CN117534063A - Reaction device and reaction process for graphite anode material of battery - Google Patents
Reaction device and reaction process for graphite anode material of battery Download PDFInfo
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- CN117534063A CN117534063A CN202311338404.7A CN202311338404A CN117534063A CN 117534063 A CN117534063 A CN 117534063A CN 202311338404 A CN202311338404 A CN 202311338404A CN 117534063 A CN117534063 A CN 117534063A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 31
- 239000010439 graphite Substances 0.000 title claims abstract description 31
- 239000010405 anode material Substances 0.000 title abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 213
- 239000000463 material Substances 0.000 claims abstract description 120
- 239000011248 coating agent Substances 0.000 claims abstract description 72
- 238000000576 coating method Methods 0.000 claims abstract description 72
- 238000003763 carbonization Methods 0.000 claims abstract description 48
- 238000001816 cooling Methods 0.000 claims description 81
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 31
- 239000003546 flue gas Substances 0.000 claims description 31
- 238000007599 discharging Methods 0.000 claims description 28
- 238000002485 combustion reaction Methods 0.000 claims description 18
- 238000005253 cladding Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims 1
- 238000005469 granulation Methods 0.000 abstract description 30
- 230000003179 granulation Effects 0.000 abstract description 30
- 238000000034 method Methods 0.000 abstract description 23
- 239000000126 substance Substances 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 238000005507 spraying Methods 0.000 description 13
- 239000010426 asphalt Substances 0.000 description 12
- 238000007789 sealing Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 230000005465 channeling Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 210000001503 joint Anatomy 0.000 description 3
- 239000011331 needle coke Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 102000020897 Formins Human genes 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011329 calcined coke Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a reaction device of a graphite anode material of a battery, which comprises a rotary reactor sequentially provided with a coating granulation section and a carbonization section, wherein the outer wall of a cylinder body at one side close to a feeding end of the rotary reactor is provided with a plurality of heating furnaces which are distributed at intervals and used for providing heat for a coating material making section, the heating furnaces sequentially comprise a first heating furnace, a second heating furnace and a third heating furnace along the material flow direction, and the internal temperature T of a rotary reactor section corresponding to the first heating furnace, the second heating furnace and the third heating furnace is controlled 1 、T 2 、T 3 And residence time t 1 、t 2 、t 3 . The invention also provides a continuous coating granulation-carbonization reaction device and process for the graphite anode material of the battery. The invention uses the temperature parameter during coating and granulatingThe control is that the coated granulation product has high tap density, small specific surface area and good physical and chemical properties, and the finally obtained graphite anode material has good electrochemical properties.
Description
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a preparation process and a preparation device of a negative electrode material.
Background
At present, graphite anode materials used in the lithium ion battery industry on a large scale are generally subjected to cladding granulation before graphitization so as to improve electrochemical performance, and carbonization is adopted to reduce material volatile matters and improve material tap density so as to improve material loading and operation safety of graphitization chemical industry. The preparation process of the graphite anode material of the lithium ion battery comprises the following steps of: firstly, petroleum coke/needle coke and asphalt are respectively crushed into 8-10 microns and 2-3 microns by a crushing device; mixing the two materials according to a certain proportion, then sending the mixture into a coating reaction kettle, arranging a resistance wire outside the reaction kettle, transferring heat to materials in the reaction kettle through the wall, controlling the temperature of the materials according to a certain temperature control curve, and finishing softening, melting of asphalt and coating and carbonization of focusing powder. However, the highest temperature of the materials is limited by heat transfer of equipment, the aromatic hydrocarbon which can be decomposed only at 650 ℃ when the high temperature of the asphalt is higher than 650 ℃ can not be decomposed, the materials which are coated on the reaction kettle are cooled to be lower than 100 ℃ by a cooling kettle of a water-cooling jacket indirect cooling device, then the materials are sent into a roller kiln or a tunnel kiln to be heated to 1000 ℃, the aromatic hydrocarbon in the asphalt is further decomposed and carbonized, then the materials are sent into a graphitization furnace to complete graphitization at about 3000 ℃, and the graphite anode material of the carbon-based lithium battery is obtained after cooling and treatment.
The existing coating granulation-carbonization process for graphite anode materials of lithium ion batteries has the following problems: 1. the main thermal equipment reaction kettle and the cooling kettle are intermittent operation equipment, and the single equipment has low processing capacity and high labor cost; 2. the single equipment has small processing capacity and low production efficiency due to heat transfer limitation; 3. the thermal system is unreasonable, the materials are heated to 650 ℃ in the coating reaction kettle, the materials are cooled to normal temperature by an indirect water cooling method through a cooling kettle during discharging, then the materials are sent into a roller kiln or a tunnel kiln, the temperature is raised to about 1000 ℃ again, and then the materials are cooled to normal temperature, so that the energy waste is serious.
