CN116813349A - Graphite box plate material for negative electrode material graphitized box furnace and preparation method thereof - Google Patents
Graphite box plate material for negative electrode material graphitized box furnace and preparation method thereof Download PDFInfo
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- CN116813349A CN116813349A CN202310925589.5A CN202310925589A CN116813349A CN 116813349 A CN116813349 A CN 116813349A CN 202310925589 A CN202310925589 A CN 202310925589A CN 116813349 A CN116813349 A CN 116813349A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000010439 graphite Substances 0.000 title claims abstract description 60
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 60
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 46
- 239000000571 coke Substances 0.000 claims abstract description 31
- 239000010426 asphalt Substances 0.000 claims abstract description 28
- 238000000465 moulding Methods 0.000 claims abstract description 22
- 238000005087 graphitization Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000002006 petroleum coke Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000004898 kneading Methods 0.000 claims abstract description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 11
- 230000006698 induction Effects 0.000 claims description 9
- 238000007580 dry-mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 239000011294 coal tar pitch Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005056 compaction Methods 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 3
- 230000008569 process Effects 0.000 abstract description 7
- 239000007770 graphite material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000003763 carbonization Methods 0.000 abstract description 5
- 239000002360 explosive Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000010406 cathode material Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000000462 isostatic pressing Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011295 pitch Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011300 coal pitch Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- 241000274582 Pycnanthus angolensis Species 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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
- C04B35/522—Graphite
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a graphite box plate material for a negative electrode material graphitizing box furnace and a preparation method thereof, wherein the preparation method specifically comprises the following steps: s1: kneading the dried aggregate and the binder into paste, wherein the aggregate is prepared by mixing graphitized petroleum coke, graphitized asphalt coke and raw coke; s2: molding the paste obtained in the step S1 into a green body; s3: and (3) cooling the green body obtained in the step (S2), and roasting for one time to obtain the graphite box plate material for the negative electrode material graphitization box furnace. The graphite box plate material prepared by the invention has good volume density and mechanical strength, and has the matching of holes with different sizes, so that the purpose that the graphite box plate material can block combustible and explosive small molecular gas and organic substances in the high-temperature carbonization process of the negative electrode graphite material is realized.
Description
Technical Field
The invention belongs to the technical field of carbon graphite materials, relates to a graphite box plate for a box-type furnace, and in particular relates to a graphite box plate material for a box-type furnace by graphitizing a negative electrode material and a preparation method thereof.
Background
The energy density of a lithium ion battery depends on the cathode material to a great extent, and from commercialization of the lithium ion battery to the present, the cathode material used is the most mature and most widely used carbon graphite material.
The graphite anode material must undergo graphitization treatment to complete crystallization of the microstructure, and the graphitization process can be classified into a direct method and an indirect method according to a heating mode and can be classified into an intermittent type and a continuous type according to an operation mode. The common negative electrode graphitizing furnaces include Acheson graphitizing furnaces, internal series graphitizing furnaces, grid box plate graphitizing furnaces and the like. The quality of the cathode materials produced by different furnace types is obviously different because of great differences in the furnace loading modes and production processes of various furnace types, the use of carbon crystal substance powder, auxiliary materials and the like. The Acheson furnace is characterized in that a negative electrode blank is placed in a single-hole crucible, an electric heating carbon crystal substance powder is filled in a furnace core, an outer layer is insulated by a heat insulation material and a furnace wall, high temperature of 2800-3100 ℃ is generated mainly by heating the carbon crystal substance powder after electrification, the negative electrode material in the crucible is indirectly heated, and finally high-temperature graphitization of the negative electrode material is achieved. The internal string graphitizing furnace is to put the cathode blank into a porous crucible, then put the crucible into the graphitizing furnace in a serial connection mode end to end, the electrode crucible is used as a carrier and a heating body, and the current generates high temperature through the electrode crucible to directly heat the internal cathode material. And after the two sides and the upper cover are filled with heat preservation materials, graphitization is completed through power transmission. The box plate graphitizing furnace is characterized in that a negative electrode blank is directly placed into a large box body which is installed by a carbon plate or a carbon graphite plate in advance, a carbon graphite cover plate is used as a resistor, and heat preservation materials are placed on the upper part and the two sides of the box plate graphitizing furnace, and then high-temperature heating is completed through power transmission. The technical characteristics of the traditional Acheson graphitizing furnace and the serial graphitizing furnace are combined, the upright posts and the anode plates which form the material box structure form a heating body together, current is sent into a furnace core heating body through a furnace end electrode, and the generated high temperature directly heats the cathode material in the furnace core heating body, so that the purpose of rapid and efficient graphitization is achieved. Meanwhile, the effective loading capacity of the box plate type graphitizing furnace is 1-2 times that of a common Acheson furnace single-hole crucible furnace, so that the graphitizing efficiency of the cathode blank can be greatly improved. So the box plate type graphitizing furnace is widely used.
