CN110872117A - Preparation method and device of spherical graphite for power battery - Google Patents
Preparation method and device of spherical graphite for power battery Download PDFInfo
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- CN110872117A CN110872117A CN201811009725.1A CN201811009725A CN110872117A CN 110872117 A CN110872117 A CN 110872117A CN 201811009725 A CN201811009725 A CN 201811009725A CN 110872117 A CN110872117 A CN 110872117A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000010439 graphite Substances 0.000 title claims abstract description 128
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 102
- 239000000428 dust Substances 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000000227 grinding Methods 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000007599 discharging Methods 0.000 claims description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000000746 purification Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000010298 pulverizing process Methods 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 8
- 229910021382 natural graphite Inorganic materials 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 20
- 239000010406 cathode material Substances 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BNTHIFZVZMSNEF-UHFFFAOYSA-N [N+](=O)(O)[O-].F.S(O)(O)(=O)=O.Cl Chemical compound [N+](=O)(O)[O-].F.S(O)(O)(=O)=O.Cl BNTHIFZVZMSNEF-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 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
- C01B32/21—After-treatment
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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
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
-
- 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
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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
- 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
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Abstract
The invention provides a method and a device for preparing spherical graphite for a power battery, which adopt a process of combining ultramicro primary grinding, ultramicro fine grinding and multiple ultramicro grading, and the prepared spherical graphite has good sphericity and narrow particle size distribution (D)503-12 μm), and the tap density is high, thereby meeting the use requirements of the cathode material of the high-end power battery; and can utilize preparation D50Is tailing generated in the process of spherical graphite with the particle size of 13-25 mu m and is used as preparation D50Is a raw material of spherical graphite with small grain diameter of 3-12 mu m, the utilization rate of the raw material of graphite is improved by 25-35 percent, the process flow is simple, and the energy consumption is reducedThe crushed air directly enters the next stage for cyclic crushing and grading, the middle is provided with a pipeline for conveying, the whole device is fully sealed, and the dust-containing air flow is subjected to dust removal, then intensively enters a blind ditch and then enters secondary dust removal treatment, so that pollution-free discharge is achieved.
Description
Technical Field
The invention belongs to the technical field of graphite preparation, relates to a method and a device for preparing spherical graphite for a power battery, and particularly relates to a medium particle size D50A method and a device for preparing spherical graphite with the diameter of 3-12 mu m.
Background
Lithium ion batteries have become a new generation of secondary batteries following nickel-metal hydride batteries in the nineties of the last century because of their advantages of high operating voltage, high energy density, long cycle life, small self-discharge, no memory effect, etc. At present, the cathode material of commercial lithium ion batteries is still the dominant graphite material, wherein natural graphite is widely applied due to high charge and discharge capacity, good charge and discharge platform, wide source and low cost.
In recent years, with increasing demands for miniaturization, weight reduction, multifunction, and long-term driving of electronic products, vehicles, and energy storage devices, demands for high energy density and high rate performance of lithium ion batteries have been increasing. The existing research shows that the smaller the median particle size of the spherical graphite is, the better the sphericity is, the shorter the distance between lithium ions embedded into the graphite sphere and separated from the graphite sphere is, the faster the charging and discharging speed under large current is, the better the multiplying power performance is, and the use requirement of the power battery can be met. The traditional preparation process of the spherical graphite adopts a jet mill to prepare the median particle diameter (D) of the spherical graphite through the procedures of multiple times of coarse crushing, fine crushing, spheroidizing shaping, classified screening and the like50) The minimum is 14 mu m, the median diameter of the spherical graphite is difficult to further reduce, and the use requirement of a high-end power battery cannot be met.
Disclosure of Invention
The invention aims to provide a preparation method and a device of spherical graphite for a power battery, wherein the preparation method and the device can effectively reduce the particle size of the spherical graphite and improve the product yield; the invention aims to solve the technical problem of preparing the D by using natural crystalline flake graphite and earthy graphite50Is spherical graphite with the diameter of 3-12 mu m, and meets the high-rate use requirement of high-end power batteries.
The invention mainly solves the technical problems through the following technical scheme:
a preparation method of spherical graphite comprises the following steps:
(1) superfine primary crushing: feeding natural crystalline flake graphite and earthy graphite with carbon content of more than 90% into one or more (for example, 2-5) groups of serially connected ultramicro primary crusher sets;
(2) superfine grinding: sending the graphite powder collected in the step (2) into one or more groups (for example, 3-7 groups) of superfine pulverizer sets connected in series;
optionally, (3) purifying and drying.
According to the invention, in the step (1), the superfine primary grinding machine set is used for grinding and grading graphite particles. The superfine primary crusher set comprises at least two superfine crushers, a superfine classifier and a cyclone collector; the ultrafine grinder comprises an ultrafine grinder feed inlet and an ultrafine grinder discharge outlet, the ultrafine grinder comprises an ultrafine grinder feed inlet, an ultrafine grinder first discharge outlet and an ultrafine grinder second discharge outlet, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet and a cyclone collector dust removal air outlet; the system comprises at least two ultrafine crushers, an ultrafine classifier and a cyclone collector, wherein the at least two ultrafine crushers, the ultrafine classifier and the cyclone collector are connected in series, a first discharge port of the ultrafine classifier is connected with a feed inlet of the cyclone collector, a second discharge port of the ultrafine classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a next ultrafine primary crushing unit or connected in parallel to be connected into a feed inlet of the ultrafine fine crushing unit, and a dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan;
according to the invention, the rotation speed of the grading impeller of the ultrafine grinder in the step (1) is increased from 800rpm to 1600rpm one by one, the increase of the rotation speed of each ultrafine grinder is equal or unequal from the 2 nd, and the grinding time of each ultrafine grinder is 15-25 minutes;
according to the invention, D of the graphite powder collected by the second discharge port of the classifier and the discharge port of the cyclone collector in the last group of superfine primary grinding units in the step (1)50Preferably, it is5-14 μm, tap density of 0.7-0.85g/cm3；
According to the invention, in the step (2), the superfine pulverizer set is used for shaping particles and regulating and controlling the particle size distribution of the particles. The superfine pulverizer set comprises at least two superfine pulverizers, a superfine classifier and a cyclone collector; the ultrafine grinder comprises an ultrafine grinder feed inlet and an ultrafine grinder discharge outlet, the ultrafine grinder comprises an ultrafine grinder feed inlet, an ultrafine grinder first discharge outlet and an ultrafine grinder second discharge outlet, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet and a cyclone collector dust removal air outlet; the at least two ultrafine crushers, the ultrafine classifier and the cyclone collector are connected in series, a first discharge port of the ultrafine classifier is connected with a feed port of the cyclone collector, and a second discharge port of the ultrafine classifier and a discharge port of the cyclone collector are connected in parallel to be connected with a feed port of the ultrafine crusher in the next ultrafine fine crushing unit; in the last group of superfine pulverizer units, a second discharge port of the superfine classifier is connected to a first feed bin, and a discharge port of the cyclone collector is connected with a first tail feed bin; and the dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan.
