CN115676815A - Manufacturing device and method for molten iron inoculated artificial graphite cathode material - Google Patents
Manufacturing device and method for molten iron inoculated artificial graphite cathode material Download PDFInfo
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- CN115676815A CN115676815A CN202210889452.4A CN202210889452A CN115676815A CN 115676815 A CN115676815 A CN 115676815A CN 202210889452 A CN202210889452 A CN 202210889452A CN 115676815 A CN115676815 A CN 115676815A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 244
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 122
- 229910021383 artificial graphite Inorganic materials 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000010406 cathode material Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
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- 239000010439 graphite Substances 0.000 claims abstract description 194
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- 239000002243 precursor Substances 0.000 claims abstract description 67
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- 238000001816 cooling Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000009736 wetting Methods 0.000 claims abstract description 9
- 238000006073 displacement reaction Methods 0.000 claims abstract description 7
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- 238000011081 inoculation Methods 0.000 claims description 25
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000005087 graphitization Methods 0.000 description 11
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- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 provides a device and a method for manufacturing an economical and environment-friendly molten iron inoculated artificial graphite cathode material, wherein the device mainly comprises the following steps: the device comprises a vacuum system, a furnace body, a heating and temperature measuring system, a graphite crucible, a piston assembly with enhanced dispersion function, a displacement control system and an artificial graphite powder negative pressure suction and cache system; the upper surface of a piston assembly (CP 1) is conical, the included angle between a bus and a central line of the piston assembly (CP 1) is less than 45 degrees, and a plurality of graphite rods are arranged at the bottom of the piston assembly (CP 1) to play a role in enhancing dispersion of forced flow and local shearing on a liquid/solid two-phase mixed material (L/S); the high-temperature molten iron has a wetting angle lower than 90 degrees to the graphite precursor fine powder, has higher saturated solubility to carbon elements, and has the capability of selectively dissolving amorphous carbon and surface high-activity carbon; and (L/S) cooling to a low-temperature range, and allowing carbon precipitated in low-temperature molten iron to realize epiphytic crystallization on the surface of the graphite powder to form the artificial graphite negative electrode material mainly with the coated core-shell structure.
Description
Technical Field
The invention belongs to the field of lithium ion secondary batteries, and particularly relates to an artificial graphite negative electrode material used in the lithium ion secondary battery, a novel molten iron inoculation manufacturing device and a manufacturing method thereof.
Background
The lithium ion secondary battery has high energy density and no memory effect, is widely applied to the fields of mobile phones, notebook computers, electric automobiles, energy storage and the like, is used as a power battery and an energy storage battery of the mobile energy of the electric automobiles or electric trucks at present, and has the market requirements of long service life, high energy density, good charge-discharge rate characteristic and low manufacturing cost. The graphite negative electrode material has high specific capacity, low reduction potential, good electrochemical reversibility, low volume expansion rate, high electronic conductivity and wide raw material sources, and is the mainstream negative electrode material of the current lithium ion secondary battery.
Commercial negative electrode materials mainly include artificial graphite and natural graphite. The natural graphite has the advantages of low cost and high compaction density, and has the main defects that the natural graphite powder has rough surface, more active sites and large specific surface area, and the reaction consumes more wasted lithium source in the process of forming an SEI film on the surface of a negative electrode active material during the first charge and discharge, so that the first charge and discharge efficiency is low; in addition, the polycrystal anisotropy of the natural graphite is obvious, the volume expansion of the negative electrode material is not easy to offset each other during charging/discharging, the battery is easy to bulge, the electrode group spacing fluctuation is large, and the cycle life of the battery is shortened rapidly; in addition, the anisotropy of the polycrystal also causes that the insertion/extraction of lithium ions can only be carried out from certain end faces of the graphite powder polycrystal, so that the effective insertion/extraction area is smaller, the charge/discharge rate characteristic of the battery is poorer, lithium is easy to precipitate during quick charge, and the safety of the battery is poorer.
