Graphitic resin anode and method of making same

Abstract

The application relates to the technical field of resin anodes, and particularly discloses a graphite resin anode and a preparation method thereof, wherein the resin anode comprises the following raw materials in parts by weight: 5-25 parts by weight of graphite material; 60-85 parts by weight of petroleum calcined coke; 10-15 parts by weight of thermosetting phenolic resin material; and 0-1 parts by weight of pitch; wherein the viscosity of the thermosetting phenolic resin is greater than or equal to 16000 mPa.s (25 DEG C).

Description

Technical Field

[0001] This application relates to the technical field of resin anodes, specifically to a graphitic resin anode and its preparation method. Background Technology

[0002] The electrolytic aluminum industry is currently facing a triple transformation: "carbon tariff pressure + high cost pressure + technological upgrading". Traditional asphalt anodes have high resistivity (58~62μΩ·m), high carbon consumption (410~430kg / ton of aluminum), and excessive environmental emissions (VOCs≥200mg / m³). 3 This addresses issues such as [missing information - likely related to carbon trading barriers]. Therefore, a resin anode is provided to meet the demand for "high-end green leadership," helping companies circumvent carbon trading barriers and enhance their market competitiveness. Summary of the Invention

[0003] This application provides a graphitic resin anode and its preparation method. Appropriate graphite is added to significantly improve the conductivity of the resin anode; and an appropriate phenolic resin is further incorporated to significantly improve the conductivity and strength of the resin anode.

[0004] This application involves the following: 1. A graphitic resin anode, comprising the following raw materials in parts by weight: Graphite material 5-25 parts by weight; petroleum calcined coke 60-85 parts by weight; thermosetting phenolic resin material 10-15 parts by weight; asphalt 0-1 parts by weight; The viscosity of the thermosetting phenolic resin is ≥16000 mPa•s (25℃).

[0005] In some preferred embodiments, the graphitic resin anode comprises the following raw materials in parts by weight: 8-20 parts by weight of graphite material; 68-85 parts by weight of petroleum calcined coke; 10-15 parts by weight of thermosetting phenolic resin material; 0-1 parts by weight of asphalt.

[0006] In some preferred embodiments, the graphitic resin anode comprises the following raw materials in parts by weight: 8-13 parts by weight of graphite material; 76-85 parts by weight of petroleum calcined coke; 10-15 parts by weight of thermosetting phenolic resin material; 0-1 parts by weight of asphalt.

[0007] In some embodiments, the particle size of the graphite material is less than 100 mesh; preferably less than 200 mesh.

[0008] 2. The graphitic resin anode according to claim 1, wherein the viscosity of the thermosetting phenolic resin is 20,000~60,000 mPa•s (25°C), preferably 30,000~50,000 mPa•s (25°C);

[0009] 3. The graphitic resin anode according to item 1 or 2, wherein the thermosetting phenolic resin is a lignin-modified thermosetting phenolic resin.

[0010] In some embodiments, the preparation method of the thermosetting phenolic resin includes: alkali-catalyzed polycondensation of phenol and formaldehyde, lignin-filled blending, and metal ion complexation.

[0011] In this application, the addition or absence of lignin and its amount significantly improve the performance of the graphite resin anode, such as affecting its resistivity. Therefore, lignin needs to be added in an appropriate amount. In the preparation of thermosetting phenolic resin in this application, the addition of lignin is mainly through physical mixing, where its dissolution in the resin is the primary concern. However, in the preparation of the graphite resin anode, lignin reacts during the subsequent calcination process: the calcination process initiates premature cross-linking of the resin, forming a rigid glassy carbon skeleton at around 300°C. This skeleton provides a supporting template for the pitch mesophase, fills the skeleton cracks, and together constructs a multiphase structure with low resistivity and high strength.

[0012] 4. The graphitic resin anode according to claim 3, wherein the phenol and formaldehyde undergo alkali-catalyzed condensation polymerization at a temperature range of 70-78°C for 0.5-3.5 h; and / or During the alkali-catalyzed polycondensation of phenol and formaldehyde, the alkali-catalyzed catalyst is selected from any one or more combinations of the following: triethylamine, triethanolamine, imidazoles (e.g., 2-methylimidazole, imidazole, 2-ethyl-4-methylimidazole, etc.), sodium hydroxide, calcium hydroxide, barium hydroxide, and ammonia; and / or During the catalytic condensation of phenol and formaldehyde, the molar ratio of phenol to formaldehyde is less than 1:1.

[0013] 5. The graphitic resin anode according to item 3 or 4, wherein, when the lignin-filled blend is used, the mass ratio of lignin to phenol is ≥1:3; preferably (1~3):3; more preferably (1~1.5):3.

[0014] 6. The graphitic resin anode according to any one of items 3 to 5, wherein the lignin-filled blend is further dehydrated to a viscosity ≥16000 mPa•s (25°C); preferably 20000~60000 mPa•s (25°C); more preferably 30000~50000 mPa•s (25°C).

[0015] In some embodiments, when metal ions are complexed, the metal is selected from any one or more combinations of the following group: iron, nickel, zinc, copper, cobalt, manganese, barium, calcium, magnesium, lead, and chromium; preferably, the metal is a combination of iron and nickel.

[0016] 7. The graphitic resin anode according to any one of claims 1 to 6, wherein the particle size of the graphite material is ≤0.08 mm; preferably 0.03 to 0.075 mm; more preferably 0.05 to 0.075 mm; and / or The ash content of the graphite material is ≤0.2wt%; and / or The resistivity of the graphite material is ≤100 μΩ·m; and / or The sulfur content in the graphite material is ≤0.5wt%.

[0017] 8. The graphitic resin anode according to any one of items 1 to 7, wherein, based on the total weight of the petroleum calcined coke, the petroleum calcined coke comprises the following parts by weight of raw materials: 25-45 parts of 200-mesh calcined petroleum coke, 5-15 parts of 0-1mm calcined petroleum coke, 15-30 parts of 1-3mm calcined petroleum coke, and 15-30 parts of 3-6mm calcined petroleum coke.

[0018] 9. The graphitic resin anode according to any one of items 1 to 8, wherein the softening point of the pitch is 105 to 115°C; and / or The asphalt contains ≥18wt% β-resin, and / or The coking value of the asphalt is ≥54%.

[0019] 10. A method for preparing the graphitic resin anode according to any one of items 1 to 9, comprising the following steps: Mixing: Mixing and kneading petroleum calcined coke, graphite materials, thermosetting phenolic resin and asphalt; Molding: The mixed materials are vibrated to form a green body; or, the mixed materials are vibrated to form a green body and then flash-cured to obtain a green body. Calcination: The green blank is calcined and then cooled to obtain the graphitic resin anode.

[0020] 11. The preparation method according to item 10, wherein, The mixing process includes the following steps: dry mixing the calcined petroleum coke and graphite material until uniform, then adding the thermosetting phenolic resin and the asphalt for wet mixing, and finally cooling and discharging the mixture after uniform mixing; or The mixing process includes the following steps: dry mixing the petroleum calcined coke, graphite material, and thermosetting phenolic resin evenly, then adding the asphalt and wet mixing, and finally cooling and discharging the mixture after it is evenly mixed.

[0021] 12. The preparation method according to item 11, wherein the mixing temperature is 40~55°C, and / or The dry mixing time is 5-15 minutes; and / or The wet mixing time is 20-40 minutes.

[0022] 13. The preparation method according to any one of items 10-12, wherein, during vibration molding, The molding temperature is 35~40℃; and / or The excitation force for the molding is 70~90t; and / or The molding time is 100~150s.

[0023] 14. The preparation method according to any one of items 10-13, wherein, during flash curing, The flash temperature is 300~350℃; and / or The flashing time is 15~40s.