Still preferably, the discharge gate of cyclone collector and the discharge gate of dust remover access in parallel to first tail feed bin.
According to the invention, the rotation speed of the grading impeller of the ultrafine grinder in the step (2) is gradually reduced from 1600rpm to 500rpm, the reduction amount of each rotation speed is equal or unequal, and the grinding time of each ultrafine grinder is 20-25 minutes; or, the rotation speed of the grading impeller of the ultrafine grinder in the step (2) is increased from 1000rpm to 2000rpm one by one, the increment of each rotation speed is equal or unequal, and the grinding time of each ultrafine grinder is 20-25 minutes; reducing the rotation speed from 1600rpm to 500rpm one by one, wherein the reduction amount of each rotation speed is equal or unequal, and the crushing time of each ultrafine crusher is 20-25 minutes;
according to the invention, the graphite particles D collected in the first silo in step (2)50Preferably 3 to 12 μm, for example, 3 to 5 μm, 5 to 7 μm, 8 to 10 μm, 11 to 12 μm and the like(ii) a The graphite particle size range is preferably 1 to 45 μm, for example 1 to 30 μm, 2 to 45 μm, 3 to 45 μm, 6 to 30 μm; tap density is more than or equal to 0.55g/cm3For example, 0.55 to 0.9g/cm3The specific surface area is 8.5-15.0m2(ii)/g; the graphite particles are spherical, approximately spherical, oval and potato-shaped, and the particle size distribution is uniform;
according to the invention, the structure of the ultrafine pulverizer in the step (1) is the same as that of the step (2), the ultrafine pulverizer integrates the dual functions of ultrafine grinding and air flow classification, and can simultaneously complete two processing procedures of ultrafine grinding and ultrafine powder sorting, wherein the ultrafine pulverizer is at least one of an air flow ultrafine grinding classifier, a jet type ultrafine grinding classifier, a vertical ultrafine grinder and a horizontal ultrafine grinder, and preferably is an air flow ultrafine grinder; the ultramicro classifier is an airflow ultramicro classifier; the yield of each ultrafine grinder in the step (1) is 50-1500kg/h, preferably 800-; the yield of each ultrafine grinder in the step (2) is 15-600kg/h, preferably 200-500 kg/h;
according to the invention, the purification in step (3) is carried out by reacting the material with an acidic aqueous solution. The acidic aqueous solution is one or more mixed aqueous solution of hydrochloric acid, hydrofluoric acid, nitric acid and sulfuric acid. Preferably, a mixture of a plurality of acids is used, and the ratio of the acids is preferably hydrochloric acid: hydrofluoric acid: nitric acid: sulfuric acid 0-4: 1-2: 0-4: 0-2. The temperature of the purification reaction is 50-120 ℃. The purification reaction time is 1-24 hours, and the fixed carbon content of the purified natural graphite is more than 99.95%. After the purification reaction in step (3) is completed, the material is preferably dried.
According to the invention, D of the natural crystalline flake graphite or earthy graphite in step (1)50Preferably 8 to 13 μm, for example, 8 to 10 μm, 9 to 11 μm, 10 to 12 μm, etc.; the graphite particle size range is preferably 1 to 45 μm, for example 5 to 40 μm, 1 to 30 μm, 3 to 30 μm, 5 to 45 μm;
according to the present invention, the natural crystalline flake graphite or earthy graphite in step (1) is not particularly limited, and may be graphite particles conventionally used for preparing power batteries, which are known to those skilled in the art; the preparation method of the natural crystalline flake graphite or the earthy graphite in the step (1) is also not particularly limited, and for example, the natural crystalline flake graphite or the earthy graphite prepared by the following method is selected:
(a) primary crushing: feeding natural crystalline flake graphite and earthy graphite with particle size larger than 0.05mm (such as 0.074-0.8 mm) and carbon content more than 90% into one or more (such as 2-4) primary pulverizer sets connected in series;
(b) fine crushing: conveying the graphite powder treated in the step (a) into one or more groups (for example, 1-3 groups) of secondary crusher sets connected in series;
(c) shaping: conveying the graphite powder treated in the step (b) into one or more groups (for example, 1-3 groups) of final-stage pulverizer sets connected in series;
optionally, (d) purifying and drying.
According to the invention, in step (a), the primary crusher set is used to effect primary crushing. Each group of primary crusher units comprises at least two crushers and a cyclone collector, each crusher comprises a crusher feeding port and a crusher discharging port, and each cyclone collector comprises a cyclone collector feeding port, a cyclone collector discharging port and a cyclone collector dedusting air outlet; the at least two crushers are connected with a cyclone collector in series, a discharge port of the cyclone collector is connected with a feed port of a crusher in the next primary crusher set or is connected with a feed port of a secondary crusher set, and a dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan;
according to the invention, the rotation speed of the grading impeller of the pulverizer in the step (a) is increased from 1000rpm to 2000rpm one by one, and the increment of the rotation speed of each pulverizer is equal or unequal from the 2 nd station, and the pulverizing time of each pulverizer is 10-20 minutes; illustratively, step (a) includes 2 sets of primary crusher units connected in series, and each set of primary crusher units includes 3 crushers, so step (a) includes 6 crushers in total, wherein the rotation speed of the classifying impeller of the first crusher is 1000rpm, the rotation speed of the classifying impeller of the sixth crusher is 2000rpm, and the rotation speeds of the classifying impellers of the other 4 crushers sequentially increase in the material sequence, and the increasing amounts may be the same or different;
according to the invention, D of the graphite powder collected in the cyclone collector of the last group of primary crusher units in step (a)50Preferably 20-30 μm;
according to the invention, in step (b), the secondary crusher set is used to effect regrinding. Each group of secondary crusher sets comprises at least two crushers, a classifier and a cyclone collector, the crushers comprise crusher feed inlets and crusher discharge outlets, the classifier comprises a classifier feed inlet, a classifier first discharge outlet and a classifier second discharge outlet, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet and a cyclone collector dedusting air outlet; the at least two crushers, the classifier and the cyclone collector are connected in series, a first discharge port of the classifier is connected with a feed port of the cyclone collector, a second discharge port of the classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a feed port of a crusher in the next secondary crusher set or connected into a feed port of a last crusher set, and a dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan.
