CN112299849B - Method for preparing battery carbon rod by using regenerated graphite - Google Patents
Method for preparing battery carbon rod by using regenerated graphite Download PDFInfo
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- CN112299849B CN112299849B CN202011215272.5A CN202011215272A CN112299849B CN 112299849 B CN112299849 B CN 112299849B CN 202011215272 A CN202011215272 A CN 202011215272A CN 112299849 B CN112299849 B CN 112299849B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 73
- 239000010439 graphite Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 239000010426 asphalt Substances 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000007772 electrode material Substances 0.000 claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021383 artificial graphite Inorganic materials 0.000 claims abstract description 10
- 238000005087 graphitization Methods 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 7
- 239000011335 coal coke Substances 0.000 claims abstract description 7
- 239000002006 petroleum coke Substances 0.000 claims abstract description 7
- 238000007580 dry-mixing Methods 0.000 claims abstract description 6
- 239000002008 calcined petroleum coke Substances 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000012216 screening Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 13
- 238000004939 coking Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 125000001309 chloro group Chemical class Cl* 0.000 claims 2
- 238000000746 purification Methods 0.000 abstract description 10
- 238000011282 treatment Methods 0.000 abstract description 6
- 150000003841 chloride salts Chemical class 0.000 abstract description 4
- 238000000748 compression moulding Methods 0.000 abstract description 2
- 238000011403 purification operation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 239000012535 impurity Substances 0.000 description 6
- 150000001804 chlorine Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
- C04B35/532—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
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- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/522—Graphite
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Abstract
The invention discloses a method for preparing a battery carbon rod by using regenerated graphite, which comprises the steps of taking graphite tailings in the production process of a graphite electrode material as a regenerated graphite raw material, washing the regenerated graphite raw material with hydrogen peroxide, and carrying out dry mixing on the washed graphite tailings, calcined petroleum coke and chloride salt to obtain a first graphite powder mixture; wet mixing the first graphite powder mixture with asphalt, granulating, performing pre-graphitization treatment and purification, and screening after circularly performing purification operation for several times to obtain artificial graphite powder; the artificial graphite powder, the coal coke powder, the carbon black and the petroleum coke powder are dry-mixed in proportion and then added into the asphalt for heating and wet-mixing, after the wet-mixing is finished, the wet-mixed mixture is subjected to compression molding in a mold pressing device by using a mold, then the molded wet-mixed mixture is prepared into a green product, and the green product is molded after roasting to obtain a finished product. The invention can greatly reduce the production cost and effectively improve the resource utilization rate by purifying the graphite tailings in the production process of the graphite electrode material and preparing the high-quality battery carbon rod.
Description
Technical Field
The invention relates to the technical field of recycling of graphite waste, in particular to a method for preparing a battery carbon rod by using recycled graphite.
Background
Graphite is widely applied to the fields of metallurgy, machinery, environmental protection, chemical industry, fire resistance, electronics, medicine, military industry, aerospace and the like due to the unique structure and a plurality of excellent properties, becomes a non-metallic material essential for the development of modern industry and high, new and advanced technologies, and has more and more important status in the development of national economy. The level of fixed carbon content in graphite directly determines the application properties of graphite.
One of the common graphite carbon products is a graphite electrode, and during preparation of the graphite electrode material, graphite with carbon content of more than 90% needs to be repeatedly crushed, so that the average particle size, density and specific surface area of graphite powder are continuously reduced, and a graphite powder raw material for preparing the graphite electrode is obtained, wherein graphite tailings of 25-30% can be generated in the product, and can only be used for low-quality applications such as coatings, fireproof materials, low-grade lubricating materials and pencils, and great resource waste is caused. If the graphite material can be recycled, and high-grade graphite powder is obtained after purification and is prepared into the graphite electrode, on one hand, the waste of the graphite raw material can be reduced, on the other hand, the use cost of the graphite material can be reduced, and the graphite electrode has better technical and economic effects.
