CN104733721A - Method for preparing lithium nickel cobalt manganese oxide ternary cathode material in liquid-phase sugar coating and spray drying manners - Google Patents
Method for preparing lithium nickel cobalt manganese oxide ternary cathode material in liquid-phase sugar coating and spray drying manners Download PDFInfo
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- CN104733721A CN104733721A CN201510063408.8A CN201510063408A CN104733721A CN 104733721 A CN104733721 A CN 104733721A CN 201510063408 A CN201510063408 A CN 201510063408A CN 104733721 A CN104733721 A CN 104733721A
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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
- 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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- 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
- H01M4/52—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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Abstract
The invention discloses a method for preparing a lithium nickel cobalt manganese oxide ternary cathode material in liquid-phase sugar coating and spray drying manners. The method comprises the steps of firstly mixing sulphate liquids of Ni, Co and Mn, performing a coprecipitation reaction under an alkaline condition to prepare a ternary composite precursor (NixCoyMnz)(OH)2, filtering, washing, drying, adding the ternary composite precursor, a soluble metal lithium compound, a rare earth compound to a sugar-dissolved solvent, uniformly mixing, and spray drying to obtain a sugar-coated rare-earth-element-doped ternary precursor, finally performing high-temperature calcination to obtain a rare-earth-element-doped ternary material LiNixCoyMnzRnO2, wherein R is a doped rare earth element, the sum of x, y and z is equal to 1, and n is not less than 0.002 and is not greater than 0.1. According to the method for preparing the lithium nickel cobalt manganese oxide ternary cathode material in the liquid-phase sugar coating and spray drying manners, sugar coating is utilized, so that the dissipation of pungent smell is reduced in a spray drying process; the prepared stoichiometric-ratio ternary material has the advantages that the secondary particle dispersity is good, the size is uniform, the infiltration of electrolyte is facilitated, the diffusion rate of lithium ions is increased basically, and the impedance of the lithium ions during diffusion is reduced, so that the electrical property of a material is improved, and the stable production is convenient.
Description
Technical field
The present invention relates to the method that the coated spraying dry of a kind of liquid phase sugar prepares nickle cobalt lithium manganate tertiary cathode material.
Background technology
Lithium ion battery, as energy-storage battery of new generation, just obtains fast development in various consumer electronics product field, and demonstrates potential using value at electric automobile, electric vehicle and space industry.And the performance of lithium ion battery and cost depend on positive electrode to a great extent.At present, the specific capacity of lithium ion battery negative material reaches the twice of positive electrode, thus the lower bottleneck having become the development of restriction lithium ion battery of positive electrode specific capacity, therefore study anode material for lithium-ion batteries, development and improvement lithium ion battery are had important practical significance.
Because of nickel ternary cobalt lithium manganate material inherit cobalt acid lithium, lithium nickelate, LiMn2O4 advantage to have specific capacity high, platform voltage is high, and tap density is large, crystal structure is stablized, preparation technology is simple, the features such as operating cost is low, and the indispensability having become anode material for lithium-ion batteries one of is selected.But cobalt nickel lithium manganate ternary material can't replace existing anode material for lithium-ion batteries completely, main cause has 2 points: ternary material many employings coprecipitation of current industrial production prepares presoma, then mix lithium by dry method or wet method, eventually pass high-temperature calcination and prepare ternary material.One: adopt dry method or wet method to mix lithium and cause presoma even not with mixing of lithium, and grain diameter is wayward, makes the stability of final products be difficult to control; Its two nickle cobalt lithium manganate is that high temperature synthesizes through the insulation calcining of certain hour more than 850 DEG C, crystal grain meeting fast growth in calcination process, and granularity is difficult to control, and causes the discharge capacity first of material and cycle performance to be subject to negative effect; Its three: lithium ion is close with nickel ion radius, in charge and discharge process nickel ion easily occupy lithium ion position occur crystal structure cave in.Caving in of crystal structure not only destroys Li
+transmission channel, and Li deviate from by battery
2after O, ion is reset and is obstructed, and octahedral voids is occupied, does not have enough positions for Lithium-ion embeding, cause and analyse lithium, had a strong impact on the performance of electrical property after electric discharge.