[0024] 15. The preparation method according to any one of items 10 to 14, wherein the calcination comprises the following steps: First heating stage: Heating to 280~330℃ at a heating rate of 10~15℃ / h; Second heating stage: Continue heating at a rate of 15~20℃ / h to 950~1200℃; Cooling stage: Cool at a rate of 15~30℃ / h or allow to cool naturally to 180~220℃, then cool to room temperature.

[0025] 16. The preparation method according to item 15, wherein the second heating stage is maintained at a temperature of 950~1200℃ for 5~8 hours.

[0026] Beneficial effects This application achieves a graphitic resin anode with significantly superior strength and conductivity by adjusting the viscosity and addition ratio of thermoplastic phenolic resin and the addition ratio of graphite material. The advantages of using a higher viscosity phenolic resin are: higher viscosity resin has lower flowability, allowing for more uniform coating of carbon aggregate particles, reducing interparticle voids, and increasing the density of the green body, thus laying the foundation for the high strength and low porosity of the final product. Simultaneously, the higher viscosity resin forms a stronger bonding network during the curing stage after molding, significantly improving the flexural and compressive strength of the green body and reducing the breakage rate during production (such as handling and transfer). Detailed Implementation

[0027] It should be noted that certain terms are used in the specification and claims to refer to specific components. Those skilled in the art will understand that different terms may be used to refer to the same component. This specification and claims do not distinguish components based on differences in terminology, but rather on differences in their functions.

[0028] As used throughout the specification and claims, the terms "comprising" or "including" are open-ended and should be interpreted as "comprising but not limited to". The subsequent descriptions in the specification are preferred embodiments for carrying out this application; however, these descriptions are for the purpose of understanding the general principles of the specification and are not intended to limit the scope of this application. The scope of protection of this application shall be determined by the appended claims. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains.

[0029] It should be understood that the embodiments of this application described herein include embodiments that are "composed of" and / or "substantially composed of". References to values ​​or parameters of "about" herein include (and describe) variations of that value or parameter itself. For example, a reference to "about X" includes a description of "X".

[0030] As used herein, references to “not” values ​​or parameters generally refer to and describe “except” values ​​or parameters. For example, “The method is not used to treat type X cancer” means that the method is used to treat cancers other than type X.

[0031] As used in this article, the term “approximately XY” has the same meaning as “approximately X to approximately Y”.

[0032] As used herein and in the appended claims, the singular forms “a / an” and “the” include the plural objects unless the context clearly indicates otherwise. It should also be noted that claims may be drafted to exclude any optional elements. Therefore, this statement is intended as a preliminary basis for the use of exclusive terms such as “only” or “merely” in conjunction with the description of the elements of the claim, or for the use of the limitation of “no”.

[0033] As used herein, the term "and / or" in words such as "A and / or B" is intended to include both A and B; A or B; A (alone); and B (alone). Similarly, as used herein, the term "and / or" in words such as "A, B and / or C" is intended to include each of the following embodiments: A, B and C; A, B or C; A or C; A or B; B or C; A and C; A and B; B and C; A (alone); B (alone); and C (alone).

[0034] As used in this article, "asphalt" is a product of deep processing of coal tar, mainly produced by further processing the residues after refining chemicals such as benzene, industrial naphthalene, and anthracene oil from high-temperature coal tar. During coal tar processing, the residue after distillation to remove liquid fractions is called coal tar pitch. Coal tar pitch is the main component of coal tar, accounting for approximately 50% to 60% of the total. It is generally believed that its main components are polycyclic aromatic hydrocarbons (PAHs) and their derivatives. The specific compound composition is very complex, and differences in raw coal type and processing technology can lead to variations in composition. At room temperature, coal tar pitch is a black, brittle, lustrous block with an unpleasant odor. It is easily combustible when melted and is toxic. Coal tar pitch has low temperature stability, good adhesion to mineral aggregates, poor climatic stability (large temperature variations), and contains a high amount of harmful components, especially carcinogenic PAHs such as benzo[a]pyrene, making it one of the main sources of such pollutants in the environment.

[0035] As used herein, "lignin" is intended to encompass any type of lignin, such as lignin derived from hardwoods, softwoods, or annular plants. Lignin may also be chemically modified. In some embodiments, lignin is purified or isolated.

[0036] As used in this article, "petroleum calcined coke" can be classified into high-sulfur coke, medium-sulfur coke and low-sulfur coke according to its sulfur content. Among them, the sulfur content of low-sulfur coke is less than 1.5%, the sulfur content of medium-sulfur coke is between 1.5% and 3%, and the sulfur content of high-sulfur coke is higher than 3%. The sulfur content is measured with reference to GB / T 387-1990.

[0037] In this application, the viscosity of the thermosetting phenolic resin is tested using a rotational viscometer method, which determines the viscosity by measuring the resistance encountered by the rotor rotating in the liquid. The viscosity of the thermosetting phenolic resin in this application is determined using a rotational viscometer. This is a commonly used method. The specific steps of the test method are as follows: First, prepare a suitable rotational viscometer, such as the common Brookfield rotational viscometer. Pour the phenolic resin sample into a suitable measuring container; the shape and size of the container should meet the requirements of the viscometer, generally a cylindrical cup. Ensure that the amount of sample is sufficient to completely immerse the rotor of the viscometer. Adjust the rotational speed of the viscometer; the choice of speed depends on the approximate viscosity range of the phenolic resin. For phenolic resins with lower viscosity, a higher speed can be selected, such as 30 r / min or 60 r / min; for phenolic resins with higher viscosity, a lower speed such as 2 r / min or 5 r / min may be necessary. Then, slowly place the rotor into the sample and wait for the viscometer reading to stabilize before recording it. For example, when testing a phenolic resin used for wood bonding, a rotor is placed in the resin sample and rotated at a speed of 5 r / min. After a few minutes, the reading stabilizes at 2500 mPa•s. This value is the viscosity of the phenolic resin under these conditions.

[0038] In this application, "β-resin in asphalt" refers to components that are insoluble in toluene but soluble in quinoline. β-resin in asphalt is a medium- to high-molecular-weight polycyclic aromatic hydrocarbon that plays a crucial role in the adhesion, coking properties, and carbon material performance of asphalt. As is known to those skilled in the art, methods for determining the β-resin content in asphalt include, for example, solvent extraction-gravimetric analysis and column chromatography. Relevant testing standards may include, for example, GB / T 2292 "Determination of Toluene-Insoluble Matter Content in Coking Products" and ASTM D6560.

[0039] In this application, "coking value of asphalt" refers to the percentage of the mass of solid carbon residue remaining after high-temperature pyrolysis and polycondensation of asphalt under air-isolated conditions, relative to the mass of the original asphalt sample. It is also called residual carbon value or coking rate. It is a core indicator for measuring the thermal stability and coking performance of asphalt, directly determining its ability to form a carbon skeleton in the preparation of carbon materials (such as graphite electrodes and carbon fibers). A higher coking value indicates a higher carbonization yield of the asphalt, resulting in better strength and density of the finished product. Methods for detecting the coking value of asphalt can include, for example, the air-isolated high-temperature pyrolysis-gravimetric method. Standards that can be referenced include GB / T 2293 "Determination of Coking Value of Coking Pitch Products" and ASTM D2416. During high-temperature pyrolysis, for example, the residue can be roasted in the absence of oxygen at 550℃.

[0040] Specific embodiments of this application will now be described in more detail with reference to examples. It should be understood that this application may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of this application and to fully convey the scope of this application to those skilled in the art.