However, the graphite box plates adopted by the existing box plate type graphitizing furnace have low density and low mechanical strength, and volatile matters and combustible gas are generated in the graphitizing process of the cathode material, so that high-pressure furnace spraying accidents are extremely easy to cause. Therefore, how to improve the volume density and the mechanical strength of the graphite box plate material for the box plate type graphitization furnace and regulate the open porosity of the box plate material are technical problems to be solved urgently by the person skilled in the art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the graphite box plate material for the negative electrode material graphitization box furnace and the preparation method thereof, and the prepared graphite box plate material has good volume density and mechanical strength and has the matching of holes with different sizes, so that the purpose that the graphite box plate material can block combustible and explosive small molecular gas and organic substances in the high-temperature carbonization process of the negative electrode graphite material is realized.
The technical scheme of the invention is realized as follows:
the preparation method of the graphite box plate material for the negative electrode material graphitized box furnace specifically comprises the following steps:
s1: kneading the dried aggregate and the binder into paste, wherein the aggregate is prepared by mixing graphitized petroleum coke, graphitized asphalt coke and raw coke;
s2: molding the paste obtained in the step S1 into a green body;
s3: and (3) cooling the green body obtained in the step (S2), and roasting for one time to obtain the graphite box plate material for the negative electrode material graphitization box furnace.
Further, the aggregate comprises primary aggregate, secondary aggregate, tertiary aggregate and quaternary aggregate according to the particle size, wherein the particle size D of the primary aggregate 1 Is not less than 3D 1 Less than or equal to 6mm, and accounting for 26-28% of all aggregate; particle diameter D of secondary aggregate 2 Is 1 to be less than or equal to D 2 Less than 3mm, the mass of the aggregate accounts for 21-23% of the total aggregate; particle diameter D of three-stage aggregate 3 Is 0 < D 3 Less than or equal to 1mm, and accounts for 13-15% of all aggregate; the four-level aggregate is mixed powder of graphitized petroleum coke and graphitized asphalt coke, the D50 of the four-level aggregate is 55-65 mu m, and the mass of the four-level aggregate accounts for 36-38% of the total aggregate.
Wherein the mass ratio of the graphitized petroleum coke, the graphitized asphalt coke and the raw coke in the primary aggregate, the secondary aggregate and the tertiary aggregate is 7-9:1-3:0.5-0.9; the mass ratio of the graphitized petroleum coke powder to the graphitized asphalt coke powder in the four-stage aggregate is 7-9:1-3.
Further, the drying temperature is 180-200 ℃ and the drying time is 1-2 h when the aggregate is dried.
Further, the binder is a mixture of modified medium-temperature coal tar pitch and a naphthalene binder, wherein the naphthalene binder accounts for 3-5 wt% of the binder.
Further, the viscosity of the naphthalene-based adhesive is less than or equal to 100 mPa.s, and the carbon residue value is more than or equal to 60%.
Further, in the step S1, the mass ratio of the aggregate to the binder is 3-4:1.
Further, the specific steps of step S1 are as follows: firstly dry-mixing the aggregate at 150-160 ℃ for 20-30 min, then adding the liquid binder twice for wet-mixing, wherein the wet-mixing temperature is 180-200 ℃ and the wet-mixing time is 30-50 min, so that the binder is completely wrapped on the surface of the aggregate, and the paste is obtained.
Further, the specific steps of step S2 are as follows: vibration molding assisted mold pressing under the induction of a thermomagnetic field of a vulcanizing press is used, the mold pressing temperature is 160-170 ℃, the molding pressure is 4-6 MPa, and the pressure maintaining time is 50-70 s; and then carrying out isostatic compaction, wherein the molding pressure is 160-200 MPa, and the pressure maintaining time is 9-11 min, so as to obtain the green body.