At present, the mainstream of the industry is to use artificial graphite as a negative active material, such as the artificial graphite obtained by carrying out high-temperature graphitization treatment at 2800-3100 ℃ on all mesocarbon microbeads or calcined needle coke, wherein the polycrystalline body of the artificial graphite is basically isotropic, the surface of the powder is smooth, the number of active sites on the surface of the powder is relatively small, the specific surface area is small, the first efficiency of a battery is higher than that of natural graphite, the cycle life is long, the multiplying power characteristic is good, and the defects are that the artificial graphite needs to be graphitized at high temperature, the processing period is long, and the energy consumption is high; the high-temperature graphitization temperature of the prior artificial graphite is as high as 2800-3100 ℃, the graphitization degree of the graphite precursor is improved by mainly utilizing the thermal diffusion of carbon atoms at high temperature to participate in crystallization again, and the traditional Acheson graphitization furnace and the graphite precursor raw material powder bodyLoosely arranged in a graphite crucible, and the tap density is less than 1.10g/cm 3 (ii) a Carbon resistance granules are filled between graphite crucibles, 70-80% of heating heat is used for the process auxiliary materials and external heat insulation materials, in order to produce uniformity of products, heating and heat insulation time is required to be nearly 15 days, cooling time is nearly 10 days, the processing period of one furnace is nearly one month, the whole energy consumption is high, the effective energy utilization rate is low, the processing period is long, the capital occupation period is long, and the method becomes a bottleneck link of reducing cost of artificial graphite.
In order to reduce the cost of the artificial graphite, the mainstream improvement on the raw material is to adopt a core-shell structure coated product, for example, natural graphite powder or needle coke powder is coated and modified by adopting graphite precursors such as asphalt or furfural resin, and then medium/high temperature carbonization and high temperature graphitization are carried out to prepare the artificial graphite, so that the coating process is complex, the product manufacturing period is long, and the overall energy consumption is still high; in addition, the interface strength between the shell and the core of the traditional coating type artificial graphite powder material is limited, the coating uniformity is difficult to control, and the coating shell layer is easily crushed during strong rolling during the manufacture of the negative pole piece, so that the first effect and the cycle life quality of the battery are fluctuated.
The invention is provided in order to overcome the disadvantages of the existing method and device for manufacturing the artificial graphite cathode material.
Disclosure of Invention
The invention provides a manufacturing device and a method for inoculating artificial graphite cathode material with molten iron, which are economical, environment-friendly, high in energy utilization efficiency, high in production speed, high in product graphitization degree and high in primary efficiency, and the manufacturing device is mainly technically characterized by mainly comprising the following steps: the device comprises a vacuum system, a water-cooled furnace body, an electromagnetic induction heating and temperature measuring system, a graphite crucible for inoculating an artificial graphite cathode material with molten iron in the furnace body, an attached heat-insulating layer of the graphite crucible, a graphite main piston (CP 1)/graphite auxiliary piston (CP 2) assembly with enhanced dispersion function, two independent up-down displacement control systems thereof, and an artificial graphite powder negative pressure suction and cache system; the graphite main piston (CP 1)/graphite auxiliary piston (CP 2) combination with the enhanced dispersion function has the following main characteristics: (T1), the graphite main piston (CP 1) is in clearance fit with the inner circle of the graphite crucible and can controllably and independently move up and down for adjustment; (T2) the upper surface of the graphite main piston (CP 1) is a conical slope surface for preventing molten iron and graphite precursor fine powder from being retained to influence the uniformity of the product, and the included angle between a bus of the conical slope surface and the center line of the graphite main piston (CP 1) is less than 45 degrees, and more preferably less than or equal to 30 degrees; (T3), more than 10 graphite rods are fixedly installed at the bottom of the (CP 1) of the graphite main piston, the diameter of each graphite rod is 20-60 mm, and when the graphite main piston (CP 1) moves up and down for dispersion, the graphite rods fixed at the bottom have the enhanced dispersion function of forced flowing and local shearing on liquid/solid two-phase mixed materials (L/S) of molten iron and graphite precursor fine powder; (T4), a through hole (H1) is formed in the graphite main piston (CP 1), a graphite auxiliary piston (CP 2) is in clearance fit with the inner circle of the through hole (H1), the graphite auxiliary piston (CP 2) is parallel to or coincided with the central line of the graphite main piston (CP 1), the graphite auxiliary piston (CP 2) can independently and controllably move up and down relative to the graphite main piston (CP 1), and the graphite auxiliary piston and the graphite main piston (CP 1) are combined in up and down coordinated motion, so that a liquid/solid two-phase mixture (L/S) of molten iron and graphite precursor fine powder can be enhanced and dispersed; (T5) a through hole (H2) is formed in the center of the graphite auxiliary piston (CP 2) and used for adsorbing the graphite precursor fine powder packaged in the steel barrel under negative pressure or directly spraying the graphite precursor fine powder into the molten high-temperature molten iron in a positive pressure gas flow conveying mode through the through hole (H2) and a graphite pipe extending and immersed in the molten iron; the manufacturing device is provided with small holes (H3) and/or (H4) and/or (H5) on the side wall of the upper part of a graphite crucible, and is provided with a corresponding graphite pipeline, wherein the (H3) and/or (H4) are used for blowing inert gas from the outside to fluidize artificial graphite powder floating from molten iron, and the (H5) is used for transferring the fluidized artificial graphite powder to an external buffer storage bin by adopting a negative pressure suction mode, buffering and continuously cooling; the artificial graphite powder negative pressure suction and buffer system can also adopt the following technical scheme: when the artificial graphite powder floating to the surface of molten iron is collected, inert gases such as nitrogen or argon are blown from a through hole (H2) in the center of the auxiliary piston (CP 2) and a graphite pipe extending out of the through hole, and the artificial graphite powder is sucked into the buffer container by adopting a negative pressure dust suction mode from (H3) and/or (H4) and/or (H5) to the outside at the same time or respectively.