[0041] Performance testing methods: Select resin prebaked anodes with no cracks or gaps and a rounded shape, and test their resistivity, bulk density and compressive strength according to the testing methods in YS / T63.2-2024, YS / T 63.7-2024 and YS / T 63.15-2024 respectively.

[0042] This application provides a graphitic resin anode, which comprises the following raw materials in parts by weight: 8-25 parts by weight of graphite material; 60-85 parts by weight of calcined petroleum coke; 10-15 parts by weight of thermosetting phenolic resin material; 0-1 parts by weight of asphalt. The viscosity of the thermosetting phenolic resin is ≥16000 mPa•s (25℃).

[0043] In some embodiments, the graphite material, based on parts by weight of the graphitic resin anode, is 5-25 parts by weight, 5-22 parts by weight, 5-20 parts by weight, 5-18 parts by weight, 5-16 parts by weight, 5-13 parts by weight, 8-25 parts by weight, 8-22 parts by weight, 8-20 parts by weight, 8-18 parts by weight, 8-16 parts by weight, 8-13 parts by weight, 10-25 parts by weight, 10-22 parts by weight, 10-20 parts by weight, 10-18 parts by weight, 10-16 parts by weight, 10-13 parts by weight, 13-25 parts by weight. Any weight range of 13-22 parts by weight, 13-20 parts by weight, 13-18 parts by weight, 13-16 parts by weight, or 5-25 parts by weight; for example, it can be any weight range of 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, or 5-25 parts by weight.

[0044] In some embodiments, the petroleum calcined coke is 60-85 parts by weight, 60-80 parts by weight, 60-78 parts by weight, 63-85 parts by weight, 63-80 parts by weight, 63-78 parts by weight, 65-85 parts by weight, 65-80 parts by weight, 65-78 parts by weight, 68-85 parts by weight, 68-80 parts by weight, 68-78 parts by weight, 72-85 parts by weight, 72-80 parts by weight, 72-78 parts by weight, 76-85 parts by weight, 76-80 parts by weight, 76-78 parts by weight, or 60-80 parts by weight, based on the weight of the graphite resin anode. Any weight range within the range of 5 parts by weight; for example, it can be 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, 81 parts by weight, 82 parts by weight, 83 parts by weight, 84 parts by weight, 85 parts by weight, or any weight range of 60 to 85 parts by weight.

[0045] In some embodiments, the thermosetting phenolic resin material is 10 to 15 parts by weight or any part by weight within the range of 10 to 15 parts by weight, based on the weight of the graphite resin anode; for example, it can be 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight or any part by weight within the range of 10 to 15 parts by weight.

[0046] In some embodiments, the asphalt, based on the weight parts of the graphite resin anode, is 0-1 parts by weight, 0.01-1 parts by weight, 0.05-1 parts by weight, 0.1-1 parts by weight, 0.2-1 parts by weight, 0.3-1 parts by weight, 0.4-1 parts by weight, 0.5-1 parts by weight, 0.6-1 parts by weight, 0.7-1 parts by weight, 0.8-1 parts by weight, 0.9-1 parts by weight, or any weight range within the range of 0-1 parts by weight; for example, it can specifically be 0 parts by weight (i.e., no asphalt), 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, or any weight range within the range of 0-1 parts by weight.

[0047] In some embodiments, the thermosetting phenolic resin has a viscosity ≥16000 mPa•s (25°C), ≥18000 mPa•s (25°C), ≥20000 mPa•s (25°C), ≥25000 mPa•s (25°C), ≥30000 mPa•s (25°C), ≥35000 mPa•s (25°C), ≥40000 mPa•s (25°C), ≥45000 mPa•s (25°C), or ≥50000 mPa•s (25°C).In some embodiments, the viscosity of the thermosetting phenolic resin is 16,000~60,000 mPa•s (25°C), 18,000~60,000 mPa•s (25°C), 20,000~60,000 mPa•s (25°C), 22,000~60,000 mPa•s (25°C), 25,000~60,000 mPa•s (25°C), 30,000~60,000 mPa•s (25°C), 32,000~60,000 mPa•s (25°C), 36,000~60,000 mPa•s (25°C), 38,000~60,000 mPa•s (25°C), 40,000~60,000 mPa•s (25°C), 45,000~60,000 mPa•s (25°C), 50,000~60,000 mPa•s (25°C). mPa•s (25℃), 55000~60000 mPa•s (25℃), 16000~550000 mPa•s (25℃), 18000~55000 mPa•s (25℃), 20000~55000 mPa•s (25℃), 22000~55000 mPa•s (25℃), 25000~55000 mPa•s (25℃), 30000~55000 mPa•s (25℃), 32000~55000 mPa•s (25℃), 36000~55000 mPa•s (25℃), 38000~55000 mPa•s (25℃), 40000~55000 mPa•s (25℃), 45000~55000 mPa•s (25℃), 50000~55000 mPa•s (25℃), 55000~55000 mPa•s (25℃), 16000~50000 mPa•s (25℃), 18000~50000 mPa•s (25℃), 20000~50000 mPa•s (25℃), 22000~50000 mPa•s (25℃), 25000~50000 mPa•s (25℃), 30000~50000 mPa•s (25℃), 32000~50000 mPa•s (25℃), 36000~50000 mPa•s (25℃), 38000~50000 mPa•s (25℃), 40000~50000 mPa•s Any viscosity range within the range of (25℃), 45000~50000 mPa•s (25℃), 50000~50000 mPa•s (25℃), 55000~50000 mPa•s (25℃) or 16000~60000 mPa•s (25℃);Specifically, it can be any viscosity within the range of 16000 mPa•s (25℃), 18000 mPa•s (25℃), 20000 mPa•s (25℃), 22000 mPa•s (25℃), 25000 mPa•s (25℃), 30000 mPa•s (25℃), 32000 mPa•s (25℃), 34000 mPa•s (25℃), 36000 mPa•s (25℃), 38000 mPa•s (25℃), 40000 mPa•s (25℃), 45000 mPa•s (25℃), 50000 mPa•s (25℃), 55000 mPa•s (25℃), 60000 mPa•s (25℃), or 16000~60000 mPa•s (25℃).

[0048] In some embodiments, the thermosetting phenolic resin is a lignin-modified thermosetting phenolic resin.

[0049] In some embodiments, the preparation method of the thermosetting phenolic resin includes: alkali-catalyzed polycondensation of phenol and formaldehyde, lignin-filled blending, and metal ion complexation.

[0050] In some embodiments, the reaction temperature during the catalytic condensation of phenol and formaldehyde is 70-78°C; specifically, it can be any temperature within the range of 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, or 70-78°C. In some embodiments, the reaction time during the catalytic condensation of phenol and formaldehyde is 0.5-3.5 hours; specifically, it can be any time within the range of 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, or 0.5-3.5 hours.

[0051] In some embodiments, during the base-catalyzed polycondensation of phenol and formaldehyde, the base-catalyzed catalyst is selected from any one or more combinations of the following group: triethylamine, triethanolamine, imidazoles (2-methylimidazole), sodium hydroxide, calcium hydroxide, barium hydroxide, and ammonia. In some embodiments, during the base-catalyzed polycondensation of phenol and formaldehyde, the base-catalyzed catalyst is triethylamine.

[0052] In some embodiments, when the lignin-filled blend is made, the mass ratio of lignin to phenol is any range within the range of ≥1:3, ≥1.1:3, ≥1.2:3, ≥1.3:3, ≥1.4:3, ≥1.5:3, or ≥1:3. In some embodiments, when the lignin-filled blend is made, the mass ratio of lignin to phenol is any range within the range of (1~3):3, (1~1.5):3, or (1~3):3; specifically, it can be any mass ratio within the range of 1:3, 1.1:3, 1.2:3, 1.3:3, 1.4:3, 1.5:3, or ≥1:3.