According to the invention, the rotating speed of the grading impeller of the pulverizer in the step (b) is increased from 2500rpm to 4000rpm one by one, the increment of each rotating speed is equal from the 2 nd station, and the pulverizing time of each pulverizer is 20-35 minutes;
according to the invention, D of the graphite powder collected at the discharge port of the cyclone collector and the second discharge port of the classifier in the last group of secondary crusher units in the step (b)50Preferably 13-25 μm, tap density < 0.9g/cm3The graphite particles are spherical, approximately spherical, oval and potato-shaped, and a large amount of fine powder is arranged on the surfaces of the graphite particles, the surfaces are rough and the sphericity is poor;
according to the invention, in step (c), the final pulverizer set is used for particle shaping and particle size distribution control. Each group of last-stage crusher sets comprises at least two crushers, a classifier and a cyclone collector; the crusher comprises a crusher feeding port and a crusher discharging port, the classifier comprises a classifier feeding port, a classifier first discharging port and a classifier second discharging port, and the cyclone collector comprises a cyclone collector feeding port, a cyclone collector discharging port and a cyclone collector dedusting air outlet; the at least two crushers, the classifier and the cyclone collector are connected in series, a first discharge port of the classifier is connected with a feed port of the cyclone collector, and a second discharge port of the classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a feed port of a crusher in the next last-stage crusher set; in the last group of the last crusher units, a second discharge port of the classifier is connected to a second bin, and a discharge port of the cyclone collector is connected to a second tail bin; and the dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan.
Preferably, the discharge port of the cyclone collector and the discharge port of the dust removing device are connected in parallel to a second tail stock bin.
Still preferably, the discharge gate of cyclone collector and the discharge gate parallel connection of dust remover insert the second tail feed bin.
According to the invention, in the step (c), the rotating speed of the grading impeller of the pulverizer is gradually reduced from 2000rpm to 600rpm, the reduction amount of each rotating speed is equal or unequal, and the pulverizing time of each pulverizer is 20-25 minutes;
according to the invention, the graphite particles collected at the second discharge port of the classifier in the last group of the last pulverizer set in the step (c) are spherical, approximately spherical, oval or potato-shaped; graphite particles D50Preferably 13 to 25 μm, for example, 14 to 16 μm, 15 to 17 μm, 17 to 19 μm, 20 to 23 μm, etc.; the graphite particle size range is preferably 3.5 to 60 μm, for example 5 to 60 μm, 5 to 45 μm, 6 to 50 μm, 7 to 60 μm; tap density is more than or equal to 0.9g/cm3For example, 0.9 to 1.2g/cm3The specific surface area is 4.5-8.5m2(ii)/g; fine powder is not on the surface of the graphite particles, the surface is smooth, and the sphericity is good;
according to the invention, the particles D of the graphite tailings collected in the second tailing silo of step (c)50Preferably 8 to 13 μm, for example, 8 to 10 μm, 9 to 11 μm, 10 to 12 μm, etc.; the graphite particle size range is preferably 1 to 45 μm, for example 5 to 40 μm, 1 to 30 μm, 3 to 30 μm, 5 to 45 μm; tap density is more than or equal to 0.75g/cm3For example, 0.75 to 0.9g/cm3；
According to the invention, the graphite tailings collected in the second tailing bin in the step (c) are used as the raw material in the step (1).
According to the invention, the purification in step (d) is carried out by reacting the feed with an aqueous acidic solution. The acidic aqueous solution is one or more mixed aqueous solution of hydrochloric acid, hydrofluoric acid, nitric acid and sulfuric acid. Preferably, a mixture of a plurality of acids is used, and the ratio of the acids is preferably hydrochloric acid: hydrofluoric acid: nitric acid: sulfuric acid 0-4: 1-2: 0-4: 0-2. The temperature of the purification reaction is 50-120 ℃. The purification reaction time is 1-24 hours, and the fixed carbon content of the purified natural graphite is more than 99.95%. After the purification reaction of step (d) is completed, the material is preferably dried.
According to the invention, the pulverizer in the step (a), the step (b) and the step (c) has the same structure and mainly comprises components such as a turbine, a main shaft, a grading impeller, a screen and the like, wherein the pulverizer is at least one of an airflow vortex micro-pulverizer, a high-pressure micro-pulverizer, a rod-type mechanical micro-pulverizer, an impact micro-pulverizer and a pendulum pulverizer, and is preferably an airflow vortex micro-pulverizer; the classifier is at least one of an airflow classifier, a jet flow classifier and a micron classifier; the yield of each pulverizer in the step (a) is 50-1500kg/h, preferably 800-1200 kg/h; the output of each pulverizer in the step (b) and each pulverizer in the step (c) is 30-800kg/h, preferably 200-500 kg/h;
the present invention also provides an apparatus for preparing spheroidal graphite, the apparatus comprising: one or more groups of superfine primary crusher sets and one or more groups of superfine fine crusher sets; the above devices are connected in series in turn. Optionally, the apparatus further comprises a first bin and a first tail bin; the superfine primary crusher set and the superfine fine crusher set are connected in series; and the superfine fine pulverizer set is connected with the first bin and the first tailing bin.
According to the invention, the first bunker is used for collecting graphite particles obtained from the superfine pulverizer set,
according to the invention, the first tailing bin is used for collecting graphite tailing particles obtained from an ultra-fine pulverizer set.
According to the invention, the superfine primary grinding unit comprises at least two superfine grinders, an ultramicro classifier and a cyclone collector; the ultrafine grinder comprises an ultrafine grinder feed inlet and an ultrafine grinder discharge outlet, the ultrafine grinder comprises an ultrafine grinder feed inlet, an ultrafine grinder first discharge outlet and an ultrafine grinder second discharge outlet, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet and a cyclone collector dedusting air outlet; the system comprises at least two ultrafine crushers, an ultrafine classifier and a cyclone collector, wherein the at least two ultrafine crushers, the ultrafine classifier and the cyclone collector are connected in series, a first discharge port of the ultrafine classifier is connected with a feed inlet of the cyclone collector, a second discharge port of the ultrafine classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a next ultrafine primary crushing unit or connected in parallel to be connected into a feed inlet of the ultrafine fine crushing unit, and a dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan;
according to the invention, the ultrafine fine grinding machine set comprises at least two ultrafine grinding machines, an ultrafine classifier and a cyclone collector; the ultrafine grinder comprises an ultrafine grinder feed inlet and an ultrafine grinder discharge outlet, the ultrafine grinder comprises an ultrafine grinder feed inlet, an ultrafine grinder first discharge outlet and an ultrafine grinder second discharge outlet, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet and a cyclone collector dedusting air outlet; the system comprises at least two ultrafine crushers, an ultrafine classifier and a cyclone collector, wherein the at least two ultrafine crushers, the ultrafine classifier and the cyclone collector are connected in series, a first discharge port of the ultrafine classifier is connected with a feed inlet of the cyclone collector, a second discharge port of the ultrafine classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a next ultrafine fine crushing unit, a second discharge port of the ultrafine classifier in the last group of ultrafine fine crushing units is connected into a first stock bin, and a discharge port of the cyclone collector in the last group of ultrafine fine crushing units is connected into a first tail stock bin; and the dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan.
