CN106848252A - One kind evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery - Google Patents
One kind evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery Download PDFInfo
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- CN106848252A CN106848252A CN201710156059.3A CN201710156059A CN106848252A CN 106848252 A CN106848252 A CN 106848252A CN 201710156059 A CN201710156059 A CN 201710156059A CN 106848252 A CN106848252 A CN 106848252A
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- 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
- H01M4/362—Composites
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- H—ELECTRICITY
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The durothermic method of ternary anode material of lithium battery is improved the invention discloses one kind evaporation aluminum fluoride.Using fluid bed as evaporated device; aluminum fluoride is set to distil; in the aluminum fluoride atmosphere that distils; nanoscale cobalt nickel lithium manganate ternary material contacts evaporation with aluminum fluoride with suspended state; after cooling uniformly one layer of ultra-thin aluminum fluoride diaphragm is wrapped on nanoscale cobalt nickel lithium manganate ternary material subparticle surface; by wrapping aluminum fluoride, the resistance to elevated temperatures of nickle cobalt lithium manganate is set to improve to 300 DEG C, and electric conductivity is improved.It is uneven that means using pure physics cladding of the invention overcome the clad for carrying out chemistry cladding acquisition using aluminum fluoride in the prior art, and then influence battery efficiency, and the effect process cycle is long, high cost, have the technological deficiencies such as pollution, it is good there is provided a kind of covered effect, preparation method process is simple, can carry out large-scale industrial production pattern.
Description
Technical field
The present invention relates to battery material field, and in particular to it is resistance to that one kind evaporation aluminum fluoride improves ternary anode material of lithium battery
The method of warm nature.
Background technology
By long-term fast development, lithium ion battery has achieved a series of rapid progresses, it is considered to be electric automobile is most
One of potential energy source.The ternary material LiNi of layer structure1/3Co1/3Mn1/3O2Because discharge capacity is high, security
The good, structural stability of energy is good, low cost and other advantages, it is considered to be used as the lithium ion cell positive material that electric automobile energy is originated
One of optimal selection of material.Ternary lithium material can decompose at 200 DEG C or so, and ternary lithium material chemical reaction more
Acutely, oxygen molecule is discharged, causes electrolyte to burn rapidly under high temperature action.Due to security and service life problem, great Rong
Amount high voltage ternary lithium power battery pack is abnormally dangerous, as maximum bottleneck when hindering.Although at present overcharge protection,
Overcurrent protection prevents ternary material temperature from raising, but the heat-resisting quantity of material is not solved preferably all the time.In order to improve
The security of nickel-cobalt-manganese ternary material, the conventional means of current industry include bulk phase-doped hetero atom, optimized production process and
The means of surface modification come improve its chemical property and improve ternary lithium dynamical battery security.
For the modified measures of surface modification, Application No. 201410250912.4 uses carbon-coating nickel cobalt manganic acid lithium, bag
The high rate performance and cyclical stability of positive electrode are improve after covering, but carbon coating is present.Application No.
201310312317.4 are coated using fluorapatite to nickle cobalt lithium manganate, and the cyclical stability of material is improved.Adopt
The diaphragm of stabilization can more be formed compared to oxide and phosphate as coating with aluminum fluoride, while being fluorinated in cyclic process
Aluminium can be between stabilizing actives and electrolyte interface, improve positive electrode cycle performance and heat endurance, Er Qieke
Lithium ion is set to be embedded in faster speed.
Application No. 201610303771.7 discloses the preparation side that a kind of aluminum fluoride coats nickel-cobalt lithium manganate cathode material
, first be added to for nickel-cobalt lithium manganate cathode material in the aluminium salt compound solution for having configured and at the uniform velocity stir, by Fluorine source compound by method
Solution is added drop-wise in above-mentioned mixed solution, and solution is evaporated after dripping to the state that is evaporated, and is dried after ageing, is obtained solid powder and is put
Enter tube furnace to be calcined in a nitrogen atmosphere, the nickle cobalt lithium manganate of aluminum fluoride cladding is obtained.Application No. 201510421209.X is public
A kind of AlF is opened3The preparation method of coated porous ball-shaped lithium-ion battery material precursor, by the soluble-salt of nickel, cobalt and manganese
Add in organic solvent, mist projection granulating adds fluoride salt and the stirring of aluminum salt solution constant temperature, and scrubbed filtration drying is obtained.