[0053] In some embodiments, the lignin-filled blend is further dehydrated to a viscosity ≥16000 mPa•s (25°C), ≥18000 mPa•s (25°C), ≥20000 mPa•s (25°C), ≥25000 mPa•s (25°C), ≥30000 mPa•s (25°C), ≥35000 mPa•s (25°C), ≥40000 mPa•s (25°C), ≥45000 mPa•s (25°C), or ≥50000 mPa•s (25°C). In some embodiments, the lignin-filled blend is further dehydrated to a viscosity of 16,000~60,000 mPa•s (25°C), 18,000~60,000 mPa•s (25°C), 20,000~60,000 mPa•s (25°C), 22,000~60,000 mPa•s (25°C), 25,000~60,000 mPa•s (25°C), 30,000~60,000 mPa•s (25°C), 32,000~60,000 mPa•s (25°C), 36,000~60,000 mPa•s (25°C), 38,000~60,000 mPa•s (25°C), 40,000~60,000 mPa•s (25°C), or 45,000~60,000 mPa•s. (25℃), 50000~60000 mPa•s (25℃), 55000~60000 mPa•s (25℃), 16000~55000 mPa•s (25℃), 18000~55000 mPa•s (25℃), 20000~55000 mPa•s (25℃), 22000~55000 mPa•s (25℃), 25000~55000 mPa•s (25℃), 30000~55000 mPa•s (25℃), 32000~55000 mPa•s (25℃), 36000~55000 mPa•s (25℃), 38000~55000 mPa•s (25℃), 40000~55000 mPa•s (25℃), 45000~55000 mPa•s (25℃), 50000~55000 mPa•s (25℃), 55000~55000 mPa•s (25℃), 16000~50000 mPa•s (25℃), 18000~50000 mPa•s (25℃), 20000~50000 mPa•s (25℃), 22000~50000 mPa•s (25℃), 25000~50000 mPa•s (25℃), 30000~50000 mPa•s (25℃), 32000~50000 mPa•sAny viscosity range within the following temperature ranges: 36000~50000 mPa•s (25℃), 38000~50000 mPa•s (25℃), 40000~50000 mPa•s (25℃), 45000~50000 mPa•s (25℃), 36000~45000 mPa•s (25℃), 38000~45000 mPa•s (25℃), 40000~45000 mPa•s (25℃), 36000~43000 mPa•s (25℃), 38000~43000 mPa•s (25℃), 40000~43000 mPa•s (25℃), or 16000~60000 mPa•s (25℃); specifically, for example, 16000 mPa•s. (25℃), 18000 mPa•s (25℃), 20000 mPa•s (25℃), 22000 mPa•s (25℃), 25000 mPa•s (25℃), 30000 mPa•s (25℃), 32000 mPa•s (25℃), 34000 mPa•s (25℃), 36000 mPa•s (25℃), 37000 mPa•s (25℃), 38000 mPa•s (25℃), 39000 mPa•s (25℃), 40000 mPa•s (25℃), 41000 mPa•s (25℃), 42000 mPa•s (25℃), 43000 mPa•s (25℃), 44000 mPa•s (25℃), 45000 mPa•s Any viscosity within the range of 50000 mPa•s (25℃), 55000 mPa•s (25℃), 60000 mPa•s (25℃), or 16000~60000 mPa•s (25℃).

[0054] In some embodiments, the particle size of the graphite material is ≤0.08 mm or any range thereof. In this application, the graphite material is commercially available graphite material that has been pulverized and sieved, with the sieve passing through the sieve. The particle size of the graphite material refers to the maximum aperture of the sieve through which the graphite material can pass. A 200-mesh sieve corresponds to an aperture of approximately 0.074 mm; ≤0.08 mm is approximately the sieve passing through a 200-mesh sieve. In some embodiments, the particle size of the graphite material is 0.03~0.075 mm, 0.05~0.075 mm, or any range thereof; for example, it can be any particle size within the range of 0.03 mm, 0.04 mm, 0.05 mm, 0.06 mm, 0.07 mm, 0.075 mm, or 0.03~0.075 mm. In some embodiments, the ash content of the graphite material is ≤0.2 wt%. In some embodiments, the resistivity of the graphite material is ≤100 μΩ·m. In some embodiments, the sulfur content in the graphite material is ≤0.5wt%.

[0055] In some embodiments, the softening point of the asphalt is 105-115°C. In some embodiments, the β-resin content in the asphalt is ≥18wt%. In some embodiments, the coking value of the asphalt is ≥54%.

[0056] This application also provides a method for preparing the above-mentioned graphitic resin anode, comprising the following steps: Mixing: Mixing and kneading petroleum calcined coke, graphite materials, thermosetting phenolic resin and asphalt; Molding: The mixed materials are vibrated to form a green body; or, the mixed materials are vibrated to form a green body and then flash-cured to obtain a green body. Calcination: The green blank is calcined and then cooled to obtain the graphitic resin anode.

[0057] In some embodiments, the kneading process includes the following steps: dry mixing the calcined petroleum coke and graphite material until uniform, then adding the thermosetting phenolic resin and the asphalt for wet mixing, and finally cooling and discharging the mixture after uniform mixing. In some embodiments, the kneading process includes the following steps: dry mixing the calcined petroleum coke, graphite material, and thermosetting phenolic resin until uniform, then adding the asphalt for wet mixing, and finally cooling and discharging the mixture after uniform mixing.

[0058] In some embodiments, the kneading temperature is 40-55°C; specifically, it can be any temperature within the range of 40°C, 42°C, 44°C, 45°C, 46°C, 48°C, 50°C, 52°C, 53°C, 54°C, 55°C, or 40-55°C. In some embodiments, the dry mixing time is 5-15 minutes; specifically, it can be any time within the range of 5-15 minutes, including 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, or 5-15 minutes. In some embodiments, the wet mixing time is 20-40 minutes; specifically, it can be any time within the range of 20 minutes, including 20 minutes, 22 minutes, 24 minutes, 26 minutes, 28 minutes, 30 minutes, 32 minutes, 34 minutes, 36 minutes, 38 minutes, 40 minutes, or 20-40 minutes. At this kneading temperature, the viscosity of the thermosetting phenolic resin is maintained within the range of 1000~2000 mPa•s. Within this range, the thermosetting phenolic resin exhibits good flowability, allowing for thorough and uniform mixing with graphite materials and aggregates, thus achieving kneading. It is also important to note that the viscosity of the prepared thermosetting phenolic resin must be ≥16000 mPa•s (25℃) to ensure that, during kneading, the viscosity is maintained within the range of 1000~2000 mPa•s at a suitable heating temperature.

[0059] In some embodiments, the vibration molding temperature is 35-40°C; specifically, it can be any temperature within the range of 35°C, 36°C, 37°C, 38°C, 39°C, 40°C, or 35-40°C. In some embodiments, the vibration molding excitation force is 70-90t; specifically, it can be any excitation force within the range of 70t, 72t, 74t, 76t, 78t, 80t, 82t, 84t, 86t, 90t, or 70-90t. In some embodiments, the vibration molding time is 100-150s; specifically, it can be any time within the range of 100s, 110s, 120s, 130s, 140s, 150s, or 100-150s. In this application, vibration molding requires molding the sample with appropriate temperature, excitation force, and molding time. During this process, it is important to ensure that the sample is molded to an appropriate degree to guarantee that it can be molded without deformation (e.g., breakage, volume increase) after the molding conditions are withdrawn (especially vibration force). In this application, adjusting the molding temperature to 35~40℃ results in a viscosity of 6000~7000 mPa•s for the thermosetting phenolic resin.