According to the invention, the discharge port of the cyclone collector and the discharge port of the dust removing equipment (such as the discharge port of the dust remover) are connected in parallel to a first tail stock bin.
According to the invention, the apparatus further comprises one or more primary crusher sets, one or more secondary crusher sets, one or more final crusher sets; the above devices are serially linked in turn. Optionally, the apparatus further comprises a second bin and a second tail bin; the primary crusher set, the secondary crusher set and the final crusher set are connected in series; the last-stage pulverizer set is connected with a second bin and a second tailing bin; and the second material bin is connected with an ultramicro primary crushing unit.
According to the invention, the second silo is used for collecting graphite particles obtained from the last-stage pulverizer group;
according to the invention, the second tailing bin is used for collecting graphite tailing particles obtained from a final-stage pulverizer set;
according to the invention, the primary crusher set comprises at least two crushers and a cyclone collector, the crushers comprise crusher feed inlets and crusher discharge outlets, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet and a cyclone collector dedusting air outlet; the at least two crushers are connected with a cyclone collector in series, a discharge port of the cyclone collector is connected with a feed port of a crusher in the next primary crusher set or is connected with a feed port of a secondary crusher set, and a dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan;
according to the invention, the secondary crusher set comprises at least two crushers, a classifier and a cyclone collector, wherein each crusher comprises a crusher feed inlet and a crusher discharge outlet; the classifier comprises a classifier feeding hole, a classifier first discharging hole and a classifier second discharging hole, and the cyclone collector comprises a cyclone collector feeding hole, a cyclone collector discharging hole and a cyclone collector dedusting air outlet; the at least two crushers, the classifier and the cyclone collector are connected in series, a first discharge port of the classifier is connected with a feed port of the cyclone collector, a second discharge port of the classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a feed port of a crusher in the next-stage crusher set or connected into a feed port of a last-stage crusher set, and a dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan;
according to the invention, the last-stage pulverizer group comprises at least two pulverizers, a classifier and a cyclone collector, wherein each pulverizer comprises a pulverizer feeding port and a pulverizer discharging port; the classifier comprises a classifier feeding hole, a classifier first discharging hole and a classifier second discharging hole, and the cyclone collector comprises a cyclone collector feeding hole, a cyclone collector discharging hole and a cyclone collector dedusting air outlet; the at least two crushers, the classifier and the cyclone collector are connected in series, a first discharge port of the classifier is connected with a feed port of the cyclone collector, a second discharge port of the classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a feed port of a crusher in the next last-stage crusher set, a second discharge port of the classifier in the last-stage crusher set is connected into a second bin, and a discharge port of the cyclone collector in the last-stage crusher set is connected into a second tail bin; and the dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan.
According to the invention, the discharge port of the cyclone collector and the discharge port of the dust removing equipment (such as the discharge port of the dust remover) are connected in parallel to a second tail stock bin.
According to the invention, the primary crusher set, the secondary crusher set, the final crusher set, the superfine primary crusher set and the superfine fine crusher set are connected through a conveying pipeline.
The invention has the beneficial effects that:
1. the invention adopts a process combining ultramicro primary grinding and ultramicro fine grinding, wherein the ultramicro primary grinding rotating speed is sequentially increased, thereby avoiding that a large amount of particles with the diameter less than 1 mu m are generated in the grinding process of the natural graphite and improving the product yield. The superfine grinding speed is increased and then decreased or the superfine grinding speed is decreased sequentially and multiple superfine grading techniques are adopted, so that the prepared spherical graphite has good sphericity and narrow particle size distribution (D)503-12 μm), high tap density, and high dynamic propertyThe use requirement of the anode material of the power battery;
2. preparation D is utilized in the invention50Is tailing generated in the process of spherical graphite with the particle size of 13-25 mu m and is used as preparation D50The graphite is a raw material of spherical graphite with small particle size of 3-12 mu m, the utilization rate of the graphite raw material is improved by 25-35%, and meanwhile, industrial waste is changed into valuable, the product yield is high, the process flow is simple, and the energy consumption is reduced;
3. the preparation device of the invention is characterized in that a plurality of groups of crushed single devices are connected end to end, raw materials are directly fed into the next stage for cyclic crushing and grading after being crushed in the first stage, a pipeline is arranged in the middle for conveying, the whole device is fully sealed, dust-containing air flow is collected after dust removal and then fed into a blind ditch for secondary dust removal treatment, and pollution-free discharge is achieved.
Drawings
FIG. 1 shows a preparation D according to the invention50Is a process flow diagram of a preferred embodiment of 3-12 μm.
FIG. 2 shows a schematic view of a preferred embodiment of the present invention D50Scanning electron micrographs of 8 μm product.
FIG. 3 shows a preparation D of the present invention50A process flow diagram according to a preferred embodiment of 13 to 25 μm.
FIG. 4 shows a schematic view of a preferred embodiment of the present invention D50Scanning electron micrographs of 17 μm product.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the description of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalents also fall within the scope of the present invention, and the process flow diagram of the present invention is shown in fig. 1 and fig. 3.
In FIG. 1, 4 is the first material bin, and 7 is the first material bin, D50A bin with the size of 3-12 mu m, 41 and 51 ultrafine crushers, 12 cyclone collectors, 32 an airflow ultrafine classifier, 5 a dust remover, 6 a high-pressure centrifugal fan and 8 a first tail bin.
In FIG. 3, 1 is the second material bin, 11, 21 and 31 are the airflow vortex micro-disintegrators, 12 is the cyclone collector, 22 is the airflow classifier, and 2 is the second material bin, namely D50A stock bin of 13-25 μm, a second tail stock bin 3, a dust remover 5 and a high-pressure centrifugal fan 6.
