.5C), the capacity of 2C discharge and the percent value (C of 0.5C loading capacity
2C/ C
0.5C), and 1C charges and discharge 300 all capability retentions.
Embodiment 1
As shell material (coating material), the weight ratio of graphite and resol is 1: 0.10 to adopt resol powder (Wuxi City A Erzi chemical industry ltd, 100 ℃ of softening temperatures) in the present embodiment.
The preparation process is following: takes by weighing 9 gram resol (containing 1 gram solidifying agent-hexamethylenetetramine) and is dissolved in the 100 gram ethanolic solns, mix with 91 gram natural graphites again, and subsequent use.Mixture is poured in the reaction kettle, be raised to 75 ℃, fully flood and be raised to 80 ℃ behind the 2h ethanol distillation reclaimed from room temperature; Again temperature is raised to 200 ℃ after having steamed ethanol, the TRT is 2h, makes the resin completely solidified; Stirring-granulating constantly in temperature-rise period; Cooling then drops to discharging after the room temperature, sieves.Graphite after sieving is put into High Temperature Furnaces Heating Apparatus, under nitrogen protection atmosphere, heats up 1200 ℃ gradually, is incubated 2 hours, is cooled to room temperature naturally, obtains D
50It is the composite graphite material of 15.6 μ m.Product cut size D between 3 batches
50Differ less than 0.2 μ m.Its electromicroscopic photograph is as shown in Figure 1, and visible composite graphite material is caking not.
Make negative pole with this graphite; Cobalt acid lithium is done anodal; 1M-LiPF6 EC: DMC: EMC=1: 1: 1 solution is done the electrolytic solution assembling and is helped battery, and the capacity that discharges with 3C is 85% of a 0.5C loading capacity, and the capacity that discharges with 2C is 95% of a 0.5C loading capacity; And charge and discharge 300 all capability retentions 91% with 1C, as shown in Figure 3.
Embodiment 2
As shell material, the weight ratio of graphite and epoxy resin is 1: 0.10 to adopt epoxy powder (Suzhou Speical Chemical Co., Ltd., 120 ℃ of softening temperatures) in the present embodiment.
The preparation process is following: takes by weighing 9 gram epoxy resin (containing 1.2 gram solidifying agent-mphenylenediamines) and is dissolved in the 100 gram tetrahydrofuran solutions, mix with 91 gram natural graphites again, and subsequent use.Mixture is poured in the reaction kettle, be raised to 60 ℃, fully flood and be raised to 68 ℃ behind the 1h THF distillation reclaimed from room temperature; Again temperature is raised to 200 ℃ after having steamed THF, the TRT is 6h, makes the resin completely solidified; Stirring-granulating constantly in temperature-rise period; Cooling then drops to discharging after the room temperature, sieves.Graphite after sieving is put into High Temperature Furnaces Heating Apparatus, under nitrogen protection atmosphere, heats up 1200 ℃ gradually, is incubated 2 hours, is cooled to room temperature naturally, obtains D
50It is the composite graphite material of 15.5 μ m.
Help battery with this negative material assembling, the capacity that discharges with 3C is 84% of a 0.5C loading capacity, and the capacity that discharges with 2C is 93% of a 0.5C loading capacity, and charges and discharge 300 all capability retentions 92% with 1C, and is as shown in Figure 3.
Embodiment 3
As shell material, the weight ratio of graphite and PVF is 1: 0.10 to adopt PVF powder (Hangzhou De Sen Science and Technology Ltd., 145 ℃ of softening temperatures) in the present embodiment.
The preparation process is following: takes by weighing 9 gram PVFs and is dissolved in the 100 gram acetate, mix with 91 gram natural graphites again, and subsequent use.Mixture is poured in the reaction kettle, be raised to 110 ℃, fully flood and be raised to 120 ℃ behind the 6h acetate distillation reclaimed from room temperature; Again temperature is raised to 400 ℃ after having steamed acetate, the TRT is 11h, makes the resin completely solidified; Stirring-granulating constantly in temperature-rise period; Cooling then drops to discharging after the room temperature, sieves.Graphite after sieving is put into High Temperature Furnaces Heating Apparatus, under nitrogen protection atmosphere, heats up 1200 ℃ gradually, is incubated 2 hours, is cooled to room temperature naturally, obtains D
50It is the composite graphite material of 15.3 μ m.
Help battery with this negative material assembling, the capacity that discharges with 3C is 83% of a 0.5C loading capacity, and the capacity that discharges with 2C is 92% of a 0.5C loading capacity, and charges and discharge 300 all capability retentions 89% with 1C, and is as shown in Figure 3.
