CN113526481A - Method for preparing lithium ion battery anode material by fluidized sintering - Google Patents
Method for preparing lithium ion battery anode material by fluidized sintering Download PDFInfo
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- CN113526481A CN113526481A CN202010294952.4A CN202010294952A CN113526481A CN 113526481 A CN113526481 A CN 113526481A CN 202010294952 A CN202010294952 A CN 202010294952A CN 113526481 A CN113526481 A CN 113526481A
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- 238000005245 sintering Methods 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000010405 anode material Substances 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000002425 crystallisation Methods 0.000 claims abstract description 29
- 230000008025 crystallization Effects 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 21
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 19
- 239000008187 granular material Substances 0.000 claims description 14
- 239000010406 cathode material Substances 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005243 fluidization Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 26
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000000354 decomposition reaction Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 8
- 229910013716 LiNi Inorganic materials 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 5
- 229910001947 lithium oxide Inorganic materials 0.000 description 5
- 239000011236 particulate material Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009768 microwave sintering Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- 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
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- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a method for preparing a lithium ion battery anode material by fluidized sintering, which comprises the following steps: step 1, mixing materials; step 2, granulating; step 3, fluidizing and presintering; step 4, high-temperature crystallization; step 5, crushing: and 6, demagnetizing and grading. According to the invention, a large amount of waste gas generated by the precursor and the lithium salt is discharged in time through fluidized pre-sintering, and decomposition of the precursor, melting of the lithium salt and preliminary combination reaction of the precursor and the lithium salt are realized at the same time; fluxing agents which are easy to form and generate alkali corrosion do not exist in the high-temperature crystallization kiln, so that the problem of forming of the anode material of the lithium ion battery prepared by the dynamic kiln is solved; no decomposition gas products are formed in the high-temperature crystallization kiln, and the atmosphere in the kiln is stable and easy to control; the mass and heat transfer process is enhanced, the production energy consumption is obviously reduced, and the consistency and batch stability of the product are obviously improved; the method realizes the preparation of the lithium ion battery anode material by a large-scale, continuous and short-time sintering method.
Description
Technical Field
The invention relates to the field of preparation of lithium ion battery anode materials, in particular to a method for preparing a lithium ion battery anode material by a fluidized sintering method.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, good safety performance and the like, is widely applied to the fields of 3C products, electric automobiles and the like, and becomes one of the most widely applied batteries with the most development prospect at present. The global lithium ion battery yield in 2018 is 188.8GWh, and the industrial scale reaches $ 412 billion. In 2018, the goods output of lithium ion batteries in China already occupies 57% of the world, and the lithium ion batteries are the biggest manufacturing country of the lithium ion batteries in the world beyond Korea and Japan. The anode material accounts for 30-40% of the total cost of the lithium ion battery, directly determines the working voltage, capacity, service life, safety and cost of the battery, and is one of the most important materials of the lithium ion battery.
According to statistics, in 2019, the goods output of the lithium ion battery anode material in China reaches 40.4 ten thousand tons, the output value exceeds 800 hundred million yuan, and the output of the lithium ion battery anode material continuously keeps 30-50% of composite growth rate in the next few years. With the further development of new energy vehicles and energy storage markets, on one hand, the batch type static sintering kilns with low single-furnace capacity, such as pushed slab kilns and roller kilns, are difficult to meet the requirement for manufacturing large-scale lithium ion battery anode materials; on the other hand, the problems caused by low efficiency and high energy consumption of the anode material sintering equipment hinder the further mass production and application of the anode material. Taking a roller kiln for sintering the layered oxide cathode material as an example, firstly, a mixture of a precursor and a lithium salt is placed in a sagger, and the mass and heat transfer in the sagger during the gas-solid reaction process is insufficient; secondly, the temperature field distribution of a high-temperature section in the furnace is not uniform due to the cold air introduced into the one-section type kiln; finally, the gas generated by decomposing the precursor and the lithium salt in the kiln stays in the kiln for a long time, and the atmosphere in the kiln is difficult to control, so that the physicochemical property and the electrochemical performance of the lithium ion battery anode material are influenced. Therefore, the development of a high-efficiency green technology for preparing the lithium ion battery cathode material with high productivity and sufficient mass and heat transfer is urgently needed.
