CN108417827A - A kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery - Google Patents
A kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery Download PDFInfo
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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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
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- 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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- Y02E60/10—Energy storage using batteries
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Abstract
The invention belongs to field of lithium; provide a kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery; water-soluble lithium source, nickel source, cobalt source, manganese source are distinguished corresponding chelating agent to mix; then it is mixed according to nickelic ratio; high-pressure fog enters spray chamber; it is nitrogen protection in spray chamber, high pressure sprays into the stearic acid of melting fluidised form, and the nickelic ternary predecessor of condensation cladding atomization forms microballoon blank in sinking watching;Then lye ageing is added in blank microballoon, sintering obtains the complete spherical nickelic ternary electrode material of lithium battery of monocrystalline.
Description
Technical field
The invention belongs to field of lithium, and in particular to a kind of pre- encapsulated to prepare nickelic ternary electrode material of lithium battery
Method.
Background technology
Ternary battery combines cobalt acid lithium good cycle, lithium nickelate Fabrication of High Specific Capacitance by the synergistic effect of NiCo-Mn/Al
Amount and LiMn2O4 the advantages of having a safety feature at low cost.Nickel determines that electricity, cobalt determine charge and discharge in each component of ternary material
Electric speed, manganese determine stability, and with the increase of nickel content, the specific discharge capacity of battery is consequently increased, thermal stability and appearance
Amount conservation rate decreases.But with ternary battery security be improved with technique evolution, more nickelic ternary material is the general trend of events
Become.
The ternary material of rich nickel system has the advantages such as capacity is high, price is low, is the important hair of current tertiary cathode material
Open up direction.But its cyclical stability of the ternary material of rich nickel system is poor, the expansion and contraction of particle, meeting in cyclic process
A large amount of cracks are generated in inside, and then are reacted with electrolyte, rock salt phase is formed on surface, leads to declining for active material circulation volume
Subtract.
Chinese invention patent application number 201710168183.1 discloses a kind of silicon substrate nickel cobalt manganese lithium ternary electrode of lithium cell
Material and preparation method thereof.Disclose a kind of silicon substrate nickel cobalt manganese lithium ternary electrode material of lithium battery and preparation method thereof, using nickel,
Cobalt, manganese salt prepare predecessor, and introducing organosilicon in preparation process forms colloidal sol, are carried out to colloidal sol using pneumatic spray drying device
Spray drying, while graphene slurry is introduced, in flash drying process, graphene becomes intergranular space obstacle, limitation
The size of particle, inhibits its undue growth, obtains epigranular, silicon substrate nickel cobalt manganese lithium ternary battery material with good conductivity
Material.The invention provides the above method effectively solution, and ternary electrode material of lithium battery is tied due to its nickel content height in practical applications
Structure stability is poor, and then the technical issues of influence battery security, is effectively improved ternary electrode material of lithium battery stability,
And then improve ternary lithium battery safety in utilization.
The crystal electrons structure feature of nickelic ternary anode material for lithium-ion batteries, pattern and nickel content variation are to, system
Preparation Method and doping and coating modification have a major impact nickelic NCM material properties.On the one hand nickelic NCM materials are required
Pattern is on the other hand fine spherical shape is needed by higher compactness;Therefore, it in the mutual mixed stage of raw material, not only requires to divide
It dissipates uniformly, and requires to obtain monocrystal material, form good monocrystalline in fine range.At present by high temperature solid-state method, altogether
The precipitation method, colloidal sol-gel method, spray drying process obtain the size and shape of nickelic NCM materials, due to the process of preparation method
Control is different, and there are larger differences.Although can also have to obtain fine particle, it is to obtain after grinding, easily generates
The fine powder that monocrystalline destroys, fine powder are different from complete single crystal grain, are highly prone to electrolyte dissolving, and active material cycle is caused to be held
The decaying of amount, seriously affects service life and safety.
Invention content
The object of the present invention is to for fine powder is also easy to produce in existing nickelic ternary material preparation process, it is difficult to obtain complete
Monocrystalline this defect, the present invention proposes a kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery.Technology point
Lithium source, nickel source, cobalt source, the manganese source for being soluble in water distinguish corresponding chelating agent mixing(For example lithium salts selection is easier to lithium
The chelating agent of ions binding), then being mixed according to nickelic ratio, high-pressure fog enters spray chamber, is nitrogen protection in spray chamber,
High pressure sprays into the stearic acid of melting fluidised form, and it is young to form microballoon for the nickelic ternary predecessor of condensation cladding atomization in sinking watching
Shape;Then lye ageing is added in blank microballoon, sintering obtains the complete spherical nickelic ternary electrode material of lithium battery of monocrystalline.
