CN109987650A - Nickel-cobalt lithium manganate cathode material, preparation method and application - Google Patents
Nickel-cobalt lithium manganate cathode material, preparation method and application Download PDFInfo
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- CN109987650A CN109987650A CN201910342205.0A CN201910342205A CN109987650A CN 109987650 A CN109987650 A CN 109987650A CN 201910342205 A CN201910342205 A CN 201910342205A CN 109987650 A CN109987650 A CN 109987650A
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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
- 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
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of preparation method of nickel-cobalt lithium manganate cathode material, the following steps are included: preparing includes nickel source, the mixed solution of cobalt source and manganese source, strong base solution and inorganic salt solution containing ammonium ion, the mixed solution, the strong base solution and the inorganic salt solution containing ammonium ion are mixed simultaneously and carry out Rapid coprecipitation reaction, the pH value that control carries out the Rapid coprecipitation reaction is 10-12, the first suspension is obtained, first suspension is separated and obtains sediment；The sediment is configured to the second suspension, second suspension is subjected to ball milling；The second suspension after ball milling is spray-dried, precursor powder is obtained；The precursor powder is mixed with lithium source, obtains mixture；And calcine the mixture, obtain the nickel-cobalt lithium manganate cathode material.The present invention also provides a kind of nickel-cobalt lithium manganate cathode material, positive plate and lithium ion batteries.
Description
Technical field
The present invention relates to field of batteries more particularly to a kind of nickel-cobalt lithium manganate cathode materials, preparation method and application.
Background technique
With the development of society, energy and environmental problem becomes increasingly conspicuous, electric vehicle alleviates traditional combustion as effective means
Oily vehicle bring energy environment issues.Energy supply core component of the lithium ion battery as electric vehicle, the development bottleneck master of performance
Be positive electrode, at present for lithium ion power battery cathode material using it is more be LiFePO4, spinelle mangaic acid
Lithium and nickle cobalt lithium manganate since the requirement to electric vehicle course continuation mileage is higher and higher, therefore have high-energy density and higher pressure real
The nickel-cobalt lithium manganate cathode material of density receives the favor of people.Nickel-cobalt lithium manganate cathode material passes through tri- kinds of members of Ni-Co-Mn
The synergistic effect of element, combines the good cycle performance of cobalt acid lithium, the high security of the height ratio capacity of lithium nickelate and LiMn2O4 with
Low cost.
The preparation method of nickel-cobalt lithium manganate cathode material, study more has hydro-thermal method, sol-gel method, fused salt at present
Method, spray pyrolysis etc..But these preparation methods are unsuitable for producing in enormous quantities, are primarily due to low output, expensive starting materials,
And synthesis process is difficult to control.So what is be widely adopted at present is coprecipitation, coprecipitation ternary sediment is first passed through
Presoma, then presoma is mixed with lithium source, by high-temperature calcination, finally obtain tertiary cathode material.But conventional coprecipitation
The process time that method synthesizes presoma is long, high due to requiring presoma pattern, therefore needs in the synthesis process to synthesis condition
Strict control, and obtained presoma needs to carry out the drying process of long period.
Summary of the invention
In view of this, it is necessary to provide a kind of preparation sides of the relatively simple nickel-cobalt lithium manganate cathode material of synthesis technology
Method, to solve the above problems.
In addition, there is a need to provide a kind of nickel-cobalt lithium manganate cathode material.
In addition, there is a need to provide a kind of positive plate and lithium ion battery including the nickel-cobalt lithium manganate cathode material.
A kind of preparation method of nickel-cobalt lithium manganate cathode material, comprising the following steps:
It prepares including nickel source, the mixed solution of cobalt source and manganese source, strong base solution and inorganic salt solution containing ammonium ion, it will
It is anti-that the mixed solution, the strong base solution and the inorganic salt solution containing ammonium ion mix progress Rapid coprecipitation simultaneously
It answers, the pH value that control carries out the Rapid coprecipitation reaction is 10-12, obtains the first suspension, separates first suspension
Obtain sediment；
The sediment is configured to the second suspension, second suspension is subjected to ball milling；
The second suspension after ball milling is spray-dried, precursor powder is obtained；
The precursor powder is mixed with lithium source, obtains mixture；And
The mixture is calcined, the nickel-cobalt lithium manganate cathode material is obtained.