Chinese patent document CN102092699A discloses a method for preparing a lithium iron phosphate anode material by a continuous microwave sintering method: the method adopts microwave sintering equipment, the temperature distribution in a sintering kiln is uniform, and the preparation of the lithium iron phosphate material with excellent electrochemical performance is facilitated; according to the method, three microwave sintering kilns are connected in series to form a continuous and three-stage sintering process of pretreatment, presintering and sintering of the lithium iron phosphate precursor, and the aim of efficiently and continuously preparing the lithium iron phosphate anode material is fulfilled in a non-oxidizing atmosphere.
PCT patent document PCT/KR2012/001872 discloses a method for preparing a lithium ion electrode material using a rotary kiln: the method comprises the steps of placing materials in a sealed heatable barrel with a certain inclination angle, enabling the materials to roll and advance along with the rotation of a furnace body, enabling mass and heat transfer in a kiln to be more sufficient, maintaining the positive pressure of 0.01-1kPa in the furnace by inert gas, and roasting at 400-1000 ℃ to obtain the required lithium ion battery electrode material. By the method, the lithium ion battery electrode material with better electrochemical performance, such as carbon-coated LiFePO, can be continuously prepared in a large scale in a non-oxidizing atmosphere or an inert atmosphere4。
Although the method partially solves the problems of high energy consumption, low yield and the like of the intermittent kiln, the oxide type lithium ion battery anode material cannot be prepared, the furnace forming problem caused by lithium salt is not solved, and the application of the method in the preparation of the oxide type lithium ion battery anode is greatly limited.
In order to solve the problem of material sintering in a dynamic sintering kiln, PCT patent document PCT/JP2010/062620 and chinese patent document CN105428589A disclose a preparation method for preparing an oxide type lithium ion battery cathode material: the method comprises the steps of preparing spherical or ellipsoidal particles with a certain size from a precursor and lithium salt powder, and sintering the particles in a rotary kiln, so that the sintering of the kiln is better avoided while the heat efficiency is improved and the sintering time is reduced, and the purpose of preparing the oxide type lithium ion battery anode material by continuous heating and sintering is realized.
However, none of the above publications can fundamentally solve the problem of furnace formation caused by a lithium salt flux such as lithium carbonate, lithium hydroxide, lithium oxide in the raw material; in addition, the precursor and lithium salt are decomposed to produce a gas such as CO2、H2O and the like stay in the one-section dynamic heating kiln for a long time, which is not beneficial to controlling the atmosphere and the temperature in the kiln.
Disclosure of Invention
The invention provides a method for preparing a lithium ion battery anode material by fluidized sintering, and aims to greatly improve the mass transfer effect of gas-solid reaction in the material preparation process, solve the problems of nonuniform temperature distribution in a kiln, difficult control of atmosphere and furnace accretion and realize low energy consumption and large-scale production of the lithium ion battery anode material with good consistency.
In order to achieve the above object, an embodiment of the present invention provides a method for preparing a positive electrode material of a lithium ion battery by fluidized sintering, including the following steps:
step 1, mixing materials:
weighing lithium salt and a precursor according to a metering ratio, adding the lithium salt and the precursor into a mixing device, and mixing to obtain a mixed material, wherein the stoichiometric ratio of lithium atoms in the lithium salt to total metal atoms in the precursor is 0-1.5: 1.
step 2, granulation:
granulating the mixed material by granulation equipment to obtain spherical or ellipsoidal granular materials; wherein, a binder is added in the granulation process, and the particle size of the spherical or ellipsoidal particle material is as follows: 10um < d <10 cm.
Step 3, fluidization presintering:
conveying the granular materials to fluidized dynamic pre-sintering equipment for pre-sintering, and introducing hot gas A heated by a hot blast stove A into the fluidized dynamic pre-sintering equipment, wherein the temperature of the hot gas A is as follows: 200 deg.C<TA<At 1300 deg.C, the flow direction of hot gas A is opposite to the movement direction of the granular material, so that the granular material is in fluidized state, and the presintering time t1Comprises the following steps: for 10min<t1<The pre-sintering is carried out for 600min, a pre-sintered material is obtained after pre-sintering, gas generated by decomposing the particle material is discharged out of fluidized dynamic pre-sintering equipment along with hot air A, the gas is conveyed to a hot air furnace A after solid is separated, and the solid obtained by separation and the pre-sintered material enter the next high-temperature crystallization process;
and 4, high-temperature crystallization:
conveying the pre-sintered material to a high-temperature crystallization furnace for high-temperature crystallization, and introducing hot air B heated by a hot air furnace B, wherein the temperature of the hot air B is as follows: 200 deg.C<TB<1500 ℃ high temperature crystallization time t2Comprises the following steps: 60min<t2<1200 min; after finishing mass transfer and heat transfer, the hot air B is discharged out of the high-temperature crystallization furnace, and is conveyed to the hot air furnace B after solid is separated; the solid obtained by separation and the crystal particle material crystallized at high temperature enter the next crushing procedure;
step 5, crushing:
crushing the crystal particle material crystallized at high temperature into a powder material;
step 6, demagnetizing and grading:
the powder material sequentially passes through a demagnetizing and grading device to obtain the lithium ion battery anode materials with different particle sizes.