[0060] In some embodiments, the flash curing temperature is 300~350℃; specifically, it can be any temperature within the range of 300℃, 310℃, 320℃, 330℃, 340℃, 350℃, or 300~350℃. In some embodiments, the flash curing time is 15~40s; specifically, it can be any time within the range of 15s, 17s, 19s, 21s, 23s, 25s, 27s, 29s, 31s, 33s, 35s, 37s, 39s, 40s, or 15~40s.

[0061] In some implementations, the calcination includes the following steps: First heating stage: Heating to 280~330℃ at a heating rate of 10~15℃ / h (for example, it can be heated to 280℃, 290℃, 300℃, 310℃, 320℃, 330℃ or any temperature within the range of 280~330℃); Second heating stage: Continue heating at a rate of 15~20℃ / h to 950~1200℃ (for example, it can be heated to 950℃, 1000℃, 1050℃, 1100℃, 1150℃, 1200℃ or any temperature within the range of 950~1200℃). Cooling stage: Cool at a rate of 15~30℃ / h or cool naturally to 180~220℃ (for example, it can be heated to 180℃, 190℃, 200℃, 210℃, 220℃ or any temperature within the range of 180~220℃), and then cool to room temperature.

[0062] In some implementations, the second heating stage is maintained at a temperature of 950~1200℃ for 5~8 hours; for example, it can be any time within the range of 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h or 5~8h.

[0063] Example 1 The graphite resin anode is prepared by the following method: (a) Raw material preparation 1. Petroleum calcined coke: Weigh out 40 parts by weight of 200-mesh petroleum calcined coke, 10 parts by weight of 0-1mm petroleum calcined coke, 25 parts by weight of 1-3mm petroleum calcined coke, and 25 parts by weight of 3-6mm petroleum calcined coke, and mix them evenly in a mixer. During this mixing process, the ratio of 200-mesh petroleum calcined coke: 0-1mm petroleum calcined coke: 1-3mm petroleum calcined coke: 3-6mm petroleum calcined coke is 40:10:25:25 (by weight). Of this, 15% is medium-sulfur coke and 70% is high-sulfur coke.

[0064] 2. Thermosetting phenolic resin: Thermosetting phenolic resin with a viscosity of 40000±100mPa•s (25℃).

[0065] The preparation method of this thermosetting phenolic resin is as follows: 300g of phenol, 429g of 37% formaldehyde, and 6g of triethylamine were added to a reaction flask, and the mixture was heated to 73-75℃ and held at that temperature for 2 hours. Then, 120g of lignin was added, and the mixture was dehydrated under reduced pressure until the viscosity reached 40000±10cp / 25℃. Finally, 2g of ferric chloride and 6g of nickel chloride were added to obtain the desired thermosetting phenolic resin. The final viscosity of the thermosetting phenolic resin was 40000±100 mPa•s (25℃).

[0066] The lignin was purchased from Jinan Shengquan Group Co., Ltd., product model SQDT-1, batch number A24B160007. The lignin has an ash content of <0.5wt% and a phenolic hydroxyl content of 1.25mol / kg.

[0067] 3. Modified asphalt: Commercially available. Liquid modified asphalt has a softening point of 100~115℃, a particle size of 100-200 mesh, a β-resin content of ≥18wt%, and a coking value of ≥54%. Preheat it to 160~170℃ before use.

[0068] 4. Graphite material: Crush commercially available graphite material to a 200-mesh sieve and collect the sieve residue. The ash content of this graphite material is ≤0.2wt.%, the resistivity of the sieve residue (i.e., graphite powder) is ≤100μΩ·m, the sulfur content is ≤0.5wt%, and it contains no metallic impurities.

[0069] (b) Mixing: 76 parts by weight of the petroleum calcined coke prepared in step (a), 13 parts by weight of graphite material, and 0.5 parts by weight of modified asphalt were added to a preheated silo. After preheating to 50°C with hot air, the mixture was transferred to a mixing pot and dry-mixed for 10 min. Subsequently, 10.5 parts by weight of the thermosetting phenolic resin prepared in step (a) were added (i.e., petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin = 76:13:0.5:10.5, by weight), and wet-mixed at 50°C for 30 min. At this mixing temperature, the viscosity of the thermosetting phenolic resin was approximately 1200 mPa•s.

[0070] (c) Molding: The material mixed in step (b) is placed in a specific mold, the mold temperature is controlled at 37±2℃, and the material is shaped using a vibration molding machine with an excitation force of 80 tons for 120 seconds; thus, a green body is prepared with a density ≥1.70g / cm³. 3The vibratory-formed green body was then placed in a flash furnace and treated at 320°C for 25 seconds. After removal, the compressive strength of the green body was measured to be 13.5 MPa.

[0071] (d) Calcination: The flash-cured green body is placed in a high-temperature calcining furnace for heat treatment, as follows.

[0072] First heating stage: The temperature is increased from room temperature to 300℃ at a heating rate of 12℃ / h to slowly remove the volatiles in the anode, while the phenolic resin begins to carbonize initially. High-temperature calcination stage (i.e., the second heating stage): The temperature is increased to 1050℃ at a heating rate of 18℃ / h and held at this temperature for 6 hours to complete the densification of the carbon material and improve the mechanical strength and conductivity of the anode. Cooling stage: Allow the temperature to drop naturally to 200℃, then allow it to cool naturally to room temperature to avoid thermal stress caused by rapid cooling, which could lead to anode cracking. The furnace atmosphere must be strictly controlled throughout the roasting process to ensure the oxygen content is below 3% (vol.%) to prevent oxidation of the anode.

[0073] Example 2 The graphite resin anode is prepared by the following method: (a) Raw material preparation The petroleum calcined coke, thermosetting phenolic resin, and modified asphalt are the same as in Example 1.

[0074] Graphite material: Commercially available graphite material is pulverized to a 200-mesh sieve, and the undersize material is recorded as graphite fragments; commercially available graphite material is pulverized to a 300-mesh sieve, and the undersize material is recorded as graphite powder; the obtained graphite fragments and graphite powder are mixed in a 1:1 mass ratio to obtain the desired graphite material. The ash content of this graphite material is ≤0.2wt.%, the resistivity of the undersize material (i.e., graphite powder) is ≤100μΩ·m, the sulfur content is ≤0.5wt%, and it contains no metallic impurities.

[0075] (b) Mixing: 68 parts by weight of petroleum calcined coke, 20 parts by weight of graphite material, and 0.5 parts by weight of modified asphalt prepared in step (a) were added to a preheated silo. After preheating with hot air to 50°C, the mixture was transferred to a mixing pot and dry-mixed for 10 min. Then, 11.5 parts by weight of thermosetting phenolic resin prepared in step (a) were added (i.e., petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin = 68:20:0.5:11.5 by weight) and wet-mixed at 50°C for 30 min.

[0076] (c) Molding: Same as in Example 1, and will not be repeated here.

[0077] (d) Calcination: Same as in Example 1, and will not be repeated here.

[0078] Examples 3-5 and Comparative Examples 1-7 The only difference between Examples 3-5, Comparative Examples 1-7 and Example 1 is the mass ratio of petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin during step (b) mixing, as follows: In Example 3, the specific step (b) of mixing is as follows: 81 parts by weight of petroleum calcined coke prepared by the method in step (a), 8 parts by weight of graphite material, and 0.5 parts by weight of modified asphalt are added to a preheated silo. After preheating with hot air to 50°C, the mixture is transferred to a mixing pot and dry-mixed for 10 minutes. Subsequently, 10.5 parts by weight of thermosetting phenolic resin prepared by the method in step (a) are added (i.e., petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin = 81:8:0.5:10.5, by weight), and wet-mixed at 50°C for 30 minutes. All other steps are the same as in Example 1.