In the prior art, the main methods for preparing high-purity graphite are a chemical purification method and a high-temperature purification method. The chemical purification method is divided into an alkali acid method and a hydrofluoric acid method, and the process relates to the treatment of acid-alkali wastewater, so that the hidden danger of environmental pollution exists, and the industrial application of the method is further limited. The high-temperature purification method utilizes the characteristic that the boiling point of impurities or reaction products of the impurities in the graphite concentrate is far lower than the boiling point of graphite, and the temperature is raised to the threshold temperature of impurity gasification under a certain atmosphere condition, so that the purposes of impurity removal and purification are achieved. Compared with a chemical purification method, the purity of the graphite material subjected to high-temperature roasting treatment is higher, and the influence on the environment is smaller, so that the method is a main development direction of a graphite purification process in the future. However, in the prior art, the high-temperature roasting purification of graphite is mostly applied to the treatment process of natural graphite raw materials, and no relevant application exists in the field of graphite recovery.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing a battery carbon rod by using regenerated graphite, so as to solve the defects in the technical background.
The technical problem solved by the invention is realized by adopting the following technical scheme:
a method for preparing a battery carbon rod by using regenerated graphite specifically comprises the following operation steps:
s1, taking graphite tailings in the production process of the graphite electrode material as a regenerated graphite raw material, washing the regenerated graphite raw material with 1.5-1.8% hydrogen peroxide water, and then dry-mixing the washed regenerated graphite raw material with calcined petroleum coke and chloride salt, wherein the proportion of the regenerated graphite raw material is controlled to be 60-70 wt%, and the proportion of the chloride salt is controlled to be 0.07-1.5 wt%; after mixing, a first graphite powder mixture is obtained.
S2, heating and wet-mixing the first graphite powder mixture and asphalt according to the mass ratio of 4: 1-3: 1, and when the wet-mixing time is still 45min, performing auxiliary dispersion by using ultrasonic equipment until the wet-mixing is finished to obtain a wet mixed material; the coking value of the asphalt is more than 55%, and the softening point of the asphalt is 78-85 ℃.
S3, granulating the wet mixed material prepared in the step S2 by using a mould to prepare particles with the particle size of less than 2cm or block materials with the side length of less than 2cm, and putting the block materials into a graphitization furnace to sequentially carry out vacuum sectional heating roasting:
roasting at 1400-1700 ℃ for 120-150 h;
roasting at 2000-2300 ℃ for 50-60 h;
roasting at the temperature of 2350-2500 ℃ for 2-3 h;
and naturally cooling after roasting.
S4, sequentially crushing and smashing the cooled roasted material, circularly performing the steps S1, S2 and S3 as a regenerated graphite raw material for 2-3 times, and screening the obtained roasted material to obtain artificial graphite powder.
S5, dry-mixing 70 wt% of artificial graphite powder, 10-15 wt% of coal coke powder, 2-3 wt% of carbon black and the balance of petroleum coke powder, then adding the mixture into asphalt, controlling the mass ratio of the asphalt to be 25-30 wt% of the mass of the dry-mixed mixture, and heating and wet-mixing.
S6, after the wet mixing is finished, the wet mixed mixture is molded in a mold pressing device by using a mold, then the molded wet mixed mixture is made into a raw product, and the raw product is molded after being roasted to obtain a finished product.
Further, the wet mixing temperature is controlled to be 140 to 180 ℃ and the wet mixing time is controlled to be 1 to 3 hours when the heating wet mixing is performed in the step S2 and the step S5.
Further, in the step S3, the degree of vacuum maintained in the furnace is 1X 10 when the vacuum firing is performed in the graphitization furnace -2 ～3×10 -2 Pa。
By way of further limitation, in the step S5, the particle diameters of the coal coke powder, the carbon black and the petroleum coke powder as raw materials do not exceed 70 μm; and the particle size of the artificial graphite powder is not more than 50 mu m.
In the step S6, when the green product is baked in the baking furnace, the temperature increase rate of the baking is 8 ℃/h when the temperature of the baking furnace is below 300 ℃, the temperature increase rate of the baking is 5 ℃/h when the temperature is between 300 ℃ and 600 ℃, the temperature is increased to 1200 ℃ according to the temperature increase rate of 3 ℃/h after the temperature is 600 ℃, and the temperature is maintained for 24-32 h to complete the baking.