Patent application CN113101887A discloses a continuous reaction treatment device for graphite negative electrode materials of lithium ion batteries/phosphates of lithium ion batteries and ternary positive electrode materials, which can well solve the problems. However, the temperature of the continuous reaction equipment is only divided into two areas, namely a coating granulation reaction temperature area (medium-low temperature area) and a carbonization temperature area (high temperature area), the temperature of a coating granulation section is difficult to accurately control, the channeling temperature of a heating furnace is serious, and the temperature control requirement of the low temperature area of 250-400 ℃ is difficult to meet by the traditional burner heating. The defects and the defects can lead to a rapid increase of temperature curve in the inner length direction of the rotary reactor, the temperature is too high during coating and granulating, the volatilization rate of the volatile matters of the materials is too high during coating and granulating, the tap density of a coating and granulating product is low, the specific surface area is large, and the physical and chemical properties of the final product are low.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings in the background art, and provides a reaction device of a battery graphite anode material with high tap density and small specific surface area and a continuous coating granulation-carbonization reaction process. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the utility model provides a reaction unit of battery graphite class negative pole material, includes the rotary reactor that is equipped with cladding pelleting section and carbomorphism section in proper order, the rotary reactor is equipped with on the one side barrel outer wall that is close to its feed end and is used for providing a plurality of interval distribution's of heat for cladding material section of making, a plurality of the heating furnace is first heating furnace, second heating furnace and third heating furnace in proper order along the material flow direction, just first heating furnace, second heating furnace and third heating furnace are used for controlling the inside temperature T of its heated rotary reactor section respectively 1 、T 2 、T 3 And the residence time t of the material in the corresponding rotary reactor sections of the first heating furnace, the second heating furnace and the third heating furnace respectively 1 、t 2 、t 3 The following relation is satisfied:
wherein ρ is 1 To the tap density, ρ of the discharged product 0 To the tap density of the initial material, beta 1 To the specific surface area of the discharged product, beta 0 The specific surface area of the initial material is less than or equal to 250 ℃ and less than or equal to T 1 ≤T 2 ≤T 3 ≤750℃，t 1 、t 2 、t 3 All are 20-180min, coefficient k 1 ＝(0.8-3)×10 4 Min, coefficient k 2 ＝(1.5-3.5)×10 4 Min, coefficient k 3 ＝(4.5-10)×10 4 Min, coefficient k 4 ＝(0.5-3)×10 3 Min, coefficient k 5 ＝(3-9)×10 3 ℃.min。
In the above reaction apparatus, T is preferably 1 、T 2 、T 3 250-400 ℃, 300-500 ℃, 450-750 ℃ and t respectively 1 、t 2 、t 3 20-60min, 30-100min and 20-80min respectively.
In the above reaction apparatus, T is preferably 1 、T 2 、T 3 250-400 deg.C, 400-450 deg.C, 450-650 deg.C, coefficient k 1 ＝(0.8-1.1)×10 4 Min, coefficient k 2 ＝(1.6-2.0)×10 4 Min, coefficient k 3 ＝(6.5-8.5)×10 4 Min, coefficient k 4 ＝(0.8-2)×10 3 Min, coefficient k 5 ＝(4-8)×10 3 ℃.min。
In the above-mentioned reaction apparatus, preferably,and->Considering that the difference of the temperature of each temperature interval and the residence time of the materials in the interval can influence the tap density and the specific surface area of the product, and the main influencing factors of the tap density and the specific surface area are different,the present invention requires control of temperature, residence time, and coefficient k to satisfy the above-described relation.
In the above reaction apparatus, preferably, the heating mode of the first heating furnace is hot air heating, and the heating modes of the second heating furnace and the third heating furnace are gas burner combustion heating.
In the above reaction device, preferably, the hot air discharged from the first heating furnace is sent to the inlet of the first combustion-supporting fan of the second heating furnace through the first induced draft fan to be used as the combustion-supporting air of the second heating furnace, so as to realize energy saving of the combustion system.
The research of the inventor finds that the residence time of different temperature sections during the coating granulation reaction has great influence on the tap density and specific surface area of a coated granulation product, specifically, the low-melting-point asphaltene substances in the materials to be coated are slowly and fully melted and coated on the surfaces of particles, and small particles are adhered to large particles to form secondary particles, the process ensures the sufficient residence time, ensures that the low-melting-point asphaltene can fully enter the holes in the particles in the dynamics of the coating reaction, fills the defects, reduces the holes of the particles, and realizes the full and complete coating of the surfaces of the particles. Prevent low-melting point asphaltene substances from being volatilized and carbonized rapidly due to overlarge temperature rising rate and not fully coating the particle surfaces, so that the tap density is reduced. The materials with fully coated particle surfaces are further slowly heated at 300-500 ℃ to crack heavy components in the asphaltene into low molecular substances to volatilize, and the partially activated molecules in the asphaltene are subjected to polycondensation and dehydrogenation to form an intermediate phase, so that the particle surfaces are coated with the materials, the dynamic rate of the process cannot be too high, otherwise, the heating rate is too high, the asphaltene components on the coated particle surfaces are quickly volatilized to form new secondary holes, so that the specific surface is increased and the tap density is reduced. The asphaltene on the surface of the particles forms a stable partially carbonized coating layer, volatile matters are discharged at the temperature of 450-750 ℃ and semicoke is formed for densification, and the temperature rising rate can be properly increased in the process.
In a more preferred embodiment, the residence time at 250-450℃during the coating granulation should be suitably prolonged in order to increase the tap density of the coated granulation product. In order to reduce the specific surface area of the product after coating granulation, the residence time of the coating granulation at 450-650 ℃ should be prolonged appropriately. According to the research results, the negative electrode base material and the coating material are mixed and then sequentially pass through a specific temperature zone and a specific residence time for heating reaction during continuous coating granulation reaction, and the final product has high tap density and small specific surface area. In a more preferred scheme, a coating section heating furnace of the rotary reactor is divided into three sections, the temperature of the first heating furnace is controlled to be 250-400 ℃, the temperature of the second heating furnace is controlled to be 400-450 ℃, and the temperature of the third heating furnace is controlled to be 450-650 ℃, so that the requirement of heating a material in a temperature division region within the range of 250-450 ℃ of the coating section of the rotary reactor is met, and the condition that the temperature of a low-temperature section is not controlled due to temperature channeling in the furnace when a single heating furnace is adopted in the coating section of the rotary reactor is prevented, and the reaction time of the low-temperature region is too short is further caused. By adopting the control of the coated granulation temperature zone and combining the control of the residence time of the materials in each section, the reaction time of the materials in each temperature zone can be controlled, and the final product has high density, small specific surface area and good physical and chemical properties.
