CN104733721B - The method that liquid phase sugar cladding spray drying prepares nickle cobalt lithium manganate tertiary cathode material - Google Patents
The method that liquid phase sugar cladding spray drying prepares nickle cobalt lithium manganate tertiary cathode material Download PDFInfo
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Abstract
The invention discloses the method that a kind of sugar cladding spray drying of liquid phase prepares nickle cobalt lithium manganate tertiary cathode material, tri compound presoma (Ni is made in coprecipitated reaction in the basic conditions after first Ni, Co, Mn sulfate liquor are mixedxCoyMnz)(OH)2After filtering, washing, drying, the tri compound presoma, soluble metal lithium compound, rare earth compound are added in the solvent for having dissolved sugar, the ternary precursor that sugar coats and is doped with rare earth element is obtained by spray drying after well mixed, most can be obtained through rare earth doped ternary material LiNi after high-temperature calcination afterwardsxCoyMnzRnO2, wherein R is the rare earth element, x+y+z=1,0.002≤n≤0.1 of doping.Using sugar cladding in this method, distributing for penetrating odor is reduced in spray-drying process.The ternary material second particle good dispersion for the stoichiometric proportion that the present invention is prepared, it is uniform in size --- be conducive to the infiltration of electrolyte, fundamentally improve the diffusion rate of lithium ion, reduce the impedance in lithium ion diffusion process, so as to improve the electrical property of material, it is easy to steady production.
Description
Technical field
The present invention relates to the method that a kind of sugar cladding spray drying of liquid phase prepares nickle cobalt lithium manganate tertiary cathode material.
Background technology
Lithium ion battery just obtains fast development as energy-storage battery of new generation in various consumer electronics product fields,
And show potential application value in electric automobile, electric vehicle and space industry.And the performance of lithium ion battery
Positive electrode is depended greatly on cost.At present, the specific capacity of lithium ion battery negative material reaches positive electrode
Twice so that positive electrode specific capacity it is relatively low have become restriction lithium ion battery development bottleneck, therefore research lithium ion
Cell positive material, has important practical significance for developing and improving lithium ion battery.
Because ternary nickel-cobalt lithium manganate material inherit cobalt acid lithium, lithium nickelate, LiMn2O4 advantage have specific capacity high, platform
Voltage is high, and tap density is big, and crystal structure is stable, and preparation technology is simple, the low feature of operating cost, it has also become lithium ion battery
One of indispensable selection of positive electrode.But cobalt nickel lithium manganate ternary material can't replace existing lithium ion battery completely just
Pole material, main cause has at 2 points：Presoma, Ran Houtong are prepared using coprecipitation more than the ternary material industrially produced at present
Cross dry or wet and mix lithium, eventually pass high-temperature calcination and prepare ternary material.One：Mixing lithium using dry or wet causes forerunner
The mixing of body and lithium is not uniform enough, and grain diameter is whard to control so that the stability of final products is difficult to control to；Secondly nickel cobalt
LiMn2O4 is to calcine synthesis in insulation of 850 DEG C of high temperature above through certain time, the crystal grain meeting fast growth in calcination process, and
Granularity is difficult to control to, and causes the discharge capacity first and cycle performance of material to become negatively affected；Thirdly：Lithium ion and nickel ion
Radius is close, and nickel ion easily occupies lithium ion position generation crystal structure and caved in charge and discharge process.Crystal structure collapses
Collapse and not only break up Li+Transmission channel, and battery abjection Li2Ion is reset and is obstructed after O, and octahedral voids are occupied, after electric discharge
There is no enough positions to supply Lithium-ion embeding, cause to analyse lithium, had a strong impact on the performance of electrical property.
The content of the invention
For it is existing the problem of, it is an object of the invention to provide a kind of chemical property it is good, be easy to the liquid of steady production
The method that mutually spray drying of sugar cladding prepares nickle cobalt lithium manganate tertiary cathode material.