Further, during primary roasting, the green body is placed in a stainless steel crucible, the green body is buried by a buried material, then the green body is placed in a roasting furnace, nitrogen or argon is introduced in the roasting process, the green body is roasted for 2 to 4 hours at 900 to 1200 ℃, after the temperature is reduced to 150 to 300 ℃ through program control, the green body is naturally cooled to room temperature, and the volume density of 1.70 to 1.72g/cm is obtained 3 Is used for graphitizing the graphite box plate material for the box-type furnace.
Compared with the prior art, the invention has the following beneficial effects:
1. the method for designing the sleeve baby adopts a multi-element cooperative construction of a mutual wrapping structure of large, medium and small fine powder particles and a multi-level hole, and can effectively improve the volume density and mechanical strength of the graphite box plate material by adopting a vibration molding auxiliary mould pressing mode under the induction of a thermomagnetic field, meanwhile, the cooperative construction of multi-level aggregate can realize the collocation of different holes of the graphite box plate material, the formed pore structure is beneficial to the gas discharge and is not beneficial to the entry of external gas, and in the high-temperature carbonization process of the negative electrode graphite material, the pressure in the furnace is higher than the external pressure, so that the external gas is difficult to enter the furnace, and the purpose that the box plate carbon material can block combustible and explosive small molecular gas and organic matters in the high-temperature carbonization process of the negative electrode graphite material is realized.
2. The invention adopts the mixture of naphthalene-based binder and modified medium-temperature coal tar pitch as the binder, which not only plasticizes the aggregate and leads the whole paste to have higher pressure side transmission coefficient and leads the briquette to have enough density and strength, but also leads the two binders of naphthalene-based binder and modified medium-temperature coal tar pitch to have similar physical and chemical properties with the aggregate, thereby coking and forming sticky coke when roasting, leading the aggregate to be solidified into a whole and leading the whole block to have mechanical strength, thereby being beneficial to improving the mechanical strength of the graphite box plate material. In addition, the naphthalene-based adhesive is mostly formed by crosslinking 3-4 benzene rings, and has the advantages of high carbon residue, good fluidity, narrow molecular weight distribution and the like, for example, naphthalene asphalt, and the addition of the naphthalene-based adhesive can fully and uniformly wet aggregate after the adhesive is melted into liquid and permeate into gaps among aggregate powder, so that the volume density and the mechanical strength of the graphite box plate material are further improved.
3. The carbon material of the box plate prepared by the method has smaller hardness and is convenient for cutting and processing, so that the carbon material of the box plate has good processability. The kneading temperature and the forming temperature are higher, so that the uniformity of paste and briquettes is improved, and the uniformity of thermal expansion is guaranteed, and in addition, the design of the multi-hole sleeve doll can ensure that volatile gas is only discharged but not fed, and meanwhile, the effective conduction of heat can be realized, so that the problem that a box plate carbon material is easy to crack or the local spraying furnace is caused by excessive internal pressure of a graphitization box furnace due to volatile carbonization is avoided.
4. According to the invention, the graphitized petroleum coke, the graphitized asphalt coke and the raw coke are used as aggregate, and the graphitized petroleum coke can improve the overall heat and electric conductivity of the graphite box plate material due to the special drainage basin structure; and the forming mode of mould pressing and isostatic pressing can improve the volume density of the graphite box plate material, and is beneficial to the transmission of electrons and phonons, thereby being beneficial to improving the electric conduction and heat conduction capabilities of the graphite box plate material, and further being beneficial to the construction of a thermal field in the furnace when the box plate material prepared by the invention is used for manufacturing the box plate type graphitization furnace.
5. The preparation method is simple, convenient to operate and beneficial to industrialized popularization and application, and the prepared graphite box plate material has the flexural strength more than or equal to 12MPa, the compressive strength more than or equal to 37MPa, the Shore hardness more than or equal to 30HS and the bulk density more than or equal to 1.70g/cm 3 The resistivity is 25-40 mu omega m, and the current density is 0.05-2.8A/cm 2 Thermal shock resistance requirements of electrical loads.