In addition, the heating mode of the first heating furnace is hot air heating, the heating temperature is easier to control, heat exchange hot air can be utilized, and energy sources are saved.
The invention controls the internal temperature T of the heated rotary reactor section by using a first heating furnace, a second heating furnace and a third heating furnace respectively 1 、T 2 、T 3 And the residence time t of the material in the corresponding rotary reactor sections of the first heating furnace, the second heating furnace and the third heating furnace respectively 1 、t 2 、t 3 Satisfy the above relation and pass through each coefficient k 1 、k 2 And the like, the tap density and the specific surface area of the discharged product can be controlled, so that the electrochemical performance of the product is optimal.
In the above reaction device, preferably, a fourth heating furnace for providing heat for the carbonization section is provided on the outer wall of the cylinder at the carbonization section, the fourth heating furnace is disposed close to the third heating furnace, the internal temperature of the fourth heating furnace for controlling the heated rotary reactor section is 600-1150 ℃, and the internal temperature of the fourth heating furnace heated rotary reactor section is higher than the internal temperature of the third heating furnace heated rotary reactor section.
In the above reaction device, preferably, a first cooling component for primarily cooling the material after passing through the carbonization section is further arranged on the outer wall of the cylinder of the rotary reactor, the first cooling component is arranged close to the carbonization section, and the first cooling component is used for cooling the reaction material to below 200 ℃; and a second cooling component for further cooling the reaction materials to below 60 ℃ is arranged behind the first cooling component along the material flow direction. A first cooling component is arranged between the carbonization section of the rotary reactor and the middle discharging system to cool the reaction materials below 200 ℃, and a second cooling component is arranged between the middle discharging system and the discharging system to cool the materials below 60 ℃. The first cooling component and the second cooling component comprise a cooling machine, a water inlet pipe, a water outlet pipe, a spraying mechanism, a water spraying collecting tank, a water return pump and the like, wherein the water spraying collecting tank is arranged at the lower parts of the rotary reactor and the cooling machine, and the spraying mechanism is arranged above the rotary reactor and the cooling machine.
In the above reaction device, preferably, the carbonized flue gas discharged from the rotary reactor enters the flue gas incinerator through a flue gas pipeline after being dedusted by a flue gas deduster, the flue gas incinerator is provided with a hot gas outlet, and the hot gas outlet is communicated to a hot air inlet of the first heating furnace through a hot air furnace after being connected with a heat exchanger; and the flue gas pipeline is provided with a heat preservation device for preventing carbonized flue gas from condensing in the pipeline.
In the above reaction device, preferably, the rotary reactor is arranged obliquely, the feeding end of the rotary reactor is at a high position, and the discharging end of the rotary reactor is at a low position; the included angle between the central axis of the rotary reactor and the horizontal line is less than or equal to 10 degrees. The feeding end of the rotary reactor is provided with a kiln tail box body and a kiln tail sealing device, the discharging end of the rotary reactor is provided with a kiln head box body and a kiln head sealing device, and the kiln tail box body is provided with a smoke outlet for exhausting carbonized smoke in the rotary reactor; and the kiln tail sealing device and the kiln head sealing device are connected with a nitrogen pipeline.
In the above reaction apparatus, it is preferable that the first heating furnace, the second heating furnace, the third heating furnace, the fourth heating furnace and the cooling unit are all coaxial with the rotary reactor and are arranged at intervals.
As a general technical concept, the present invention also provides a continuous coating granulation-carbonization reaction process for a graphite negative electrode material of a battery using the above reaction apparatus, comprising the steps of:
s1: starting the rotary reactor, and starting the first heating furnace, the second heating furnace, the third heating furnace and the fourth heating furnace of the carbonization section to enable different parts of the rotary reactor to reach preset temperatures; turning on the first cooling assembly;
s2: the material obtained by mixing the negative electrode base material and the cladding material is sent into a rotary reactor through a feeding system;
s3: the materials entering the rotary reactor pass through a coating granulation section (corresponding to a section heated by a first heating furnace, a second heating furnace and a third heating furnace), a carbonization section (corresponding to a section heated by a fourth heating furnace) and a preliminary cooling section (corresponding to a section cooled by a first cooling component) of the rotary reactor in sequence through rotation and self-pushing, and the residence time of the materials in the coating granulation section is controlled;
s4: and (5) delivering the cooled material through a discharging system to complete the continuous coating granulation-carbonization reaction.
The invention relates to a reaction device for a graphite anode material of a battery, which sequentially comprises a feeding system, a kiln tail box, a rotary reactor, a kiln head box, an intermediate discharging system, a second cooling assembly and a discharging system along the material flow direction, wherein the feeding system and the intermediate discharging system are in butt joint with corresponding feeding ends and discharging ends of the rotary reactor, and the rotary reactor comprises a graphite anode material coating granulating section connected with the feeding ends, a carbonization section connected with the coating granulating section and a primary cooling section, so that the reaction material is sequentially and continuously conveyed from the feeding ends, the coating granulating section, the carbonization section and the primary cooling section to the discharging ends.
A first heating furnace, a second heating furnace and a third heating furnace which are used for realizing coating granulation of the reaction materials by heating are arranged outside the coating granulation section of the rotary reactor; a fourth heating furnace for carbonizing the reaction materials by heating is arranged outside the carbonization section of the rotary reactor; and a water spraying device for cooling the reaction materials through water spraying is arranged outside the first cooling component and the second cooling component of the rotary reactor. The heating mode of the first heating furnace is hot air heating, and the heating modes of the second, third and fourth heating furnaces are natural gas burner burning heating. The second, third and fourth heating furnaces comprise a furnace body and heating elements which are arranged on the furnace body and extend into the furnace body. The third and fourth heating furnaces have higher temperature, and heat is recovered through the regenerative burner.