It follows that in using the aluminum fluoride cladding raising durothermic scheme of ternary anode material of lithium battery, coating mode
It is by chemical reaction, in nickel-cobalt lithium manganate cathode material Surface Creation aluminum fluoride by aluminium salt and fluoride.But, chemistry cladding
Treatment is often faced with coating thickness, composition easily to be influenceed by reaction condition, and the clad of acquisition is uneven, influence battery effect
Rate.Additionally, chemistry cladding processes long preparation period, the use of some toxic raw materials also brings influence to environment, is unfavorable for big rule
Mould industrialized production.
The content of the invention
In consideration of it, the present invention proposes that a kind of evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery, gram
Clothes are coated using aluminum fluoride by chemical reaction in the prior art, and the clad of acquisition is uneven, and the cladding cycle is long,
It is unfavorable for the technological deficiency of large-scale industrial production, covered effect of the present invention is good, preparation method process is simple, and use
Cost of material and equipment cost are cheap, can meet industrialization development demand.
The present invention provides a kind of evaporation aluminum fluoride and improves the durothermic method of ternary anode material of lithium battery, using fluid bed
As evaporated device, comprise the following steps：
（1）Fluorination aluminum feedstock is added in fluidized-bed bottom, the fluid bed chamber is vacuumized, kept in the fluid bed chamber
Under vacuum condition, it is 700-750 DEG C to set bed body temperature, aluminum fluoride is distilled, into high-temperature fluorination aluminium gas phase zone；
（2）Nickle cobalt lithium manganate ternary dusty material is added into the fluid bed by charging mechanism, by air blower after gas is heated
Feeding fluidized-bed bottom, contacts, so that nickle cobalt lithium manganate ternary powder material through distribution grid with nickle cobalt lithium manganate ternary dusty material
Material forms fluidisation state and is contacted with gaseous fluorinated aluminium phase；
（3）Nickle cobalt lithium manganate ternary powder is blown boiling by air-flow, and in high-temperature fluorination aluminium gas phase zone, nickle cobalt lithium manganate ternary powder turns into
Nucleus, aluminum fluoride gas phase under airflow function, can be circulated 3-5 times by moment absorption in its surface heterogeneous medium forming core, fully ensure that bag
Cover completely, then after Slow cooling, obtain the nickle cobalt lithium manganate ternary dusty material that surface wraps thin aluminum fluoride diaphragm.
Preferably, step（1）The bed body is heated, controls the bed body programming rate for 2-10 DEG C/min, make aluminum fluoride
Distillation.
Preferably, step（1）The aluminum fluoride particle diameter is 6-16nm.
Preferably, step（2）The nickle cobalt lithium manganate ternary dusty material particle diameter is 100-500nm.
Preferably, step (2) is described gas is heated after the fluidized-bed bottom is sent into by air blower, including：
The gas is heated to 30-80 DEG C, the gas is sent into fluidized-bed bottom, control fluidizing velocity for 4-6m/s, tower
In 12-90Pa, distribution grid air pressure is 3-40Pa for internal pressure control, wherein, the gas is that purity is 99.0%-99.99%'s
Nitrogen, argon gas, helium.
Preferably, step（3）It is 15-20 DEG C/min that the Slow cooling controls fluid cooling velocity.
The present invention by evaporating aluminum fluoride air mass in fluid bed, using air-flow by nanoscale nickle cobalt lithium manganate tertiary cathode
It is quick in nanoscale nickle cobalt lithium manganate tertiary cathode material subparticle surface fluorination aluminium in material subparticle feeding fluid bed
Heterogeneous forming core, uniformly wraps one layer of ultra-thin aluminum fluoride and protects after cooling on nanoscale cobalt nickel lithium manganate ternary material subparticle surface
Cuticula, forms the nickle cobalt lithium manganate tertiary cathode material with heat-resisting quantity.Its significant advantage is that clad ratio reaches 99%, bag
Cover thickness uniform, composition is single, by wrapping aluminum fluoride, the resistance to elevated temperatures of nickle cobalt lithium manganate is improved to 300 DEG C, and it is conductive
Property improve, the application for ternary new material in dynamic lithium battery provides technical support.The letter of aluminum fluoride technique is deposited with the present invention
It is single, and the cost of material that uses and equipment cost are cheap, can meet industrialization development demand.