Drawings
FIG. 1 is a polarized light micrograph of a pressed surface and a cross section of a graphite box plate material for a negative electrode material graphitization box furnace obtained in example 1.
FIG. 2 is a polarized light micrograph of a pressed surface and a cross section of a graphite box plate material for a negative electrode material graphitization box furnace obtained in example 2.
FIG. 3 is a polarized light micrograph of a pressed surface and a cross section of a graphite box plate material for a negative electrode material graphitization box furnace obtained in example 3.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
Example 1
Aggregate (27 wt% of primary aggregate with the particle size of [3mm,6mm ], 22wt% of secondary aggregate with the particle size of [1mm,3mm ], [1mm,3 mm), 14wt% of tertiary aggregate with the particle size of (0 mm,1 mm), 37wt% of quaternary aggregate with the D50 of 55-65 mu m, wherein the mass ratio of graphitized oil coke, graphitized asphalt coke and raw coke in the primary aggregate, the secondary aggregate and the tertiary aggregate is 8:1.2:0.8; the mass ratio of the graphitized petroleum coke powder to the graphitized asphalt coke powder in the four-stage aggregate is 8:2), and drying for 1h at 180 ℃ to remove the moisture in the aggregate and the gas adsorbed on the pore surfaces of the aggregate; and then dry-mixing for 30min at 160 ℃, and after dry-mixing uniformly, adding a liquid binder for wet-mixing, wherein the liquid binder is added in two steps, the temperature of the first addition is 180 ℃, the temperature of the second addition is 185 ℃, the wet-mixing time is 40min, and the binder completely wraps the surfaces of graphitized coke particles, so that a paste is obtained, wherein the binder is a mixture of modified medium-temperature coal tar pitch and naphthalene pitch, the naphthalene pitch accounts for 5wt% of the binder, and the mass ratio of the binder to the aggregate is 1:4.
And (3) taking the paste evenly kneaded out of the pot, using a vibration molding auxiliary mold under the induction of a thermomagnetic field of a vulcanizing press, wherein the temperature of the vibration molding auxiliary mold under the induction of the magnetic field is 165 ℃, the molding pressure is 5MPa, the pressure maintaining time is 60s, and then carrying out isostatic pressing, the molding pressure is 200MPa, and the pressure maintaining time is 10min, so as to obtain the box plate carbon block green compact.
Placing the green body in a stainless steel crucible, burying the green body with a burying material, placing in a roasting furnace, introducing nitrogen or argon during roasting, roasting at 1050 deg.C for 4 hr, cooling to 200deg.C under program control, naturally cooling to room temperature to obtain the product with volume density of 1.72g/cm 3 Is used for graphitizing the graphite box plate material for the box-type furnace.
Example 2
The method comprises the steps of (1) mixing aggregate (26 wt% of primary aggregate with the particle size of [3mm,6mm ], 23wt% of secondary aggregate with the particle size of [1mm,3mm ], [1mm,3 mm) and 15wt% of tertiary aggregate with the particle size of (0 mm,1 mm) with the particle size of 55-65 mu m and 36wt% of quaternary aggregate with the D50 of 55-65 mu m, wherein the mass ratio of graphitized petroleum coke, graphitized asphalt coke and raw coke in the primary aggregate, the secondary aggregate and the tertiary aggregate is 7:2.5:0.5; the mass ratio of the graphitized petroleum coke powder to the graphitized asphalt coke powder in the four-stage aggregate is 7:3), and the four-stage aggregate is baked for 1h at 190 ℃ to remove the moisture in the aggregate and the gas adsorbed on the pore surfaces of the aggregate; and then dry-mixing for 30min at 150 ℃, and after the dry-mixing and uniform mixing, adding a liquid medium-temperature binder for wet-mixing, wherein the liquid binder is added in a mode of adding the liquid binder twice, the temperature of the first addition is 190 ℃, the temperature of the second addition is 195 ℃, and the wet-mixing time is 50min, so that the binder completely wraps the surfaces of graphitized coke particles, thereby obtaining the paste, wherein the binder is a mixture of modified medium-temperature coal asphalt and naphthalene asphalt, the naphthalene asphalt accounts for 4wt% of the binder, and the mass ratio of the binder to the aggregate is 1:3.
