CN101209837A - 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, insert lithium capacity height, 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 enter 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 not as the graphite ideal.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, absorbed the polymkeric substance RESEARCH OF PYROCARBON again and the organic electrolyte compatibility is good, the caused graphite linings of inserting altogether that has prevented lithium ion and electrolytic solution is peeled 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, Resins, epoxy, 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 Resins, epoxy 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 Resins, epoxy 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 matrix material must 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, easily 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, 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 what the separation of this method solvent was adopted 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 to be solved in the present invention 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 be 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 by Powdered high molecular polymer being dissolved into boiling point, carry out thorough mixing with graphite again, mixture is stirred intensification, abundant impregnated graphite, organic solvent and stirring-granulating are removed in distillation then, continuing heats up again makes polymer cure, 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 production time, 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 carries out in temperature-rise period, 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 now being 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.
In order to make the graphite composite material prevented from caking after the coating, and then make final modified graphite product prevented from caking, the corresponding organic solvent of said each high molecular polymer of the present invention is from the existing known solvent that can dissolve this high molecular polymer, select boiling point to be no more than the organic solvent of the softening temperature of high molecular polymer, for example the corresponding organic solvent of Resins, epoxy is selected tetrahydrofuran (THF) for use, toluene, ethanol, organic solvents such as ether, resol adopts ethanol, acetone and other organic solvent, polyvinyl formal adopts acetate, formic acid, the phenols equal solvent, Polyurethane adopts N, dinethylformamide, organic solvents such as N,N-dimethylacetamide.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 as resol, Resins, epoxy 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 polymkeric substance.For example: per 100 parts of resol 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, as polyvinyl acetal, Polyurethane etc., do not need to 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 time length can more abundant impregnated graphite, 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 recycled, 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 polymkeric substance 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 to carry out under protection of inert gas.
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 and 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 company limited, 100 ℃ of softening temperatures) in the present embodiment.
Preparation process is as follows: 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 standby.Mixture is poured in the reactor, be raised to 75 ℃ from room temperature, fully being raised to 80 ℃ behind the dipping 2h reclaims ethanol distillation, temperature is raised to 200 ℃ again after having steamed ethanol, the heating-up time 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, heats up 1200 ℃ under nitrogen protection atmosphere 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 as shown in Figure 1, 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, capacity with the 3C discharge is 85% of a 0.5C loading capacity, capacity with the 2C discharge is 95% of a 0.5C loading capacity, and charge and discharge 300 all capability retentions 91%, as shown in Figure 3 with 1C.
Embodiment 2
As shell material, the weight ratio of graphite and Resins, epoxy is 1: 0.10 to adopt epoxy powder (Suzhou Speical Chemical Co., Ltd., 120 ℃ of softening temperatures) in the present embodiment.
Preparation process is as follows: takes by weighing 9 gram Resins, epoxy (containing 1.2 gram solidifying agent-mphenylenediamines) and is dissolved in the 100 gram tetrahydrofuran solutions, mix with 91 gram natural graphites again, and standby.Mixture is poured in the reactor, be raised to 60 ℃ from room temperature, fully be raised to 68 ℃ behind the dipping 1h with tetrahydrofuran (THF) distillation recovery, temperature is raised to 200 ℃ again after having steamed tetrahydrofuran (THF), the heating-up time 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, heats up 1200 ℃ under nitrogen protection atmosphere 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%, as shown in Figure 3 with 1C.
Embodiment 3
As shell material, the weight ratio of graphite and polyvinyl formal is 1: 0.10 to adopt polyvinyl formal powder (Hangzhou De Sen Science and Technology Ltd., 145 ℃ of softening temperatures) in the present embodiment.
Preparation process is as follows: takes by weighing 9 gram polyvinyl formals and is dissolved in the 100 gram acetate, mix with 91 gram natural graphites again, and standby.Mixture is poured in the reactor, be raised to 110 ℃ from room temperature, fully be raised to 120 ℃ behind the dipping 6h with acetate distillation recovery, temperature is raised to 400 ℃ again after having steamed acetate, the heating-up time 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, heats up 1200 ℃ under nitrogen protection atmosphere 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%, as shown in Figure 3 with 1C.
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.
Preparation process is as follows: 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 standby.Mixture is poured in the reactor, be raised to 150 ℃ from room temperature, be raised to 155 ℃ with N after fully flooding 12h, the dinethylformamide distillation is reclaimed, steamed N, temperature is raised to 400 ℃ again behind the dinethylformamide, the heating-up time 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, heats up 1000 ℃ under nitrogen protection atmosphere 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 Resins, epoxy is 1: 0.10.
Preparation process is as follows: 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 again; 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; heating-up time 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 as shown in Figure 2, 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, with natural graphite is that battery is helped in the 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 (10)
1. the method for modifying of a graphite, it comprises 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 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, 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.
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 Resins, epoxy, 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 tetrahydrofuran (THF), ethanol, acetate and N, one or more in the dinethylformamide.
5. method of modifying as claimed in claim 1 is characterized in that also adding during step 1. the solidifying agent of high molecular polymer; 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.
6. method of modifying as claimed in claim 1 is characterized in that the weight ratio of 2. middle macromolecule polymer solution of step and graphite is 1: 1～2, and wherein the weight ratio of graphite and high molecular polymer is 1: 0.03～0.50.
7. method of modifying as claimed in claim 1 is characterized in that the time of dipping was 1～12 hour during step 2..
8. method of modifying as claimed in claim 1 is characterized in that 3. step adopts the distillatory method to remove organic solvent, and the described solidified time is 1-12 hour.
9. method of modifying as claimed in claim 1 is characterized in that 3. step is to carry out under protection of inert gas.
10. the modified graphite that makes as each described method of modifying of claim 1～9.
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| 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 |
| 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 |
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