Has the advantages that: the method for preparing the battery carbon rod by using the regenerated graphite can effectively utilize the graphite tailings in the production process of the graphite electrode material, purify the graphite tailings and prepare the battery carbon rod as a high-carbon component, the product can be effectively improved, the process quality indexes of the product are greatly improved compared with those of a common battery carbon rod, the resistivity of the product is reduced to about 0.002 omega/cm from about 0.0035 omega/cm of a traditional battery carbon plate, and the energy density of a battery can be effectively improved; meanwhile, as the graphite tailings in the production process of the graphite electrode material are fertilizers and are high-carbon products after graphitization, the volatility is low, the difficulty of flue gas collection can be reduced by the partial proportion of carbon components during roasting and carbonization, and the production environment is further purified.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
In the embodiment, graphite tailings in the production process of the graphite electrode material are used as a raw material of regenerated graphite, the graphite tailings in the production process of the graphite electrode material have surface defects as the raw material of the regenerated graphite, and need to be modified by low-concentration hydrogen peroxide, in the embodiment, 1.5% hydrogen peroxide is used, and the effects of eliminating the surface defects and reducing surface tip atoms can be achieved through mild hydrogen peroxide oxidation, so that the passivated graphite tailings are activated.
The method comprises the steps of treating and drying a regenerated graphite raw material, and mixing the regenerated graphite raw material, calcined petroleum coke and chloride salt according to the mass ratio of 65%, 34% and 1% to obtain a first graphite powder mixture. The chlorine salt is mainly used for purifying the regenerated graphite raw material in the subsequent calcining process, because the chlorine salt has certain fluidity when the temperature rises to the melting point temperature, at the moment, chlorine ions are dispersed on the surface of the graphite or in gaps of flakes and are fully fused with impurity elements embedded in the regenerated graphite raw material to form metal chloride or complex with lower boiling point for discharge; and because the chlorine salt is an external activating impurity, the addition amount of the chlorine salt is not too large, and the amount of the chlorine salt used in the graphite tailing in the production process of the graphite electrode material is controlled to be 0.07-1.5 wt%.
Heating and wet-mixing the first graphite powder mixture and asphalt with a coking value of more than 55% and a softening point of 78-85 ℃ according to a mass ratio of 3:1, controlling the wet-mixing temperature to 160 ℃ during heating and wet-mixing, controlling the wet-mixing time to 2h, starting ultrasonic equipment to perform auxiliary dispersion when the wet-mixing time is still 45min, utilizing energy generated by ultrasonic waves to break up asphalt polymers, reducing the viscosity of the asphalt, controlling the ultrasonic power to 2400W and the ultrasonic frequency to 40K during the period, performing ultrasonic auxiliary treatment until the wet-mixing is finished, and determining the ultrasonic viscosity reduction ratio of the coal asphalt to be 12.6%. In the process, the viscosity of a pure asphalt system without any solvent is reduced by the operation steps of ultrasonic auxiliary treatment, so that the distribution stability of graphite powder in the asphalt system is improved, the specific gravity of the graphite powder in unit volume is improved, the raw materials are rapidly stirred and uniformly mixed in the graphitization process, and the graphite tailings in the production process of low-quality graphite electrode materials are fixed, upgraded and purified, so that the preparation quality of the battery carbon rod is improved.
Granulating the wet mixture prepared in the step by using a mould to prepare particles with the particle size of less than 2cm or block materials with the side length of less than 2cm, and putting the block materials into a graphitization furnace to sequentially perform vacuum degree of 2 multiplied by 10 -2 Vacuum sectional roasting of Pa: firstly, roasting for 120 hours at 1600 ℃ during roasting; then roasting for 55 hours at the temperature of 2200 ℃; finally, roasting for 2 hours at 2400 ℃, and naturally cooling after roasting is finished, wherein the roasting temperature curve can obviously improve the purity of a sintered sample; the processes of mixing, wet mixing, granulating, roasting and crushing are circularly carried out for 3 times, and then the obtained roasted material is sieved, ground and sieved to obtain the artificial graphite powder with the particle size of less than 50 mu m.
Grinding coal coke powder, carbon black and petroleum coke powder to a particle size of less than 75 mu m, dry-mixing the coal coke powder, the carbon black and the petroleum coke powder with artificial graphite powder, adding the mixture into asphalt with a coking value of more than 55% and a softening point of 78-85 ℃ after the mixture is uniformly dry-mixed, controlling the mass ratio of the asphalt to be 28 wt% of the sum of the dry-mixed mixture, heating and wet-mixing the mixture, controlling the wet-mixing temperature to be 160 ℃ and the wet-mixing time to be 1 h.
