CN1278436C - Method for preparing a carbon cathode material of lithium ion battery - Google Patents
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Abstract
The present invention relates to a method for preparing a carbon negative electrode material of a lithium ion battery. The present invention is carried out according to the following steps in sequence: water-soluble polymer or a water-solubility organic compound is dissolved in water; an additive and graphite powder are added proportionally and are uniformly stirred on a mixing device; the temperature rises so as to evaporate water content; in the process of evaporating the water content, the additive and the graphite powder which are mixed are continuously stirred and pelletized; then, the additive and the graphite powder are put in the hot air and solidified; subsequently, the additive and the graphite powder are put in a high temperature furnace to be heated and carbonized under the protective atmosphere; a composite graphite material which has a shell-core structure is obtained by cooling to the room temperature. The present invention has the advantages of simple and easy operation, green environmental protection and easy industrial production. Modified graphite prepared by the present invention has the advantages of high charge-discharge efficiency at the first time, high reversible specific capacity and favorable cycle performance.
Description
[technical field]
The present invention relates to battery terminal material technology field, particularly a kind of preparation method of lithium rechargeable battery carbon negative pole material.
[background technology]
Lithium ion battery is as a kind of new green power, compare with traditional ni-mh nickel-cadmium cell the voltage height is arranged, the life-span is long, energy density is high advantage, yet also exist the shortcoming of fast charging and discharging performance difference, this and the used negative material of lithium ion battery have much relations.
Negative material is generally material with carbon element in the lithium ion battery, as graphite, coke, RESEARCH OF PYROCARBON etc.Native graphite has higher specific capacity, but compatible relatively poor with electrolyte, and the coulombic efficiency that circulates first is lower, and since in charge and discharge process the expansion of graphite linings cause peeling off of graphite linings with shrinking, make cycle performance relatively poor.The native graphite of highly crystalline has the orientation of height in addition, is unfavorable for that big electric current charges and discharge fast, also is unfavorable for the slurry film-making simultaneously.
The amorphous carbon that obtains behind the polymer cracking is generally better to the compatibility of organic electrolyte, has cyclical stability preferably, but its irreversible capacity is bigger, and discharge platform is also not as the graphite ideal.
In order to improve the performance of negative material, there is Many researchers to coat the last layer RESEARCH OF PYROCARBON now in the graphite particle outside, can improve the compatibility of graphite and electrolyte on the one hand, RESEARCH OF PYROCARBON mostly is amorphous carbon on the other hand, crystallite does not have distribution of orientations, the quick embedding embedding that helps lithium ion goes out, thereby has improved the high rate during charging-discharging of graphite.Pyrolytic carbon layer is coated on outside the core graphite in addition, can stop peeling off of graphite linings, thereby improves the cycle performance of graphite.
This respect has more patent, as U.S. Patent Number:5,908,715, Date ofPatent:June.1 1999.As solvent, in graphite surface coated epoxy resin, polyparaphenylene's RESEARCH OF PYROCARBON, this patent claims to have heavy-current discharge with acetone, benzene etc., good invertibity and long electrical properties such as cycle life.
Chinese patent publication number CN1224251A, open day on July 28th, 1999, denomination of invention is a kind of carbon negative electrode material of lithium ion cell and preparation method thereof, with the absolute ethyl alcohol is solvent, the phenolic resins or the Lauxite of the different degrees of cross linking are coated on the native graphite, form material with carbon element through the pyrolysis carbonization again with core-shell structure.This patent claims that the negative material in this invention has high reversible capacity and cycle efficieny.
Chinese patent publication number CN1304187A, open day July 18 calendar year 2001, denomination of invention is the method for composite graphite negative electrode material for lithium cell and preparation thereof, with N.N-dimethyl formamide, acetone etc. as solvent, polyacrylonitrile, Kynoar, poly epoxy resin etc. are coated graphite, claim that the composite graphite that obtains has preferable performance.
Yet all use a large amount of organic solvents among the preparation method of above-mentioned patent, as acetone, N, dinethylformamide, ethanol etc., cost is higher, and the operating procedure complexity has bigger pollution in process of production, not enough environmental protection.The composite graphite that obtains behind this external application organic solvent dissolution RESEARCH OF PYROCARBON presoma generally will pass through follow-up ball mill grinding process, causes the breakage of coating layer easily and come off in this process, influences the electrical property of material.