Summary of the invention
For existing problem, the object of the present invention is to provide a kind of method that chemical property is good, the coated spraying dry of liquid phase sugar that is that be convenient to steady production prepares nickle cobalt lithium manganate tertiary cathode material.
To achieve these goals, technical scheme of the present invention is such: the coated spraying dry of a kind of liquid phase sugar prepares the method for nickle cobalt lithium manganate tertiary cathode material, it is characterized in that: be prepared as follows: after first being mixed by the sulfate liquor of Ni, Co, Mn, coprecipitation reaction obtains tri compound presoma (Ni in the basic conditions
xco
ymn
z) (OH)
2after filtration, after washing, drying, this tri compound presoma, soluble metal lithium compound, rare earth compound being added has dissolved in sugared solvent, sugar is obtained by spraying dry coated and be doped with the ternary precursor of rare earth element, finally by obtaining after high-temperature calcination through rare earth doped ternary material LiNi after mixing
xco
ymn
zr
no
2, wherein R be doping rare earth element, x+y+z=1,0.002≤n≤0.1.
Adopt such scheme, first the method adopts liquid phase to mix lithium, makes the tri compound presoma of nickel cobalt manganese and soluble lithium salt reach desirable admixture in the liquid phase.
Secondly increase sugar when liquid phase mixes lithium, the sugar in liquid phase adds the toughness of solution, reduces intergranular dispersiveness, effectively prevents the reunion between ternary precursor.Viscous solution sugar when hig h-speed centrifugal spray drying is converted into glassy state, presoma is disperseed evenly, sphericity is higher meanwhile completes granulation again.The coated granular precursor good dispersion of sugar prepared by the method, size is even, sphericity is high, and average grain diameter is 3 ~ 5 μm.The second particle of sample loosens, and is conducive to the infiltration of electrolyte, fundamentally improves the diffusion rate of lithium ion, reduces the impedance in lithium ion diffusion process, thus improves high rate performance and the cycle performance of material.Prepared sample is dressed up battery first discharge specific capacity and can be reached more than 200mAh/g.
In addition, at present when preparing ternary material, little employing spraying dry mixes lithium, because the lithium compounds such as lithium hydroxide, lithium nitrate, lithium acetate, lithium chloride can give out unpleasant penetrating odor when spraying dry, we are coated by sugar in this process, reduce distributing of lithium compound penetrating odor.
Finally, the present invention also adds rare earth element, due to electron structure [Xe] 4f that rare earth element is special
0-145d
0-16s
2, after losing two 6s and 5d or 4f electronics, define modal Ln
3+wherein La
3+, Gd
3+, Lu
3+4f subgrade be respectively full sky, partly fill, full up state, be all stable state according to these states of Hund's rule, therefore, the Ln being positioned at their both sides has and obtains or lose electronics to reach or close to the trend of aforementioned stable state.The doping of rare earth element not only changes host lattice electronic structure and chemical bonding structure, and can effectively suppress cation mixing in charge and discharge process, stabilizes crystal structure, decreases irreversible capacity, improves the capacity and cycle performance that discharge first.In addition, the doping refinement of rare earth element crystal grain, substantially reduces the evolving path of lithium ion and effectively inhibits the increase of Charge-transfer resistance, thus improving the high rate performance of material in itself.
Preferably: the sugar adopted is: one or more in glucose, sucrose, starch, fructose, galactolipin, maltose, according to mass ratio, sugared content is the 2%-10% of tri compound presoma.Raw material are cheap and easy to get.
In such scheme: described soluble metal lithium compound is one or more in lithium hydroxide, lithium nitrate, lithium acetate, lithium chloride, and described solvent is deionized water, cheap and easy to get.These lithium compounds can be water-soluble, can reach desirable mixing state in mixed lithium process.
In such scheme: described rare earth compound is one or more in lanthana, cerium oxide, samarium oxide, gadolinium oxide, luteium oxide and praseodymium oxide.