The invention relates to a manufacturing method of a molten iron inoculated artificial graphite cathode material, which utilizes the characteristics that high-temperature molten iron has better wetting capacity to graphite precursor refined powder in a high-temperature range of 1850-2150 ℃ (TH), a wetting angle is less than 90 degrees, the high-temperature molten iron in The (TH) high-temperature range has preferential selective dissolution characteristic to amorphous area part carbon and surface high-activity carbon in the graphite precursor refined powder compared with crystalline carbon in the graphite precursor refined powder, the high-temperature molten iron has relatively higher saturated solubility to carbon element in the graphite precursor refined powder, and the graphite three-point piston assembly utilizes the technical characteristics in The (TH) high-temperature range, enhances and disperses the graphite precursor refined powder in the high-temperature molten iron, and uniformly disperses the graphite precursor refined powder in the high-temperature molten iron, continuously pressing the graphite precursor fine powder by using a graphite piston assembly and immersing the graphite precursor fine powder in high-temperature molten iron, wherein the total time for high-temperature inoculation of the immersed graphite precursor fine powder in a (TH) high-temperature interval is 30-360 minutes, and preferably 60-120 minutes in consideration of balance of production efficiency and quality, so that the dissolution of carbon in an amorphous region part of the graphite precursor fine powder and the erosion of high-activity carbon on the surface of powder by the high-temperature molten iron are realized, meanwhile, a certain thermal diffusion and recrystallization process can be carried out on carbon elements in the graphite precursor fine powder in The (TH) high-temperature interval, and the high-temperature inoculation treatment in the enhanced dispersion and pressing states of The (TH) high-temperature interval can also be alternately carried out in multiple time periods; then keeping the liquid/solid mixture of the molten iron and the graphite precursor refined powder subjected to high-temperature inoculation continuously pressed by the graphite piston assembly, simultaneously cooling the molten iron and the graphite precursor refined powder from The (TH) high-temperature range to a 1350-1650 ℃ (TL) low-temperature range, wherein the relatively low-temperature molten iron has relatively low saturated solubility to carbon elements in the cooling process, supersaturated carbon dissolved in the molten iron can be dynamically separated out from the molten iron, part of the separated carbon can realize epiphytic crystallization on the surface of the graphite precursor refined powder, and a small part of the carbon is directly separated out from the molten iron to grow into artificial graphite powder, and after the temperature is reduced to The (TL) temperature range and the total time of low-temperature inoculation is kept between 30-360 minutes, the artificial graphite powder is subjected To (TL)The reinforced dispersion of the temperature interval and the low-temperature inoculation treatment under the pressing state can also be alternately carried out in a plurality of time periods, preferably, the total time of the low-temperature inoculation is kept between 60 and 120 minutes, and the artificial graphite powder mainly in a natural cladding type core-shell structure is formed; moving the graphite piston assembly upwards, floating the artificially coated graphite powder or partially naturally precipitated graphite powder to a position above the liquid level of the low-temperature molten iron by using the poor wettability of the relatively low-temperature molten iron in the low-temperature range (TL) and the wetting angle of the artificially coated graphite powder to be larger than 90 degrees and using the huge density difference between the artificially coated graphite powder and the low-temperature molten iron, sucking the floated graphite powder out by using negative pressure, storing the graphite powder in a material buffer container, continuously cooling the artificially coated graphite powder to 200 ℃ under the protection of inert gas or under the vacuum condition, discharging the graphite powder out of the furnace, sorting particles and removing magnetism to obtain the molten iron inoculated artificial graphite cathode material, wherein the XRD test d002 is smaller than 0.3390 nm, and the true density is 2.17-2.27g/cm 3 The gram capacity is more than 350mAh/g, and the first charge-discharge efficiency is more than 93%.