Support devices for forming support for the corresponding positions of the rotary reactor are arranged outside the rotary reactor at intervals; the rotary reactor comprises a reactor body and a rotary driving piece, wherein the reactor body is arranged in the first heating furnace, the second heating furnace, the third heating furnace and the fourth heating furnace in a penetrating way and is in butt joint with the feeding system and the discharging system, and the rotary driving piece is arranged outside the reactor body and drives the reactor body to rotate.
The feeding system of the rotary reactor is communicated with the kiln tail box body through a feeding screw mechanism, and the discharge end of the rotary reactor is connected with the second cooling assembly through the middle discharge system and then discharged through the discharge system. Kiln tail sealing devices and kiln head sealing devices are respectively arranged on two sides of the feeding and discharging materials of the rotary reactor so as to ensure that external air does not enter the reactor; the sealing devices on the two sides of the material inlet and outlet of the rotary reactor and the second cooling assembly are provided with nitrogen inlet pipelines so as to ensure that nitrogen is filled into the reactor and ensure that the material is subjected to cladding granulation-carbonization reaction under the protection of nitrogen inert atmosphere.
When the reaction device for the graphite anode material of the battery is in operation, the rotary reactor is started first, so that the rotary reactor is operated and rotated; then starting the first heating furnace, the second heating furnace, the third heating furnace, the fourth heating furnace, the first cooling assembly and the second cooling assembly to enable the body of the corresponding section to reach a corresponding preset temperature zone; starting the feeding system again, and enabling materials (such as needle coke and asphalt mixed according to a certain proportion) to enter the rotary reactor through the feeding system; and finally, starting a discharging system to ensure that the materials subjected to the coating carbonization are output from the discharging system. Compared with the traditional structure, the device realizes the continuity of the working procedures of coating, carbonizing and cooling the battery graphite negative electrode material through the integrated rotary reactor, ensures the consistency of products and obviously improves the quality of the products; the equipment for coating the anode material coating reaction kettle, cooling the cooling kettle, carbonizing the roller kiln or the tunnel kiln and indirectly cooling water is replaced, the process flow and the labor intensity and the number of operators are greatly simplified, the energy consumption per ton of products is also greatly reduced, the equipment investment, the labor cost and the energy consumption cost are obviously reduced, and the equipment can be enlarged; meanwhile, the computer automatic control is easy to realize, so that the production cost is greatly reduced.
Compared with the prior art, the invention has the advantages that:
1. according to the reaction device for the graphite anode material of the battery, through controlling the temperature parameters (the temperature and the residence time meet the relation) during coating and granulating, the volatilization rate of the material during coating and granulating is proper, the tap density of a coating and granulating product is high, the specific surface area is small, the physical and chemical properties are good, and the electrochemical properties of the finally obtained graphite anode material are good.
2. According to the reaction device for the graphite anode material of the battery, the heating zone of the coating and granulating section of the rotary reactor is divided into three sections of coating and granulating sections, so that the temperature channeling problem caused by single heating temperature of the coating and granulating section is avoided, the three sections of temperature partitions of the coating and granulating section can ensure that the coating and granulating process is effectively carried out, the coating and granulating (such as asphalt coating coke powder) reaction is carried out orderly, the volatile component volatilization rate is controllable, the tap density of the product is higher, and the specific surface area is stable and controllable.
3. The reaction device and the process for the graphite negative electrode material of the battery have the advantages that the obtained graphite negative electrode product has high tap density, small specific surface area and good physical and chemical properties.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 shows a reaction apparatus for a graphite-based negative electrode material of a battery of example 1.
Fig. 2 is a process flow chart of a continuous coating granulation-carbonization reaction process of the graphite-based negative electrode material of the battery of example 1.
Legend description:
1. a feed system; 2. a kiln tail box body; 3. kiln tail sealing device; 4. a rotary reactor; 5. a first heating furnace; 6. a second heating furnace; 7. a third heating furnace; 8. a fourth heating furnace; 9. a first cooling assembly; 10. kiln head sealing device; 11. a kiln head box body; 12. a support device; 13. a driving device; 14. a second cooling assembly; 15. hot blast stove; 16. a first combustion fan; 17. a first induced draft fan; 18. a second induced draft fan; 19. a second combustion fan; 20. a third induced draft fan; 21. a water spraying collecting tank; 22. a water return pump; 23. a discharging system; 24. a flue gas dust remover.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
as shown in FIG. 1, the reaction device of the graphite anode material of the battery of the embodiment comprises a rotary reactor 4 which is sequentially provided with a coating granulation section and a carbonization section, wherein the rotary reactor 4A plurality of heating furnaces which are distributed at intervals and used for providing heat for the coating material making section are arranged on the outer wall of the cylinder body at one side close to the feeding end of the cylinder body, the heating furnaces are sequentially a first heating furnace 5, a second heating furnace 6 and a third heating furnace 7 along the material flow direction, and the first heating furnace 5, the second heating furnace 6 and the third heating furnace 7 are respectively used for controlling the internal temperature T of the section of the rotary reactor 4 heated by the heating furnaces 1 、T 2 、T 3 And the residence time t of the material in the zone of the rotary reactor 4 corresponding to the first 5, second 6 and third 7 heating furnaces, respectively 1 、t 2 、t 3 The following relation is satisfied:
wherein ρ is 1 To the tap density, ρ of the discharged product 0 To the tap density of the initial material, beta 1 To the specific surface area of the discharged product, beta 0 The specific surface area of the initial material is less than or equal to 250 ℃ and less than or equal to T 1 ≤T 2 ≤T 3 ≤750℃，t 1 、t 2 、t 3 All are 20-180min, coefficient k 1 ＝(0.8-3)×10 4 Min, coefficient k 2 ＝(1.5-3.5)×10 4 Min, coefficient k 3 ＝(4.5-10)×10 4 Min, coefficient k 4 ＝(0.5-3)×10 3 Min, coefficient k 5 ＝(3-9)×10 3 ℃.min。
In the present embodiment, T 1 、T 2 、T 3 250-400 ℃, 300-500 ℃, 450-750 ℃ and t respectively 1 、t 2 、t 3 20-60min, 30-100min and 20-80min respectively. More preferably, T 1 、T 2 、T 3 250-400 deg.C, 400-450 deg.C, 450-650 deg.C, coefficient k 1 ＝(0.8-1.1)×10 4 Min, coefficient k 2 ＝(1.6-2.0)×10 4 Min, coefficient k 3 ＝(6.5-8.5)×10 4 Min, coefficient k 4 ＝(0.8-2)×10 3 Min, coefficient k 5 ＝(4-8)×10 3 And (3) carrying out temperature control and min. Further toIt is preferable that the method comprises the steps of, and->
In the present embodiment, the heating mode of the first heating furnace 5 is hot air heating, and the heating modes of the second heating furnace 6 and the third heating furnace 7 are burner combustion heating.