In such scheme: being prepared as of described tri compound presoma: by the sulfate liquor of Ni, Co, Mn in molar ratio Ni:Co:Mn=5:3:2 mix and be salting liquid, sodium hydroxide solution containing ammonia is aqueous slkali, aqueous slkali and salting liquid are joined in reactor, keep pH 9.5 ~ 11.5, coprecipitation reaction, has reacted rear washing, filtration, drying has obtained tri compound presoma (Ni
0.5co
0.3mn
0.2) (OH)
2.Ammonia in the program is as chelating agent.
In such scheme: add water and sugared mixing and stirring first in a kettle., then by obtained ternary precursor (Ni
0.5co
0.3mn
0.2) (OH)
2with soluble lithium compounds, rare earth compound (Ni in molar ratio
0.5co
0.3mn
0.2) (OH)
2: add after Li:R=1:1:n prepares burden in reactor, circulation stirring 5 ~ 10h, spray-dried sugared coated presoma.
In such scheme: coated for pulverous sugar persursor material is heated to 850 DEG C ~ 960 DEG C with the programming rate of 1 ~ 30 DEG C/min under air or oxygen atmosphere, and constant temperature 5 ~ 15h, then be cooled to room temperature, obtained LiNi after sieving
xco
ymn
zr
no
2sample powder.
The invention has the beneficial effects as follows: compared with prior art, the present invention is doped with rare earth element, adopt the coated mixed lithium spray drying process of liquid phase sugar, soluble lithium salt reaches mixing of perfect condition with complex ternary presoma in the syrup having certain viscosity, and presoma and lithium salts carry out granulation again during hig h-speed centrifugal spray drying, prepare the ternary material of stoichiometric proportion, this material secondary particle dispersion is good, size is even---be conducive to the infiltration of electrolyte, fundamentally improve the diffusion rate of lithium ion, improve the high rate performance of material in itself, reduce the impedance in lithium ion diffusion process, thus improve the electrical property of material, be convenient to steady production.And adopt sugar coated, in spray-drying process, reduce distributing of penetrating odor.
Accompanying drawing explanation
In Fig. 1, a, b, c, d are prepared Sample Scan Electronic Speculum figure in embodiment 1,2,3,4 respectively;
In Fig. 2, a, b, c, d are the figure of electric discharge first of prepared sample in embodiment 1,2,3,4 respectively;
In Fig. 3, a, b, c, d are the step cycle graph of prepared sample in embodiment 1,2,3,4 respectively.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described:
Embodiment 1:
By the sulfate liquor of Ni, Co, Mn in molar ratio Ni:Co:Mn=Ni:Co:Mn=5:3:2 obtain salting liquid after mixing, the molar concentration of the sulfate liquor of Ni, Co, Mn is 2mol/L.Add in reactor by sodium hydroxide solution and above-mentioned salting liquid containing ammonia, by the charging rate of adjustment aqueous slkali, control pH is at 9.5-11.5, and coprecipitation reaction, has reacted rear washing, filtration, drying obtain tri compound presoma (Ni
0.5co
0.3mn
0.2) (OH)
2.Sodium hydroxide solution containing ammonia is prepared as follows: joined by ammoniacal liquor in sodium hydroxide solution, mix and obtain, and in the solution finally obtained, the molar concentration of NaOH is 4mol/L, NH
3mass concentration be 5%.
Get the lanthana La of 1mol lithium hydroxide LiOH, 0.002mol
2o
3, 1mol ternary precursor compound (Ni
0.5co
0.3mn
0.2) (OH)
2add deionized water after mixing be solvent and dissolved agitation cycle 8h in the reactor of the glucose of ternary precursor mass fraction 5%, then sugared coated precursor powder is obtained by spraying dry, by coated for sugar precursor powder in the Muffle furnace being connected with air, 920 DEG C are raised to the programming rate of 15 DEG C/min, after constant temperature 8h, naturally cool to room temperature again to take out, obtain the positive electrode LiNi of rare-earth-doped modification
0.5co
0.3mn
0.2la
0.004o
2.Can find out that from Fig. 1 a sample particle size prepared by the method is even, particle diameter is less about 3 ~ 5 μm.