Specific technical solution of the present invention is as follows:
A kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery, by water-soluble lithium source, nickel source, cobalt source,
Manganese source distinguishes corresponding chelating agent mixing, is then mixed according to nickelic ratio, and high-pressure fog enters spray chamber, and high pressure sprays into
The stearic acid for melting fluidised form, the nickelic ternary predecessor of condensation cladding atomization forms microballoon blank in sinking watching;Then will
Lye ageing is added in microballoon blank, and sintering obtains the complete spherical nickelic ternary electrode material of lithium battery of monocrystalline, specific steps
It is as follows:
S01:Soluble lithium source, soluble nickel source, soluble cobalt source, soluble manganese source are distinguished corresponding chelating agent and mixed
It closes, the chelate of the chelate of lithium, the chelate of nickel, the chelate of cobalt and manganese is respectively obtained, then by four kinds of metallo-chelates
By lithium, nickel, cobalt, manganese 1:0.8:0.1:0.1 molar ratio mixing, is dissolved in deionized water, forms mixed solution;
S02:Mixed solution is sprayed under the high pressure of 5-10MPa and enters spray chamber, forms the nickelic ternary predecessor of atomization, together
When under the high pressure of 10-20MPa spray into melting fluidised form stearic acid;
S03:Be atomized indoor spray stearic acid condensed in sinking watching cladding atomization nickelic ternary predecessor formed it is micro-
Ball blank;
S04:Then lye ageing is added in microballoon blank, sintering obtains the complete spherical nickelic ternary electrode of lithium cell of monocrystalline
Material.
Common, the prior art is being further processed after mixing the soluble salt of lithium source, nickel source, cobalt source, manganese source, due to
Ion aggregation properties, in the same drop ion dispersion and it is uneven, especially big droplet difference when, this difference is more
Obviously, therefore, the fine powder for grinding generation is not complete monocrystalline, is reflected in battery electrode, and the distribution of thickness unevenness causes
Electrode performance homogeneity is poor, and even, fine powder is more easy to react with electrolyte, and cycle performance of battery is caused to be deteriorated.
In order to solve this problem, lithium source, nickel source, cobalt source, manganese source are passed through different chelant ties, chelating agent by the present invention
Selection be respectively more easy to combine chelating agent, such as lithium salts select be easier to lithium ion combination chelating agent, same metal from
A kind of sub chelate formed with chelating agent is stablized than the complex compound for singly nibbling ligand formation with identical coordination atom, this
The special stability of kind is that stability caused by this formation due to chelate ring is increased title since cyclization generates
Be chelating effect.It is then that lithium metal, nickel, cobalt, manganese are formed into chelate respectively using chelating effect in the present invention, to be formed
More stable structure, chelating agent includes inorganic and organic two class, and most of is organic compounds, and common chelating agent has more
Phosphate, amino carboxylic acid, 1,3- diketone, hydroxycarboxylic acid, polyamines etc.;It is selected respectively for lithium metal, nickel, cobalt, manganese in the present invention
Corresponding polyphosphate is as chelating agent;Pass through and form chelate so that the metal-lithium ion of script, nickel ion, cobalt from
Son, manganese ion volume become larger, and formation is lithium chelate group, nickel chelate group, cobalt chelates group, manganic chelates base
Group, to increase the surface area of metal-lithium ion, nickel ion, cobalt ions, manganese ion, is at this time divided the chelate of formation
Mixing is dissipated, since each droplet size is fixed, after metal-lithium ion, nickel ion, cobalt ions, manganese ion volume increase,
The number of ions for being included in each drop is reduced, so that existing relative error reduces each other, such as script one
Can include 300 ions in a drop, then existing worst error is 300 between two drops, but when in a drop
Molecular number is up to after 100, then worst error has also reformed into 100, therefore in the present invention by lithium metal, nickel, cobalt,
Manganese is processed to form chelate so that the uniformity of each ion dispersion gets a promotion in each drop, overcomes and precipitates uneven make
At all kinds of self-dispersings it is uneven so that be deposited in each capsule and carry out;And it is encapsulated re-sinter, obtained particle has been
Whole single crystal grain, few fine powder generate, and can be obviously improved the cycle performance of nickelic ternary electrode.