A kind of evaporation aluminum fluoride that the present invention is provided improves the durothermic method of ternary anode material of lithium battery, with existing skill
Art is compared, its protrusion the characteristics of and excellent effect be：
1st, the present invention is in fluid bed by evaporating aluminum fluoride air mass, using air-flow by nanoscale nickle cobalt lithium manganate tertiary cathode material
It is quickly different in nanoscale nickle cobalt lithium manganate tertiary cathode material subparticle surface fluorination aluminium in material subparticle feeding fluid bed
Matter forming core, its clad ratio reaches 99%, and cladding thickness is uniform, and the resistance to elevated temperatures of nickle cobalt lithium manganate battery is coated using aluminum fluoride
It is obviously improved with electric conductivity.
2nd, the present invention uses fluid bed as evaporated device, in nanoscale nickle cobalt lithium manganate tertiary cathode material subparticle
Surface is deposited with one layer of aluminum fluoride, the nickle cobalt lithium manganate tertiary cathode material with heat-resisting quantity of formation, i.e., using pure physics bag
The means covered overcome chemistry cladding long processing period, have the features such as defects such as pollution, pollution high and low with production efficiency, carry
Having supplied one kind can carry out large-scale industrial production pattern.
3rd, directly using aluminum fluoride powder as raw material, abundance is cheap, and impurity content is low, has for the present invention
Obvious economic benefit.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as into the present invention
Scope be only limitted to following example.In the case where above method thought of the present invention is not departed from, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）Fluorination aluminum feedstock is added in fluidized-bed bottom, aluminum fluoride particle diameter used is 6nm, and the fluid bed chamber is taken out very
Sky, it is 10 to keep the Chamber vacuum degree-3Pa, sets bed body temperature as 700 DEG C, controls bed body programming rate for 2 DEG C/min, makes
Aluminum fluoride distils, into high-temperature fluorination aluminium gas phase zone；
（2）It is 10 according to aluminum fluoride and the nickle cobalt lithium manganate ternary dusty material mass ratio:1 metering ratio takes nickle cobalt lithium manganate
Ternary dusty material, nickle cobalt lithium manganate ternary dusty material particle diameter is 100nm, the nickle cobalt lithium manganate ternary dusty material that will be taken
The fluid bed is added by charging mechanism, purity is sent into the fluid bed bottom for 99.99% nitrogen is heated to 30 DEG C by air blower
Portion, controls fluidizing velocity for 6m/s, and pressure is 12Pa in tower body, and distribution grid air pressure is 3Pa, and nitrogen is through distribution grid and nickel cobalt mangaic acid
Lithium ternary dusty material is contacted, and nickle cobalt lithium manganate ternary powder is blown into boiling forms fluidisation state, delivers into high-temperature fluorination aluminium gas phase
Area, nickle cobalt lithium manganate ternary dusty material is contacted with gaseous fluorinated aluminium phase；
（3）Nickle cobalt lithium manganate ternary powder turns into nucleus in gas phase zone, and aluminum fluoride gas phase can be adsorbed different on its surface moment
Matter forming core, under airflow function, circulates 3 times, through fully cladding, after controlling fluid cooling velocity to be cooled down for 15 DEG C/min,
It is the nickle cobalt lithium manganate ternary dusty material that 800nm surfaces wrap thin aluminum fluoride diaphragm to obtain granularity.
It is 99.2% by the evaporation aluminum fluoride cladding ternary anode material of lithium battery clad ratio prepared by the present embodiment, cladding
Thickness is uniform, and button-shaped lithium ion battery is made as anode material for lithium-ion batteries, in 300 DEG C of lithium ion battery in 3.7V,
First discharge specific capacity is 210mAh/g under the current density of 20mA/g, and by 100 cycle charge-discharges, specific capacity is 95%.Steam
Plating aluminum fluoride cladding ternary anode material of lithium battery production efficiency is 10t/h.