To achieve these goals, the technical scheme is that such：It is prepared by a kind of liquid phase sugar cladding spray drying
The method of nickle cobalt lithium manganate tertiary cathode material, it is characterised in that：It is prepared as follows：First by Ni, Co, Mn sulfate
Tri compound presoma (Ni is made in coprecipitation reaction in the basic conditions after solution mixingxCo yMnz)(OH)2, through filtering, washing
Wash, dry after, by the tri compound presoma, soluble metal lithium compound, rare earth compound add dissolved sugar solvent
In, the ternary precursor that sugar coats and is doped with rare earth element is obtained by spray drying after being well mixed, most forged afterwards through high temperature
It can be obtained through rare earth doped ternary material LiNi after burningxCoyMnz RnO2, wherein R is the rare earth element of doping, x+y+
Z=1,0.002≤n≤0.1.
Using such scheme, this method first mixes lithium using liquid phase, makes the tri compound presoma and solubility of nickel cobalt manganese
Lithium salts reaches preferable admixture in the liquid phase.
Secondly the sugar when liquid phase mixes lithium in increase sugar, liquid phase adds the toughness of solution, reduces intergranular point
Property is dissipated, the reunion between ternary precursor is effectively prevented.Viscous solution sugar in hig h-speed centrifugal spray drying is converted into glass
State, makes that at the same time presoma is scattered evenly, sphericity is higher completes to granulate again.Sugar cladding presoma prepared by this method
Particle dispersion is good, and uniform in size, sphericity is high, and average grain diameter is 3~5 μm.The second particle of sample is loose, is conducive to electrolysis
The infiltration of liquid, fundamentally improves the diffusion rate of lithium ion, the impedance in lithium ion diffusion process is reduced, so as to improve
The high rate performance and cycle performance of material.Prepared sample dresses up battery first discharge specific capacity up to more than 200mAh/g.
In addition, at present when preparing ternary material, seldom using the mixed lithium of spray drying, be because lithium hydroxide, lithium nitrate,
The lithium compounds such as lithium acetate, lithium chloride spray drying when can give out unpleasant penetrating odor, in this process we
By sugar cladding, distributing for lithium compound penetrating odor is reduced.
Finally, the present invention is additionally added rare earth element, due to the special electron structure of rare earth element [Xe] 4f0-145d0- 16s2, after two 6s and 5d or 4f electronics are lost, form most common Ln3+Wherein La3+、Gd3+、Lu3+4f subgrades
It is respectively complete empty, partly fill, full up state, according to Hund's rule, these states are all stable states, therefore, positioned at their both sides
Ln, which has, to be obtained or loses electronics to reach or close to the trend of aforementioned stable state.The doping of rare earth element not only changes master
Body lattice electron structure and chemical bonding structure, and can effectively suppress cation mixing in charge and discharge process, stabilize crystalline substance
Body structure, reduces irreversible capacity, improves the capacity and cycle performance discharged first.In addition, the doping of rare earth element is thin
Crystal grain is changed, has substantially reduced the diffusion path of lithium ion and effectively inhibit the increase of Charge-transfer resistance, so that in essence
The upper high rate performance for improving material.
Preferably：The sugar used for：One kind in glucose, sucrose, starch, fructose, galactolipin, maltose
Or more than one, 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：The soluble metal lithium compound is in lithium hydroxide, lithium nitrate, lithium acetate, lithium chloride
One or more, the solvent be deionized water, it is cheap and easy to get.These lithium compounds can be dissolved in water, in mixed lithium mistake
Preferable mixing state can be reached in journey.
In such scheme：The rare earth compound is lanthana, cerium oxide, samarium oxide, gadolinium oxide, luteium oxide and oxidation
One or more in praseodymium.
In such scheme：The tri compound presoma is prepared as：By Ni, Co, Mn sulfate liquor by mole
Compare Ni：Co：Mn=5：3：2 well mixed as salting liquids, the sodium hydroxide solution containing ammonia is aqueous slkali, and aqueous slkali is molten with salt
Liquid is added in reactor, keeps pH 9.5~11.5, coprecipitation reaction washs after having reacted, filters, is dried to obtain ternary
Composite precursor (Ni0.5Co0.3Mn0.2)(OH)2.Ammonia in the program is used as chelating agent.