As being further improved for this programme, the nitrogen of atomization building volume 30-50% is filled in the spray chamber as protection gas
Body.
As being further improved for this programme, the solubility lithium source, soluble nickel source, soluble cobalt source, soluble manganese
Source is respectively lithium hydroxide, nickel sulfate, cobaltous sulfate, manganese sulfate.
As being further improved for this programme, the sprayed volume ratio of the stearic acid and mixed solution is(3-5):1.
As being further improved for this programme, the lye is sodium bicarbonate.
As being further improved for this programme, the digestion time is 5-10 hours.
As being further improved for this programme, the sintering temperature is 500 DEG C -1000 DEG C.
As being further improved for this programme, the sintering time is 10-30 minutes.
As being further improved for this programme, the spray chamber condensation temperature is 3-5 DEG C.In condensation process, containing lithium,
Nickel, cobalt, manganese misty water droplet be adsorbed on stearic acid surface, form nickelic ternary predecessor and form microballoon blank.
The nickelic ternary electrode material of lithium battery and polyvinylidene fluoride in mass ratio 8 be prepared into the above method:1 is mixed
It closes, is ground into slurry, be coated on aluminium foil, for 24 hours, taking-up is cut into electrode film for drying in 60 DEG C of vacuum drying chambers, you can
Obtain positive plate of lithium battery;Method described above prepare positive plate be anode, by be sequentially put into from top to bottom gasket, electrolyte, every
Film and metal lithium sheet cathode manufacture to obtain lithium battery.
Compared with prior art, the present invention the feature and excellent effect of its protrusion are:It is common, the prior art be by
Lithium source, nickel source, cobalt source, manganese source soluble salt mixing after be further processed, due to ion aggregation properties, in the same drop
Ion dispersion and it is uneven, especially big droplet difference when, this difference becomes apparent from, and therefore, grinds the fine powder of generation
Not complete monocrystalline, is reflected in battery electrode, and the distribution of thickness unevenness causes electrode performance homogeneity poor, even, fine
Powder is more easy to react with electrolyte, and cycle performance of battery is caused to be deteriorated.Significant advantage of the present invention is:By lithium source, nickel source, cobalt source,
Manganese source passes through different chelant ties(The selection of chelating agent and the chelating agent for being respectively more easy to combine), then dispersion mixing is carried out,
Preferably solve the uniformity of each ion dispersion in each drop;Further by encapsulated rear reprecipitation, precipitation is overcome not
All kinds of self-dispersings are uneven caused by uniformly so that are deposited in each capsule and carry out;And the encapsulated particle for re-sintering, obtaining
For complete single crystal grain, few fine powder generates, and can be obviously improved the cycle performance of nickelic ternary electrode.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery of kind, by lithium hydroxide, nickel sulfate, cobaltous sulfate, sulfuric acid
Manganese is mixed with citric acid, ethylenediamine tetra-acetic acid, tartaric acid, gluconic acid chelating agent respectively, respectively obtains the chelate of lithium, nickel
The chelate of chelate, the chelate of cobalt and manganese, then by four kinds of metallo-chelates by lithium, nickel, cobalt, manganese 1:0.8:0.1:0.1
Molar ratio mixing, solvent in deionized water, formed mixed solution;Mixed solution is sprayed under the high pressure of 5MPa entrance
Spray chamber forms the nickelic ternary predecessor of atomization, and the nitrogen of atomization building volume 30% is filled in spray chamber as protective gas, mist
It is 3 DEG C to change room temperature, while the stearic acid of melting fluidised form, wherein stearic acid and mixed solution are sprayed under the high pressure of 10MPa
Sprayed volume ratio is 3:1;Be atomized indoor spray condensed in sinking watching cladding atomization nickelic ternary predecessor formed
Then blank microballoon is added sodium bicarbonate solution and is aged 5 hours, is sintered 10 minutes, obtained with 500 DEG C of temperature by microballoon blank
The complete spherical nickelic ternary electrode material of lithium battery of monocrystalline.