In this embodiment, the hot air discharged from the first heating furnace 5 is sent to the inlet of the first combustion fan 16 of the second heating furnace 6 through the first induced draft fan 17 as the combustion air of the second heating furnace 6.
In this embodiment, the outer wall of the barrel body of the carbonization section of the rotary reactor 4 is provided with a fourth heating furnace 8 for providing heat for the carbonization section, the fourth heating furnace 8 is arranged close to the third heating furnace 7, the internal temperature of the section of the rotary reactor 4 heated by the fourth heating furnace 8 is controlled to be 600-1150 ℃, and the internal temperature of the section of the rotary reactor 4 heated by the fourth heating furnace 8 is higher than the internal temperature of the section of the rotary reactor 4 heated by the third heating furnace 7.
In the embodiment, a first cooling component 9 for primarily cooling the material after passing through the carbonization section is further arranged on the outer wall of the cylinder body of the rotary reactor 4, the first cooling component 9 is arranged close to the carbonization section, and the first cooling component 9 is used for cooling the reaction material to below 200 ℃; a second cooling module 14 for further cooling the reaction mass to below 60 ℃ is also provided downstream of the first cooling module 9 in the mass flow direction.
In the embodiment, carbonized flue gas discharged from the rotary reactor 4 enters a flue gas incinerator through a flue gas pipeline after being dedusted by a flue gas deduster 24, and the flue gas incinerator is provided with a hot gas outlet which is communicated with a hot air inlet of the first heating furnace 5 through a hot air furnace 15 after being connected with a heat exchanger; the flue gas pipeline is provided with a heat preservation device for preventing carbonized flue gas from condensing in the pipeline.
In the embodiment, the rotary reactor 4 is obliquely arranged, the feeding end of the rotary reactor 4 is at a high position, and the discharging end of the rotary reactor 4 is at a low position; the included angle between the central axis of the rotary reactor 4 and the horizontal line is less than or equal to 10 degrees.
As shown in fig. 2, the continuous coating granulation-carbonization reaction process of the graphite anode material of the battery by using the reaction device in this embodiment includes the following steps:
s1: starting the rotary reactor 4, and starting the first heating furnace 5, the second heating furnace 6, the third heating furnace 7 and the fourth heating furnace 8 of the carbonization section to enable different parts of the rotary reactor 4 to reach preset temperatures; turning on the first cooling module 9;
s2: the materials obtained by mixing the negative electrode base material and the cladding material are sent into a rotary reactor 4 through a feeding system 1;
s3: the materials entering the rotary reactor 4 pass through a coating granulating section and a carbonizing section of the rotary reactor 4 in sequence through the rotation and self-pushing of the rotary reactor 4, and the residence time of the materials in the coating granulating section is controlled;
s4: the cooled material is sent out through a discharging system 23, and the continuous coating granulation-carbonization reaction is completed.
Specifically, the reaction device for the graphite cathode material of the battery of the embodiment comprises a feeding system 1, a kiln tail box 2, a rotary reactor 4, a kiln head box 11, an intermediate discharging system, a second cooling component 14 and a discharging system 23, wherein the feeding system 1 and the discharging system 23 are in butt joint with corresponding feeding ends and discharging ends of the rotary reactor 4, and the rotary reactor 4 comprises a graphite cathode material coating granulating section connected with the feeding ends and a graphite cathode material carbonizing section and a cooling section connected with the coating granulating section, so that the reaction materials are sequentially and continuously conveyed from the feeding ends, the coating granulating section, the carbonizing section and the cooling section to the discharging ends. A first heating furnace 5, a second heating furnace 6 and a third heating furnace 7 which are used for realizing the cladding granulation of the reaction materials by heating are arranged outside the cladding granulation section of the rotary reactor 4; a fourth heating furnace 8 for carbonizing the reaction materials by heating is arranged outside the carbonization section of the rotary reactor 4; outside the first cooling module 9 and the second cooling module 14 of the rotary reactor 4 are arranged water spraying devices for cooling the reaction mass by spraying water.