[summary of the invention]
The objective of the invention is to, overcome the complex process that exists in the prior art, complex operation, big, the defect of high cost of pollution, thereby the preparation method of the lithium ion carbon negative pole material of a kind of simple first charge-discharge efficiency height of technological operation of environmental protection, high reversible specific capacity and stable cycle performance is provided.
The objective of the invention is to be achieved through the following technical solutions,
A kind of preparation method of carbon negative electrode material of lithium ion cell comprises the following steps:
(1) high molecular weight water soluble polymer or water-soluble organic compounds is soluble in water, add a certain proportion of graphite powder, stirring and evenly mixing in agitating device;
(2) elevated temperature to 40～90 ℃ transpiring moisture, in the transpiring moisture process, do not stop stirring-granulating, place 60～120 ℃ of hot-airs to solidify then 1～24 hour, obtain the graphite composite material that the surface is coated with high molecular weight water soluble polymer or water-soluble organic compounds presoma;
(3) with above-mentioned graphite composite material under protective atmosphere in the high temperature furnace programming rate with 0.5-30 ℃/min rise to 200～600 ℃ of constant temperature 0.2～4 hour, programming rate with 0.5-30 ℃/min rises to 600～1500 ℃ of constant temperature 0.5～12 hour again, be cooled to room temperature, obtain to have the composite graphite material of core-shell structure;
Wherein, can be spherical natural graphite or scale native graphite as the graphite of core material, average grain diameter is 5～40 μ m, is 1～30: 100 as the high molecular weight water soluble polymer RESEARCH OF PYROCARBON of shell or the weight ratio of water-soluble organic compounds RESEARCH OF PYROCARBON and graphite;
The present invention can also carry out as follows:
(1) high molecular weight water soluble polymer or water-soluble organic compounds is soluble in water, add certain proportion of additive and graphite powder, stirring and evenly mixing in agitating device;
(2) elevated temperature to 60～80 ℃ transpiring moisture, in the transpiring moisture process, do not stop stirring-granulating, place 80～120 ℃ of hot-airs to solidify then 6～12 hours, obtain the graphite composite material that the surface is coated with high molecular weight water soluble polymer or water-soluble organic compounds presoma;
(3) with above-mentioned graphite composite material under protective atmosphere in the high temperature furnace programming rate with 5-20 ℃/min rise to 400～500 ℃ of constant temperature 0.5～2 hour, programming rate with 5-20 ℃/min rises to 900～1200 ℃ of constant temperature 2～6 hours again, be cooled to room temperature, obtain to have the composite graphite material of core-shell structure;
Wherein, can be spherical natural graphite or scale native graphite as the graphite of core material, average grain diameter is 7～25 μ m.Described additive is selected from one or more in acetylene black, carbon black, furnace black, Delanium, aquadag, carbon nano-tube, copper powder, zinc powder, nickel powder, the silver powder, and weight is 0.1～5% of graphite weight.As the high molecular weight water soluble polymer RESEARCH OF PYROCARBON of shell or the weight ratio of water-soluble organic compounds RESEARCH OF PYROCARBON and graphite is 5～20: 100;
Carbon negative electrode material of lithium ion cell preparation method's of the present invention advantage is:
(1) solvent of using among the present invention is a water, does not have the pollution problem of organic solvent, is a kind of preparation method of environmental protection;
(2) solvent of using among the present invention is a water, utilizes simple and conveniently than Recovery of Organic Solvent, and cost is very low;
(3) solvent of using among the present invention is a water, and the very easy pulverizing of the composite graphite material with core-shell structure of production has reduced equipment investment, helps large-scale industrial production;
(4) adopt the carbon negative pole material of preparation method's preparation of the present invention to have high first charge-discharge efficiency and stable cycle performance, the additive of doping helps improving the conductivity or the lithium storage content of composite graphite, has improved reversible specific capacity.
[description of drawings]
The SEM figure of the negative material that Fig. 1 makes for embodiment 2.
The SEM figure of the negative material that Fig. 2 makes for embodiment 7.
The 063048A type lithium ion battery cyclic curve figure that Fig. 3 makes for the negative material that makes with embodiment 2.