[0079] In Example 4, the specific step (b) of mixing is as follows: 72.5 parts by weight of petroleum calcined coke prepared by the method in step (a), 16 parts by weight of graphite material, and 0.5 parts by weight of modified asphalt are added to a preheated silo. After preheating with hot air to 50°C, the mixture is transferred to a mixing pot and dry-mixed for 10 minutes. Subsequently, 11 parts by weight of thermosetting phenolic resin prepared by the method in step (a) are added (i.e., petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin = 72.5:16:0.5:11, by weight), and wet-mixed at 50°C for 30 minutes. All other steps are the same as in Example 1.

[0080] In Example 5, the specific step (b) of mixing is as follows: 66 parts by weight of petroleum calcined coke prepared by the method in step (a), 22 parts by weight of graphite material, and 0.5 parts by weight of modified asphalt are added to a preheated silo. After preheating with hot air to 50°C, the mixture is transferred to a mixing pot and dry-mixed for 10 minutes. Subsequently, 11.5 parts by weight of thermosetting phenolic resin prepared by the method in step (a) are added (i.e., petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin = 66:22:0.5:11.5, by weight), and wet-mixed at 50°C for 30 minutes. All other steps are the same as in Example 1.

[0081] In Comparative Example 1, the specific step (b) of mixing was as follows: 57.5 parts by weight of petroleum calcined coke prepared by the method in step (a), 30 parts by weight of graphite material, and 0.5 parts by weight of modified asphalt were added to a preheated silo, preheated to 50°C with hot air, and then transferred to a mixing pot for dry mixing for 10 min; subsequently, 12 parts by weight of thermosetting phenolic resin prepared by the method in step (a) were added (i.e., petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin = 57.5:30:0.5:12, weight ratio), and wet mixed at 50°C for 30 min. All other steps were the same as in Example 1.

[0082] In Comparative Example 2, the specific step (b) of mixing was as follows: 52.5 parts by weight of petroleum calcined coke prepared by the method in step (a), 35 parts by weight of graphite material, and 0.5 parts by weight of modified asphalt were added to a preheated silo, preheated to 50°C with hot air, and then transferred to a mixing pot for dry mixing for 10 min; subsequently, 12 parts by weight of thermosetting phenolic resin prepared by the method in step (a) were added (i.e., petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin = 52.5:35:0.5:12, weight ratio), and wet mixed at 50°C for 30 min. All other steps were the same as in Example 1.

[0083] In Comparative Example 3, the specific step (b) of mixing was as follows: 45.5 parts by weight of petroleum calcined coke prepared by step (a), 42 parts by weight of graphite material, and 0.5 parts by weight of modified asphalt were added to a preheated silo, preheated to 50°C with hot air, and then transferred to a mixing pot for dry mixing for 10 min; subsequently, 12 parts by weight of thermosetting phenolic resin prepared by step (a) were added (i.e., petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin = 45.5:42:0.5:12, weight ratio), and wet mixed at 50°C for 30 min. All other steps were the same as in Example 1.

[0084] In Comparative Example 4, the specific step (b) of mixing was as follows: 40.5 parts by weight of petroleum calcined coke prepared by step (a), 47 parts by weight of graphite material, and 0.5 parts by weight of modified asphalt were added to a preheated silo, preheated to 50°C with hot air, and then transferred to a mixing pot for dry mixing for 10 min; subsequently, 12 parts by weight of thermosetting phenolic resin prepared by step (a) were added (i.e., petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin = 40.5:47:0.5:12, weight ratio), and wet mixed at 50°C for 30 min. All other steps were the same as in Example 1.

[0085] In Comparative Example 5, the specific step (b) of mixing was as follows: 84 parts by weight of petroleum calcined coke prepared by the method in step (a), 5 parts by weight of graphite material, and 0.5 parts by weight of modified asphalt were added to a preheated silo, preheated to 50°C with hot air, and then transferred to a mixing pot for dry mixing for 10 min; subsequently, 10.5 parts by weight of thermosetting phenolic resin prepared by the method in step (a) were added (i.e., petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin = 84:5:0.5:10.5, by weight), and wet mixed at 50°C for 30 min. All other steps were the same as in Example 1.

[0086] In Comparative Example 6, the specific step (b) of mixing was as follows: 88 parts by weight of petroleum calcined coke prepared by the method in step (a), 1 part by weight of graphite material, and 0.5 parts by weight of modified asphalt were added to a preheated silo, preheated to 50°C with hot air, and then transferred to a mixing pot for dry mixing for 10 min; subsequently, 10.5 parts by weight of thermosetting phenolic resin prepared by the method in step (a) were added (i.e., petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin = 88:1:0.5:10.5, by weight), and wet mixed at 50°C for 30 min. All other steps were the same as in Example 1.

[0087] In Comparative Example 7, the specific step (b) of mixing was as follows: 64 parts by weight of petroleum calcined coke prepared by step (a), 25 parts by weight of graphite material, and 0.5 parts by weight of modified asphalt were added to a preheated silo, preheated to 50°C with hot air, and then transferred to a mixing pot for dry mixing for 10 min; subsequently, 10.5 parts by weight of thermosetting phenolic resin prepared by step (a) were added (i.e., petroleum calcined coke: graphite material: modified asphalt: thermosetting phenolic resin = 64:25:0.5:10.5, by weight), and wet mixed at 50°C for 30 min. All other steps were the same as in Example 1.

[0088] The resistivity and compressive strength of the graphite resin anode obtained by the above implementation scheme are shown in Table 1. The appearance of the resin anode for cracks is also shown in Table 1. Among them, "slight cracks" means that there are 1 to 3 cracks, and each crack is 1 to 3 cm long; "many cracks" means that there are more than 3 cracks, and each crack is 1 to 3 cm long; "no obvious cracks" means that there are no cracks visible to the naked eye.

[0089] Table 1 Performance of various graphite resin anodes

[0090] Note: "-" in Table 1 indicates that the sample was not verified to be cracked.

[0091] The data in Table 1 show that while increasing the amount of graphite material significantly improves the resistivity and conductivity of the graphite resin anode, it also reduces its compressive strength. In this application, the added graphite material is, for example, graphite powder, which has low strength; adding a large amount of graphite powder will directly affect the compressive strength of the resulting resin anode. Furthermore, comparing the appearance of the resin anodes in Examples 1-5 shows that the amount of graphite material added should not be excessive, otherwise it will affect the integrity of the resin anode's appearance; this may be because excessive graphite material affects the uniformity of the raw material mixing, thus affecting the product's appearance.

[0092] Examples 6-9, Comparative Examples 8-10 The only difference between Examples 6-9 and Comparative Examples 8-10 and Example 1 is the viscosity of the selected thermosetting phenolic resin, as detailed below: In Comparative Example 8, the viscosity of the thermosetting phenolic resin was 16000±100 mPa•s (25℃).

[0093] The preparation method of this thermosetting phenolic resin is as follows: 300g of phenol, 429g of 37% formaldehyde, and 6g of triethylamine were added to a reaction flask, and the mixture was heated to 73-75℃ and held at that temperature for 2 hours. Then, 120g of lignin was added, and the mixture was dehydrated under reduced pressure until the viscosity reached 16000±100 cp / 25℃. Subsequently, 2g of ferric chloride and 6g of nickel chloride were added to obtain the desired thermosetting phenolic resin. The final viscosity of the thermosetting phenolic resin was 16000±100 mPa•s (25℃). When kneaded under the conditions described in Example 1, the viscosity of the thermosetting phenolic resin was approximately 500 mPa•s.