The present invention will be described in further detail with reference to the accompanying drawings and examples. The preparation method of the spherical graphite with the median particle size of 3-12 mu m comprises the following steps:
(1) feeding the first raw material into 2-5 groups of serially connected ultramicro primary crusher sets by using a high-pressure feeding sealed pipeline with the pressure of 0.3-0.6 MPa, wherein the rotating speed is 800-1600 rpm, the rotating speed is gradually increased, and the crushing time of each crusher is 10-20 minutes;
the superfine pulverizer can simultaneously complete superfine pulverization and micro powder classification, the first raw material is pulverized at a lower rotating speed in a shorter time, graphite particles with qualified particle sizes automatically flow into the classifier along with air flow for secondary classification, and the situation that a large amount of graphite particles with diameters smaller than 1 micrometer are generated in the superfine pulverization process of the first raw material is avoided. The rotation speed of each primary crusher is gradually increased, and D of graphite particles50Gradually decreasing to 5-14 μm, and tap density of 0.7-0.8g/cm3；
(2) Sending the graphite powder collected in the step (1) into 3-7 groups of serially connected superfine pulverizer sets through a high-pressure feeding sealed pipeline with the pressure of 0.3-0.6 MPa, wherein the rotating speed is gradually reduced from 1600rpm to 500rpm, and the pulverizing time of each superfine pulverizer is 20-35 minutes; or, the rotation speed of the grading impeller of the ultrafine grinder in the step (2) is increased from 1000rpm to 2000rpm one by one, the increment of each rotation speed is equal or unequal, and the grinding time of each ultrafine grinder is 20-25 minutes; reducing the rotation speed from 1600rpm to 500rpm one by one, wherein the reduction amount of each rotation speed is equal or unequal, and the crushing time of each ultrafine crusher is 20-25 minutes;
the grading impeller has high rotating speed and long action time in the initial stage of the superfine fine grinding process, the impact force on the graphite particles is large, and the D of the graphite particles50Rapidly reducing until reaching the granularity (D) of the cathode material of the rate type lithium ion battery503-12 μm), graphite particlesThe shape of the graphite particles is changed into spherical, approximately spherical, oval or potato shape, but a large amount of fine graphite particles appear, the particle size is not uniform, and the tap density is less than 0.5g/cm3(ii) a Although the particle size of graphite particles (D) at this time503-12 μm) meets the use requirement of the cathode material of the rate lithium ion battery, but the tap density is less than 0.5g/cm3The use requirements cannot be met; with the continuous reduction of the rotating speed of the superfine pulverizer, the impact force on graphite particles is smaller, the specific surface is gradually polished to be smooth, the shape and the particle size of the graphite particles are basically unchanged, a large amount of fine powder is discharged by the superfine classifier and the cyclone collector, the particle size distribution of the graphite particles is uniform, no fine powder exists on the surfaces of the graphite particles, the surfaces of the graphite particles are smooth, and the sphericity is good (see fig. 2); d of graphite particles collected at second outlet of ultramicro classifier503-12 μm, tap density > 0.75g/cm3The discharge port of the cyclone collector and the discharge port of the optional dust removing equipment collect waste materials;
(3) and (3) purification: using the spherical natural graphite in a mass ratio of 0-4: 1-2: 0-4: 0-2 hydrochloric acid-hydrofluoric acid-nitric acid-sulfuric acid mixed acid solution reacts for 1-24 hours at 50-120 ℃, then is washed to be neutral and dried, and the fixed carbon content of the purified natural graphite is more than 99.95%.
It should be noted that the raw material in the first raw material bin 4 may be prepared by a method known in the art and have a particle size of D50Preferably 8-12 μm, and a tap density of 0.75-0.9g/cm3The graphite particles of (3) can also be prepared by the following method:
(a) feeding natural crystalline flake graphite and earthy graphite with the particle size of 0.074-0.8 mm and the carbon content of not less than 90% into 2-4 groups of primary crushing units connected in series through a high-pressure feeding sealed pipeline with the pressure of 0.3-0.6 MPa, wherein the rotating speed is 1000-2000 rpm, the rotating speed is gradually increased, and the crushing time of each crusher is 10-20 minutes.
D of graphite particles with increasing rotation speed of each pulverizer50Gradually reduced, but under the condition of lower rotating speed and shorter time, the impact force on the graphite particles is smaller, thereby avoiding the occurrence of the condition that a large amount of particles with the diameter less than 4 mu m are generated in the primary crushing process of the graphite raw materialThe product yield is improved;
(b) feeding the material in the step (a) into 1-3 sets of secondary pulverizer sets connected in series by a high-pressure feeding sealed pipeline with the pressure of 0.3-0.6 MPa, wherein the rotating speed is 2500-4000 rpm, the rotating speed is gradually increased, and the pulverizing time of each pulverizer is 20-35 minutes;
the pulverizer has high rotating speed and long pulverizing time in the secondary pulverizing process, the impact force on the graphite particles is large, and the D of the graphite particles50Rapidly reducing until reaching the particle size of the negative electrode material of the capacity type lithium ion battery, changing the shape of graphite particles into spherical, approximately spherical, oval or potato shape, but generating a large amount of fine graphite particles with uneven particle size, wherein the tap density of the graphite particles is less than 0.9g/cm3；
(c) Feeding the material in the step (b) into 1-3 groups of serially connected final-stage pulverizer sets through a high-pressure feeding sealed pipeline with the pressure of 0.3-0.6 MPa, wherein the rotating speed is reduced from 2000rpm to 600rpm one by one, and the pulverizing time of each pulverizer is 20-25 minutes;
the particle size (D) of the graphite particles after the treatment in step (b)5013-25 μm) meets the use requirement of the negative electrode material of the capacity type lithium ion battery, but the tap density is less than 0.9g/cm3The use requirements cannot be met; the rotation speed of the last-stage pulverizer is lower, the impact force on graphite particles is smaller, the specific surface is gradually polished to be smooth, the shape and the particle size of the graphite particles are basically not changed, a large amount of fine powder is discharged by a classifier and a cyclone collector, the particle size distribution of the graphite particles is uniform, no fine powder exists on the surfaces of the graphite particles, the surfaces are smooth, and the sphericity is good (see figure 4); d of graphite particles collected by the second discharge port of the last group of classifiers5013-25 μm, tap density > 0.9g/cm3(ii) a Collecting graphite tailings and tailings graphite particles D from a discharge port of a cyclone collector and optionally a discharge port of a dust removal device50Preferably 8-12 μm, and a tap density of 0.75-0.9g/cm3(ii) a And (3) collecting the graphite tailings in a second tailing bin to serve as the raw material in the step (1), namely the raw material in the first raw material bin.
Examples 1 to 9
The process flow for examples 1-9 is as described above, the specific process parameters are shown in Table 1, the test data for examples 1-9 are shown in Table 2, and the process parameters for preparation examples 1-7 are shown in Table 3.
TABLE 1 Process parameters for examples 1-9
In the above table, 3 sets of 2 micronizer units in the micronization step (1) represent 3 sets of micronizer units in series, wherein 2 micronizer units are connected in series in each set of micronizer unit; the other stations such as 4 groups and 2 stations have the same meaning, and are not described in detail herein.