Preferably, in the step 1, the stoichiometric ratio of lithium atoms in the lithium salt to total metal atoms in the precursor is 0.9-1.1: 1.
preferably, in the step 2, the binder is one or more of steam and biomass starch.
Preferably, in step 2, the particle size of the spherical or ellipsoidal particulate material is 50um < d <5 mm.
Preferably, in step 3, the hot gas A has the components of air and N2、H2、CO2、Ar、CO、H2O、O2One or more of He and Ne.
Preferably, the temperature of the hot gas a is: 500 deg.C<TA<1000℃。
Preferably, in the step 4, the high-temperature sintering furnace adopts fluidized dynamic sintering equipment or static sintering equipment.
Preferably, in the step 4, the hot gas B has the components of air and N2、H2、CO2、Ar、CO、H2O、O2One or more of He and Ne.
Preferably, the temperature of the hot gas B is: 600 deg.C<TB<1100℃。
The scheme of the invention has the following beneficial effects:
(1) the fluidized presintering can discharge a large amount of waste gas generated by the precursor and lithium salt in time, and the atmosphere in the kiln can be better controlled; simultaneously realizing the decomposition of the precursor, the melting of lithium salt and the preliminary combination reaction of the precursor and the lithium salt;
(2) the decomposition of the precursor and the lithium salt is completed in the pre-sintering process, and a fluxing agent which is easy to form a furnace and generates alkali corrosion does not exist in the high-temperature crystallization kiln, so that the problem of furnace formation of the lithium ion battery anode material prepared by a dynamic kiln is solved;
(3) the mass transfer and heat transfer processes of the gas-solid reaction between the reaction gas and the raw material are enhanced, the production energy consumption of the unit lithium ion battery anode material is obviously reduced, and the consistency and batch stability of the product are obviously improved;
(4) no decomposition gas products are formed in the high-temperature crystallization kiln, and the atmosphere in the kiln is stable and easy to control;
(5) the lithium ion battery anode material is prepared by a large-scale, continuous and short-time sintering method, and the annual capacity of a single production line can exceed 5 ten thousand tons per year; the production cost of the unit lithium ion battery anode material is reduced.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Example 1
As shown in fig. 1, an embodiment of the present invention provides a method for preparing a positive electrode material of a lithium ion battery by fluidized sintering, including the following steps:
step 1, mixing materials:
the precursor FePO4With Li2CO3According to the stoichiometric ratio of 1.05: 1, weighing, and simultaneously adding the weighed materials into a high-speed mixer for mixing;
step 2, granulation:
putting the uniformly mixed materials into a roller pressing type granulator for granulation, so that the size of the obtained spherical granular materials is 50um < d <5mm, wherein the particle size of less than 20% of the spherical granular materials is less than 250 um; 2 wt.% of water vapor was added as a binder during the granulation process;
step 3, fluidization presintering:
pre-sintering the granular material obtained in the step (2) by adopting a fluidized bed furnace, and introducing hot gas A heated by an external combustion hot blast stove into the fluidized bed furnace, wherein the hot gas A is 95 percent of N2With 5% of H2At 700 ℃, gas is counter-currently fed into the fluidized bed furnace relative to the particulate material to fluidize the particulate material, and the pre-sintering time t is1For 60min, after sufficient mass and heat transfer, the particulate material is heated, and the Li in the particulate material2CO3After decomposition, lithium oxide and CO are formed2Lithium oxide with FePO precursor4Combining under reducing atmosphere to generate initial crystal LiFePO with incomplete crystal4；CO2Discharging the mixture out of the fluidized bed furnace along with the hot air A, separating solids and conveying the solids to the hot air furnace A; separating the solid obtained and the initial crystalline LiFePO obtained by presintering4The solid particles enter the next high-temperature crystallization process together;
and 4, high-temperature crystallization:
adopting a rotary kiln to carry out primary crystallization on LiFePO4Continuously sintering at high temperature, introducing hot gas B heated by an external combustion hot blast stove B into the rotary kiln, wherein the hot gas B accounts for 95% of N2And 5% of H2At a temperature of 800 ℃ for a high temperature crystallization time t2At the temperature provided by hot gas B, the LiFePO is initially crystallized for 300min4Completing the processes of high-temperature crystallization, crystal structure ordering and the like to obtain the LiFePO with complete crystallization4Crystal particles; after finishing mass transfer and heat transfer, the hot air B is discharged out of the high-temperature crystallization furnace and separated into LiFePO4Conveying the crystal to a hot blast stove B, and separating to obtain LiFePO4The crystal enters the next crushing procedure;
step 5, crushing:
adopting an airflow crusher to crush the LiFePO obtained in the step 44LiFePO obtained by separating hot air B from crystal particles4Crushing the crystal particles into powder materials;
step 6, demagnetizing and grading:
the powder material obtained in the step 5 passes through the electric current in sequenceMagnetic separator and air flow classifier to obtain LiFePO with different grain sizes4A lithium ion battery anode material.