In such scheme：Water and sugared mixing and stirring are added in a kettle. first, then by before obtained ternary
Drive body (Ni0.5Co0.3Mn0.2)(OH)2With soluble lithium compounds, rare earth compound (Ni in molar ratio0.5Co0.3Mn0.2)(OH)2：
Li：R=1：1：N added after dispensing in reactor, circulation stirring 5~10h, spray-dried sugared cladding presoma.
In such scheme：By powdered sugar cladding persursor material under air or oxygen atmosphere with 1~30 DEG C/
Min programming rate is heated to 850 DEG C~960 DEG C, and 5~15h of constant temperature, is cooled to room temperature, is made after sieving
LiNixCoyMnz RnO2Sample powder.
The beneficial effects of the invention are as follows：Compared with prior art, the present invention is doped with rare earth element, is coated using liquid phase sugar
Mixed lithium spray drying process, soluble lithium salt reaches the mixed of perfect condition in the syrup for have certain viscosity with complex ternary presoma
Close, and presoma is granulated again with lithium salts during hig h-speed centrifugal spray drying, prepares the ternary material of stoichiometric proportion, should
Material secondary particle dispersion is good, uniform in size --- and be conducive to the infiltration of electrolyte, fundamentally improve the diffusion of lithium ion
Speed, improves the high rate performance of material, the impedance in lithium ion diffusion process is reduced, so as to improve material in itself
Electrical property, is easy to steady production.And using sugar cladding, distributing for penetrating odor is reduced in spray-drying process.
Brief description of the drawings
A, b, c, d are prepared Sample Scan electron microscope in embodiment 1,2,3,4 respectively in Fig. 1；
A, b, c, d are the electric discharge figure first of prepared sample in embodiment 1,2,3,4 respectively in Fig. 2；
A, b, c, d are the step circulation figure of prepared sample in embodiment 1,2,3,4 respectively in Fig. 3.
Embodiment
With reference to specific embodiment, the present invention will be further described：
Embodiment 1：
By Ni, Co, Mn sulfate liquor Ni in molar ratio：Co：Mn=Ni：Co：Mn=5:3:2 it is well mixed after obtain
Salting liquid, the molar concentration of Ni, Co, Mn sulfate liquor is 2mol/L.By the sodium hydroxide solution containing ammonia and above-mentioned salt
Solution is added in reactor, and by adjusting the charging rate of aqueous slkali, pH is in 9.5-11.5 for control, and coprecipitation reaction has reacted
After wash, filter, be dried to obtain tri compound presoma (Ni0.5Co0.3Mn0.2)(OH)2.Sodium hydroxide solution containing ammonia according to
It is prepared by following method：Ammoniacal liquor is added in sodium hydroxide solution, well mixed to obtain, NaOH in the solution finally obtained
Molar concentration be 4mol/L, NH3Mass concentration be 5%.
Take 1mol lithium hydroxides LiOH, 0.002mol lanthana La2O3, 1mol ternary precursor compounds
(Ni0.5Co0.3Mn0.2)(OH)2Deionized water is added after mixing to be solvent and dissolved the Portugal of ternary precursor mass fraction 5%
Agitation cycle 8h in the reactor of grape sugar, then by being spray-dried to obtain sugared cladding precursor powder, precursor is coated by sugar
End is raised to after 920 DEG C, constant temperature 8h, then naturally cool to room in the Muffle furnace of air is connected with 15 DEG C/min programming rate
Temperature is taken out, and obtains the positive electrode LiNi of rare-earth-doped modification0.5Co0.3Mn0.2La0.004O2.It can be seen that party's legal system from Fig. 1 a
Standby sample particle is uniform in size, and particle diameter is smaller about 3~5 μm.
The positive electrode that the mixed lithium spray drying composite rare earth doping of liquid phase sugar cladding is modified
LiNi0.5Co0.3Mn0.2La0.004O2Powder, acetylene black, PVDF in mass ratio 90:5:5 are well mixed, and are then coated in
On 0.018mm aluminium foil, anode pole piece is obtained after fully drying, then battery is filled to obtain in the glove box full of argon gas；Finally exist
Charge-discharge performance test is carried out on LAND cell testers：Charge-discharge test is carried out with 0.2C multiplying powers, charging/discharging voltage is
4.2~3.0V, room temperature measures first discharge specific capacity for 207mAh/g, and the circulation of 0.5C-5C multiplying powers lower step is compared after discharging 20 times
Capacity still has 177mAh/g, has fully demonstrated the superior high rate performance of material and good cycle performance.It is it referring to Fig. 2 a
0.2C discharges figure first, and Fig. 3 a are 0.5C-5C circulation figures.