And (3) taking the paste evenly kneaded out of the pot, using a vibration molding auxiliary mold under the induction of a thermomagnetic field of a vulcanizing press, wherein the temperature of the vibration molding auxiliary mold under the induction of the magnetic field is 160 ℃, the molding pressure is 4MPa, the pressure maintaining time is 70s, and then carrying out isostatic pressing, the molding pressure is 200MPa, and the pressure maintaining time is 10min, so as to obtain the box plate carbon block green compact.
Placing the green body in a stainless steel crucible, burying the green body with a burying material, placing in a roasting furnace, introducing nitrogen or argon during roasting, roasting at 1200deg.C for 3h, cooling to 300deg.C under program control, and naturally cooling to room temperature to obtain a product with a volume density of 1.71g/cm 3 Is used for graphitizing the graphite box plate material for the box-type furnace.
Example 3
Aggregate (28 wt% of primary aggregate with the particle size of [3mm,6mm ], 21wt% of secondary aggregate with the particle size of [1mm,3mm ], [1mm,3 mm), 13wt% of tertiary aggregate with the particle size of (0 mm,1 mm) and 38wt% of quaternary aggregate with the D50 of 55-65 mu m, wherein the mass ratio of graphitized oil coke, graphitized asphalt coke and raw coke in the primary aggregate, the secondary aggregate and the tertiary aggregate is 9:1:0.9; the mass ratio of the graphitized petroleum coke powder to the graphitized asphalt coke powder in the four-stage aggregate is 9:1), and the four-stage aggregate is baked for 2 hours at 200 ℃ to remove the moisture in the aggregate and the gas adsorbed on the pore surfaces of the aggregate; and then dry-mixing for 30min at 150 ℃, and after the dry-mixing and uniform mixing, adding a liquid medium-temperature binder for wet-mixing, wherein the liquid binder is added in a mode of adding the liquid binder twice, the temperature of the first addition is 180 ℃, the temperature of the second addition is 190 ℃, and the wet-mixing time is 30min, so that the binder completely wraps the surfaces of graphitized coke particles, and a paste is obtained, wherein the binder is a mixture of modified medium-temperature coal asphalt and naphthalene asphalt, the naphthalene asphalt accounts for 3wt% of the binder, and the mass ratio of the binder to the aggregate is 1:4.
And (3) taking the paste evenly kneaded out of the pot, using a vibration molding auxiliary mold under the induction of a thermomagnetic field of a vulcanizing press, wherein the temperature of the vibration molding auxiliary mold under the induction of the magnetic field is 170 ℃, the molding pressure is 6MPa, the pressure maintaining time is 70s, and then carrying out isostatic pressing, the molding pressure is 200MPa, and the pressure maintaining time is 10min, so as to obtain the box plate carbon block green compact.
Placing the green body in a stainless steel crucible, burying the green body with a burying material, placing in a roasting furnace, introducing nitrogen or argon during roasting, roasting at 900 ℃ for 4 hours, cooling to 150 ℃ under program control, and naturally cooling to room temperature to obtain the product with a volume density of 1.70g/cm 3 Is used for graphitizing the graphite box plate material for the box-type furnace.