The heating mode of the first heating furnace 5 is hot air heating, and the heating modes of the second heating furnace 6, the third heating furnace 7 and the fourth heating furnace 8 are natural gas burner burning heating. In the process of establishing the first, second, third and fourth temperature fields, as no material exists in the rotary reactor 4, no volatile matters enter the incinerator for incineration treatment, hot air of the first heating furnace 5 is provided by a hot blast stove 15 for combusting natural gas. After the materials enter the rotary reactor 4 for treatment, the flue gas enters an incinerator for incineration, and hot air obtained by heat exchange between high-temperature waste gas generated by the flue gas incineration and fresh air enters the hot air furnace 15 to provide a heat source for the first heating furnace 5. The hot air at the outlet of the first heating furnace 5 is sent out to the inlet of the first combustion-supporting fan 16 of the second heating furnace 6 through the first induced draft fan 17 to be used as the combustion air of the second heating furnace 6 to realize energy saving of a combustion system, a natural gas combustion burner device is arranged on the second heating furnace 6, natural gas and the combustion air sent in through the first combustion-supporting fan 16 are mixed to burn and release heat, and the combustion waste gas of the second heating furnace 6 is discharged outside through the second induced draft fan 18. The third heating furnace 7 and the fourth heating furnace 8 are respectively provided with a natural gas combustion burner device, natural gas and combustion air fed by the second combustion-supporting fan 19 are mixed and combusted to release heat, and combustion waste gas of the third heating furnace 7 and the fourth heating furnace 8 is discharged outside through the third induced fan 20.
The first cooling component 9 and the second cooling component 14 comprise a cooling machine, a water inlet pipe, a water outlet pipe, a spraying mechanism, a water spraying collecting tank 21, a water return pump 22 and the like, wherein the water spraying collecting tank 21 is arranged at the lower parts of the rotary reactor 4 and the cooling machine, and the spraying mechanism is arranged above the rotary reactor 4 and the cooling machine.
Nitrogen with purity not lower than 99% is introduced into the kiln tail box body 2, the kiln tail sealing device 3, the kiln head box body 11, the kiln head sealing device 10 and the second cooling component 14 of the rotary reactor 4 so that the materials react under the protection of nitrogen inert atmosphere.
The outside of the rotary reactor 4 is provided with supporting devices 12 at intervals for supporting the respective corresponding positions of the rotary reactor 4. Because the rotary reactor 4 is of a continuous integral structure, the length of the rotary reactor is longer, and the supporting devices 12 are arranged at intervals, so that the rotary reactor 4 is conveniently supported, and the stability of equipment is improved.
A driving device 13 for rotationally driving the rotary reactor 4 is installed outside the rotary reactor 4.
A flue gas dust remover 24 (gravity/filtration treatment device) is arranged on a flue gas outlet pipeline of the kiln tail box body 2 of the rotary reactor 4 to carry out dust purification on flue gas so as to prevent dust from settling and blocking in a subsequent flue gas pipeline. An electric tracing device is arranged on a flue gas outlet pipeline of a kiln tail box body 2 of the rotary reactor 4 so as to prevent low boiling point substances such as asphalt in flue gas from condensing in the flue gas pipeline to block the pipeline.
Specifically, the continuous coating granulation-carbonization reaction process of the graphite anode material of the battery of the embodiment comprises the following steps: firstly, starting the rotary reactor 4 and the first cooling component 9, and filling the nitrogen atmosphere in the rotary reactor 4 and the second cooling component 14; then starting each heating furnace and condensed water arranged outside the first cooling component 9 and the second cooling component 14 to enable the corresponding sections to reach the corresponding preset temperature areas; starting the feeding system 1 again, and conveying the mixed materials (such as needle coke and asphalt) mixed according to a certain proportion into the rotary reactor 4 through the feeding system 1; and finally, starting the middle discharging system and the discharging system 23 to ensure that the materials subjected to coating carbonization are output from the discharging system 23.
In order to better understand the scheme in the above embodiment, the present embodiment provides a process for coating, granulating and carbonizing an artificial graphite anode material, and the preparation method thereof includes the following steps:
(1) Selecting ash less than 0.6%, sulfur less than 0.5%, volatile less than 13%, and water<10% of petroleum coke is used as raw material, and is dried to moisture by a roller dryer<3, grinding with a mechanical mill, wherein the particle size distribution D of the ground coke powder 50 Material a was obtained =10 μm.
(2) Mixing the material A with asphalt with a softening point of 200-250 ℃ to obtain a mixture of 100:4, sending the mixture into a mixer for mixing to obtain a material B; the mixed materials are sent into a continuous feed bin through a vacuum feeder and then sent into a rotary reactor 4 through a screw conveyor,then coating granulation and carbonization are carried out under the protection of nitrogen, the included angle between the axis of the rotary reactor 4 and the horizontal line is 1.5 degrees, the rotating speed is 0.5rpm, the temperatures of the first heating furnace 5, the second heating furnace 6, the third heating furnace 7 and the fourth heating furnace 8 are respectively controlled to 300 ℃, 450 ℃, 650 ℃ and 950 ℃, and the residence time of materials in the areas of the first heating furnace 5, the second heating furnace 6, the third heating furnace 7 and the fourth heating furnace 8 is respectively 20min, 30min, 20min and 40min, and the coefficient k is the same as the coefficient k 1 Taking 1×10 4 Min, coefficient k 2 1.7X10 were taken 4 Min, coefficient k 3 Taking 6.5X10 4 Min, coefficient k 4 1.9X10 were taken 3 Min, coefficient k 5 Taking 6.5X10 3 And (3) cooling at the temperature of the second step for min to obtain a coated granulating carbonized product C.