Embodiment 2
The pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery of kind, by lithium hydroxide, nickel sulfate, cobaltous sulfate, sulfuric acid
Manganese distinguishes corresponding chelating agent mixing, respectively obtains the chelating of the chelate of lithium, the chelate of nickel, the chelate of cobalt and manganese
Object, then by four kinds of metallo-chelates by lithium, nickel, cobalt, manganese 1:0.8:0.1:0.1 molar ratio mixing, solvent is in deionization
In water, mixed solution is formed;Mixed solution is sprayed under the high pressure of 8MPa and enters spray chamber, before forming the nickelic ternary of atomization
Object is driven, the nitrogen of atomization building volume 50% is filled in spray chamber as protective gas, atomization room temperature is 3 DEG C, while in 10-20MPa
High pressure under spray into melting fluidised form stearic acid, wherein the sprayed volume ratio of stearic acid and mixed solution be 3:1;It is atomized indoor
The nickelic ternary predecessor that spray condenses cladding atomization in sinking watching forms microballoon blank, and then blank microballoon is added
Sodium bicarbonate solution is aged 5 hours, is sintered 20 minutes with 800 DEG C of temperature, and the complete spherical nickelic ternary lithium electricity of monocrystalline is obtained
Pond electrode material.
Embodiment 3
The pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery of kind, by lithium hydroxide, nickel sulfate, cobaltous sulfate, sulfuric acid
Manganese distinguishes corresponding chelating agent mixing, respectively obtains the chelating of the chelate of lithium, the chelate of nickel, the chelate of cobalt and manganese
Then four kinds of metallo-chelates are pressed 1 by object:8:1:1 molar ratio is mixed by lithium, nickel, cobalt, manganese 1:0.8:0.1:0.1 mole
Ratio mixing is closed, and solvent forms mixed solution in deionized water;Mixed solution is sprayed under the high pressure of 10MPa and enters mist
Change room, form the nickelic ternary predecessor of atomization, the nitrogen of atomization building volume 40% is filled in spray chamber as protective gas, atomization
Room temperature is 5 DEG C, while the stearic acid of melting fluidised form, the wherein spray of stearic acid and mixed solution are sprayed under the high pressure of 20MPa
Mist volume ratio is 5:1;Be atomized indoor spray condensed in sinking watching cladding atomization nickelic ternary predecessor formed it is micro-
Then blank microballoon is added sodium bicarbonate solution and is aged 5 hours, is sintered 20 minutes with 900 DEG C of temperature, obtain list by ball blank
Brilliant complete spherical nickelic ternary electrode material of lithium battery.
Embodiment 4
The pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery of kind, by lithium hydroxide, nickel sulfate, cobaltous sulfate, sulfuric acid
Manganese distinguishes corresponding chelating agent mixing, respectively obtains the chelating of the chelate of lithium, the chelate of nickel, the chelate of cobalt and manganese
Object, then by four kinds of metallo-chelates by lithium, nickel, cobalt, manganese 1:0.8:0.1:0.1 molar ratio mixing, solvent is in deionization
In water, mixed solution is formed;Mixed solution is sprayed under the high pressure of 10MPa and enters spray chamber, forms the nickelic ternary of atomization
Predecessor, the nitrogen of atomization building volume 50% is filled in spray chamber, and to be used as protective gas, atomization room temperature be 5 DEG C, while in 20MPa
High pressure under spray into melting fluidised form stearic acid, wherein the sprayed volume ratio of stearic acid and mixed solution be 4:1;It is atomized indoor
The nickelic ternary predecessor that spray condenses cladding atomization in sinking watching forms microballoon blank, and then blank microballoon is added
Sodium bicarbonate solution is aged 10 hours, is sintered 25 minutes with 1000 DEG C of temperature, and the complete spherical nickelic ternary lithium of monocrystalline is obtained
Battery electrode material.