Embodiment 2：
Ni, Co, Mn sulfate liquor are pressed into Ni：Co：Mn=5:3:Obtain salting liquid after 2 mixed in molar ratio are uniform, Ni,
The molar concentration of Co, Mn sulfate liquor is 2mol/L.Sodium hydroxide solution containing ammonia and above-mentioned salting liquid are added anti-
Answer in kettle, by adjusting the charging rate of aqueous slkali, keep pH in 9.5-11.5, coprecipitation reaction, washing, mistake after having reacted
Filter, be dried to obtain tri compound presoma (Ni0.5Co0.3Mn0.2)(OH)2.Sodium hydroxide solution containing ammonia is made as follows
It is standby：Ammoniacal liquor is added in sodium hydroxide solution, well mixed to obtain, the molar concentration of NaOH in the solution finally obtained
For 4mol/L, NH3Mass concentration be 5%.
Take lithium hydroxide LiOH and ternary precursor compound (Ni0.5Co0.3Mn0.2)(OH)2Each 1mol, is added after mixing
Deionized water be solvent and dissolved ternary precursor mass fraction 5% glucose reactor in agitation cycle 8h, then
By being spray-dried to obtain sugared cladding precursor powder, by sugar cladding precursor powder in the Muffle furnace of air is connected with, with 15 DEG C/
Min is raised to after 920 DEG C, constant temperature 8h, then naturally cools to room temperature taking-up, obtains positive electrode LiNi0.5Co0.3Mn0.2O2.From Fig. 1 b
In it can be seen that the sample particle for preparing of this method is uniform in size, but about more than ten microns bigger than normal of particle diameter.
Positive electrode LiNi prepared by the mixed lithium spray drying of liquid phase sugar cladding0.5Co0.3Mn0.2O2Powder, acetylene black,
PVDF in mass ratio 90:5:5 are well mixed, and are then coated on 0.018mm aluminium foil, and positive pole pole is obtained after fully drying
Piece, then fill to obtain battery in the glove box full of argon gas；Charge-discharge performance test is finally carried out on LAND cell testers：
Charge-discharge test is carried out with 0.2C multiplying powers, charging/discharging voltage is 4.2~3.0V, and room temperature measures first discharge specific capacity and is
Specific capacity still has a 156mAh/g after 196mAh/g, 0.5C-5C multiplying power lower step circulation electric discharge 20 times, the high rate performance of material and follows
Ring better performances.Discharged first figure for its 0.2C referring to Fig. 2 b, Fig. 3 b are that 0.5C-5C multiplying powers step circulates figure.
Embodiment 3：
Ni, Co, Mn sulfate liquor are pressed into Ni：Co：Mn=5:3:Obtain salting liquid after 2 mixed in molar ratio are uniform, Ni,
The molar concentration of Co, Mn sulfate liquor is 2mol/L.Sodium hydroxide solution containing ammonia and above-mentioned salting liquid are added anti-
Answer in kettle, by adjusting the charging rate of aqueous slkali, control pH is in 9.5-11.5, coprecipitation reaction, washing, mistake after having reacted
Filter, be dried to obtain tri compound presoma (Ni0.5Co0.3Mn0.2)(OH)2.Sodium hydroxide solution containing ammonia is made as follows
It is standby：Ammoniacal liquor is added in sodium hydroxide solution, well mixed to obtain, the molar concentration of NaOH in the solution finally obtained
For 4mol/L, NH3Mass concentration be 5%.
Take 1mol lithium hydroxides LiOH, 0.002mol lanthana La2O3, 1mol ternary precursor compounds
(Ni0.5Co0.3Mn0.2)(OH)2, dry mixed is carried out, 8h is stirred in high-speed mixer and mixing, then by the precursor mixed
End is raised to after 920 DEG C, constant temperature 8h in the Muffle furnace of air is connected with 15 DEG C/min, then naturally cools to room temperature taking-up, obtains dilute
The positive electrode LiNi of native doping vario-property0.5Co0.3Mn0.2La0.004O2.It can be seen that the sample of this method preparation is whole from Fig. 1 c
Body particle diameter is smaller, but granular size is uneven.