In the table, 2 sets of ultrafine grinding units in the ultrafine grinding of step (2) are connected in series at 1000rpm to 2000rpm and gradually increased, each time 20min, 5 sets of 2 sets are connected in series at 1600rpm to 500rpm and gradually decreased, and each time 20min represents that 7 sets of ultrafine grinding units in series are adopted, wherein 2 ultrafine grinding units are connected in series in each set of ultrafine grinding units, and the rotating speed of the first two sets of ultrafine grinding units is gradually increased from 1000rpm to 2000 rpm; the rotating speed of the last five groups of superfine pulverizer sets is gradually reduced from 1600rpm to 500 rpm; other embodiments have the same meaning, and are not repeated herein.
The physical and chemical indexes of the spherical graphite of the above examples 1 to 9 were measured, and specifically, the following were measured: measuring the sphericity of the sample by using an image particle method analyzer; testing the particle size distribution of a sample by using a laser particle size analyzer; measuring the tap density of the strain by using a Quantachrome AutoTap tap density instrument; measuring the specific surface area by adopting a nitrogen adsorption BET method; measuring the fixed carbon content of the sample by adopting an atomic absorption instrument; testing the micro-morphology of the sample by adopting a scanning electron microscope; the test structure is as follows:
table 2 test data for graphite powder collected at the second outlet of the last group of attritors in step (2) of examples 1-9
Wherein: product yield-first bin graphite quality/first raw material bin quality
TABLE 3 Process parameters of preparation examples 1 to 7
The physical and chemical indexes of the spherical graphite prepared in the preparation examples 1 to 7 are as follows: measuring the sphericity of the sample by using an image particle method analyzer; testing the particle size distribution of a sample by using a laser particle size analyzer; measuring the tap density of the strain by using a Quantachrome AutoTap tap density instrument; measuring the specific surface area by adopting a nitrogen adsorption BET method; measuring the fixed carbon content of the sample by adopting an atomic absorption instrument; testing the micro-morphology of the sample by adopting a scanning electron microscope; the test structure is as follows:
TABLE 4 test data of graphite powder collected at the second outlet of the last classifier and tailings collected at the outlets of the cyclone collector and the dedusting apparatus in step (c) of preparation examples 1 to 7
Wherein: product yield-second bin graphite quality/raw material quality
As can be seen from the above examples and preparations, D can be prepared by the process of the present invention50The graphite is spherical graphite with the particle size of 3-12 mu m, has good sphericity and high tap density, and meets the requirement of the power battery industry on the spherical graphite with small particle size; and can utilize preparation D50Is tailing generated in the process of spherical graphite with the particle size of 13-25 mu m and is used as preparation D50Is a raw material of spherical graphite with small grain size of 3-12 mu m, and the utilization rate of the graphite raw material is improved by 25-35 percent.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of spherical graphite comprises the following steps:
(1) superfine primary crushing: feeding natural crystalline flake graphite and earthy graphite with carbon content of more than 90% into one or more (for example, 2-5) groups of serially connected ultramicro primary crusher sets;
(2) superfine grinding: sending the graphite powder collected in the step (2) into one or more groups (for example, 3-7 groups) of superfine pulverizer sets connected in series;
optionally, (3) purifying and drying.
2. The method according to claim 1, wherein in step (1), the micronizer set comprises at least two micronizers, an ultramicro classifier and a cyclone collector; the ultrafine grinder comprises an ultrafine grinder feed inlet and an ultrafine grinder discharge outlet, the ultrafine grinder comprises an ultrafine grinder feed inlet, an ultrafine grinder first discharge outlet and an ultrafine grinder second discharge outlet, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet and a cyclone collector dust removal air outlet; the system comprises at least two ultrafine crushers, an ultrafine classifier and a cyclone collector, wherein the at least two ultrafine crushers, the ultrafine classifier and the cyclone collector are connected in series, a first discharge port of the ultrafine classifier is connected with a feed inlet of the cyclone collector, a second discharge port of the ultrafine classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a next ultrafine primary crushing unit or connected in parallel to be connected into a feed inlet of the ultrafine fine crushing unit, and a dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan;
preferably, the rotation speed of the classifying impeller of the ultrafine grinder in the step (1) is increased from 800rpm to 1600rpm one by one, the increase of the rotation speed of each ultrafine grinder is equal or unequal from the 2 nd, and the grinding time of each ultrafine grinder is 15-25 minutes;
preferably, the last one described in step (1)D for grouping the graphite powder collected by the second discharge port of the classifier and the discharge port of the cyclone collector in the ultramicro primary crusher set50Preferably 5-14 μm, and a tap density of 0.7-0.85g/cm3。
3. The method according to claim 1 or 2, wherein in the step (2), the ultrafine pulverizer group comprises at least two ultrafine pulverizers, an ultrafine classifier and a cyclone collector; the ultrafine grinder comprises an ultrafine grinder feed inlet and an ultrafine grinder discharge outlet, the ultrafine grinder comprises an ultrafine grinder feed inlet, an ultrafine grinder first discharge outlet and an ultrafine grinder second discharge outlet, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet and a cyclone collector dust removal air outlet; the at least two ultrafine crushers, the ultrafine classifier and the cyclone collector are connected in series, a first discharge port of the ultrafine classifier is connected with a feed port of the cyclone collector, and a second discharge port of the ultrafine classifier and a discharge port of the cyclone collector are connected in parallel to be connected with a feed port of the ultrafine crusher in the next ultrafine fine crushing unit; in the last group of superfine pulverizer units, a second discharge port of the superfine classifier is connected to a first feed bin, and a discharge port of the cyclone collector is connected with a first tail feed bin; and the dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan.
Preferably, the discharge port of the cyclone collector and the discharge port of the dust remover are connected in parallel to a first tail stock bin.
Preferably, the rotation speed of the grading impeller of the ultrafine grinder in the step (2) is gradually reduced from 1600rpm to 500rpm, the reduction amount of each rotation speed is equal or unequal, and the grinding time of each ultrafine grinder is 20-25 minutes; or, the rotation speed of the grading impeller of the ultrafine grinder in the step (2) is increased from 1000rpm to 2000rpm one by one, the increment of each rotation speed is equal or unequal, and the grinding time of each ultrafine grinder is 20-25 minutes; reducing the rotation speed from 1600rpm to 500rpm one by one, wherein the reduction amount of each rotation speed is equal or unequal, and the crushing time of each ultrafine crusher is 20-25 minutes;
preferably, in step (2)Graphite particles D collected in the first silo50Preferably 3-12 μm, the graphite particle size range is preferably 1-45 μm, and the tap density is more than or equal to 0.55g/cm3The specific surface area is 8.5-15.0m2/g；
Preferably, the output of each ultrafine grinder in the step (1) is 50-1500kg/h, preferably 800-1200 kg/h; the output of each ultrafine grinder in the step (2) is 15-600kg/h, preferably 200-500 kg/h.