Embodiment 2
（1）Fluorination aluminum feedstock is added in fluidized-bed bottom, aluminum fluoride particle diameter used is 10nm, and the fluid bed chamber is taken out very
Sky, it is 10 to keep the Chamber vacuum degree-3Pa, sets bed body temperature as 700 DEG C, controls bed body programming rate for 4 DEG C/min, makes
Aluminum fluoride distils, into high-temperature fluorination aluminium gas phase zone；
（2）It is 12 according to aluminum fluoride and the nickle cobalt lithium manganate ternary dusty material mass ratio:1 metering ratio takes nickle cobalt lithium manganate
Ternary dusty material, nickle cobalt lithium manganate ternary dusty material particle diameter is 150nm, the nickle cobalt lithium manganate ternary dusty material that will be taken
The fluid bed is added by charging mechanism, purity is sent into the fluid bed bottom for 99.0% helium is heated to 40 DEG C by air blower
Portion, controls fluidizing velocity for 4m/s, and pressure is 20Pa in tower body, and distribution grid air pressure is 10Pa, and helium is through distribution grid and nickel cobalt manganese
Sour lithium ternary dusty material contact, blows nickle cobalt lithium manganate ternary powder boiling and forms fluidisation state, delivers into high-temperature fluorination aluminium gas
Phase region, nickle cobalt lithium manganate ternary dusty material is contacted with gaseous fluorinated aluminium phase；
（3）Nickle cobalt lithium manganate ternary powder turns into nucleus in gas phase zone, and aluminum fluoride gas phase can be adsorbed different on its surface moment
Matter forming core, under airflow function, circulates 5 times, through fully cladding, after controlling fluid cooling velocity to be cooled down for 20 DEG C/min,
It is the nickle cobalt lithium manganate ternary dusty material that 1000nm surfaces wrap thin aluminum fluoride diaphragm to obtain granularity.
It is 99% by the evaporation aluminum fluoride cladding ternary anode material of lithium battery clad ratio prepared by the present embodiment, cladding is thick
Degree is uniform, and button-shaped lithium ion battery is made as anode material for lithium-ion batteries, in 300 DEG C of lithium ion battery in 3.7V,
First discharge specific capacity is 210mAh/g under the current density of 20mA/g, and by 100 cycle charge-discharges, specific capacity is 94%.Steam
Plating aluminum fluoride cladding ternary anode material of lithium battery production efficiency is 10t/h.
Embodiment 3
（1）Fluorination aluminum feedstock is added in fluidized-bed bottom, aluminum fluoride particle diameter used is 10nm, and the fluid bed chamber is taken out very
Sky, it is 10 to keep the Chamber vacuum degree-2Pa, sets bed body temperature as 730 DEG C, controls bed body programming rate for 6 DEG C/min, makes
Aluminum fluoride distils, into high-temperature fluorination aluminium gas phase zone；
（2）It is 13 according to aluminum fluoride and the nickle cobalt lithium manganate ternary dusty material mass ratio:1 metering ratio takes nickle cobalt lithium manganate
Ternary dusty material, nickle cobalt lithium manganate ternary dusty material particle diameter is 200nm, the nickle cobalt lithium manganate ternary dusty material that will be taken
The fluid bed is added by charging mechanism, purity is sent into the fluid bed bottom for 99.5% nitrogen is heated to 30 DEG C by air blower
Portion, controls fluidizing velocity for 5m/s, and pressure is 40Pa in tower body, and distribution grid air pressure is 25Pa, and nitrogen is through distribution grid and nickel cobalt manganese
Sour lithium ternary dusty material contact, blows nickle cobalt lithium manganate ternary powder boiling and forms fluidisation state, delivers into high-temperature fluorination aluminium gas
Phase region, nickle cobalt lithium manganate ternary dusty material is contacted with gaseous fluorinated aluminium phase；
（3）Nickle cobalt lithium manganate ternary powder turns into nucleus in gas phase zone, and aluminum fluoride gas phase can be adsorbed different on its surface moment
Matter forming core, under airflow function, circulates 5 times, through fully cladding, after controlling fluid cooling velocity to be cooled down for 15 DEG C/min,
It is the nickle cobalt lithium manganate ternary dusty material that 1200nm surfaces wrap thin aluminum fluoride diaphragm to obtain granularity.
It is 99.5% by the evaporation aluminum fluoride cladding ternary anode material of lithium battery clad ratio prepared by the present embodiment, cladding
Thickness is uniform, and button-shaped lithium ion battery is made as anode material for lithium-ion batteries, in 300 DEG C of lithium ion battery in 3.7V,
First discharge specific capacity is 213mAh/g under the current density of 20mA/g, and by 100 cycle charge-discharges, specific capacity is 96%.Steam
Plating aluminum fluoride cladding ternary anode material of lithium battery production efficiency is 10t/h.