By the positive electrode LiNi of rare-earth-doped modification0.5Co0.3Mn0.2La0.004O2Powder, acetylene black, PVDF are in mass ratio
90:5:5 are well mixed, and are then coated on 0.018mm aluminium foil, and anode pole piece is obtained after fully drying, then full of
The glove box of argon gas fills to obtain battery；Charge-discharge performance test is finally carried out on LAND cell testers：With 0.2C multiplying powers
Charge-discharge test is carried out, charging/discharging voltage is 4.2~3.0V, and room temperature measures first discharge specific capacity for 187mAh/g, 0.5C-5C
Specific capacity has 157mAh/g after the circulation of multiplying power lower step is discharged 20 times, embodies the preferable high rate performance of material and cycle performance.
Discharged first figure for its 0.2C referring to Fig. 2 c, Fig. 3 c are that 0.5C-5C multiplying powers step circulates figure.
Embodiment 4：
Ni, Co, Mn sulfate liquor are pressed into Ni：Co：Mn=5:3:Obtain salting liquid after 2 mixed in molar ratio are uniform, Ni,
The molar concentration of Co, Mn sulfate liquor is 2mol/L.Sodium hydroxide solution containing ammonia and above-mentioned salting liquid are added anti-
Answer in kettle, by adjusting the charging rate of aqueous slkali, control pH is in 9.5-11.5, coprecipitation reaction, washing, mistake after having reacted
Filter, be dried to obtain tri compound presoma (Ni0.5Co0.3Mn0.2)(OH)2.Sodium hydroxide solution containing ammonia is made as follows
It is standby：Ammoniacal liquor is added in sodium hydroxide solution, well mixed to obtain, the molar concentration of NaOH in the solution finally obtained
For 4mol/L, NH3Mass concentration be 5%.
Take lithium hydroxide LiOH and ternary precursor compound (Ni0.5Co0.3Mn0.2)(OH)2Each 1mol, 0.002mol's
Lanthana La2O3, carry out dry mixed, high-speed mixer and mixing stir 8h, then the precursor powder mixed is being connected with
In the Muffle furnace of air, it is raised to 15 DEG C/min after 920 DEG C, constant temperature 8h, then naturally cools to room temperature taking-up, obtains positive electrode
LiNi0.5Co0.3Mn0.2O2.It can be seen that the sample particle size of this method preparation is uneven from Fig. 1 d, and overall particle diameter is larger.
By positive electrode LiNi0.5Co0.3Mn0.2O2Powder, acetylene black, PVDF in mass ratio 90:5:5 are well mixed, then
It is coated on 0.018mm aluminium foil, obtains anode pole piece after fully drying, then button is filled to obtain in the glove box full of argon gas
Battery；Charge-discharge performance test is finally carried out on LAND cell testers：Charge-discharge test is carried out with 0.2C multiplying powers, filled
Discharge voltage is 4.2~3.0V, and room temperature measures first discharge specific capacity for 163mAh/g, and the circulation of 0.5C-5C multiplying powers lower step is put
Specific capacity is 122mAh/g after electric 20 times, and the high rate performance and cycle performance of material are poor.Put first for its 0.2C referring to Fig. 2 d
Electrograph, Fig. 3 d are that 0.5C-5C multiplying powers step circulates figure.
From Fig. 1-3 as can be seen that the trielement composite material performance that embodiment 1 is obtained is better than embodiment 2-4.
Embodiment 5
Ni, Co, Mn sulfate liquor are pressed into Ni：Co：Mn=5:3:After 2 mixed in molar ratio are uniform, Ni, Co, Mn sulphur
The molar concentration of acid salt solution is 4mol/L.Sodium hydroxide solution containing ammonia and above-mentioned salting liquid are added in reactor, led to
The charging rate of aqueous slkali is overregulated, pH is in 9.5-11.5 for control, and coprecipitation reaction is washed after having reacted, filters, is dried to obtain
Tri compound presoma (Ni0.5Co0.3Mn0.2)(OH)2.Sodium hydroxide solution containing ammonia is prepared as follows：By ammoniacal liquor plus
Enter into sodium hydroxide solution, well mixed to obtain, the molar concentration of NaOH is 8mol/L in the solution finally obtained,
NH3Mass concentration be 15%.