Comparative example 1
This example is different from example 1 in that the aggregate in this example has a particle size of [3mm,6mm]27wt% of primary aggregate with the particle size of [1mm,3mm ], 22wt% of secondary aggregate with the particle size of (0 mm,1 mm), 51wt% of tertiary aggregate with the particle size of (0 mm,1 mm), and no quaternary aggregate with the D50 of 55-65 mu m. The volume density of the graphite box plate material for the graphitized box furnace of the obtained cathode material is 1.59g/cm 3 。
Comparative example 2
This example is different from example 1 in that the aggregate in this example has a particle size of [3mm,6mm]27wt% of a secondary aggregate with a particle size of [1mm,3 mm), 22wt% of a quaternary aggregate with a D50 of 55-65 μm, 51wt%. The volume density of the graphite box plate material for the graphitized box furnace of the anode material is 1.62g/cm 3 。
Comparative example 3
This example is different from example 1 in that the aggregate in this example has a particle size of [3mm,6mm]The weight percentage of the primary aggregate is 14 percent of the weight percentage of the tertiary aggregate with the particle size of (0 mm,1 mm) and the weight percentage of the quaternary aggregate with the D50 of 55-65 mu m is 37 percent. The volume density of the graphite box plate material for the graphitized box furnace of the anode material is 1.65g/cm 3 。
Comparative example 4
This embodiment is different from embodiment 1In this example, 49% by weight of the secondary aggregate having a particle size of [1mm,3mm ], 14% by weight of the tertiary aggregate having a particle size of (0 mm,1 mm) and 37% by weight of the quaternary aggregate having a D50 of 55 to 65. Mu.m were contained in the aggregate. The volume density of the graphite box plate material for the graphitized box furnace of the obtained cathode material is 1.67g/cm 3 。
Comparative example 5
The embodiment is different from embodiment 1 in that the aggregate does not contain graphitized petroleum coke, wherein the mass ratio of graphitized asphalt coke to raw coke in the primary aggregate, the secondary aggregate and the tertiary aggregate is 1.2:0.8; the four-level aggregate is graphitized asphalt coke powder. The volume density of the graphite box plate material for the graphitized box furnace of the anode material is 1.63g/cm 3 。
Comparative example 6
The embodiment is different from embodiment 1 in that the aggregate in the embodiment does not contain graphitized asphalt coke, wherein the mass ratio of graphitized asphalt coke to raw coke in the primary aggregate, the secondary aggregate and the tertiary aggregate is 8:0.8; the fourth-grade aggregate is all graphitized petroleum coke powder. The volume density of the graphite box plate material for the graphitized box furnace of the anode material is 1.62g/cm 3 。
Comparative example 7
This example is different from example 1 in that the aggregate in this example has a particle size of [3mm,6mm]9% by weight of secondary aggregate with the particle size of [1mm,3mm ], 14% by weight of tertiary aggregate with the particle size of (0 mm,1 mm) and 37% by weight of quaternary aggregate with the D50 of 55-65 mu m. The volume density of the graphite box plate material for the graphitized box furnace of the obtained cathode material is 1.67g/cm 3 。
Comparative example 8
This example is different from example 1 in that the binder in this example is a modified medium temperature coal pitch and no naphthalene pitch is included. The volume density of the graphite box plate material for the graphitized box furnace of the anode material is 1.69g/cm 3 。
Comparative example 9
This example is different from example 1 in that the binder in this example is naphthalene pitch and does not contain modified medium temperature coal pitch. The volume density of the graphite box plate material for the graphitized box furnace of the obtained cathode material is 1.57g/cm 3 。
Comparative example 10
This example is similar to example 1, except that naphthalene asphalt is 10wt% of the binder in this example. The volume density of the graphite box plate material for the graphitized box furnace of the anode material is 1.68g/cm 3 。
1. The graphite box sheet materials obtained in examples 1 to 3 and comparative examples 1 to 10 were tested for basic properties, and their basic properties are shown in table 1.
TABLE 1 basic Performance parameters of graphite Box Board materials obtained in examples 1-3 and comparative examples 1-10
As can be seen from the above table, the absence of any of the four grades of aggregate in the present invention results in a significant reduction in bulk density, and in addition, the change in the fraction ratio also results in a reduction in bulk density, and the absence or excess of naphthalene-based binder results in a reduction in bulk density and mechanical strength.
2. The polarized light micrographs of the pressed surface and the cross section of the graphite box plate material for a negative electrode material graphitized box furnace obtained in examples 1 to 3 are shown in fig. 1, 2 and 3, respectively, wherein (a) is a polarized light diagram of the pressed surface and (b) is a polarized light diagram of the cross section. The graph shows that the structure between the aggregates is compact, the pores among the particles are small, and no obvious cracks exist, so that the prepared graphite box plate material has excellent synchronous shrinkage performance, and the aggregates are well combined with the binder.
Finally, it should be noted that the above-mentioned examples of the present invention are only illustrative of the present invention and are not limiting of the embodiments of the present invention. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. Not all embodiments are exhaustive. Obvious changes and modifications which are extended by the technical proposal of the invention are still within the protection scope of the invention.