Embodiment 4
（1）Fluorination aluminum feedstock is added in fluidized-bed bottom, aluminum fluoride particle diameter used is 16nm, and the fluid bed chamber is taken out very
Sky, it is 10 to keep the Chamber vacuum degree-3Pa, sets bed body temperature as 700 DEG C, controls bed body programming rate for 2 DEG C/min, makes
Aluminum fluoride distils, into high-temperature fluorination aluminium gas phase zone；
（2）It is 15 according to aluminum fluoride and the nickle cobalt lithium manganate ternary dusty material mass ratio:1 metering ratio takes nickle cobalt lithium manganate
Ternary dusty material, nickle cobalt lithium manganate ternary dusty material particle diameter is 500nm, the nickle cobalt lithium manganate ternary dusty material that will be taken
The fluid bed is added by charging mechanism, the argon gas that purity is 99.0% is heated into 50 DEG C sends into the fluid bed by air blower
Bottom, controls fluidizing velocity for 6m/s, and pressure is 85Pa in tower body, and distribution grid air pressure is 35Pa, and argon gas is through distribution grid and nickel cobalt
LiMn2O4 ternary dusty material is contacted, and nickle cobalt lithium manganate ternary powder is blown into boiling forms fluidisation state, delivers into high-temperature fluorination aluminium
Gas phase zone, nickle cobalt lithium manganate ternary dusty material is contacted with gaseous fluorinated aluminium phase；
（3）Nickle cobalt lithium manganate ternary powder turns into nucleus in gas phase zone, and aluminum fluoride gas phase can be adsorbed different on its surface moment
Matter forming core, under airflow function, circulates 3 times, through fully cladding, after controlling fluid cooling velocity to be cooled down for 20 DEG C/min,
It is the nickle cobalt lithium manganate ternary dusty material that 1200nm surfaces wrap thin aluminum fluoride diaphragm to obtain granularity.
It is 99.8% by the evaporation aluminum fluoride cladding ternary anode material of lithium battery clad ratio prepared by the present embodiment, cladding
Thickness is uniform, and button-shaped lithium ion battery is made as anode material for lithium-ion batteries, in 300 DEG C of lithium ion battery in 3.7V,
First discharge specific capacity is 204mAh/g under the current density of 20mA/g, and by 100 cycle charge-discharges, specific capacity is 94%.Steam
Plating aluminum fluoride cladding ternary anode material of lithium battery production efficiency is 10t/h.
Embodiment 5
（1）Fluorination aluminum feedstock is added in fluidized-bed bottom, aluminum fluoride particle diameter used is 10nm, and the fluid bed chamber is taken out very
Sky, it is 10 to keep the Chamber vacuum degree-3Pa, sets bed body temperature as 750 DEG C, controls bed body programming rate for 10 DEG C/min,
Aluminum fluoride is set to distil, into high-temperature fluorination aluminium gas phase zone；
（2）It is 15 according to aluminum fluoride and the nickle cobalt lithium manganate ternary dusty material mass ratio:1 metering ratio takes nickle cobalt lithium manganate
Ternary dusty material, nickle cobalt lithium manganate ternary dusty material particle diameter is 150nm, the nickle cobalt lithium manganate ternary dusty material that will be taken
The fluid bed is added by charging mechanism, the nitrogen that purity is 99.0% is heated into 80 DEG C sends into the fluid bed by air blower
Bottom, controls fluidizing velocity for 5m/s, and pressure is 45Pa in tower body, and distribution grid air pressure is 15Pa, and nitrogen is through distribution grid and nickel cobalt
LiMn2O4 ternary dusty material is contacted, and nickle cobalt lithium manganate ternary powder is blown into boiling forms fluidisation state, delivers into high-temperature fluorination aluminium
Gas phase zone, nickle cobalt lithium manganate ternary dusty material is contacted with gaseous fluorinated aluminium phase；
（3）Nickle cobalt lithium manganate ternary powder turns into nucleus in gas phase zone, and aluminum fluoride gas phase can be adsorbed different on its surface moment
Matter forming core, under airflow function, circulates 3 times, through fully cladding, after controlling fluid cooling velocity to be cooled down for 20 DEG C/min,
It is the nickle cobalt lithium manganate ternary dusty material that 800nm surfaces wrap thin aluminum fluoride diaphragm to obtain granularity.