4. The method according to any one of claims 1 to 3, wherein the purification in step (3) is carried out by reacting the material with an acidic aqueous solution. The acidic aqueous solution is one or more mixed aqueous solution of hydrochloric acid, hydrofluoric acid, nitric acid and sulfuric acid. Preferably, a mixture of a plurality of acids is used, and the ratio of the acids is preferably hydrochloric acid: hydrofluoric acid: nitric acid: sulfuric acid 0-4: 1-2: 0-4: 0-2. The temperature of the purification reaction is 50-120 ℃. The purification reaction time is 1-24 hours, and the fixed carbon content of the purified natural graphite is more than 99.95%. After the purification reaction in step (3) is completed, the material is preferably dried.
Preferably, D of the natural crystalline flake graphite or the earthy graphite in the step (1)50Preferably 8-13 μm; the graphite particle size is preferably in the range of 1 to 45 μm.
5. The method according to any one of claims 1 to 4, wherein the natural crystalline flake graphite or earthy graphite in step (1) is prepared by the following method:
(a) primary crushing: feeding natural crystalline flake graphite and earthy graphite with particle size larger than 0.05mm (such as 0.074-0.8 mm) and carbon content more than 90% into one or more (such as 2-4) primary pulverizer sets connected in series;
(b) fine crushing: conveying the graphite powder treated in the step (a) into one or more groups (for example, 1-3 groups) of secondary crusher sets connected in series;
(c) shaping: conveying the graphite powder treated in the step (b) into one or more groups (for example, 1-3 groups) of final-stage pulverizer sets connected in series;
optionally, (d) purifying and drying.
6. The method of any one of claims 1-5, wherein in step (a), each set of primary crusher units comprises at least two crushers and a cyclone collector, the crushers comprise a crusher feed inlet and a crusher discharge outlet, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet, and a cyclone collector dust outlet; the at least two crushers are connected with a cyclone collector in series, a discharge port of the cyclone collector is connected with a feed port of a crusher in the next primary crusher set or is connected with a feed port of a secondary crusher set, and a dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan;
preferably, the rotation speed of the classifying impeller of the pulverizer in the step (a) is increased to 2000rpm from 1000rpm one by one, and the increment of each rotation speed is equal or unequal from the 2 nd station, and the pulverizing time of each pulverizer is 10-20 minutes;
preferably, D of the graphite powder collected by the cyclone collectors in the last group of primary crusher sets in step (a)50Preferably 20-30 μm.
7. A method according to any one of claims 1 to 6, wherein in step (b) the secondary crusher set is used to effect regrinding. Each group of secondary crusher sets comprises at least two crushers, a classifier and a cyclone collector, the crushers comprise crusher feed inlets and crusher discharge outlets, the classifier comprises a classifier feed inlet, a classifier first discharge outlet and a classifier second discharge outlet, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet and a cyclone collector dedusting air outlet; the at least two crushers, the classifier and the cyclone collector are connected in series, a first discharge port of the classifier is connected with a feed port of the cyclone collector, a second discharge port of the classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a feed port of a crusher in the next secondary crusher set or connected into a feed port of a last crusher set, and a dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan.
Preferably, the rotation speed of the classifying impeller of the pulverizer in the step (b) is increased from 2500rpm to 4000rpm one by one, and the increment of each rotation speed is equal from the 2 nd station, and the pulverizing time of each pulverizer is 20-35 minutes;
preferably, the second discharge port of the classifier in the last set of secondary crusher units in the step (b) and the discharge port of the cyclone collector collect the graphite powder D50Preferably 13-25 μm, tap density < 0.9g/cm3。
8. A method according to any one of claims 1 to 7 wherein in step (c) the final pulverizer set is used for particle shaping and particle size distribution control. Each group of last-stage crusher sets comprises at least two crushers, a classifier and a cyclone collector; the crusher comprises a crusher feeding port and a crusher discharging port, the classifier comprises a classifier feeding port, a classifier first discharging port and a classifier second discharging port, and the cyclone collector comprises a cyclone collector feeding port, a cyclone collector discharging port and a cyclone collector dedusting air outlet; the at least two crushers, the classifier and the cyclone collector are connected in series, a first discharge port of the classifier is connected with a feed port of the cyclone collector, and a second discharge port of the classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a feed port of a crusher in the next last-stage crusher set; in the last group of the last crusher units, a second discharge port of the classifier is connected to a second bin, and a discharge port of the cyclone collector is connected to a second tail bin; and the dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan.
Preferably, the discharge port of the cyclone collector and the discharge port of the dust removing device are connected in parallel to a second tail stock bin.
Still preferably, the discharge gate of cyclone collector and the discharge gate parallel connection of dust remover insert the second tail feed bin.
Preferably, the rotating speed of the grading impeller of the pulverizer in the step (c) is gradually reduced from 2000rpm to 600rpm, the reduction amount of each rotating speed is equal or unequal, and the pulverizing time of each pulverizer is 20-25 minutes;
preferably, the graphite particles collected at the second discharge port of the classifier in the last set of the last pulverizer set in the step (c) are spherical, approximately spherical, oval and potato-shaped; graphite particles D50Preferably 13 to 25 μm; the preferred range of graphite particle size is 3.5-60 μm; tap density is more than or equal to 0.9g/cm3For example, 0.9 to 1.2g/cm3The specific surface area is 4.5-8.5m2/g；
Preferably, the particles D of the graphite tailings collected in the second tailing bin of step (c)50Preferably 8-13 μm; the graphite particle size range is preferably 1-45 μm; tap density is more than or equal to 0.75g/cm3For example, 0.75 to 0.9g/cm3；
Preferably, the graphite tailings collected in the second tailing bin in the step (c) are used as the raw material in the step (1).
Preferably, the purification in step (d) is carried out by reacting the material with an acidic aqueous solution. The acidic aqueous solution is one or more mixed aqueous solution of hydrochloric acid, hydrofluoric acid, nitric acid and sulfuric acid. Preferably, a mixture of a plurality of acids is used, and the ratio of the acids is preferably hydrochloric acid: hydrofluoric acid: nitric acid: sulfuric acid 0-4: 1-2: 0-4: 0-2. The temperature of the purification reaction is 50-120 ℃. The purification reaction time is 1-24 hours, and the fixed carbon content of the purified natural graphite is more than 99.95%.