[embodiment]
Below with more detailed description the present invention,
The preparation method of a kind of carbon negative electrode material of lithium ion cell of the present invention, be earlier that high molecular weight water soluble polymer or water-soluble organic compounds is soluble in water, said high molecular weight water soluble polymer or water-soluble organic compounds are some water soluble polymer resins such as water-soluble poly oxirane, water-soluble epoxy resin, and the water-soluble poly urethane is resin, water-soluble plastic cement, water-soluble polyester, soluble polyurethane, polyacrylamide, polyamide polyureas; Water soluble polyether, water-soluble poval formal, polyvinyl alcohol, Sodium Polyacrylate, water-soluble macromolecule organic compound such as phthalocyanine compound, water-soluble azo compounds, water soluble surfactant active and washing agent type organic such as tween, neopelex etc.; Water-soluble cellulose such as methylcellulose, hydroxyethylcellulose, carboxymethyl cellulose, hydroxypropyl methylcellulose, the water soluble polymer shitosan, arabogalactan, water soluble starch, one or more of some high polymer hydrolyzed product such as oligosaccharides, oligopeptides.Used in fact high molecular weight water soluble polymer or water-soluble organic compounds kind are very unimportant, as long as the water-soluble macromolecule amount organic substance of pyrolysis carbonization at high temperature just can be suitable for.Its concentration is to contain water soluble polymer polymer or water-soluble organic compounds 10～400 grams in 1 premium on currency, and better is 40～150 grams.Add graphite powder by weight, graphite as core material can be spherical natural graphite or scale native graphite, average grain diameter is 5～40 μ m, that better is 7～25 μ m, average grain diameter adopts the laser light scattering particle size analyzer to measure gained D50, average grain diameter too small specific surface is long-pending then big, is unfavorable for the raising of reversible capacity, and average grain diameter is unfavorable for Li too greatly
+Fully embed and take off embedding, make also difficulty of pole piece in the production, uncomfortable cooperation battery material.General spherical graphite is better than flaky graphite covered effect, because the flaky graphite particle shape is regular inadequately, and the coating layer cracky.As the high molecular weight water soluble polymer RESEARCH OF PYROCARBON of shell or the weight ratio of water-soluble organic compounds RESEARCH OF PYROCARBON and graphite is 1～30: 100, and better is 5～20: 100.For discharge and the storage lithium that increases material, also can add additive, described additive is selected from and is in acetylene black, carbon black, furnace black, Delanium, aquadag, carbon nano-tube, copper powder, zinc powder, nickel powder, the silver powder one or more, and weight is 0.1～5% of graphite weight.Graphite, additive and the most of high molecular weight water soluble polymer or the directly weighing of water-soluble organic compounds that are coated.The amount of the finished product composite graphite that obtains is at last deducted initial graphite and weight of additive, can obtain the weight of RESEARCH OF PYROCARBON.
After in solution, adding graphite powder and additive, on mixing arrangement, mixed 0.5～48 hour, purpose is that it is mixed.Elevated temperature to 40～90 ℃ evaporation section or whole moisture, be good with 60～80 ℃ again, in the transpiring moisture process, do not stop stirring-granulating, place 60～120 ℃ of hot-airs to solidify then 1～24 hour, to solidify 6～12 hours in 80～120 ℃ of hot-airs, obtain the graphite composite material that the surface is coated with high molecular weight water soluble polymer or water-soluble organic compounds presoma again for good.With above-mentioned graphite composite material under protective atmosphere in the high temperature furnace programming rate with 0.5-30 ℃/min rise to 200～600 ℃ of constant temperature 0.2～4 hour, the programming rate with 0.5-30 ℃/min rises to 600～1500 ℃ of constant temperature 0.5～12 hour again; Wherein rise to 400～500 ℃ of constant temperature 0.5～2 hour with the programming rate of 5-20 ℃/min again, rise to 900～1200 ℃ of constant temperature 2～6 hours for good with the programming rate of 5-20 ℃/min again, be cooled to room temperature, obtain to have the composite graphite material of core-shell structure.Used protective atmosphere is nitrogen or argon gas in the high temperature cabonization process, and air inlet speed is 1～100L/min, is good with 5～20L/min again.Can repeat above step if needed, promptly repeatedly be coated with the composite graphite material that obtains having multiple pyrolytic carbon layer.