Example 2:
step 1, mixing materials:
the precursor Ni0.6Co0.2Mn0.2(OH)21.1 with LiOH according to the stoichiometric ratio: 1, weighing, and adding into a high-speed mixer for mixing;
step 2, granulation:
granulating the uniformly mixed materials by a roller pressing type granulator to obtain spherical granular materials with the size of 50um < d <5mm, wherein the particle size of less than 20% of the spherical granular materials is less than 300 um; 2 wt.% of water vapor was added as a binder during the granulation process;
step three: fluidization presintering:
presintering by using a fluidized flash roasting furnace, and introducing hot gas A heated by an external combustion hot blast stove into the fluidized flash roasting furnace, wherein the hot gas A is air, the temperature is 750 ℃, and the presintering time t is1Feeding gas into fluidized flash roaster in countercurrent flow relative to the granular material for 120min to make the granular material in fluidized state, heating the granular material after sufficient mass and heat transfer, and Ni0.6Co0.2Mn0.2(OH)2Decomposition to form Ni0.6Co0.2Mn0.2OxAnd H2Decomposition of O, LiOH to form lithium oxide and H2O, lithium oxide and Ni0.6Co0.2Mn0.2OxChemically synthesizing into initial crystal LiNi with incomplete crystal in weak oxidizing atmosphere0.6Co0.2Mn0.2O2Solid particles; h2Discharging the O out of the fluidized bed furnace along with the hot air A, separating solids and conveying the solids to the hot air furnace A; the solid obtained by separation and the primary crystalline LiNi obtained by presintering0.6Co0.2Mn0.2O2The solid particles enter the next high-temperature crystallization process together;
and 4, high-temperature crystallization:
adopting a fluidized bed furnace to carry out primary sinteringCrystalline LiNi0.6Co0.2Mn0.2O2The solid particles are sintered at high temperature, and hot gas B heated by an external combustion hot blast stove B is introduced into the fluidized bed furnace, wherein the hot gas B is 95 percent of O2With 5% air at 1000 deg.C for high temperature crystallization time t2For 480min, LiNi was primary-crystallized0.6Co0.2Mn0.2O2The solid particles finish the processes of high-temperature crystallization, crystal structure ordering and the like in hot gas B to obtain the LiNi with complete crystallization0.6Co0.2Mn0.2O2Crystal particles; after finishing mass transfer and heat transfer, the hot air B is discharged out of the fluidized bed furnace and LiNi is separated0.6Co0.2Mn0.2O2Conveying the crystal particles to a hot blast stove B, and separating to obtain LiNi0.6Co0.2Mn0.2O2The crystal particles enter the next crushing procedure;
step 5, crushing:
and (4) adopting a jet mill to subject the LiNi obtained in the step (4) to LiNi0.6Co0.2Mn0.2O2Crushing the crystal particles into powder materials;
step 6, demagnetizing and grading:
sequentially passing the powder material through an electromagnetic separator and an air flow classifier to obtain LiNi with different grain diameters0.6Co0.2Mn0.2O2A lithium ion battery anode material.