Embodiment 4
As shell material, the weight ratio of graphite and Polyurethane is 1: 0.10 to adopt Polyurethane powder (Tianjin Yue Hai chemical industry trade Co., Ltd, 170 ℃ of softening temperatures) in the present embodiment.
The preparation process is following: takes by weighing 9 gram Polyurethanes and is dissolved in 100 gram N, in the dinethylformamide solution, mix with 91 gram natural graphites again, and subsequent use.Mixture is poured in the reaction kettle, be raised to 150 ℃, be raised to 155 ℃ with N after fully flooding 12h from room temperature; The dinethylformamide distillation is reclaimed, and has steamed N, again temperature is raised to 400 ℃ behind the dinethylformamide; TRT is 3h, makes the resin completely solidified, stirring-granulating constantly in temperature-rise period; Cooling then drops to discharging after the room temperature, sieves.Graphite after sieving is put into High Temperature Furnaces Heating Apparatus, under nitrogen protection atmosphere, heats up 1000 ℃ gradually, is incubated 2 hours, is cooled to room temperature naturally, obtains D
50It is the composite graphite material of 15.5 μ m.
Help battery with this negative material assembling, the capacity that discharges with 3C is 86% of a 0.5C loading capacity, and the capacity that discharges with 2C is 93% of a 0.5C loading capacity, and charges and discharge 300 all capability retentions 90% with 1C.
Embodiment 5
Present embodiment adopts the raw material identical with embodiment 1, unique different be that the weight ratio of graphite and resol is 1: 0.18.Obtain D at last
50It is the composite graphite material of 17.5 μ m.
Help battery with this negative material assembling, the capacity that discharges with 3C is 87% of a 0.5C loading capacity, and the capacity that discharges with 2C is 96% of a 0.5C loading capacity, and charges and discharge 300 all capability retentions 92% with 1C.
Embodiment 6
Present embodiment adopts the raw material identical with embodiment 1, unique different be that the weight ratio of graphite and resol is 1: 0.40.Obtain D at last
50It is the composite graphite material of 18.3 μ m.
Help battery with this negative material assembling, the capacity that discharges with 3C is 85% of a 0.5C loading capacity, and the capacity that discharges with 2C is 94% of a 0.5C loading capacity, and charges and discharge 300 all capability retentions 90% with 1C.
Embodiment 7
Present embodiment adopts the raw material identical with embodiment 1, unique different be that the weight ratio of graphite and resol is 1: 0.04.Obtaining D50 at last is the composite graphite material of 15.3 μ m.
Help battery with this negative material assembling, the capacity that discharges with 3C is 84% of a 0.5C loading capacity, and the capacity that discharges with 2C is 93% of a 0.5C loading capacity, and charges and discharge 300 all capability retentions 90% with 1C.
Comparative example 1
Adopt the method for Chinese invention patent CN1282115 to coat, adopt D
50The potato shape natural graphite that is 15.1 μ m is as core material, and liquid-state epoxy resin is as shell material, and ethanol is as organic solvent, and the weight ratio of graphite and epoxy resin is 1: 0.10.
The preparation process is following: take by weighing 7.8 gram liquid-state epoxy resins and be dissolved in the 60 gram ethanolic solns, mix with 91 gram natural graphites, stir and form paste mixture; Adding 1.2 gram solidifying agent (mphenylenediamine) solution descend to solidify 2 hours and be warming up to 400 ℃ at 150 ℃ and carry out charing in paste mixture; TRT is 1 hour, takes out cured article and pulverizes 200 mesh sieves, then crushed material is heated up under nitrogen protection atmosphere 1200 ℃ gradually; Be incubated 2 hours, obtain D
50It is the composite graphite material of 23.5 μ m.Its electromicroscopic photograph is as shown in Figure 2, and visible composite graphite material becomes more caking.
Help battery with this negative material assembling, the capacity that discharges with 3C is 65% of a 0.5C loading capacity, and the capacity that discharges with 2C is 75% of a 0.5C loading capacity, and charges and discharge 300 all capability retentions 85% with 1C.
Comparative example 2
Identical with the process of embodiment assemble; Unique different be to make negative material with the identical natural graphite that does not coat; Use natural graphite to help battery as negative material assembling, with the capacity of 3C discharge less than 50% of 0.5C loading capacity, with the capacity of 2C discharge less than 70% of 0.5C loading capacity; And charge and discharge 300 all capability retentions＜80% with 1C, as shown in Figure 3.