Preferably, the yield per pulverizer in step (a) is 50-1500kg/h, preferably 800-1200 kg/h; the output of each crusher in step (b) and each crusher in step (c) is 30-800kg/h, preferably 200-500 kg/h.
9. An apparatus for preparing spheroidal graphite, the apparatus comprising: one or more groups of superfine primary crusher sets and one or more groups of superfine fine crusher sets; the above devices are connected in series in turn. Optionally, the apparatus further comprises a first bin and a first tail bin; the superfine primary crusher set and the superfine fine crusher set are connected in series; and the superfine fine pulverizer set is connected with the first bin and the first tailing bin.
Preferably, the first bin is used for collecting graphite particles obtained from an ultra-fine grinding machine set,
preferably, the first tailing bin is used for collecting graphite tailing particles obtained from the superfine pulverizer set.
Preferably, the superfine primary pulverizer set comprises at least two superfine pulverizers, a superfine classifier and a cyclone collector; the ultrafine grinder comprises an ultrafine grinder feed inlet and an ultrafine grinder discharge outlet, the ultrafine grinder comprises an ultrafine grinder feed inlet, an ultrafine grinder first discharge outlet and an ultrafine grinder second discharge outlet, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet and a cyclone collector dedusting air outlet; the system comprises at least two ultrafine crushers, an ultrafine classifier and a cyclone collector, wherein the at least two ultrafine crushers, the ultrafine classifier and the cyclone collector are connected in series, a first discharge port of the ultrafine classifier is connected with a feed inlet of the cyclone collector, a second discharge port of the ultrafine classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a next ultrafine primary crushing unit or connected in parallel to be connected into a feed inlet of the ultrafine fine crushing unit, and a dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan;
preferably, the ultrafine fine grinding machine set comprises at least two ultrafine grinding machines, an ultrafine classifier and a cyclone collector; the ultrafine grinder comprises an ultrafine grinder feed inlet and an ultrafine grinder discharge outlet, the ultrafine grinder comprises an ultrafine grinder feed inlet, an ultrafine grinder first discharge outlet and an ultrafine grinder second discharge outlet, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet and a cyclone collector dedusting air outlet; the system comprises at least two ultrafine crushers, an ultrafine classifier and a cyclone collector, wherein the at least two ultrafine crushers, the ultrafine classifier and the cyclone collector are connected in series, a first discharge port of the ultrafine classifier is connected with a feed inlet of the cyclone collector, a second discharge port of the ultrafine classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a next ultrafine fine crushing unit, a second discharge port of the ultrafine classifier in the last group of ultrafine fine crushing units is connected into a first stock bin, and a discharge port of the cyclone collector in the last group of ultrafine fine crushing units is connected into a first tail stock bin; and the dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan.
Preferably, the discharge port of the cyclone collector and the discharge port of the dust removing device (such as the discharge port of the dust remover) are connected in parallel to the first tail stock bin.
10. The apparatus of claim 9, further comprising one or more primary pulverizer sets, one or more secondary pulverizer sets, one or more final pulverizer sets; the above devices are serially linked in turn. Optionally, the apparatus further comprises a second bin and a second tail bin; the primary crusher set, the secondary crusher set and the final crusher set are connected in series; the last-stage pulverizer set is connected with a second bin and a second tailing bin; and the second material bin is connected with an ultramicro primary crushing unit.
Preferably, the second bin is used for collecting graphite particles obtained from the last-stage pulverizer group; the second tailing bin is used for collecting graphite tailing particles obtained from a last-stage pulverizer set;
preferably, the primary crusher set comprises at least two crushers and a cyclone collector, the crushers comprise a crusher feed inlet and a crusher discharge outlet, and the cyclone collector comprises a cyclone collector feed inlet, a cyclone collector discharge outlet and a cyclone collector dedusting air outlet; the at least two crushers are connected with a cyclone collector in series, a discharge port of the cyclone collector is connected with a feed port of a crusher in the next primary crusher set or is connected with a feed port of a secondary crusher set, and a dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan;
preferably, the secondary crusher set comprises at least two crushers, a classifier and a cyclone collector, and the crushers comprise crusher feed inlets and crusher discharge outlets; the classifier comprises a classifier feeding hole, a classifier first discharging hole and a classifier second discharging hole, and the cyclone collector comprises a cyclone collector feeding hole, a cyclone collector discharging hole and a cyclone collector dedusting air outlet; the at least two crushers, the classifier and the cyclone collector are connected in series, a first discharge port of the classifier is connected with a feed port of the cyclone collector, a second discharge port of the classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a feed port of a crusher in the next-stage crusher set or connected into a feed port of a last-stage crusher set, and a dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan;
preferably, the last-stage pulverizer set comprises at least two pulverizers, a classifier and a cyclone collector, wherein each pulverizer comprises a pulverizer feeding port and a pulverizer discharging port; the classifier comprises a classifier feeding hole, a classifier first discharging hole and a classifier second discharging hole, and the cyclone collector comprises a cyclone collector feeding hole, a cyclone collector discharging hole and a cyclone collector dedusting air outlet; the at least two crushers, the classifier and the cyclone collector are connected in series, a first discharge port of the classifier is connected with a feed port of the cyclone collector, a second discharge port of the classifier and a discharge port of the cyclone collector are connected in parallel to be connected into a feed port of a crusher in the next last-stage crusher set, a second discharge port of the classifier in the last-stage crusher set is connected into a second bin, and a discharge port of the cyclone collector in the last-stage crusher set is connected into a second tail bin; and the dust removal air outlet of the cyclone collector is connected with dust removal equipment, such as a dust remover and a high-pressure centrifugal fan.
Preferably, the discharge port of the cyclone collector and the discharge port of the dust removing device are connected in parallel to a second tail stock bin.
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| CN201811009725.1A CN110872117B (en) | 2018-08-31 | 2018-08-31 | Method and device for preparing spherical graphite with median particle size of 3-12 mu m |
| PCT/CN2019/103064 WO2020043131A1 (en) | 2018-08-31 | 2019-08-28 | Spherical graphite used for lithium batteries and preparation method therefor |
| US17/269,688 US12049404B2 (en) | 2018-08-31 | 2019-08-28 | Spherical graphite for lithium battery and preparation method thereof |
| ZA2021/01828A ZA202101828B (en) | 2018-08-31 | 2021-03-18 | Spherical graphite for lithium battery and preparation method thereof |
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Denomination of invention: Preparation method and device of spherical graphite with median particle size of 3-12 m m Granted publication date: 20210831 Pledgee: Industrial Bank Co.,Ltd. Zhanjiang Branch Pledgor: ZHANJIANG JUXIN NEW ENERGY Co.,Ltd. Registration number: Y2024980046856 |