And after the wet mixing is finished, carrying out compression molding on the wet mixed mixture in a mold pressing device by using a mold, then preparing a raw product from the molded wet mixed mixture, feeding the raw product into a roasting furnace for roasting, wherein the roasting temperature rise rate is 8 ℃/h when the temperature of the roasting furnace is below 300 ℃, the roasting temperature rise rate is 5 ℃/h when the temperature is between 300 and 600 ℃, raising the temperature to 1200 ℃ according to the temperature rise rate of 3 ℃/h after the temperature is 600 ℃, keeping the temperature for 24 to 32 hours, and molding to obtain a finished product after roasting.
The battery carbon rods obtained by molding after roasting are randomly extracted by 100, and the performance of the battery carbon rods measured after screening out defective products is as follows: the carbon content is more than or equal to 94 percent (the average value is 94.22 percent), the porosity is 17 to 19 percent, the resistivity is less than 0.0032 omega/cm, and the average value is 0.0022 omega/cm. The method has excellent performance parameters, and can effectively improve the energy density of the battery by matching with a proper battery structure and a proper battery material.
The foregoing shows and describes the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A method for preparing a battery carbon rod by using regenerated graphite is characterized by comprising the following operation steps:
s1, using graphite tailings in the production process of the graphite electrode material as a regenerated graphite raw material, washing the regenerated graphite raw material with hydrogen peroxide with the concentration of 1.5-1.8%, and then dry-mixing the washed regenerated graphite raw material with calcined petroleum coke and chlorine salt, wherein the proportion of the regenerated graphite raw material is controlled to be 60-70 wt%, and the proportion of the chlorine salt is controlled to be 0.07-1.5 wt%; mixing to obtain a first graphite powder mixture;
s2, heating and wet-mixing the first graphite powder mixture and asphalt according to the mass ratio of 4: 1-3: 1, and when the wet-mixing time is still 45min, performing auxiliary dispersion by using ultrasonic equipment until the wet-mixing is finished to obtain a wet mixed material; the coking value of the asphalt is more than 55%, and the softening point is 78-85 ℃;
s3, granulating the wet mixed material prepared in the step S2 by using a mould to prepare particles with the particle size of less than 2cm or block-shaped materials with the side length of less than 2cm, and putting the block-shaped materials into a graphitization furnace to sequentially carry out vacuum subsection heating roasting:
roasting at 1400-1700 ℃ for 120-150 h
Roasting at 2000-2300 deg.c for 50-60 hr
Roasting at 2350-2500 deg.c for 2-3 hr
Naturally cooling after roasting;
s4, sequentially crushing and smashing the cooled roasted material, circularly performing the steps S1, S2 and S3 as a regenerated graphite raw material for 2-3 times, and screening the obtained roasted material to obtain artificial graphite powder;
s5, dry-mixing 70 wt% of artificial graphite powder, 10-15 wt% of coal coke powder, 2-3 wt% of carbon black and the balance of petroleum coke powder, adding the mixture into asphalt, controlling the mass ratio of the asphalt to be 25-30 wt% of the mass of the dry-mixed mixture, and heating and wet-mixing;
s6, after the wet mixing is finished, the wet mixed mixture is molded in a mold pressing device by a mold, then the molded wet mixed mixture is made into a raw product, and the raw product is molded after being roasted to obtain a finished product.
2. The method for preparing a battery carbon rod from regenerated graphite according to claim 1, wherein the wet mixing temperature is controlled to be 140-180 ℃ and the wet mixing time is controlled to be 1-3 h when the heating wet mixing is performed in the step S2 and the step S5.
3. The method for preparing a battery carbon rod using regenerated graphite as claimed in claim 1, wherein the degree of vacuum maintained in the graphitization furnace is 1 x 10 when vacuum firing is performed in the graphitization furnace in step S3 -2 ～3×10 -2 Pa。
4. The method for manufacturing a battery carbon rod using regenerated graphite according to claim 1, wherein in the step S5, the particle diameters of the coal coke powder, the carbon black and the petroleum coke powder as raw materials are not more than 70 μm; and the particle size of the artificial graphite powder is not more than 50 mu m.