In this example, the initial raw material had a tap density of 0.56g/cm3 and a specific surface area of 3.2m 2 And/g. After the process, the granularity distribution D of the discharged material C is detected 50 =15.60 μm, tap density of 0.90g/cm3, specific surface area of 1.8m 2 /g, volatile content<0.6％。
Example 2:
the reaction device and process of the battery graphite negative electrode material of this example are the same as those of example 1.
The embodiment provides a coating granulation-carbonization reaction process of an artificial graphite anode material, wherein in the step (1), coke powder is calcined coke, and the preparation method comprises the following steps:
(1) Selecting ash less than 0.5%, sulfur less than 0.5%, volatile less than 0.4%, and water<1% calcined coke is used as raw material, and is ground by a mechanical mill, and the particle size distribution D of the ground coke powder 50 Material a was obtained =8 μm.
(2) Mixing the material A with asphalt with a softening point of 200-250 ℃ to obtain a mixture of 100:10, feeding the mixture into a mixer for mixing to obtain a material B; the mixed materials are sent into a continuous feed bin through a vacuum feeder, then sent into a rotary reactor 4 through a screw conveyor, and then subjected to cladding granulation and carbonization under the protection of nitrogen, and the axis of the rotary reactor 4 and waterThe included angle of the flat lines is 1.5 degrees, the rotating speed is 1rpm, the temperatures of the first heating furnace 5, the second heating furnace 6, the third heating furnace 7 and the fourth heating furnace 8 are respectively controlled at 250 ℃, 400 ℃, 650 ℃ and 950 ℃, and the residence time of materials in the areas of the first heating furnace 5, the second heating furnace 6, the third heating furnace 7 and the fourth heating furnace 8 is respectively 20min, 40min, 25min and 40min, and the coefficient k is the coefficient k 1 Taking 0.85×10 4 Min, coefficient k 2 Taking 2.3X10 4 Min, coefficient k 3 Taking 8.5X10 4 Min, coefficient k 4 Taking 1×10 3 Min, coefficient k 5 Taking 6.5X10 3 And (3) cooling at the temperature of the second step for min to obtain a coated granulating carbonized product C.
In this example, the initial raw material had a tap density of 0.58g/cm3 and a specific surface area of 4.5m 2 And/g. After the process, the granularity distribution D of the discharged material C is detected 50 =17.50 μm, tap density 0.9g/cm3, specific surface area 1.85m 2 /g, volatile content<0.6％。
Comparative example 1:
the difference between this comparative example and example 1 is the temperature partition and residence time experienced in the rotary reactor 4 during the material coating granulation and carbonization processes.
The method specifically comprises the following steps:
(1) Step (1) of example 1 is followed.
(2) Mixing the material A with asphalt with a softening point of 200-250 ℃ to obtain a mixture of 100:4, sending the mixture into a mixer for mixing to obtain a material B; the mixed materials are sent into a continuous feed bin through a vacuum feeder, then sent into a rotary reactor 4 (the temperature of a first heating furnace 5 and the temperature of a second heating furnace 6 are respectively controlled at 400-650 ℃ (the temperature interval) and 950 ℃), then subjected to cladding granulation and carbonization reaction under the protection of nitrogen, the included angle between the axis of the rotary reactor 4 and a horizontal line is 1.5 DEG, the rotating speed is 0.5rpm, the residence time of the materials in the areas of the first heating furnace 5 and the second heating furnace 6 is 100min and 40min respectively, and the cladding granulation carbonized product C is obtained after cooling in a cooling section.
Through detection, the granularity distribution D of the material C 50 ＝13.40μm, tap density 0.68g/cm3, specific surface area 2.4m 2 /g, volatile content<0.6％。
Comparative example 2:
the difference between this comparative example and example 2 is the temperature partition and residence time experienced in the rotary reactor 4 during the material coating granulation and carbonization processes.
The method specifically comprises the following steps:
(1) Step (1) of example 2 is followed.
(2) Mixing the material A with asphalt with a softening point of 200-250 ℃ to obtain a mixture of 100:10, feeding the mixture into a mixer for mixing to obtain a material B; the mixed materials are sent into a continuous feed bin through a vacuum feeder, then sent into a rotary reactor 4 with two temperature partitions through a screw conveyor, then subjected to cladding granulation and carbonization reaction under the protection of nitrogen, the included angle between the axis of the rotary reactor 4 and a horizontal line is 1.5 degrees, the rotating speed is 1rpm, the temperatures of a first heating furnace 5 and a second heating furnace 6 are respectively controlled at 400-650 ℃ (temperature interval) and 950 ℃, the residence time of the materials in the areas of the first heating furnace 5 and the second heating furnace 6 is respectively 100min and 40min, and the cladding granulation carbonized product C is obtained after cooling through a cooling section.
Through detection, the granularity distribution D of the material C 50 =13 μm, tap density 0.69g/cm3, specific surface area 2.5m 2 /g, volatile content<0.6％。
Comparative example 3:
the difference between this comparative example and example 1 is that the residence time in the rotary reactor 4 for each temperature zone is different during the material-coating granulation and carbonization processes.
The method specifically comprises the following steps:
(1) Step (1) of example 1 is followed.
(2) The same as the other operations of step (1) of example 1, but the residence times of the materials in the areas of the first heating furnace 5, the second heating furnace 6, the third heating furnace 7 and the fourth heating furnace 8 were 15min, 20min and 40min, respectively (coefficient k 1 Taking 0.75X10 4 Min, coefficient k 2 Taking 1.1X10 4 Min, coefficient k 3-5 Can be the same as in example 1), cooledCooling the cooling section to obtain the coated granulation carbonized product C.