Embodiment 5
The pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery of kind, by lithium hydroxide, nickel sulfate, cobaltous sulfate, sulfuric acid
Manganese distinguishes corresponding chelating agent mixing, respectively obtains the chelating of the chelate of lithium, the chelate of nickel, the chelate of cobalt and manganese
Object, then by four kinds of metallo-chelates by lithium, nickel, cobalt, manganese 1:0.8:0.1:0.1 molar ratio mixing, solvent is in deionization
In water, mixed solution is formed;Mixed solution is sprayed under the high pressure of 5MPa and enters spray chamber, before forming the nickelic ternary of atomization
Object is driven, the nitrogen of atomization building volume 30% is filled in spray chamber as protective gas, atomization room temperature is 3 DEG C, while 10MPa's
The stearic acid of melting fluidised form is sprayed under high pressure, the wherein sprayed volume ratio of stearic acid and mixed solution is 5:1;It is atomized indoor mist
The nickelic ternary predecessor that shape object condenses cladding atomization in sinking watching forms microballoon blank, and carbon then is added in blank microballoon
Sour hydrogen sodium solution is aged 8 hours, is sintered 30 minutes with 800 DEG C of temperature, and the complete spherical nickelic ternary lithium battery of monocrystalline is obtained
Electrode material.
Embodiment 6
The pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery of kind, by lithium hydroxide, nickel sulfate, cobaltous sulfate, sulfuric acid
Manganese distinguishes corresponding chelating agent mixing, respectively obtains the chelating of the chelate of lithium, the chelate of nickel, the chelate of cobalt and manganese
Object, then by four kinds of metallo-chelates by lithium, nickel, cobalt, manganese 1:0.8:0.1:0.1 molar ratio mixing, solvent is in deionization
In water, mixed solution is formed;Mixed solution is sprayed under the high pressure of 10MPa and enters spray chamber, forms the nickelic ternary of atomization
Predecessor, the nitrogen of atomization building volume 50% is filled in spray chamber, and to be used as protective gas, atomization room temperature be 5 DEG C, while in 20MPa
High pressure under spray into melting fluidised form stearic acid, wherein the sprayed volume ratio of stearic acid and mixed solution be 5:1;It is atomized indoor
The nickelic ternary predecessor that spray condenses cladding atomization in sinking watching forms microballoon blank, and then blank microballoon is added
Sodium bicarbonate solution is aged 10 hours, is sintered 30 minutes with 1000 DEG C of temperature, and the complete spherical nickelic ternary lithium of monocrystalline is obtained
Battery electrode material.
Comparative example 1
By lithium hydroxide, nickel sulfate, cobaltous sulfate, manganese sulfate by lithium, nickel, cobalt, manganese 1:0.8:0.1:0.1 molar ratio mixing,
Solvent forms mixed solution in deionized water;Mixed solution is sprayed under the high pressure of 5MPa and enters spray chamber, forms atomization
Nickelic ternary predecessor, the nitrogen of atomization building volume 30% is filled in spray chamber, and to be used as protective gas, atomization room temperature be 3 DEG C, together
When under the high pressure of 10MPa spray into melting fluidised form stearic acid, wherein the sprayed volume ratio of stearic acid and mixed solution be 3:1;
It is atomized the nickelic ternary predecessor formation microballoon blank that indoor spray condenses cladding atomization in sinking watching, it then will be young
Shape microballoon is added sodium bicarbonate solution and is aged 5 hours, is sintered 10 minutes with 500 DEG C of temperature, obtains spherical nickelic ternary lithium electricity
Pond electrode material.
Comparative example 2
By lithium hydroxide, nickel sulfate, cobaltous sulfate, manganese sulfate by lithium, nickel, cobalt, manganese 1:0.8:0.1:0.1 molar ratio mixing,
Solvent forms mixed solution in deionized water;Mixed solution is sprayed under the high pressure of 5MPa and enters spray chamber, forms atomization
Nickelic ternary predecessor, the nitrogen of atomization building volume 30% is filled in spray chamber, and to be used as protective gas, atomization room temperature be 3 DEG C, so
Sodium bicarbonate solution is added in blank microballoon afterwards to be aged 5 hours, is sintered 10 minutes with 500 DEG C of temperature, obtains nickelic ternary lithium
Battery electrode material.
Slurry is made with the positive electrode in comparative example 1-2 in embodiment 1 and is coated in the two-sided of aluminium foil, positive plate is made,
Use artificial graphite for negative electrode active material, being stirring evenly and then adding into bonding agent with amount of conductive agent is made negative electrode slurry, will make
The negative electrode slurry obtained is coated uniformly on the two sides of copper foil, and negative plate is made.Using conventional commercial propene carbonate-LiPF6 electrolysis
Box hat battery testing electrical property is made after positive/negative plate is rolled, assembling, fluid injection and chemical conversion in liquid and diaphragm.