The manufacturing method of the molten iron inoculated artificial graphite cathode material mainly comprises the following main steps:
step1, preparing graphite precursor fine Powder (PG), wherein the graphite precursor raw material comprises one or more of metallurgical coke, anthracite, needle coke, shot coke, natural graphite, asphalt powder, hard carbon and other carbon materials, the graphite precursor raw material is purified by acid washing and/or alkali washing, neutralized and dried, and optionally subjected to high-temperature calcination or carbonization treatment, so that the volatilization weight loss is less than 0.5 percent and the ash content is less than 0.5 percent after 900 ℃/30 minutes of treatment under the protection of inert gas, the granularity of the powder after crushing and grading is controlled to be 5-22 micrometers and D95 is less than 35 micrometers, and the graphite precursor fine Powder (PG) is obtained;
step2, preparing high-temperature molten iron by vacuum induction smelting, performing enhanced dispersion and high-temperature inoculation on graphite precursor fine Powder (PG) in the high-temperature molten iron, filling inert gases such as nitrogen or argon into a vacuum chamber after vacuumizing for protection, heating the molten iron to more than 1350 ℃, more preferably more than 1550 ℃ and less than 2150 ℃ by induction, conveying the whole package of graphite precursor fine powder materials packaged in a steel barrel into the molten iron by adopting a graphite auxiliary piston (CP 2) with a central through hole (H2) in a negative pressure adsorption mode, or directly spraying and blowing the graphite precursor fine powder materials into the molten iron by adopting a positive pressure gas flow conveying mode through the central through hole (H2) and a graphite pipe extending and immersed in the molten iron; then heating molten iron and a liquid/solid two-phase mixed material (L/S) of graphite precursor fine powder to a high-temperature range (TH) of 1850-2150 ℃, performing enhanced dispersion processing on the liquid/solid mixed material in the high-temperature range (TH), wherein during the enhanced dispersion processing, a combination of a graphite main piston (CP 1) and a graphite auxiliary piston (CP 2) performs controllable up/down displacement movement, and the two move/move or do coordinated and matched movement on you/me and the lower/me, combining and utilizing the forced flow and local shearing functions of a plurality of graphite rods fixed on the bottom surface of the main piston to the liquid/solid two-phase mixed material (L/S), and the combination of the graphite main piston (CP 1) and the graphite auxiliary piston (CP 2) can perform the enhanced dispersion function on the liquid/solid two-phase mixed material (L/S); then, in a high-temperature interval of (TH), a graphite main piston (CP 1) and a graphite auxiliary piston (CP 2) are adopted together to press and immerse the graphite precursor fine powder in high-temperature molten iron for high-temperature inoculation, and the total time is 30-360 minutes;
step3, performing low-temperature inoculation and negative pressure suction transfer on the artificial graphite powder, cooling the mixture of the graphite precursor fine powder subjected to high-temperature inoculation and molten iron to a 1350-1650 ℃ (TL) interval under a pressing state, and performing low-temperature inoculation on the molten iron in The (TL) low-temperature interval for 30-360 minutes, preferably 60-120 minutes; then moving the graphite main piston (CP 1) and the graphite auxiliary piston (CP 2) upwards together, naturally floating the artificial graphite powder after realizing natural coating and a small part of the analyzed artificial graphite powder above the liquid level of molten iron, then blowing inert gas from (H2) or a graphite pipe extending out of the (H2) by adopting inert gas such as nitrogen or argon and the like to fluidize the artificial graphite powder after floating in the molten iron, simultaneously sucking the fluidized artificial graphite powder from (H3) and/or (H4) and/or (H5) by utilizing a negative pressure suction mode, and transferring the fluidized artificial graphite powder to a material buffer container for continuous cooling; or inert gases such as nitrogen or argon are used for introducing gas from (H3) and/or (H4) to fluidize the artificial graphite powder floating in the molten iron, and the fluidized artificial graphite powder is pumped out from (H5) by utilizing negative pressure and transferred to a material buffer container for continuous cooling; cooling the artificial graphite powder to below 200 ℃ under the protection of inert gas or under the vacuum condition, discharging, and sorting and demagnetizing particles to obtain a molten iron inoculated artificial graphite cathode material;
and Step4, continuously feeding a next batch of graphite precursor fine powder material into the molten iron, and repeatedly manufacturing the artificial graphite cathode material by the high/low temperature molten iron inoculation.
The advantages of the present invention are further explained below.
In order to prolong the service life of the graphite crucible and/or the graphite/ceramic composite material crucible and/or the graphite piston assembly and prevent the molten iron from excessively corroding graphite materials in the parts at high temperature, the initial carbon content in the raw material molten iron is preferably more than 4.5 percent when the high-temperature molten iron is prepared by vacuum induction melting.