By the positive electrode LiNi of liquid phase sugar coated mixed lithium spraying dry composite rare earth doping modification
0.5co
0.3mn
0.2la
0.004o
2powder, acetylene black, PVDF in mass ratio 90:5:5 mix, and are then coated on the aluminium foil of 0.018mm, after abundant drying, obtain anode pole piece, then fill to obtain battery at the glove box being full of argon gas; Finally on LAND cell tester, carry out charge-discharge performance test: carry out charge-discharge test with 0.2C multiplying power, charging/discharging voltage is 4.2 ~ 3.0V, it is 207mAh/g that room temperature records first discharge specific capacity, after 0.5C-5C multiplying power lower step circulation electric discharge 20 times, specific capacity still has 177mAh/g, has fully demonstrated the superior high rate performance of material and good cycle performance.Referring to Fig. 2 a for its 0.2C figure, Fig. 3 a that discharges first is 0.5C-5C circulation figure.
Embodiment 2:
Obtain salting liquid after the sulfate liquor of Ni, Co, Mn is even by Ni:Co:Mn=5:3:2 mixed in molar ratio, the molar concentration of the sulfate liquor of Ni, Co, Mn is 2mol/L.Add in reactor by sodium hydroxide solution and above-mentioned salting liquid containing ammonia, by regulating the charging rate of aqueous slkali, pH is at 9.5-11.5 in maintenance, coprecipitation reaction, has reacted rear washing, filtration, drying obtain tri compound presoma (Ni
0.5co
0.3mn
0.2) (OH)
2.Sodium hydroxide solution containing ammonia is prepared as follows: joined by ammoniacal liquor in sodium hydroxide solution, mix and obtain, and in the solution finally obtained, the molar concentration of NaOH is 4mol/L, NH
3mass concentration be 5%.
Get lithium hydroxide LiOH and ternary precursor compound (Ni
0.5co
0.3mn
0.2) (OH)
2each 1mol, add deionized water after mixing be solvent and dissolved agitation cycle 8h in the reactor of the glucose of ternary precursor mass fraction 5%, then sugared coated precursor powder is obtained by spraying dry, by coated for sugar precursor powder in the Muffle furnace being connected with air, 920 DEG C are raised to 15 DEG C/min, after constant temperature 8h, then naturally cool to room temperature taking-up, obtain positive electrode LiNi
0.5co
0.3mn
0.2o
2.Can find out that from Fig. 1 b sample particle size prepared by the method is even, but about tens microns bigger than normal of particle diameter.
By positive electrode LiNi prepared by the coated mixed lithium spraying dry of liquid phase sugar
0.5co
0.3mn
0.2o
2powder, acetylene black, PVDF in mass ratio 90:5:5 mix, and are then coated on the aluminium foil of 0.018mm, after abundant drying, obtain anode pole piece, then fill to obtain battery at the glove box being full of argon gas; Finally on LAND cell tester, carry out charge-discharge performance test: carry out charge-discharge test with 0.2C multiplying power, charging/discharging voltage is 4.2 ~ 3.0V, it is 196mAh/g that room temperature records first discharge specific capacity, after 0.5C-5C multiplying power lower step circulation electric discharge 20 times, specific capacity still has 156mAh/g, and high rate performance and the cycle performance of material are better.Referring to Fig. 2 b for its 0.2C figure, Fig. 3 b that discharges first is 0.5C-5C multiplying power step cycle graph.
Embodiment 3:
Obtain salting liquid after the sulfate liquor of Ni, Co, Mn is even by Ni:Co:Mn=5:3:2 mixed in molar ratio, the molar concentration of the sulfate liquor of Ni, Co, Mn is 2mol/L.Add in reactor by sodium hydroxide solution and above-mentioned salting liquid containing ammonia, by the charging rate of adjustment aqueous slkali, control pH is at 9.5-11.5, and coprecipitation reaction, has reacted rear washing, filtration, drying obtain tri compound presoma (Ni
0.5co
0.3mn
0.2) (OH)
2.Sodium hydroxide solution containing ammonia is prepared as follows: joined by ammoniacal liquor in sodium hydroxide solution, mix and obtain, and in the solution finally obtained, the molar concentration of NaOH is 4mol/L, NH
3mass concentration be 5%.