Pass through test:
The nickelic ternary material of embodiment 1, capacity reach 179mAh/g or more, the 500 1C charge and discharge 86% of normal temperature circulation service life
More than, 75% or more -10 DEG C of capacity retention ratios of low temperature.
The nickelic ternary material of comparative example 1, capacity 165mAh/g, the 500 1C charge and discharge 52% of normal temperature circulation service life are low
Warm -10 DEG C of capacity retention ratios 48%;
The nickelic ternary material of comparative example 2, capacity 170mAh/g, the 500 1C charge and discharge 63% of normal temperature circulation service life, low temperature -10
DEG C capacity retention ratio 54%.
The present invention greatly improves energy density and the safety of battery.
Claims (9)
1. a kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery, it is characterised in that:By water-soluble lithium
Source, nickel source, cobalt source, manganese source distinguish corresponding chelating agent mixing, are then mixed to form solution, high pressure spray according to nickelic ratio
Mist enters spray chamber, and high pressure sprays into the stearic acid of melting fluidised form, the nickelic ternary forerunner of condensation cladding atomization in sinking watching
Object forms microballoon blank;Then lye ageing is added in microballoon blank, sintering obtains the complete spherical nickelic ternary lithium electricity of monocrystalline
Pond electrode material, is as follows:
S01:Soluble lithium source, soluble nickel source, soluble cobalt source, soluble manganese source are distinguished corresponding chelating agent and mixed
It closes, the chelate of the chelate of lithium, the chelate of nickel, the chelate of cobalt and manganese is respectively obtained, then by four kinds of metallo-chelates
By lithium, nickel, cobalt, manganese 1:0.8:0.1:0.1 molar ratio mixing, is dissolved in deionized water, forms mixed solution;
S02:Mixed solution is sprayed under the high pressure of 5-10MPa and enters spray chamber, forms the nickelic ternary predecessor of atomization, together
When under the high pressure of 10-20MPa spray into melting fluidised form stearic acid;
S03:Be atomized indoor spray stearic acid condensed in sinking watching cladding atomization nickelic ternary predecessor formed it is micro-
Ball blank;
S04:Then lye ageing is added in microballoon blank, sintering obtains the complete spherical nickelic ternary electrode of lithium cell of monocrystalline
Material.
2. a kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery, feature exist according to claim 1
In:The solubility lithium source, soluble nickel source, soluble cobalt source, soluble manganese source be respectively lithium sulfate, nickel sulfate, cobaltous sulfate,
Manganese sulfate.
3. stating a kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery according to claim 1, it is characterised in that:
The nitrogen of atomization building volume 30-50% is filled in the spray chamber as protective gas.
4. a kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery, feature exist according to claim 3
In:The sprayed volume of the stearic acid and mixed solution ratio is(3-5):1.
5. a kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery, feature exist according to claim 4
In:The spray chamber condensation temperature is 3-5 DEG C.
6. a kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery, feature exist according to claim 5
In:The lye is sodium bicarbonate.
7. a kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery, feature exist according to claim 6
In:The digestion time is 5-10 hours.
8. a kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery, feature exist according to claim 7
In:The sintering temperature is 500 DEG C -1000 DEG C.
9. a kind of pre- encapsulated method for preparing nickelic ternary electrode material of lithium battery, feature exist according to claim 8
In:The sintering time is 10-30 minutes.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111200129A (en) * | 2018-11-20 | 2020-05-26 | 苏州拉瓦锂能源科技有限公司 | Preparation method of single crystal type high-nickel ternary cathode material |
CN113903908A (en) * | 2021-10-09 | 2022-01-07 | 合肥国轩高科动力能源有限公司 | High-nickel multi-element positive electrode material and preparation method and application thereof |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111200129A (en) * | 2018-11-20 | 2020-05-26 | 苏州拉瓦锂能源科技有限公司 | Preparation method of single crystal type high-nickel ternary cathode material |
CN113903908A (en) * | 2021-10-09 | 2022-01-07 | 合肥国轩高科动力能源有限公司 | High-nickel multi-element positive electrode material and preparation method and application thereof |
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