In order to balance the graphitization speed and graphitization degree, reduce radiation loss at high temperature and ensure the service life of a graphite crucible and a graphite piston, the highest temperature range (TH) of molten iron inoculation is preferably controlled to be 1850-2150 ℃; considering that the wetting angle of the high-temperature molten iron and the graphite precursor refined powder in the temperature range of 1850-2150 ℃ is lower than 90 ℃, the graphite piston assembly with the enhanced dispersion function is convenient to disperse the graphite precursor refined powder in the high-temperature molten iron uniformly at first, and then the graphite piston assembly is used for carrying out high-temperature inoculation treatment on liquid/solid two-phase materials in a pressing state, so that the graphite precursor refined powder is prevented from floating too early; in addition, the saturation solubility of the high-temperature molten iron in the temperature range (TH) to carbon elements is more than 5 wt%, and the high-temperature molten iron has the characteristics of wetting and selective high-temperature dissolution to carbon in an amorphous region in the graphite precursor fine powder and high-activity carbon on the surface of the powder; in the subsequent cooling process, supersaturated carbon dissolved in molten iron is gradually separated out, a new graphite shell layer is attached to the surface of fine powder of a graphite precursor to grow a new graphite shell layer, and the artificial graphite cathode material with a novel core-shell structure is formed, so that the isotropy characteristic of the graphite precursor can be improved.
According to the invention, the high-temperature molten iron is used for carrying out surface erosion on the graphite precursor fine powder, so that the number of active end groups of the graphite precursor fine powder is reduced, the specific surface area of the powder is reduced, and the artificial graphite material coated by attached crystallization reduces the lithium consumption in the SEI film production process, thereby reducing the irreversible capacity for the first time.
The invention utilizes the highest temperature range of 1850-2150 ℃ to perform high-temperature inoculation which is far lower than the high-temperature graphitization temperature of 2800-3100 ℃ adopted by the conventional artificial graphite, thus greatly reducing the waste of radiant heat and energy; the energy utilization efficiency of the invention is far higher than the heat efficiency of the traditional high-temperature graphitizing furnace; the method greatly reduces the heating time of graphitization, does not need secondary coating and secondary carbonization heating, reduces the total energy consumption, and can obtain the novel artificial graphite cathode material with the core-shell structure as the main part, high graphitization degree and good isotropy degree.
The invention utilizes the wettability variation between the artificial graphite powder and the low-temperature molten iron and the huge density difference between the artificial graphite powder and the low-temperature molten iron to simply and easily realize the effective natural floating separation of the artificial graphite powder and the low-temperature molten iron after the high/low-temperature molten iron inoculation, and does not need to adopt subsequent procedures such as chemical corrosion and the like to treat iron.
Drawings
Fig. 1 of the accompanying drawings of the specification is a schematic view of a graphite master piston (CP 1) according to the present invention, wherein the upper surface of the graphite master piston (CP 1) is a conical slope surface for preventing molten iron and fine graphite precursor powder leaking from a gap between the graphite master piston and a graphite crucible from staying on the upper surface of the master piston, and an included angle between a generatrix of the conical slope surface and a center line of the graphite master piston (CP 1) is 30 degrees; the bottom of the main graphite piston (CP 1) is fixedly provided with 20 graphite rods which are uniformly distributed, the diameter of each graphite rod is 30 mm, and the graphite rods are uniformly fixed on the lower part of the main graphite piston (CP 1) in a threaded connection mode.
Fig. 2 of the attached drawings of the specification is a schematic diagram of the graphite piston assembly of the present invention before enhanced dispersion and pressing of graphite precursor fine powder and high-temperature molten iron, wherein the design gap between the graphite main piston (CP 1) and the inner circle of the graphite crucible is 0.25 mm, and the design gap between the graphite auxiliary piston (CP 2) and the inner circle of the graphite main piston (CP 1) is 0.25 mm.
Fig. 3 of the accompanying drawings of the specification is a schematic view of the invention showing that the artificial graphite powder obtained after high/low temperature inoculation is sucked to an external cache device under negative pressure, an H3, H4 graphite tube arranged at the upper part of a graphite crucible is used for blowing inert gas to fluidize the artificial graphite powder, and an H5 graphite tube arranged at the upper part of the graphite crucible is used for sucking the artificial graphite powder into a cache container in a negative pressure dust collection mode. Cooling is continued.
Detailed Description
The following examples are carried out on the premise of the technical scheme and spirit of the present invention, and detailed embodiments and specific processes are given, but the scope of the present invention is not limited thereto, and any alternative or equivalent means, such as properly adjusting the carbon content in the iron material, or properly adjusting the amount of Si, ce, or other alloy elements in the iron material, or properly increasing the high temperature inoculation temperature of the molten iron, or properly decreasing the low temperature inoculation temperature of the molten iron, or properly adjusting the piston assembly of ceramic material instead of the graphite piston assembly, or properly adjusting the negative pressure adsorption of the artificial graphite powder, should be understood as falling within the scope of the present invention.