Through detection, the granularity distribution D of the material C 50 =12 μm, tap density 0.7g/cm3, specific surface area 2.0m 2 /g, volatile content<0.8%. As can be seen from this comparative example, the residence time does not meet the requirements, even if the coefficient k is set 1 、k 2 The reduction of the volume and the specific surface area cannot be achieved to the level of example 1, i.e. the temperature, residence time and coefficient k of each zone of the present invention need to be reasonably controlled to achieve excellent product performance.
Claims (10)
1. The utility model provides a reaction unit of battery graphite class negative pole material, includes rotary reactor (4) that are equipped with cladding pelletization section and carbomorphism section in proper order, its characterized in that, rotary reactor (4) are equipped with on the one side barrel outer wall that is close to its feed end and are used for providing a plurality of interval distribution's of heat for cladding material section of making, a plurality of heating furnace is first heating furnace (5), second heating furnace (6) and third heating furnace (7) in proper order along the material flow direction, just first heating furnace (5), second heating furnace (6) and third heating furnace (7) are used for controlling the inside temperature T of its heated rotary reactor (4) district section respectively 1 、T 2 、T 3 And the residence time t of the material in the sections of the rotary reactor (4) corresponding to the first heating furnace (5), the second heating furnace (6) and the third heating furnace (7) respectively 1 、t 2 、t 3 The following relation is satisfied:
wherein ρ is 1 To the tap density, ρ of the discharged product 0 To the tap density of the initial material, beta 1 To the specific surface area of the discharged product, beta 0 The specific surface area of the initial material is less than or equal to 250 ℃ and less than or equal to T 1 ≤T 2 ≤T 3 ≤750℃，t 1 、t 2 、t 3 All are 20-180min, coefficient k 1 ＝(0.8-3)×10 4 Min, coefficient k 2 ＝(1.5-3.5)×10 4 Min, coefficient k 3 ＝(4.5-10)×10 4 Min, coefficient k 4 ＝(0.5-3)×10 3 Min, coefficient k 5 ＝(3-9)×10 3 ℃.min。
2. The reaction apparatus of claim 1, wherein T is 1 、T 2 、T 3 250-400 ℃, 300-500 ℃, 450-750 ℃ and t respectively 1 、t 2 、t 3 20-60min, 30-100min and 20-80min respectively.
3. The reaction apparatus of claim 2, wherein T is 1 、T 2 、T 3 250-400 deg.C, 400-450 deg.C, 450-650 deg.C, coefficient k 1 ＝(0.8-1.1)×10 4 Min, coefficient k 2 ＝(1.6-2.0)×10 4 Min, coefficient k 3 ＝(6.5-8.5)×10 4 Min, coefficient k 4 ＝(0.8-2)×10 3 Min, coefficient k 5 ＝(4-8)×10 3 ℃.min。
4. A reaction device according to claim 3, wherein,and is also provided with
5. The reaction device according to any one of claims 1 to 4, wherein the heating mode of the first heating furnace (5) is hot air heating, and the heating modes of the second heating furnace (6) and the third heating furnace (7) are gas burner combustion heating.
6. The reaction device according to claim 5, characterized in that the hot air discharged from the first heating furnace (5) is fed into the inlet of the first combustion fan (16) of the second heating furnace (6) as combustion air of the second heating furnace (6) via the first induced draft fan (17).
7. The reaction device according to any one of claims 1-4, characterized in that the rotary reactor (4) is provided with a fourth heating furnace (8) on the outer wall of the cylinder at the carbonization section for providing heat to the carbonization section, the fourth heating furnace (8) is arranged close to the third heating furnace (7), the internal temperature of the section of the rotary reactor (4) for controlling the heating thereof by the fourth heating furnace (8) is located at 600-1150 ℃, and the internal temperature of the section of the rotary reactor (4) heated by the fourth heating furnace (8) is higher than the internal temperature of the section of the rotary reactor (4) heated by the third heating furnace (7).
8. The reaction device according to any one of claims 1 to 4, characterized in that a first cooling component (9) for primarily cooling the material after passing through the carbonization section is further arranged on the outer wall of the cylinder of the rotary reactor (4), the first cooling component (9) is arranged close to the carbonization section, and the first cooling component (9) is used for cooling the reaction material to below 200 ℃; and a second cooling component (14) for further cooling the reaction materials to below 60 ℃ is arranged behind the first cooling component (9) along the material flow direction.
9. The reaction device according to any one of claims 1 to 4, characterized in that the carbonized flue gas discharged from the rotary reactor (4) enters a flue gas incinerator through a flue gas duct after being dedusted by a flue gas deduster (24), the flue gas incinerator is provided with a hot gas discharge port which is communicated to a hot air inlet of the first heating furnace (5) through a hot air furnace (15) after being connected with a heat exchanger; and the flue gas pipeline is provided with a heat preservation device for preventing carbonized flue gas from condensing in the pipeline.
10. A continuous coating granulation-carbonization reaction process of a graphite-based negative electrode material of a battery using the reaction apparatus of any one of claims 1 to 9, characterized by comprising the steps of:
s1: starting the rotary reactor (4), and starting the first heating furnace (5), the second heating furnace (6), the third heating furnace (7) and the fourth heating furnace (8) of the carbonization section to enable different parts of the rotary reactor (4) to reach preset temperatures;
s2: the materials obtained by mixing the negative electrode base material and the coating material are sent into a rotary reactor (4) through a feeding system (1);
s3: the materials entering the rotary reactor (4) pass through a coating granulating section and a carbonizing section of the rotary reactor (4) in sequence through the rotation and self-pushing of the rotary reactor (4), and the residence time of the materials in the coating granulating section is controlled;
s4: and (3) delivering the cooled material through a discharging system (23) to complete the continuous coating granulation-carbonization reaction.
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