[0094] In Comparative Example 9, the viscosity of the thermosetting phenolic resin was 22000±100mPa•s (25℃).

[0095] The preparation method of this thermosetting phenolic resin is as follows: 300g of phenol, 429g of 37% formaldehyde, and 6g of triethylamine were added to a reaction flask, and the mixture was heated to 73-75℃ and held at that temperature for 2 hours. Then, 120g of lignin was added, and the mixture was dehydrated under reduced pressure until the viscosity reached 22000±100 cp / 25℃. Subsequently, 2g of ferric chloride and 6g of nickel chloride were added to obtain the desired thermosetting phenolic resin. The final viscosity of the thermosetting phenolic resin was 22000±100 mPa•s (25℃). When kneaded under the conditions of Example 1, the viscosity of the thermosetting phenolic resin was approximately 700 mPa•s.

[0096] In Comparative Example 10, the viscosity of the thermosetting phenolic resin was 26000±100 mPa•s (25℃).

[0097] The preparation method of this thermosetting phenolic resin is as follows: 300g of phenol, 429g of 37% formaldehyde, and 6g of triethylamine were added to a reaction flask, and the mixture was heated to 73-75℃ and held at that temperature for 2 hours. Then, 120g of lignin was added, and the mixture was dehydrated under reduced pressure until the viscosity reached 26000±100 cp / 25℃. Subsequently, 2g of ferric chloride and 6g of nickel chloride were added to obtain the desired thermosetting phenolic resin. The final viscosity of the thermosetting phenolic resin was 26000±100 mPa•s (25℃). When kneaded under the conditions of Example 1, the viscosity of the thermosetting phenolic resin was approximately 800 mPa•s.

[0098] In Example 6, the viscosity of the thermosetting phenolic resin was 32000±100 mPa•s (25℃).

[0099] The preparation method of this thermosetting phenolic resin is as follows: 300g of phenol, 429g of 37% formaldehyde, and 6g of triethylamine were added to a reaction flask, and the mixture was heated to 73-75℃ and held at that temperature for 2 hours. Then, 120g of lignin was added, and the mixture was dehydrated under reduced pressure until the viscosity reached 32000±100cp / 25℃. Subsequently, 2g of ferric chloride and 6g of nickel chloride were added to obtain the desired thermosetting phenolic resin. The final viscosity of the thermosetting phenolic resin was 32000±100 mPa•s (25℃). When kneaded under the conditions of Example 1, the viscosity of the thermosetting phenolic resin was approximately 1000 mPa•s.

[0100] In Example 7, the viscosity of the thermosetting phenolic resin was 36000±100 mPa•s (25℃).

[0101] The preparation method of this thermosetting phenolic resin is as follows: 300g of phenol, 429g of 37% formaldehyde, and 6g of triethylamine were added to a reaction flask, and the mixture was heated to 73-75℃ and held at that temperature for 2 hours. Then, 120g of lignin was added, and the mixture was dehydrated under reduced pressure until the viscosity reached 36000±100 cp / 25℃. Subsequently, 2g of ferric chloride and 6g of nickel chloride were added to obtain the desired thermosetting phenolic resin. The final viscosity of the thermosetting phenolic resin was 36000±100 mPa•s (25℃). When kneaded under the conditions described in Example 1, the viscosity of the thermosetting phenolic resin was approximately 1100 mPa•s.

[0102] In Example 8, the viscosity of the thermosetting phenolic resin was 45000±100 mPa•s (25℃).

[0103] The preparation method of this thermosetting phenolic resin is as follows: 300g of phenol, 429g of 37% formaldehyde, and 6g of triethylamine were added to a reaction flask, and the mixture was heated to 73-75℃ and held at that temperature for 2 hours. Then, 120g of lignin was added, and the mixture was dehydrated under reduced pressure until the viscosity reached 45000±100cp / 25℃. Subsequently, 2g of ferric chloride and 6g of nickel chloride were added to obtain the desired thermosetting phenolic resin. The final viscosity of the thermosetting phenolic resin was 45000±100 mPa•s (25℃). When kneaded under the conditions described in Example 1, the viscosity of the thermosetting phenolic resin was approximately 1400 mPa•s.

[0104] The resistivity, shape, and compressive strength of the graphite resin anodes obtained in the above implementation schemes are shown in Table 2. Regarding the shape, a cuboid carbon block with dimensions of 150mm*80mm*160mm was prepared according to the above method. The shape of the resin anodes obtained in each implementation scheme was then statistically analyzed. Specifically, the presence, number, and size of the cracks (e.g., length) of the resin anodes were recorded.

[0105] Table 2 Performance of various graphite resin anodes

[0106] In this application, the viscosity of the thermosetting phenolic resin should be controlled within a suitable range. When the viscosity of the thermosetting phenolic resin is too low, the following drawbacks will occur: 1. When the viscosity of the thermosetting phenolic resin is too low, it will not be able to effectively disperse and encapsulate the graphite material; therefore, during the preparation of the resin anode, the uneven dispersion of the graphite material will lead to a significant decrease in the conductivity and a significant increase in the resistivity of the resin anode. Furthermore, when the viscosity of the thermosetting phenolic resin is too low, it will not be able to effectively disperse and encapsulate the aggregate; therefore, during the preparation of the resin anode, the uneven dispersion of the aggregate will lead to a significant decrease in the compressive strength of the resin anode. 2. If the viscosity of the thermosetting phenolic resin is too low, it means that a large amount of solvent is provided when adding the thermosetting phenolic resin; therefore, more solvent needs to be removed during the preparation of the resin anode. The applicant has found that during the solvent removal process, the resin anode is prone to cracking, resulting in defective samples. 3. If the viscosity of the thermosetting phenolic resin is too low, its adhesion to other aggregates in the resin anode will be poor. During the preparation of the resin anode, it is compressed and shaped under pressure during the molding stage. After the pressure is released, due to poor adhesion, the molded resin anode springs back in shape and increases in volume. This directly leads to poor contact between graphite materials, reduced density of the graphite materials, and consequently, increased resistance of the resin anode, affecting its conductivity. Conversely, if the viscosity of the resin anode is too high, it will be impossible to work with and difficult to mix. Furthermore, regarding the compressive strength of the resin anode, based on the premise that high-viscosity thermosetting phenolic resin provides uniform dispersion of aggregates and graphite materials, a stronger bonding network will be formed after the resin cures, ultimately improving the compressive strength of the resin anode. When the viscosity of the thermosetting phenolic resin is sufficiently high, the graphite materials and aggregates are already sufficiently uniformly dispersed. Increasing its viscosity will not significantly change the conductivity and compressive strength of the resin anode; especially its compressive strength, which will be limited by the strength of the aggregates and cannot be further improved. In addition, the resulting resin anode is prone to cracking. For example, the resin anodes of Comparative Examples 8-9 showed obvious cracking.

[0107] Examples 9-12 The only differences between Examples 9-12 and Example 1 are the particle size of the selected graphite material and / or the amount added during mixing, as detailed below: In Example 9, the graphite material was prepared by pulverizing commercially available graphite material to a 100-mesh sieve and collecting the sieve residue. The graphite material had an ash content ≤0.2 wt.%, a resistivity ≤100 μΩ·m for the sieve residue (i.e., graphite powder), a sulfur content ≤0.5 wt%, and contained no metallic impurities. The amount of graphite material added during mixing was 13 parts by weight.

[0108] In Example 10, the graphite material was prepared by pulverizing commercially available graphite material to a 300-mesh sieve and collecting the sieve residue. The graphite material had an ash content ≤0.2 wt.%, a resistivity ≤100 μΩ·m for the sieve residue (i.e., graphite powder), a sulfur content ≤0.5 wt%, and contained no metallic impurities. The amount of graphite material added during mixing was 13 parts by weight.