Example 1 inoculation of molten ironThe artificial graphite cathode material has an average particle size D50 of 10-16 microns, a D95 smaller than 25 microns, an XRD test that D002 is 0.3349 nm, and a true density of 2.21-2.25g/cm 3 Gram capacity is more than 360mAh/g, and first charge-discharge efficiency is more than 94.5%; the manufacturing device of the molten iron inoculated artificial graphite cathode material mainly comprises: the device comprises a vacuum system, a water-cooled furnace body, an electromagnetic induction heating and temperature measuring system, an inflation system and a fluidization and negative pressure powder suction system, wherein a graphite crucible for inoculating artificial graphite cathode material with high-low temperature molten iron and an attached heat insulation layer of the graphite crucible are arranged in the furnace body, a graphite main piston (CP 1) which is in clearance fit with the inner circle of the graphite crucible and can be adjusted in an up-and-down displacement mode is shown in the attached drawings 1-3 of the specification, a large hole (H1) is formed in the graphite main piston (CP 1), a graphite auxiliary piston (CP 2) is in clearance fit with the inner circle of the large hole (H1), the graphite auxiliary piston (CP 2) is parallel to and coincides with the central axis of the graphite main piston (CP 1), the graphite auxiliary piston (CP 2) can perform up-and-down independent displacement control relative to the graphite main piston (CP 1), and can perform a quasi-stirring function on a liquid/molten iron solid mixed material of graphite fine powder after being combined with the up-and-down coordinated movement of the graphite main piston (CP 1), and a negative pressure adsorption hole (H2) is formed in the bottom of the graphite auxiliary piston (CP 2) and is used for adsorbing and conveying fine powder packaged in a steel barrel and placing molten iron in the molten iron; the graphite main piston (CP 1) is also provided with a hole and is provided with (H3) and/or (H4) and/or (H5) a graphite pipe, the (H3) and/or (H4) is used for introducing air from the outside to fluidize the artificial graphite powder floating from the molten iron, and the (H5) is used for transferring the floating fluidized artificial stone toner powder to an external buffer container by adopting a negative pressure dust suction mode.
The manufacturing method of the molten iron inoculated artificial graphite cathode material mainly comprises the following main steps:
step1, preparing fine graphite precursor powder, wherein the graphite precursor raw material adopts needle coke, the volatilization weight of the needle coke after 900 ℃/30 minutes treatment under the protection of inert gas is less than 0.20%, the granularity after crushing and grading is controlled to be 10-18 microns in average particle size D50, less than 25 microns in D95 and less than 0.20% in ash content;
step2, preparing high-temperature molten iron by vacuum induction smelting, performing enhanced dispersion and high-temperature molten iron inoculation, introducing argon into a vacuum chamber for protection after vacuumizing, heating the molten iron to 1700 ℃ by induction, conveying the graphite precursor fine powder material packaged by a steel barrel into the molten iron by using an auxiliary piston (CP 2) with a negative pressure adsorption hole (H2), heating the molten iron and the liquid/solid mixed material of the graphite precursor fine powder to a high-temperature range of 1950-2000 ℃ (TH), performing upward/downward reverse controllable displacement of a piston assembly in the high-temperature range, performing enhanced dispersion on the high-temperature molten iron and the graphite precursor fine powder, stopping dispersion, and performing high-temperature inoculation for 90 minutes while keeping the liquid/solid mixed material pressed by the graphite piston assembly;
step3, inoculating the artificial graphite powder at low temperature and adsorbing the artificial graphite powder under negative pressure, continuously pressing a liquid/solid mixture by using a graphite piston assembly, cooling the liquid/solid mixture together to a 1350-1450 ℃ (TL) interval, inoculating the liquid/solid mixture at low temperature for 90 minutes, floating the artificial graphite powder after realizing natural coating above the liquid level of molten iron, respectively introducing argon from (H3)/(H4) by adopting a mode shown in the attached drawing 3 of the specification to fluidize the artificial graphite powder, simultaneously sucking the artificial graphite powder from (H5) by using negative pressure, transferring the artificial graphite powder into a material buffer container, continuously cooling under the protection of argon, discharging the molten iron at the temperature of below 200 ℃, sorting particles and demagnetizing to obtain the high-low temperature molten iron inoculated artificial graphite cathode material;
and Step4, continuously adopting a graphite auxiliary piston (CP 2) to throw a next batch of steel barrel-packed graphite precursor fine powder into the molten iron, and repeatedly manufacturing the artificial graphite cathode material inoculated by the high/low temperature molten iron.