Chemical property for the prepared negative material of the preparation method who tests employing carbon negative electrode material of lithium ion cell of the present invention, composite graphite material among the present invention is mixed the furnishing pulpous state with binding agent PVDF and deionized water and stirring, be coated in copper foil surface, make the negative pole of lithium rechargeable battery, to electrode is metal lithium sheet, and electrolyte is 1MLiPF
6/ EC+DEC (1: 1) is assembled into button cell and tests.
Chemical property for the prepared negative material of the preparation method who tests employing carbon negative electrode material of lithium ion cell of the present invention, composite graphite material among the present invention is mixed the furnishing pulpous state with binding agent PVDF and deionized water and stirring, be coated in copper foil surface, make the negative pole of lithium rechargeable battery, with above-mentioned negative plate that makes and LiCoO
2The positive pole that makes with corresponding conductive agent, adhesive PTFE, and corresponding electrolyte makes positive pole by existing technology, and electrolyte is made the 063048A lithium ion battery by existing technology accordingly, discharges and recharges with cycle performance and tests.
Correlated performance parameter meaning is as follows:
First charge-discharge efficiency=(initial charge capacity/discharge capacity) first * 100%;
Wherein, initial charge capacity: refer to the electric current initial charge of 0.1C charging capacity to 4.2V;
Discharge capacity first: refer to the discharge capacity that is discharged to 3.0V with the electric current of 0.1C from 4.2V first;
Reversible specific capacity: refer to the discharge capacity/negative active core-shell material quality that is discharged to 3.0V with the electric current of 1C from 4.2V.
Circulation: 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.
[embodiment 1]
Polyacrylamide 10g is dissolved in the 200ml deionized water, adds the 100g spherical natural graphite, is warming up to 80 ℃ and stirs evaporate to dryness moisture content after 6 hours, is put in 120 ℃ of baking ovens again and solidifies 6 hours.The presoma that obtains is placed in the alumina crucible, put into high temperature resistance furnace, rise to 500 ℃ with 10 ℃/min under nitrogen protection, constant temperature 0.5 hour rises to 900 ℃ with 10 ℃/min again, constant temperature 4 hours.This carbon negative pole material and lithium are assembled into button cell to electrode.Reversible specific capacity is 328.9mAh/g, and first charge-discharge efficiency is 93.5%.
[embodiment 2]
The preparation method is identical with embodiment 1, and different is to have added 2g acetylene black.This carbon negative pole material and lithium are assembled into the 063048A lithium ion battery to electrode.
Fig. 3 detects cyclic curve figure for the battery performance that present embodiment makes, and reversible specific capacity is 340.8mAh/g, and first charge-discharge efficiency is 92.3%.
[embodiment 3]
Polyacrylamide 15g is dissolved in the 200ml deionized water, adds 0.2g carbon nano-tube and 100g spherical natural graphite, is warming up to 70 ℃ and stirs evaporate to dryness moisture content after 6 hours, is put in 90 ℃ of baking ovens again and solidifies 9 hours.The presoma that obtains is placed in the alumina crucible, put into high temperature resistance furnace, rise to 400 ℃ with 5 ℃/min under argon shield, constant temperature 1 hour rises to 900 ℃ with 5 ℃/min again, constant temperature 3 hours.This carbon negative pole material and lithium are assembled into button cell to electrode.Its reversible specific capacity is 380.7mAh/g, and first charge-discharge efficiency is 80.8%.
[embodiment 4]
Carboxymethyl cellulose 10g is dissolved in the 200ml deionized water, adds 5g acetylene black and 100g spherical natural graphite, is warming up to 60 ℃ and stirs 6 hours rear section evaporate to dryness moisture content, is put in 100 ℃ of baking ovens again and solidifies 12 hours.The presoma that obtains is placed in the alumina crucible, put into high temperature resistance furnace, rise to 500 ℃ with 10 ℃/min under argon shield, constant temperature 0.5 hour rises to 1200 ℃ with 10 ℃/min again, handles 2 hours.This carbon negative pole material and lithium are assembled into button cell to electrode.Reversible specific capacity is 335.1mAh/g, and first charge-discharge efficiency is 90.4%.