Get the lanthana La of 1mol lithium hydroxide LiOH, 0.002mol
2o
3, 1mol ternary precursor compound (Ni
0.5co
0.3mn
0.2) (OH)
2, carry out dry mixed, stir 8h in high-speed mixer and mixing, then by the precursor powder that mix in the Muffle furnace being connected with air, be raised to 920 DEG C with 15 DEG C/min, after constant temperature 8h, then naturally cool to room temperature taking-up, obtain the positive electrode LiNi of rare-earth-doped modification
0.5co
0.3mn
0.2la
0.004o
2.Can find out that from Fig. 1 c the overall particle diameter of sample prepared by the method is less, but granular size is uneven.
By the positive electrode LiNi of rare-earth-doped modification
0.5co
0.3mn
0.2la
0.004o
2powder, acetylene black, PVDF in mass ratio 90:5:5 mix, and are then coated on the aluminium foil of 0.018mm, after abundant drying, obtain anode pole piece, then fill to obtain battery at the glove box being full of argon gas; Finally on LAND cell tester, carry out charge-discharge performance test: carry out charge-discharge test with 0.2C multiplying power, charging/discharging voltage is 4.2 ~ 3.0V, it is 187mAh/g that room temperature records first discharge specific capacity, after 0.5C-5C multiplying power lower step circulation electric discharge 20 times, specific capacity has 157mAh/g, embodies the good high rate performance of material and cycle performance.Referring to Fig. 2 c for its 0.2C figure, Fig. 3 c that discharges first is 0.5C-5C multiplying power step cycle graph.
Embodiment 4:
Obtain salting liquid after the sulfate liquor of Ni, Co, Mn is even by Ni:Co:Mn=5:3:2 mixed in molar ratio, the molar concentration of the sulfate liquor of Ni, Co, Mn is 2mol/L.Add in reactor by sodium hydroxide solution and above-mentioned salting liquid containing ammonia, by the charging rate of adjustment aqueous slkali, control pH is at 9.5-11.5, and coprecipitation reaction, has reacted rear washing, filtration, drying obtain tri compound presoma (Ni
0.5co
0.3mn
0.2) (OH)
2.Sodium hydroxide solution containing ammonia is prepared as follows: joined by ammoniacal liquor in sodium hydroxide solution, mix and obtain, and in the solution finally obtained, the molar concentration of NaOH is 4mol/L, NH
3mass concentration be 5%.
Get lithium hydroxide LiOH and ternary precursor compound (Ni
0.5co
0.3mn
0.2) (OH)
2the lanthana La of each 1mol, 0.002mol
2o
3, carry out dry mixed, stir 8h in high-speed mixer and mixing, then by the precursor powder that mix in the Muffle furnace being connected with air, be raised to 920 DEG C with 15 DEG C/min, after constant temperature 8h, then naturally cool to room temperature taking-up, obtain positive electrode LiNi
0.5co
0.3mn
0.2o
2.Can find out that from Fig. 1 d sample particle size prepared by the method is uneven, and overall particle diameter is larger.
By positive electrode LiNi
0.5co
0.3mn
0.2o
2powder, acetylene black, PVDF in mass ratio 90:5:5 mix, and are then coated on the aluminium foil of 0.018mm, after abundant drying, obtain anode pole piece, then fill to obtain button cell at the glove box being full of argon gas; Finally on LAND cell tester, carry out charge-discharge performance test: carry out charge-discharge test with 0.2C multiplying power, charging/discharging voltage is 4.2 ~ 3.0V, it is 163mAh/g that room temperature records first discharge specific capacity, after 0.5C-5C multiplying power lower step circulation electric discharge 20 times, specific capacity is 122mAh/g, and high rate performance and the cycle performance of material are poor.Referring to Fig. 2 d for its 0.2C figure, Fig. 3 d that discharges first is 0.5C-5C multiplying power step cycle graph.
As can be seen from Fig. 1-3, the trielement composite material performance that embodiment 1 obtains is better than embodiment 2-4.