The invention can greatly improve the mass transfer effect of gas-solid reaction in the material preparation process, reduce the production energy consumption, solve the problem of uneven temperature distribution in the kiln, ensure that no gas product exists during high-temperature sintering through fluidized pre-sintering, the atmosphere is easy to control and the furnace is not caked, the product consistency is good, and the annual capacity of a single production line can exceed 5 ten thousand tons per year; the production cost of the unit lithium ion battery anode material is reduced, and the lithium ion battery anode material can be continuously and efficiently prepared in a large scale.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. A method for preparing a lithium ion battery anode material by fluidized sintering is characterized by comprising the following steps:
step 1, mixing materials:
weighing lithium salt and a precursor according to a metering ratio, adding the lithium salt and the precursor into a mixing device, and mixing to obtain a mixed material, wherein the stoichiometric ratio of lithium atoms in the lithium salt to total metal atoms in the precursor is 0-1.5: 1;
step 2, granulation:
granulating the mixed material by granulation equipment to obtain spherical or ellipsoidal granular materials; wherein, a binder is added in the granulation process, and the particle size of the spherical or ellipsoidal particle material is as follows: 10um < d <10 cm;
step 3, fluidization presintering:
conveying the granular materials to fluidized dynamic pre-sintering equipment for pre-sintering, and introducing hot gas A heated by a hot blast stove A into the fluidized dynamic pre-sintering equipment, wherein the temperature of the hot gas A is as follows: 200 deg.C<TA<At 1300 ℃, the flowing direction of hot gas A is opposite to the moving direction of the particle materials, so that the particle materials are in a fluidized state, and the pre-sintering time is as follows: for 10min<t1<The pre-sintering is carried out for 600min, a pre-sintered material is obtained after pre-sintering, gas generated by decomposing the particle material is discharged out of fluidized dynamic pre-sintering equipment along with hot air A, the gas is conveyed to a hot air furnace A after solid is separated, and the solid obtained by separation and the pre-sintered material enter the next high-temperature crystallization process;
and 4, high-temperature crystallization:
conveying the pre-sintered material to a high-temperature crystallization furnace for high-temperature crystallization, and introducing hot air B heated by a hot air furnace B, wherein the temperature of the hot air B is as follows: 200 deg.C<TB<1500 ℃ high temperature crystallization time t2Comprises the following steps: 60min<t2<1200min, after finishing mass transfer and heat transfer, discharging the hot air B out of the high-temperature crystallization furnace, separating solids and conveying the solids to a hot air furnace B; separating the obtained solid and the high-temperature junctionThe crystallized crystal particle materials enter the next crushing procedure together;
step 5, crushing:
crushing the crystal particle material crystallized at high temperature into a powder material;
step 6, demagnetizing and grading:
the powder material sequentially passes through a demagnetizing and grading device to obtain the lithium ion battery anode materials with different particle sizes.
2. The method for preparing the lithium ion battery cathode material through fluidized sintering according to claim 1, wherein in the step 1, the stoichiometric ratio of lithium atoms in the lithium salt to total metal atoms in the precursor is 0.9-1.1: 1.
3. the method for preparing the lithium ion battery cathode material by fluidized sintering according to claim 2, wherein in the step 2, the binder is one or more of steam and biomass starch.
4. The method for preparing the lithium ion battery cathode material by fluidized sintering according to claim 3, wherein in the step 2, the particle size of the spherical or ellipsoidal particle material is 50um < d <5 mm.
5. The method for preparing the lithium ion battery cathode material by fluidized sintering according to claim 4, wherein in the step 3, the components of the hot gas A are air and N2、H2、CO2、Ar、CO、H2O、O2One or more of He and Ne.
6. The method for preparing the lithium ion battery cathode material by fluidized sintering according to claim 5, wherein the temperature of the hot gas A is as follows: 500 deg.C<TA<1000℃。
7. The method for preparing the lithium ion battery cathode material by fluidized sintering according to claim 6, wherein in the step 4, a fluidized dynamic sintering device or a static sintering device is adopted as the high-temperature sintering furnace.
8. The method for preparing the lithium ion battery cathode material by fluidized sintering according to claim 7, wherein in the step 4, the components of the hot gas B are air and N2、H2、CO2、Ar、CO、H2O、O2One or more of He and Ne.
9. The method for preparing the lithium ion battery cathode material by fluidized sintering according to claim 8, wherein the temperature of the hot gas B is as follows: 600 deg.C<TB<1100℃。
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