[embodiment 5]
Carboxymethyl cellulose 15g is dissolved in the 200ml deionized water, adds 2g nickel powder and 100g spherical natural graphite, is warming up to 90 ℃ and stirs 3 hours rear section evaporate to dryness moisture content, is put in 110 ℃ of baking ovens again and solidifies 8 hours.The presoma that obtains is placed in the alumina crucible, put into high temperature resistance furnace, rise to 450 ℃ with 15 ℃/min under nitrogen protection, constant temperature 1.5 hours rises to 1100 ℃ with 15 ℃/min again, handles 2 hours.This carbon negative pole material and lithium are assembled into button cell to electrode.Its reversible specific capacity is 337.7mAh/g, and first charge-discharge efficiency is 89.8%.
[embodiment 6]
Polyvinyl alcohol 20g is dissolved in the 300ml deionized water, adds 3g acetylene black and 100g spherical natural graphite, is warmed up to 80 ℃ and stirs evaporate to dryness moisture content after 6 hours, is put in 80 ℃ of baking ovens again and solidifies 12 hours.The presoma that obtains is placed in the alumina crucible, put into high temperature resistance furnace, rise to 400 ℃ with 10 ℃/min under nitrogen protection, constant temperature 0.5 hour rises to 1000 ℃ with 10 ℃/min again, handles 4 hours.This carbon negative pole material and lithium are assembled into button cell to electrode.Reversible specific capacity is 345.1mAh/g, and first charge-discharge efficiency is 91.2%.
[embodiment 7]
Polyvinyl alcohol 10g is dissolved in the 200ml deionized water, adds 1g acetylene black and 100g spherical natural graphite, is warmed up to 60 ℃ and stirs 4 hours rear section evaporate to dryness moisture content, is put in 120 ℃ of drying in oven again and solidifies 4 hours.The presoma that obtains is placed in the alumina crucible, put into high temperature resistance furnace, rise to 500 ℃ with 10 ℃/min under nitrogen protection, constant temperature 0.5 hour rises to 1000 ℃ with 10 ℃/min again, handles 4 hours.Polyvinyl alcohol 10g is dissolved in the 200ml deionized water, a coating polyvinyl alcohol RESEARCH OF PYROCARBON complex spherical graphite that adds 1g acetylene black and obtain stirs 4 hours rear section evaporate to dryness moisture content again, is put in 80 ℃ of baking ovens again and solidifies 12 hours.Heating mode carbonization when once coating obtains secondary and coats complex carbon material.This carbon negative pole material and lithium are assembled into button cell to electrode.Reversible specific capacity is 342.6mAh/g, and first charge-discharge efficiency is 94.2%.
[embodiment 8]
Polyvinyl alcohol 40g is dissolved in the 300ml deionized water, adds 0.5g carbon nano-tube and 100g spherical natural graphite, is warmed up to 80 ℃ and stirs evaporate to dryness moisture content after 4 hours, is put in 90 ℃ of baking ovens again and solidifies 10 hours.The presoma that obtains is placed in the alumina crucible, put into high temperature resistance furnace, rise to 400 ℃ with 20 ℃/min under nitrogen protection, constant temperature 2 hours rises to 900 ℃ with 15 ℃/min again, handles 5 hours.This carbon negative pole material and lithium are assembled into button cell to electrode.Its reversible specific capacity is 399.6mAh/g, and first charge-discharge efficiency is 81.5%.
[embodiment 9]
Water-soluble poly oxirane 20g is dissolved in the 200ml deionized water, adds 1g carbon black and 100g spherical natural graphite, is warming up to 80 ℃ and stirs evaporate to dryness moisture content after 6 hours, is put in 120 ℃ of baking ovens again and solidifies 6 hours.The presoma that obtains is placed in the alumina crucible, put into high temperature resistance furnace, rise to 500 ℃ with 10 ℃/min under nitrogen protection, constant temperature 0.5 hour rises to 800 ℃ with 10 ℃/min again, handles 6 hours.This carbon negative pole material and lithium are assembled into button cell to electrode.Reversible specific capacity is 320.4mAh/g, and first charge-discharge efficiency is 89.7%.
[embodiment 10]
The preparation method is identical with embodiment 9, and different is that additive is the 2g copper powder.Its reversible specific capacity is 333.2.mAh/g, and first charge-discharge efficiency is 90.1%.
[comparative example 1]
The 100g spherical natural graphite is not done to coat and is handled, and with lithium electrode is assembled into button cell.Reversible specific capacity is 330.5mAh/g, and first charge-discharge efficiency is 83.9%.