Take 1mol lithium hydroxides LiOH, 0.002mol cerium oxide, 1mol ternary precursor compounds
(Ni0.5Co0.3Mn0.2)(OH)2.Water is added after mixing to be solvent and dissolved the sucrose of ternary precursor mass fraction 10%
Agitation cycle 6h in reactor, then by being spray-dried to obtain sugared cladding precursor powder, by sugar cladding precursor powder logical
Have in the Muffle furnace of air, be raised to 15 DEG C/min programming rate after 960 DEG C, constant temperature 10h, then naturally cool to room temperature and take
Go out, obtain the positive electrode LiNi of rare-earth-doped modification0.5Co0.3Mn0.2Ce0.002O2。
Embodiment 6
Ni, Co, Mn sulfate liquor are pressed into Ni：Co：Mn=5:3:After 2 mixed in molar ratio are uniform, Ni, Co, Mn sulphur
The molar concentration of acid salt solution is 2mol/L.Sodium hydroxide solution containing ammonia and above-mentioned salting liquid are added in reactor, led to
The charging rate of aqueous slkali is overregulated, pH is in 9.5-11.5 for control, and coprecipitation reaction is washed after having reacted, filters, is dried to obtain
Tri compound presoma (Ni0.5Co0.3Mn0.2)(OH)2.Sodium hydroxide solution containing ammonia is prepared as follows：By ammoniacal liquor plus
Enter into sodium hydroxide solution, well mixed to obtain, the molar concentration of NaOH is 4mol/L in the solution finally obtained,
NH3Mass concentration be 10%.
Take 1mol lithium hydroxides LiOH, 0.005mol samarium oxide, 1mol ternary precursor compounds
(Ni0.5Co0.3Mn0.2)(OH)2.Water is added after mixing to be solvent and dissolved the anti-of the starch of ternary precursor mass fraction 2%
Agitation cycle 8h in kettle is answered, then by being spray-dried to obtain sugared cladding precursor powder, sugar cladding precursor powder is being connected with
In the Muffle furnace of air, it is raised to 30 DEG C/min programming rate after 960 DEG C, constant temperature 12h, then naturally cools to room temperature and is taken out,
Obtain the positive electrode LiNi of rare-earth-doped modification0.5Co0.3Mn0.2Sm 0.01O2。
Embodiment 7
Ni, Co, Mn sulfate liquor are pressed into Ni：Co：Mn=Ni：Co：Mn=5:3:After 2 mixed in molar ratio are uniform, Ni,
The molar concentration of Co, Mn sulfate liquor is 2mol/L.Sodium hydroxide solution containing ammonia and above-mentioned salting liquid are added and reacted
In kettle, by adjusting the charging rate of aqueous slkali, control pH is in 9.5-11.5, coprecipitation reaction, washing after react, filter,
It is dried to obtain tri compound presoma (Ni0.5Co0.3Mn0.2)(OH)2.Sodium hydroxide solution containing ammonia is prepared as follows：
Ammoniacal liquor is added in sodium hydroxide solution, well mixed to obtain, the molar concentration of NaOH is in the solution finally obtained
4mol/L, NH3Mass concentration be 10%.
Take 1mol lithium hydroxides LiOH, 0.002mol Gd2O3, 1mol ternary precursor compounds (Ni0.5Co0.3Mn0.2)
(OH)2.Water is added after mixing to be solvent and dissolved agitation cycle in the reactor of the fructose of ternary precursor mass fraction 7%
5h, then by being spray-dried to obtain sugared cladding precursor powder, by sugar cladding precursor powder in the Muffle furnace of air is connected with,
It is raised to 1 DEG C/min programming rate after 850 DEG C, constant temperature 15h, then naturally cools to room temperature taking-up, obtains rare-earth-doped modification
Positive electrode LiNi0.5Co0.3Mn0.2Gd0.004O2。
The present invention is not limited to above-mentioned specific embodiment, as the sugar that is used can be for：Glucose, sucrose, starch, fruit
One or more in sugar, galactolipin, maltose.