5. The method for preparing a battery carbon rod by using regenerated graphite according to claim 1, wherein in the step S6, when the green product is baked in a baking furnace, the baking temperature rise rate is 8 ℃/h when the temperature of the baking furnace is below 300 ℃, the baking temperature rise rate is 5 ℃/h when the temperature is between 300 ℃ and 600 ℃, the temperature rises to 1200 ℃ after 600 ℃ according to the temperature rise rate of 3 ℃/h, and the baking is completed after 24-32 h.
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| CN115385691B (en) * | 2022-09-23 | 2023-02-03 | 江苏嘉明碳素新材料有限公司 | Preparation method of ultra-long regenerated graphite electrode |
| CN115626826B (en) * | 2022-11-11 | 2023-09-05 | 湖南大学 | Low-density wear-resistant carbon graphite material with independent micropores and preparation method thereof |
| CN115583835B (en) * | 2022-11-29 | 2023-04-07 | 自贡东新电碳有限责任公司 | Low-porosity high-mechanical-strength carbon graphite material and preparation method thereof |
| CN115838172A (en) * | 2022-12-26 | 2023-03-24 | 汨罗市九峰科贸有限公司 | Preparation method of graphite material for battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874793A (en) * | 2012-10-23 | 2013-01-16 | 湖南省宁乡县长宁炭素制品有限公司 | Production method of novel battery carbon rods |
| CN105272287A (en) * | 2015-10-15 | 2016-01-27 | 大同新成新材料股份有限公司 | Method for preparing graphite crucible with recycled graphite |
| CN106376121A (en) * | 2016-08-26 | 2017-02-01 | 河北顺天电极有限公司 | High-graphite carbon electrode and preparation method thereof |
| CN107673759A (en) * | 2017-11-07 | 2018-02-09 | 大同新成新材料股份有限公司 | A kind of preparation method of novel solar generating graphite heat accumulating |
| CN108101042A (en) * | 2017-12-15 | 2018-06-01 | 大同新成新材料股份有限公司 | A kind of production technology of lithium battery graphite cathode material |
| CN111018554A (en) * | 2019-11-22 | 2020-04-17 | 大同新成新材料股份有限公司 | Method for preparing ultrahigh-power graphite electrode by using graphene |
| CN111170757A (en) * | 2020-01-14 | 2020-05-19 | 大同新成新材料股份有限公司 | Preparation method of special fine-particle graphite material |
| KR102172862B1 (en) * | 2019-10-10 | 2020-11-02 | 블랙머티리얼즈 주식회사 | Manufacturing method of high purity graphite formed article using anthracite coal |
-
2020
- 2020-11-04 CN CN202011215272.5A patent/CN112299849B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874793A (en) * | 2012-10-23 | 2013-01-16 | 湖南省宁乡县长宁炭素制品有限公司 | Production method of novel battery carbon rods |
| CN105272287A (en) * | 2015-10-15 | 2016-01-27 | 大同新成新材料股份有限公司 | Method for preparing graphite crucible with recycled graphite |
| CN106376121A (en) * | 2016-08-26 | 2017-02-01 | 河北顺天电极有限公司 | High-graphite carbon electrode and preparation method thereof |
| CN107673759A (en) * | 2017-11-07 | 2018-02-09 | 大同新成新材料股份有限公司 | A kind of preparation method of novel solar generating graphite heat accumulating |
| CN108101042A (en) * | 2017-12-15 | 2018-06-01 | 大同新成新材料股份有限公司 | A kind of production technology of lithium battery graphite cathode material |
| KR102172862B1 (en) * | 2019-10-10 | 2020-11-02 | 블랙머티리얼즈 주식회사 | Manufacturing method of high purity graphite formed article using anthracite coal |
| CN111018554A (en) * | 2019-11-22 | 2020-04-17 | 大同新成新材料股份有限公司 | Method for preparing ultrahigh-power graphite electrode by using graphene |
| CN111170757A (en) * | 2020-01-14 | 2020-05-19 | 大同新成新材料股份有限公司 | Preparation method of special fine-particle graphite material |
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Application publication date: 20210202 Assignee: Anhui Rongyu Technology Co.,Ltd. Assignor: Miluo Fuyuan New Material Co.,Ltd. Contract record no.: X2023980045584 Denomination of invention: A Method for Preparing Battery Carbon Rods Using Regenerated Graphite Granted publication date: 20220923 License type: Common License Record date: 20231102 |