It is 99.8% by the evaporation aluminum fluoride cladding ternary anode material of lithium battery clad ratio prepared by the present embodiment, cladding
Thickness is uniform, and button-shaped lithium ion battery is made as anode material for lithium-ion batteries, in 300 DEG C of lithium ion battery in 3.7V,
First discharge specific capacity is 212mAh/g under the current density of 20mA/g, and by 100 cycle charge-discharges, specific capacity is 95%.Steam
Plating aluminum fluoride cladding ternary anode material of lithium battery production efficiency is 10t/h.
Claims (6)
1. a kind of evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery, is set as evaporation using fluid bed
It is standby, comprise the following steps：
（1）Fluorination aluminum feedstock is added in fluidized-bed bottom, the fluid bed chamber is vacuumized, kept in the fluid bed chamber
Under vacuum condition, it is 700-750 DEG C to set bed body temperature, aluminum fluoride is distilled, into high-temperature fluorination aluminium gas phase zone；
（2）Nickle cobalt lithium manganate ternary dusty material is added into the fluid bed by charging mechanism, by air blower after gas is heated
Feeding fluidized-bed bottom, contacts, so that nickle cobalt lithium manganate ternary powder material through distribution grid with nickle cobalt lithium manganate ternary dusty material
Material forms fluidisation state and is contacted with gaseous fluorinated aluminium phase；
（3）Nickle cobalt lithium manganate ternary powder is blown boiling by air-flow, and in high-temperature fluorination aluminium gas phase zone, nickle cobalt lithium manganate ternary powder turns into
Nucleus, aluminum fluoride gas phase under airflow function, can be circulated 3-5 times by moment absorption in its surface heterogeneous medium forming core, fully ensure that bag
Cover completely, then after Slow cooling, obtain the nickle cobalt lithium manganate ternary dusty material that surface wraps thin aluminum fluoride diaphragm.
2. a kind of evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery according to claim 1, and it is special
Levy and be：Step（1）The bed body is heated, controls the bed body programming rate for 2-10 DEG C/min, aluminum fluoride is distilled.
3. a kind of evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery according to claim 1, and it is special
Levy and be：Step（1）The aluminum fluoride particle diameter is 6-16nm.
4. a kind of evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery according to claim 1, and it is special
Levy and be：Step（2）The nickle cobalt lithium manganate ternary dusty material particle diameter is 100-500nm.
5. a kind of evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery according to claim 1, and it is special
Levy and be：Step (2) is described gas is heated after the fluidized-bed bottom is sent into by air blower, including：
The gas is heated to 30-80 DEG C, the gas is sent into fluidized-bed bottom, control fluidizing velocity for 4-6m/s, tower
In 12-90Pa, distribution grid air pressure is 3-40Pa for internal pressure control, wherein, the gas is that purity is 99.0%-99.99%'s
Nitrogen, argon gas, helium.
6. a kind of evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery according to claim 1, and it is special
Levy and be：Step（3）It is 15-20 DEG C/min that the Slow cooling controls fluid cooling velocity.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108110218A (en) * | 2017-12-19 | 2018-06-01 | 成都亦道科技合伙企业（有限合伙） | A kind of lithium battery anode structure and preparation method thereof |
| CN108832083A (en) * | 2018-05-28 | 2018-11-16 | 广东邦普循环科技有限公司 | A kind of preparation method of cladded type power battery nickle cobalt lithium manganate |
| CN109621847A (en) * | 2018-11-07 | 2019-04-16 | 中国科学院过程工程研究所 | A kind of system and method for carbon and metal oxide compound coating anode material for lithium-ion batteries |
| CN109666918A (en) * | 2018-11-07 | 2019-04-23 | 中国科学院过程工程研究所 | A kind of system and method preparing metal fluoride coated lithium ion battery positive electrode based on fluidized-bed chemical vapor deposition method |
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| CN112607723A (en) * | 2020-12-15 | 2021-04-06 | 山东玉皇新能源科技有限公司 | Method for recovering aluminum-containing lithium ion battery positive electrode leftover material |
| CN114551794A (en) * | 2021-12-17 | 2022-05-27 | 远景动力技术(江苏)有限公司 | Positive electrode active material, positive electrode, preparation method and lithium ion battery |
| CN114551794B (en) * | 2021-12-17 | 2023-08-25 | 远景动力技术(江苏)有限公司 | Positive electrode active material, positive electrode, preparation method and lithium ion battery |
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