[0109] In Example 11, the graphite material was prepared by pulverizing commercially available graphite material to a 500-mesh sieve and collecting the sieve residue. The graphite material had an ash content ≤0.2 wt.%, a resistivity ≤100 μΩ·m for the sieve residue (i.e., graphite powder), a sulfur content ≤0.5 wt%, and contained no metallic impurities. The amount of graphite material added during mixing was 20 parts by weight.

[0110] In Example 12, the graphite material was prepared by pulverizing commercially available graphite material to a 50-mesh sieve and collecting the sieve residue. The graphite material had an ash content ≤0.2 wt.%, a resistivity ≤100 μΩ·m for the sieve residue (i.e., graphite powder), a sulfur content ≤0.5 wt%, and contained no metallic impurities. The amount of graphite material added during mixing was 13 parts by weight.

[0111] The resistivity and compressive strength of the graphite resin anodes obtained by the above implementation scheme are shown in Table 3.

[0112] Table 3 Performance of various graphite resin anodes

[0113] The data in Table 3 shows that the particle size of the graphite material should not be too large, such as the 50-mesh sieve undersize in Example 12. Excessively large particle size results in poor dispersibility in the resin anode, directly affecting the resistivity of the prepared resin anode. Conversely, the particle size should not be too small, such as the 500-mesh sieve undersize in Example 11. This would result in excessively fine graphite, which, while significantly improving the conductivity of the resin anode, also exhibits lubricating properties, directly reducing the compressive strength of the prepared resin anode.

[0114] Example 13 The only difference between this embodiment and Embodiment 1 is that lignin is not added during the preparation of the thermosetting phenolic resin. The preparation method of the thermosetting phenolic resin selected in this embodiment is as follows: According to the weight proportions, 300g of phenol, 429g of 37% formaldehyde, and 6g of triethylamine were added to a reaction flask, and the temperature was raised to 73-75℃ and held at this temperature for 2 hours. Subsequently, the mixture was dehydrated under reduced pressure until the viscosity reached 40000±100cp / 25℃. Then, 2g of ferric chloride and 6g of nickel chloride were added to obtain the desired thermosetting phenolic resin. The final viscosity of the thermosetting phenolic resin was 40000±100 mPa•s(25℃) / 25℃.

[0115] Examples 14-16 The only difference between the following examples and Example 1 is the amount of lignin added during the preparation of the thermosetting phenolic resin, as shown in the table below.

[0116] Table 4 Performance of various graphite resin anodes

[0117] In this application, the addition of lignin can improve the brittleness of thermosetting phenolic resin. However, if too much lignin is added, it will also affect the adhesiveness of the phenolic resin, thereby affecting the resistivity and compressive strength of the prepared resin anode.

[0118] Examples 17-20 The only difference between the following examples and Example 1 is the molding temperature during step (c), as detailed in the table below. The volumetric deformation test method involves preparing a rectangular green carbon block with dimensions of 150mm*80mm*160mm according to the above method, processing it according to step (d), measuring the length, width, and height of the resulting resin anode, calculating its volume, and comparing it with the volume of the green carbon block to obtain the volumetric deformation percentage: (Volume of green carbon block in Example 1 - Volume of resin anode in Example 2) / Volume of green carbon block in Example 1 × 100%. In practical industrial applications, the allowable deviation in the volume of the prebaked anode is within 3%.

[0119] Table 5 Performance of various graphite resin anodes

[0120] Excessively high molding temperatures can cause the paste to dry out during mixing, resulting in low bulk density during molding. Conversely, excessively low molding temperatures can lead to poor resin flowability, hindering the resin's ability to fully wet the aggregate and penetrate its interior, also resulting in low bulk density. Low bulk density ultimately affects several product properties, such as resistivity, compressive strength, flexural strength, air reactivity, and carbon dioxide reactivity.

[0121] The description in this disclosure is provided for illustrative and descriptive purposes only and is not intended to be exhaustive or to limit the disclosure to its forms. Many modifications and variations will be apparent to those skilled in the art. The embodiments were chosen and described in order to better illustrate the principles and practical application of this disclosure and to enable those skilled in the art to understand this disclosure and to design various embodiments with various modifications suitable for a particular purpose.

Claims

1. A graphitic resin anode, comprising the following raw materials in parts by weight: Graphite material 5-25 parts by weight; petroleum calcined coke 60-85 parts by weight; thermosetting phenolic resin material 10-15 parts by weight; asphalt 0-1 parts by weight; in, The viscosity of the thermosetting phenolic resin is ≥16000 mPa•s (25℃).

2. The graphitic resin anode according to claim 1, wherein, The viscosity of the thermosetting phenolic resin is 20,000~60,000 mPa•s (25℃), preferably 30,000~50,000 mPa•s (25℃).

3. The graphitic resin anode according to claim 1 or 2, wherein, The thermosetting phenolic resin is a lignin-modified thermosetting phenolic resin. Preferably, the preparation method of the thermosetting phenolic resin includes: alkali-catalyzed polycondensation of phenol and formaldehyde, lignin-filled blending, and metal ion complexation.

4. The graphitic resin anode according to claim 3, wherein, The phenol and formaldehyde undergo alkali-catalyzed condensation polymerization, reacting at 70-78°C for 0.5-3.5 hours; and / or During the alkali-catalyzed polycondensation of phenol and formaldehyde, the alkali-catalyzed catalyst is selected from any one or more combinations of the following: triethylamine, triethanolamine, imidazoles, sodium hydroxide, calcium hydroxide, barium hydroxide, and ammonia; and / or During the catalytic condensation of phenol and formaldehyde, the molar ratio of phenol to formaldehyde is less than 1:

1.

5. The graphitic resin anode according to claim 3 or 4, wherein, When the lignin-filled blend is used, the mass ratio of lignin to phenol is ≥1:3; preferably (1~3):3; more preferably (1~1.5):

3.

6. The graphitic resin anode according to any one of claims 3 to 5, wherein, After the lignin filler is blended, it is further dehydrated to a viscosity ≥16000 mPa•s (25℃); preferably 20000~60000 mPa•s (25℃); more preferably 30000~50000 mPa•s (25℃).

7. The graphitic resin anode according to any one of claims 1 to 6, wherein, The graphite material has a particle size ≤ 0.08 mm; preferably 0.03~0.075 mm; more preferably 0.05~0.075 mm; and / or The ash content of the graphite material is ≤0.2wt%; and / or The resistivity of the graphite material is ≤100 μΩ·m; and / or The sulfur content in the graphite material is ≤0.5wt%.

8. The graphitic resin anode according to any one of claims 1 to 7, wherein, Based on the total weight of the calcined petroleum coke, the calcined petroleum coke comprises the following parts by weight of raw materials: 25-45 parts of 200-mesh calcined petroleum coke, 5-15 parts of 0-1mm calcined petroleum coke, 15-30 parts of 1-3mm calcined petroleum coke, and 15-30 parts of 3-6mm calcined petroleum coke.

9. The graphitic resin anode according to any one of claims 1 to 8, wherein, The softening point of the asphalt is 105~115℃; and / or The asphalt contains ≥18wt% β-resin, and / or The coking value of the asphalt is ≥54%.

10. A method for preparing the graphitic resin anode according to any one of claims 1 to 9, comprising the following steps: Mixing: Mixing and kneading petroleum calcined coke, graphite materials, thermosetting phenolic resin and asphalt; Molding: The mixed materials are vibrated to form a green body; or, the mixed materials are vibrated to form a green body and then flash-cured to obtain a green body. Calcination: The green blank is calcined and then cooled to obtain the graphitic resin anode.

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