Embodiment 5
The sulfate liquor of Ni, Co, Mn is pressed Ni:Co:Mn=5:3:2 mixed in molar ratio evenly after, the molar concentration of the sulfate liquor of Ni, Co, Mn is 4mol/L.Add in reactor by sodium hydroxide solution and above-mentioned salting liquid containing ammonia, by the charging rate of adjustment aqueous slkali, control pH is at 9.5-11.5, and coprecipitation reaction, has reacted rear washing, filtration, drying obtain tri compound presoma (Ni
0.5co
0.3mn
0.2) (OH)
2.Sodium hydroxide solution containing ammonia is prepared as follows: joined by ammoniacal liquor in sodium hydroxide solution, mix and obtain, and in the solution finally obtained, the molar concentration of NaOH is 8mol/L, NH
3mass concentration be 15%.
Get the cerium oxide of 1mol lithium hydroxide LiOH, 0.002mol, 1mol ternary precursor compound (Ni
0.5co
0.3mn
0.2) (OH)
2.Add water after mixing be solvent and dissolved agitation cycle 6h in the reactor of the sucrose of ternary precursor mass fraction 10%, then sugared coated precursor powder is obtained by spraying dry, by coated for sugar precursor powder in the Muffle furnace being connected with air, 960 DEG C are raised to the programming rate of 15 DEG C/min, after constant temperature 10h, naturally cool to room temperature again to take out, obtain the positive electrode LiNi of rare-earth-doped modification
0.5co
0.3mn
0.2ce
0.002o
2.
Embodiment 6
The sulfate liquor of Ni, Co, Mn is pressed Ni:Co:Mn=5:3:2 mixed in molar ratio evenly after, the molar concentration of the sulfate liquor of Ni, Co, Mn is 2mol/L.Add in reactor by sodium hydroxide solution and above-mentioned salting liquid containing ammonia, by the charging rate of adjustment aqueous slkali, control pH is at 9.5-11.5, and coprecipitation reaction, has reacted rear washing, filtration, drying obtain tri compound presoma (Ni
0.5co
0.3mn
0.2) (OH)
2.Sodium hydroxide solution containing ammonia is prepared as follows: joined by ammoniacal liquor in sodium hydroxide solution, mix and obtain, and in the solution finally obtained, the molar concentration of NaOH is 4mol/L, NH
3mass concentration be 10%.
Get the samarium oxide of 1mol lithium hydroxide LiOH, 0.005mol, 1mol ternary precursor compound (Ni
0.5co
0.3mn
0.2) (OH)
2.Add water after mixing be solvent and dissolved agitation cycle 8h in the reactor of the starch of ternary precursor mass fraction 2%, then sugared coated precursor powder is obtained by spraying dry, by coated for sugar precursor powder in the Muffle furnace being connected with air, 960 DEG C are raised to the programming rate of 30 DEG C/min, after constant temperature 12h, naturally cool to room temperature again to take out, obtain the positive electrode LiNi of rare-earth-doped modification
0.5co
0.3mn
0.2sm
0.01o
2.
Embodiment 7
The sulfate liquor of Ni, Co, Mn is pressed Ni:Co:Mn=Ni:Co:Mn=5:3:2 mixed in molar ratio evenly after, the molar concentration of the sulfate liquor of Ni, Co, Mn is 2mol/L.Add in reactor by sodium hydroxide solution and above-mentioned salting liquid containing ammonia, by the charging rate of adjustment aqueous slkali, control pH is at 9.5-11.5, and coprecipitation reaction, has reacted rear washing, filtration, drying obtain tri compound presoma (Ni
0.5co
0.3mn
0.2) (OH)
2.Sodium hydroxide solution containing ammonia is prepared as follows: joined by ammoniacal liquor in sodium hydroxide solution, mix and obtain, and in the solution finally obtained, the molar concentration of NaOH is 4mol/L, NH
3mass concentration be 10%.
Get the Gd of 1mol lithium hydroxide LiOH, 0.002mol
2o
3, 1mol ternary precursor compound (Ni
0.5co
0.3mn
0.2) (OH)
2.Add water after mixing be solvent and dissolved agitation cycle 5h in the reactor of the fructose of ternary precursor mass fraction 7%, then sugared coated precursor powder is obtained by spraying dry, by coated for sugar precursor powder in the Muffle furnace being connected with air, 850 DEG C are raised to the programming rate of 1 DEG C/min, after constant temperature 15h, naturally cool to room temperature again to take out, obtain the positive electrode LiNi of rare-earth-doped modification
0.5co
0.3mn
0.2gd
0.004o
2.