Claims (3)
1. The manufacturing device and the method for the molten iron inoculated artificial graphite cathode material are characterized in that the manufacturing device mainly comprises: the device comprises a vacuum system, a water-cooled furnace body, an electromagnetic induction heating and temperature measuring system, a graphite crucible for inoculating an artificial graphite cathode material by molten iron in the furnace body, an attached heat insulation layer of the graphite crucible, a graphite main piston (CP 1)/graphite auxiliary piston (CP 2) assembly with enhanced dispersion function, two independent up-down displacement control systems thereof and an artificial graphite powder negative pressure suction and cache system thereof; the graphite primary piston (CP 1)/graphite secondary piston (CP 2) combination with enhanced dispersion has the following main characteristics: (T1), the graphite main piston (CP 1) is in clearance fit with the inner circle of the graphite crucible and can controllably and independently move up and down for adjustment; (T2) the upper surface of the graphite main piston (CP 1) is a conical slope surface and is used for preventing molten iron and graphite precursor fine powder from being retained, and the included angle between a bus of the conical slope surface and the center line of the graphite main piston (CP 1) is smaller than 45 degrees; (T3), more than 10 graphite rods are fixedly installed at the bottom of the main graphite piston (CP 1), and when the main graphite piston (CP 1) moves up and down for dispersion, the graphite rods fixed at the bottom play a role in enhancing dispersion of liquid/solid two-phase mixed materials (L/S) of molten iron and fine graphite precursor powder by forced flowing and local shearing; (T4), a through hole (H1) is formed in the graphite main piston (CP 1), a graphite auxiliary piston (CP 2) is in clearance fit with the inner circle of the through hole (H1), the graphite auxiliary piston (CP 2) is parallel to or coincided with the central line of the graphite main piston (CP 1), the graphite auxiliary piston (CP 2) can independently and controllably move up and down relative to the graphite main piston (CP 1), and the graphite auxiliary piston and the graphite main piston (CP 1) are combined in up and down coordinated motion, so that a liquid/solid two-phase mixture (L/S) of molten iron and graphite precursor fine powder can be enhanced and dispersed; (T5) a through hole (H2) is formed in the center of the graphite auxiliary piston (CP 2) and used for adsorbing the graphite precursor fine powder packaged in the steel barrel under negative pressure or directly spraying the graphite precursor fine powder into the molten high-temperature molten iron in a positive pressure gas flow conveying mode through the through hole (H2) and a graphite pipe extending and immersed in the molten iron; the manufacturing device of the invention is provided with small holes (H3) and/or (H4) and/or (H5) on the side wall of the upper part of the graphite crucible, and is provided with a corresponding graphite pipeline, wherein the (H3) and/or (H4) is used for blowing inert gas from the outside to fluidize the artificial graphite powder floating from molten iron, and the (H5) is used for transferring the fluidized artificial graphite powder to an external storage bin by adopting a negative pressure suction mode, buffering and continuously cooling.
2. The apparatus and the method for producing an artificial graphite anode material inoculated in molten iron as claimed in claim 1, wherein the apparatus comprises a graphite crucible having a side wall provided with small central holes (H3) and/or (H4) and/or (H5) and a graphite pipe for collecting the artificial graphite powder floating on the surface of molten iron, wherein an inert gas is blown from a through hole (H2) in the center of a sub-piston (CP 2) to suck the artificial graphite powder from (H3) and/or (H4) and/or (H5) to the outside by negative pressure suction.