Table 1:
| Specific discharge capacity mAh/g circulates for the first time | Cycle charge discharge electrical efficiency (%) for the first time | |
| Comparative example 1 | 330.5 | 83.9 |
| Embodiment | ||
| 1 | 328.9 | 93.5 |
| Embodiment 2 | 340.8 | 92.3 |
| | 380.7 | 80.8 |
| Embodiment 4 | 335.1 | 90.4 |
| Embodiment 5 | 337.7 | 89.8 |
| Embodiment 6 | 345.1 | 91.2 |
| Embodiment 7 | 342.6 | 94.2 |
| Embodiment 8 | 399.6 | 81.5 |
| Embodiment 9 | 320.4 | 89.7 |
| Embodiment 10 | 333.2 | 90.1 |
As can be seen from Table 1, compare with the spherical natural graphite of not doing coating, spherical natural graphite material through the high molecular weight water soluble polymer coating, its cycle charge discharge electrical efficiency all has raising by a relatively large margin, illustrated on native graphite, to coat one deck RESEARCH OF PYROCARBON, improved the configuration of surface of graphite.Its cycle charge discharge electrical property is greatly improved.We it can also be seen that by adding additive, its specific discharge capacity also has raising by a relatively large margin.
What pay particular attention to is, carries out secondary as 7 pairs of graphite of embodiment and coats, and can improve the cycle charge discharge electrical efficiency of graphite greatly.
[embodiment 11]
The preparation method is identical with embodiment 2, and different is that core graphite is the natural shape graphite of scale.Its first reversible specific capacity be 296.5mAh/g, first charge-discharge efficiency is 75.6%.
[embodiment 12]
The preparation method is identical with embodiment 4, and different is that core graphite is the natural shape graphite of scale.Its first reversible specific capacity be 298.9mAh/g, first charge-discharge efficiency is 80.6%.
[embodiment 13]
The preparation method is identical with embodiment 9, and different is that core graphite is the natural shape graphite of scale.Its first reversible specific capacity be 297.5mAh/g, first charge-discharge efficiency is 81.6%.
[comparative example 2]
100g flakey native graphite is not done to coat and is handled, and with lithium electrode is assembled into button cell.Reversible specific capacity is 271.6mAh/g first, and first charge-discharge efficiency is 68.7%.
[comparative example 3]
Polyacrylonitrile 20 grams are dissolved in 200ml N, in the dinethylformamide, add 100 gram flakey native graphites, stir solvent evaporated after 4-12 hour.The presoma that obtains is pulverized, placed in the alumina crucible, put into high temperature resistance furnace, under nitrogen protection, handled four hours for 900 ℃.This carbon negative pole material and lithium are assembled into button cell to electrode.Reversible specific capacity is 290.8mAh/g first, and first charge-discharge efficiency is 76.3%.
Table 2:
| Specific discharge capacity mAh/g circulates for the first time | Cycle charge discharge electrical efficiency (%) for the first time | |
| Comparative example 2 | 271.6 | 68.7 |
| Comparative example 3 | 290.8 | 76.3 |
| Embodiment 11 | 296.5 | 76.5 |
| Embodiment 12 | 298.9 | 80.6 |
| Embodiment 13 | 297.5 | 81.6 |
As can be seen from Table 2, compare with the flakey native graphite of not doing coating, through flakey natural graphite material and adding additive that high molecular weight water soluble polymer coats, its reversible specific capacity and cycle charge discharge electrical efficiency all have raising by a relatively large margin.
By the result of each embodiment and comparative example and Fig. 1-3 as can be known, preparation method's environmental protection of the present invention, simple and easy to do, with low cost, be easy to suitability for industrialized production; And the negative material that utilizes the present invention to make is used for lithium rechargeable battery and has high first charge-discharge efficiency, high reversible specific capacity and stable cycle performance, can satisfy application request.