The present invention is not limited to above-mentioned specific embodiment, as the sugar that adopts can be: one or more in glucose, sucrose, starch, fructose, galactolipin, maltose.
Lithium compound is one or more in soluble lithium salt lithium hydroxide, lithium nitrate, lithium acetate, lithium chloride.Rare earth compound is one or more in lanthana, cerium oxide, samarium oxide, gadolinium oxide, luteium oxide and praseodymium oxide.Solvent can also be the alcohols solvents such as ethanol except deionized water, and we do not enumerate in an embodiment.
Should be appreciated that those of ordinary skill in the art just design according to the present invention can make many modifications and variations without the need to creative work.In a word, all technical staff in the art, all should by the determined protection range of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (7)
1. the coated spraying dry of liquid phase sugar prepares a method for nickle cobalt lithium manganate tertiary cathode material, it is characterized in that: be prepared as follows: after first being mixed by the sulfate liquor of Ni, Co, Mn, coprecipitation reaction obtains tri compound presoma (Ni in the basic conditions
xco
ymn
z) (OH)
2after filtration, after washing, drying, this tri compound presoma, soluble metal lithium compound, rare earth compound being added has dissolved in sugared solvent, sugar is obtained by spraying dry coated and be doped with the ternary precursor of rare earth element, finally by obtaining after high-temperature calcination through rare earth doped ternary material LiNi after mixing
xco
ymn
zr
no
2, wherein R be doping rare earth element, x+y+z=1,0.002≤n≤0.1.
2. the coated spraying dry of liquid phase sugar prepares the method for nickle cobalt lithium manganate tertiary cathode material according to claim 1, it is characterized in that: the sugar adopted is: one or more in glucose, sucrose, starch, fructose, galactolipin, maltose, according to mass ratio, sugared content is the 2%-10% of tri compound presoma.
3. according to claim 1 or 2, the coated spraying dry of liquid phase sugar prepares the method for nickle cobalt lithium manganate tertiary cathode material, it is characterized in that: described soluble metal lithium compound is one or more in lithium hydroxide, lithium nitrate, lithium acetate, lithium chloride, and described solvent is deionized water.
4. the coated spraying dry of liquid phase sugar prepares the method for nickle cobalt lithium manganate tertiary cathode material according to claim 3, it is characterized in that: described rare earth compound is one or more in lanthana, cerium oxide, samarium oxide, gadolinium oxide, luteium oxide and praseodymium oxide.
5. the coated spraying dry of liquid phase sugar prepares the method for nickle cobalt lithium manganate tertiary cathode material according to claim 4, it is characterized in that: being prepared as of described tri compound presoma: by the sulfate liquor of Ni, Co, Mn in molar ratio Ni:Co:Mn=5:3:2 mix and obtain salting liquid, sodium hydroxide solution containing ammonia is aqueous slkali, aqueous slkali and salting liquid are joined in reactor, control pH is 9.5 ~ 11.5, coprecipitation reaction, has reacted rear washing, filtration, drying has obtained tri compound presoma (Ni
0.5co
0.3mn
0.2) (OH)
2.
6. the coated spraying dry of liquid phase sugar prepares the method for nickle cobalt lithium manganate tertiary cathode material according to claim 5, it is characterized in that: add deionized water in a kettle. and sugar stirs, by obtained ternary precursor (Ni
0.5co
0.3mn
0.2) (OH)
2with lithium compound, rare earth compound (Ni in molar ratio
0.5co
0.3mn
0.2) (OH)
2: add after Li:R=1:1:n prepares burden in reactor, circulation stirring 5 ~ 10h, spray-dried sugared coated presoma.
7. the coated spraying dry of liquid phase sugar prepares the method for nickle cobalt lithium manganate tertiary cathode material according to claim 6, it is characterized in that: coated for pulverous sugar persursor material is heated to 850 DEG C ~ 960 DEG C with the programming rate of 1 ~ 30 DEG C/min under air or oxygen atmosphere, and constant temperature 5 ~ 15h, be cooled to room temperature again, obtained LiNi after sieving
xco
ymn
zr
no
2sample powder.
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