Claims (8)
1. the method for modifying of a graphite, it is made up of the following step:
1. high molecular polymer is dissolved in the corresponding organic solvent, does not add or add the solidifying agent of high molecular polymer, the boiling point of this organic solvent is no more than the softening temperature of high molecular polymer;
2. with step 1. macromolecule polymer solution and graphite carry out thorough mixing, mixture is stirred heats up, temperature is lower than the boiling point of this organic solvent, fully impregnated graphite; When step added solidifying agent in 1., step contains the macromolecule polymer solution of solidifying agent in 2. and the weight ratio of graphite is 1: 1～2, and wherein the ratio of the weight of graphite and high molecular polymer and solidifying agent total amount thereof is 1: 0.03～0.50; When step does not add solidifying agent in 1., step 2. in the weight ratio of macromolecule polymer solution and graphite be 1: 1～2, wherein the weight ratio of graphite and high molecular polymer is 1: 0.03～0.50;
3. with the 2. mixture continuation intensification of gained of step; Temperature is lower than the softening temperature of this high molecular polymer; Steam except that heating up again behind the organic solvent and make this high molecular polymer completely solidified; Abundant stirring-granulating in the temperature-rise period obtains the graphite composite material of surperficial coated high molecular polymkeric substance, is cooled to room temperature;
4. the graphite composite material with the 3. cooled surperficial coated high molecular polymkeric substance of step carries out conventional charing processing.
2. method of modifying as claimed in claim 1 is characterized in that the graphite during step 1. is potato shape natural graphite, its median size D
50Be 5-45 μ m.
3. method of modifying as claimed in claim 1 is characterized in that high molecular polymer during step 1. is selected from one or more in epoxy resin, polyvinyl acetal, resol and the Polyurethane.
4. method of modifying as claimed in claim 3 is characterized in that this organic solvent is selected from THF, ethanol, acetate and N, one or more in the dinethylformamide.
5. method of modifying as claimed in claim 1 is characterized in that the time of dipping was 1～12 hour during step 2..
6. method of modifying as claimed in claim 1 is characterized in that 3. step adopts the distillatory method to remove organic solvent, and the said solidified time is 1-12 hour.
7. method of modifying as claimed in claim 1 is characterized in that 3. step is under protection of inert gas, to carry out.
8. the modified graphite that makes like each described method of modifying of claim 1～7.
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| CN101859893A (en) * | 2010-05-27 | 2010-10-13 | 深圳市德兴富电池材料有限公司 | Preparation method of lithium ion battery anode material |
| DE102010033380A1 (en) | 2010-08-04 | 2012-02-09 | Bayerisches Zentrum für Angewandte Energieforschung e.V. | Large and open porous C / C composite with high internal surface, as well as methods of making the same and their use |
| WO2012051973A1 (en) | 2010-08-04 | 2012-04-26 | Bayerisches Zentrum Für Angewandte Energieforschung E.V. Zae Bayern | Large-pore and open-pore c/c composite having a high inner surface area, and process for producing it and use thereof |
| DE102011108435A1 (en) | 2011-07-26 | 2013-05-02 | Bayerisches Zentrum für Angewandte Energieforschung e.V. | Carbon-carbon composite, useful e.g. as electrode, catalyst support and adsorber, comprises large- and open porous support of carbon or organic precursor coated with nanoporous carbon material of high specific surface |
| CN114242971A (en) | 2017-12-13 | 2022-03-25 | 贝特瑞新材料集团股份有限公司 | Modified composite material, preparation method thereof and lithium ion battery |
| CN109778591B (en) * | 2019-01-11 | 2021-07-09 | 浙江理工大学 | Preparation method of hydrophilic flexible graphite composite sealing material |
| CN110127662B (en) * | 2019-05-26 | 2022-02-01 | 天津大学 | Method for preparing porous carbon by using alkali metal-assisted carbonization small-molecule organic solvent |
| CN112490443A (en) * | 2019-09-12 | 2021-03-12 | 宁波杉杉新材料科技有限公司 | Liquid-phase-coated graphite negative electrode material and preparation method thereof |
| CN112429728A (en) * | 2020-12-17 | 2021-03-02 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene material suitable for cold spraying |
| CN112479193A (en) * | 2020-12-17 | 2021-03-12 | 中国科学院宁波材料技术与工程研究所 | Graphene surface charged modification method |
| CN113437278A (en) * | 2021-07-29 | 2021-09-24 | 江西紫宸科技有限公司 | Graphite negative electrode material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304187A (en) * | 1999-12-15 | 2001-07-18 | 北京有色金属研究总院 | Composite graphite negative electrode material for lithium cell and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304187A (en) * | 1999-12-15 | 2001-07-18 | 北京有色金属研究总院 | Composite graphite negative electrode material for lithium cell and its preparation method |
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