Lithium compound is the one or more in soluble lithium salt lithium hydroxide, lithium nitrate, lithium acetate, lithium chloride.
Rare earth compound is the one or more in lanthana, cerium oxide, samarium oxide, gadolinium oxide, luteium oxide and praseodymium oxide.Solvent
The alcohols solvents such as ethanol are can also be in addition to deionized water, we do not enumerate in embodiment.
It should be appreciated that one of ordinary skill in the art can just make without creative work according to the design of the present invention
Many modifications and variations.In a word, all technical staff in the art are led on the basis of existing technology under this invention's idea
The available technical scheme of logical analysis, reasoning, or a limited experiment is crossed, all should be in the guarantor being defined in the patent claims
In the range of shield.
Claims (5)
1. a kind of method that liquid phase sugar cladding spray drying prepares nickle cobalt lithium manganate tertiary cathode material, it is characterised in that：According to
It is prepared by following method：Tri compound is made in coprecipitation reaction in the basic conditions after first Ni, Co, Mn sulfate liquor are mixed
Presoma (NixCoyMnz)(OH)2, after filtering, washing, drying, the tri compound presoma, soluble metal lithiumation are closed
Thing, rare earth compound addition have been dissolved in the solvent of sugar, are obtained sugar cladding by spray drying after being well mixed and are doped with dilute
The ternary precursor of earth elements, persursor material is coated under air or oxygen atmosphere with 1~30 DEG C/min by powdered sugar
Programming rate be heated to 850 DEG C~960 DEG C, and 5~15h of constant temperature, be cooled to room temperature, after sieving be made rare earth element mix
Miscellaneous ternary material LiNixCoyMnzRnO2Sample powder, wherein R for doping rare earth element, x+y+z=1,0.002≤n≤
0.1,
The rare earth compound is lanthana.
2. the method that the spray drying of liquid phase sugar cladding prepares nickle cobalt lithium manganate tertiary cathode material according to claim 1, its
It is characterised by：The sugar used for：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. the method that liquid phase sugar cladding spray drying according to claim 1 or claim 2 prepares nickle cobalt lithium manganate tertiary cathode material,
It is characterized in that：The soluble metal lithium compound is one kind or one in lithium hydroxide, lithium nitrate, lithium acetate, lithium chloride
More than kind, the solvent is deionized water.
4. the method that the spray drying of liquid phase sugar cladding prepares nickle cobalt lithium manganate tertiary cathode material according to claim 1, its
It is characterised by：The tri compound presoma is prepared as：By Ni, Co, Mn sulfate liquor Ni in molar ratio：Co：Mn=
5：3：2 it is well mixed obtain salting liquid, the sodium hydroxide solution containing ammonia is aqueous slkali, and aqueous slkali and salting liquid are added into reaction
In kettle, pH is 9.5~11.5 for control, and coprecipitation reaction is washed after having reacted, filtered, being dried to obtain tri compound presoma
(Ni0.5Co0.3Mn0.2)(OH)2。
5. the method that the spray drying of liquid phase sugar cladding prepares nickle cobalt lithium manganate tertiary cathode material according to claim 4, its
It is characterised by：Add deionized water in a kettle. and sugar stirs, by obtained ternary precursor (Ni0.5Co0.3Mn0.2)
(OH)2With lithium compound, rare earth compound (Ni in molar ratio0.5Co0.3Mn0.2)(OH)2：Li：R=1：1：N add after dispensing
Enter in reactor, circulation stirring 5~10h, spray-dried sugared cladding presoma.
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| CN111039330A (en) * | 2019-11-29 | 2020-04-21 | 合肥国轩电池材料有限公司 | Preparation method of nickel-cobalt-manganese ternary positive electrode spherical material |
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| CN115974171A (en) * | 2022-09-29 | 2023-04-18 | 宁夏汉尧富锂科技有限责任公司 | Cathode material prepared by wet lithium-poor process and preparation method thereof |
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