3. The manufacturing device and method of molten iron inoculated artificial graphite cathode material according to claim 1, characterized in that, the manufacturing method of molten iron inoculated artificial graphite cathode material utilizes high temperature molten iron to have better wetting ability to graphite precursor refined powder in the high temperature range of 1850-2150 ℃ (TH), wetting angle is less than 90 degrees, and carbon element in graphite precursor refined powder has relatively higher saturation solubility, the high temperature molten iron in The (TH) high temperature range firstly enhances and disperses carbon in the high temperature molten iron in the amorphous region of graphite precursor refined powder and highly active carbon on the surface, compared with crystalline carbon in the graphite precursor refined powder, the graphite piston assembly of the invention has the characteristic of preferential selective dissolution, the three-point technical characteristics are utilized in The (TH) high temperature range, the graphite piston assembly of the invention first enhances and disperses the graphite precursor refined powder in the high temperature molten iron, after the graphite precursor refined powder is uniformly dispersed in the high temperature molten iron, the graphite piston assembly is used to continuously press and immerse the graphite precursor refined powder in the high temperature molten iron, the high temperature precursor is immersed in the high temperature molten iron for 30-360 minutes, the high temperature precursor is selectively dissolved in the high temperature molten iron, and the non-active carbon element of graphite precursor is selectively dispersed in the high temperature refined powder in the high temperature molten iron melting zone, and the high temperature molten iron is also used for the high temperature molten iron dissolution process; then keeping the liquid/solid mixture of the molten iron and the graphite precursor fine powder subjected to high-temperature inoculation continuously pressing the graphite piston assembly, cooling the molten iron and the liquid/solid mixture to a low-temperature range of 1350-1650 ℃ (TL) from a (TH) high-temperature range, wherein the relatively low-temperature molten iron has relatively low saturated solubility to carbon elements in the cooling process, supersaturated carbon dissolved in the molten iron can be dynamically separated out from the molten iron, part of the separated carbon can realize epiphytic crystallization on the surface of the graphite precursor fine powder, and a small part of the carbon is directly separated out in the molten iron to grow into artificial graphite powder, and the temperature is reduced to the temperature of the artificial graphite powder(TL) forming artificial graphite powder mainly in a natural cladding type core-shell structure after the temperature interval is kept and the total low-temperature inoculation time is kept between 30 and 360 minutes; moving the graphite piston assembly upwards, floating the artificially coated graphite powder or partially naturally precipitated graphite powder to a position above the liquid level of the low-temperature molten iron by using the poor wettability of the relatively low-temperature molten iron in the low-temperature range (TL) and the wetting angle of the artificially coated graphite powder to be larger than 90 degrees and using the huge density difference between the artificially coated graphite powder and the low-temperature molten iron, sucking the floated graphite powder out by using negative pressure, storing the graphite powder in a material buffer container, continuously cooling the artificially coated graphite powder to 200 ℃ under the protection of inert gas or under the vacuum condition, discharging the graphite powder out of the furnace, sorting particles and removing magnetism to obtain the molten iron inoculated artificial graphite cathode material, wherein the XRD test d002 is smaller than 0.3390 nm, and the true density is 2.17-2.27g/cm 3 The gram capacity is more than 350mAh/g, and the first charge-discharge efficiency is more than 93%.
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| CN202210889452.4A CN115676815A (en) | 2022-07-21 | 2022-07-21 | Manufacturing device and method for molten iron inoculated artificial graphite cathode material |
| PCT/CN2023/095580 WO2024016827A1 (en) | 2022-07-21 | 2023-05-22 | Manufacturing device and method for inoculating artificial graphite negative electrode materials in molten iron |
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| WO2023226934A1 (en) * | 2022-05-22 | 2023-11-30 | 深圳市钢昱碳晶科技有限公司 | Molten-iron-inoculated artificial graphite negative electrode material and manufacturing method therefor |
| WO2024016827A1 (en) * | 2022-07-21 | 2024-01-25 | 深圳市钢昱碳晶科技有限公司 | Manufacturing device and method for inoculating artificial graphite negative electrode materials in molten iron |
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| DE102006038180A1 (en) * | 2006-08-14 | 2008-02-21 | Peter Greiner | Carbon piston for an internal combustion engine |
| RU2584676C2 (en) * | 2011-06-03 | 2016-05-20 | Каунсел Оф Сайнтифик Энд Индастриал Рисерч | Method of producing anode materials based on inclusion compounds of lithium in graphite refining foam for lithium-ion batteries |
| KR101546039B1 (en) * | 2013-11-27 | 2015-08-20 | 주식회사 포스코 | Method for recovering graphite from molten pig-iron |
| CN108545722A (en) * | 2018-06-28 | 2018-09-18 | 上海交通大学 | Serialization prepares the method and device of graphene and graphite microchip |
| CN114733287A (en) * | 2022-04-01 | 2022-07-12 | 山东钢铁股份有限公司 | Collecting device and collecting method for precipitated graphite in molten iron transfer process |
| CN115676815A (en) * | 2022-07-21 | 2023-02-03 | 李鑫 | Manufacturing device and method for molten iron inoculated artificial graphite cathode material |
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| WO2023226934A1 (en) * | 2022-05-22 | 2023-11-30 | 深圳市钢昱碳晶科技有限公司 | Molten-iron-inoculated artificial graphite negative electrode material and manufacturing method therefor |
| WO2024016827A1 (en) * | 2022-07-21 | 2024-01-25 | 深圳市钢昱碳晶科技有限公司 | Manufacturing device and method for inoculating artificial graphite negative electrode materials in molten iron |
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