Claims (10)
1. The preparation method of the graphite box plate material for the negative electrode material graphitized box furnace is characterized by comprising the following steps of:
s1: kneading the dried aggregate and the binder into paste, wherein the aggregate is prepared by mixing graphitized petroleum coke, graphitized asphalt coke and raw coke;
s2: molding the paste obtained in the step S1 into a green body;
s3: and (3) cooling the green body obtained in the step (S2), and roasting for one time to obtain the graphite box plate material for the negative electrode material graphitization box furnace.
2. The method for preparing the graphite box plate material for the negative electrode material graphitization box furnace according to claim 1, wherein the aggregate comprises primary aggregate, secondary aggregate, tertiary aggregate and quaternary aggregate according to particle size, wherein the primary aggregate has particle size D 1 Is not less than 3D 1 Less than or equal to 6mm, and accounting for 26-28% of all aggregate; particle diameter D of secondary aggregate 2 Is 1 to be less than or equal to D 2 Less than 3mm, the mass of the aggregate accounts for 21-23% of the total aggregate; particle diameter D of three-stage aggregate 3 Is 0 < D 3 Less than or equal to 1mm, and accounts for 13-15% of all aggregate; the fourth-grade aggregate is mixed powder of graphitized petroleum coke and graphitized asphalt coke, the D50 of the fourth-grade aggregate is 55-65 mu m, and the mass of the fourth-grade aggregate accounts for 36-38% of the mass of all aggregates;
wherein the mass ratio of the graphitized petroleum coke, the graphitized asphalt coke and the raw coke in the primary aggregate, the secondary aggregate and the tertiary aggregate is 7-9:1-3:0.5-0.9; the mass ratio of the graphitized petroleum coke powder to the graphitized asphalt coke powder in the four-stage aggregate is 7-9:1-3.
3. The method for preparing a graphite box plate material for a negative electrode material graphitization box furnace according to claim 1, wherein the drying temperature is 180-200 ℃ and the drying time is 1-2 h when the aggregate is dried.
4. The method for preparing the graphite box plate material for the negative electrode material graphitization box furnace according to claim 1, wherein the binder is a mixture of modified medium-temperature coal tar pitch and naphthalene-based binder, and the naphthalene-based binder accounts for 3-5 wt% of the binder.
5. The method for preparing a graphite box plate material for a negative electrode material graphitization box furnace according to claim 1, wherein the viscosity of the naphthalene-based adhesive is less than or equal to 100 mPa.s, and the carbon residue value is more than or equal to 60%.
6. The method for preparing a graphite box plate material for a negative electrode material graphitization box furnace according to claim 1 or 4, wherein in the step S1, the mass ratio of the aggregate to the binder is 3-4:1.
7. The method for preparing the graphite box plate material for the negative electrode material graphitized box furnace according to claim 1, wherein the specific steps of the step S1 are as follows: firstly dry-mixing the aggregate at 150-160 ℃ for 20-30 min, then adding the liquid binder twice for wet-mixing, wherein the wet-mixing temperature is 180-200 ℃ and the wet-mixing time is 30-50 min, so that the binder is completely wrapped on the surface of the aggregate, and the paste is obtained.
8. The method for preparing the graphite box plate material for the negative electrode material graphitized box furnace according to claim 1, wherein the specific steps of the step S2 are as follows: vibration molding assisted mold pressing under the induction of a thermomagnetic field of a vulcanizing press is used, the mold pressing temperature is 160-170 ℃, the molding pressure is 4-6 MPa, and the pressure maintaining time is 50-70 s; and then carrying out isostatic compaction, wherein the molding pressure is 160-200 MPa, and the pressure maintaining time is 9-11 min, so as to obtain the green body.
9. A according to claim 1A process for preparing the graphite box plate material for graphitizing box furnace as negative electrode material includes such steps as calcining, loading raw blank in stainless steel crucible, loading raw blank in calcining furnace, calcining at 900-1200 deg.C for 2-4 hr, cooling to 150-300 deg.C, and natural cooling to room temp. to obtain the product with volume density of 1.70-1.72 g/cm 3 Is used for graphitizing the graphite box plate material for the box-type furnace.
10. The graphite box plate material for the negative electrode material graphitized box furnace is characterized by being prepared by adopting the preparation method of the graphite box plate material for the negative electrode material graphitized box furnace according to any one of claims 1-9.
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