Claims (9)
1. the preparation method of a carbon negative electrode material of lithium ion cell comprises the following steps:
(1) high molecular weight water soluble polymer or water-soluble organic compounds is soluble in water, add a certain proportion of graphite powder, stirring and evenly mixing in agitating device;
(2) elevated temperature to 40～90 ℃ transpiring moisture, in the transpiring moisture process, do not stop stirring-granulating, place 60～120 ℃ of hot-airs to solidify then 1～24 hour, obtain the graphite composite material that the surface is coated with high molecular weight water soluble polymer or water-soluble organic compounds presoma;
(3) with above-mentioned graphite composite material under nitrogen or argon shield atmosphere in the high temperature furnace programming rate with 0.5-30 ℃/min rise to 200～600 ℃ of constant temperature 0.2～4 hour, programming rate with 0.5-30 ℃/min rises to 600～1500 ℃ of constant temperature 0.5～12 hour again, be cooled to room temperature, obtain to have the composite graphite material of core-shell structure;
Wherein, be spherical natural graphite or scale native graphite as the graphite of core material, average grain diameter is 5～40 μ m;
As the high molecular weight water soluble polymer RESEARCH OF PYROCARBON of shell or the weight ratio of water-soluble organic compounds RESEARCH OF PYROCARBON and graphite is 1～30: 100.
2. according to the preparation method of the described carbon negative electrode material of lithium ion cell of claim 1, it is characterized in that, described high molecular weight water soluble polymer or water-soluble organic compounds are water-soluble poly oxirane, water-soluble epoxy resin, the water-soluble poly urethane is resin, water-soluble plastic cement, water-soluble polyester, soluble polyurethane, one or more in polyacrylamide, the polyamide polyureas.
3. according to the preparation method of the described carbon negative electrode material of lithium ion cell of claim 1, it is characterized in that described high molecular weight water soluble polymer or water-soluble organic compounds are one or more of water soluble polyether, water-soluble poval formal, polyvinyl alcohol, Sodium Polyacrylate, phthalocyanine compound, water-soluble azo compounds.
4. according to the preparation method of the described carbon negative electrode material of lithium ion cell of claim 1, it is characterized in that described high molecular weight water soluble polymer or water-soluble organic compounds are one or more of methylcellulose, hydroxyethylcellulose, carboxymethyl cellulose, hydroxypropyl methylcellulose, water soluble polymer shitosan, arabogalactan, water soluble starch, oligosaccharides, oligopeptides.
5. according to the preparation method of the described carbon negative electrode material of lithium ion cell of claim 1, it is characterized in that, add one or more additives in acetylene black, carbon black, furnace black, Delanium, aquadag, carbon nano-tube, copper powder, zinc powder, nickel powder, the silver powder in the step (1), weight is 0.1～5% of graphite weight.
6. according to the preparation method of the described carbon negative electrode material of lithium ion cell of claim 1, it is characterized in that described graphite average grain diameter 7～25 μ m.
7. according to the preparation method of the described carbon negative electrode material of lithium ion cell of claim 1, it is characterized in that, elevated temperature to 60 in the step (2)～80 ℃ of transpiring moistures does not stop stirring-granulating in the transpiring moisture process, place 80～120 ℃ of hot-airs to solidify then 6～12 hours.
8. according to the preparation method of the described carbon negative electrode material of lithium ion cell of claim 1; it is characterized in that; in the step (3) under nitrogen or argon shield atmosphere in the high temperature furnace programming rate with 5-20 ℃/min rise to 400～500 ℃ of constant temperature 0.5～2 hour; programming rate with 5-20 ℃/min rises to 900～1200 ℃ of constant temperature 2～6 hours again, is cooled to room temperature.
9. according to the preparation method of the described carbon negative electrode material of lithium ion cell of claim 1, it is characterized in that, is 5～20: 100 as the high molecular weight water soluble polymer RESEARCH OF PYROCARBON of shell or the weight ratio of water-soluble organic compounds RESEARCH OF PYROCARBON and graphite.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031269613A CN1278436C (en) | 2003-06-20 | 2003-06-20 | Method for preparing a carbon cathode material of lithium ion battery |
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031269613A CN1278436C (en) | 2003-06-20 | 2003-06-20 | Method for preparing a carbon cathode material of lithium ion battery |
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| EP4020637A4 (en) * | 2019-09-27 | 2024-04-10 | Lg Energy Solution, Ltd. | Anode and secondary battery comprising same |
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2003
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4020637A4 (en) * | 2019-09-27 | 2024-04-10 | Lg Energy Solution, Ltd. | Anode and secondary battery comprising same |
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| CN1567617A (en) | 2005-01-19 |
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