Further, the nickel source, cobalt source and manganese source are water soluble salt, and the water soluble salt includes sulfate, nitric acid
At least one of salt, chlorate and acetate, the highly basic include potassium hydroxide, sodium hydroxide, in lithium hydroxide at least
It is a kind of；The inorganic salts containing ammonium ion include at least one of ammonium hydroxide, ammonium sulfate, ammonium chloride, ammonium fluoride, and the lithium source is
At least one of lithium hydroxide, lithium carbonate, lithium nitrate and lithium acetate.
Further, the total mole number of nickel element, cobalt element and manganese element is x in the precursor powder, in lithium source
The molal quantity of elemental lithium is y, the x:y=1:1.03~1:1.1.
Further, the calcining includes the first calcination stage and the second calcination stage, and first calcination stage is will
First the pre-burning 2h-5h at 450 DEG C -500 DEG C, heating rate are 5-10 DEG C/min to the mixture, and second calcination stage is
750 DEG C -1000 DEG C are warming up to the heating rate of 1-3 DEG C/min, keeps the temperature 9h-18h at this temperature.
Further, in the second calcination stage, when the molal quantity of nickel element is less than or equal to the nickel element, cobalt element
And the total mole number of manganese element 50% when, the mixture is calcined in air atmosphere；When the molal quantity of nickel element
Greater than the total mole number 50% when, the mixture is calcined under oxygen atmosphere.
Further, it is 500-1000r/min, reaction temperature that the condition of the Rapid coprecipitation reaction, which includes mixing speed,
Degree is 40 DEG C -60 DEG C, charging rate 12.5mL/min-30mL/min, reaction time 0.5h-2h.
The chemical general formula of a kind of nickel-cobalt lithium manganate cathode material, the nickel-cobalt lithium manganate cathode material is
LiNiaCobMn1-a-bO2, the 0 < a < 1,0 <b < 1, a:b=1:1-8:1；The nickel-cobalt lithium manganate cathode material is by nanoscale
The second particle composition that is agglomerated into of primary particle, the partial size of the primary particle is 100nm-500nm, and the second particle is big
It causes to be spherical, the partial size of the second particle is 1 μm -30 μm.
Further, the second particle partial size D50 of the nickel-cobalt lithium manganate cathode material is 12 μm -13 μm, D10 4.0
μm -5.0 μm, D90 is 30 μm -32 μm, and grading curve is in normal distribution.
A kind of positive plate, the positive plate include collector and the coating material for being set to the collection liquid surface, described
Coating material includes the nickel-cobalt lithium manganate cathode material, conductive material and binder.
A kind of lithium ion battery, including the positive plate, negative electrode tab, be set between the positive plate and negative electrode tab every
Film and electrolyte.
The preparation method of nickel-cobalt lithium manganate cathode material provided by the present invention is based on Rapid coprecipitation and combines spray drying
Technology obtains having high sphericity and the uniform nickel-cobalt lithium manganate cathode material of particle diameter distribution, the preparation method is conducive to contract
The generated time of short precursor of nickel-cobalt-lithium-manganese-oxide, and the reaction time of Rapid coprecipitation process is short, simple process, cost is relatively low,
Suitable for produce in enormous quantities, have it is huge can industrialization production value.Simultaneously preparation method provided by the present invention according to nickel,
The difference of the composition ratio of three kinds of elements of cobalt and manganese, can prepare the different nickel-cobalt lithium manganate cathode material of performance.The present invention
The nickel-cobalt lithium manganate cathode material of offer has high charging and discharging capacity, high voltage and high temperature circulation stability and good
High rate performance.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of nickel-cobalt lithium manganate cathode material provided in an embodiment of the present invention.
Fig. 2 is the X ray diffracting spectrum (XRD) of nickel-cobalt lithium manganate cathode material prepared by the embodiment of the present invention 1.
Fig. 3 A, Fig. 3 B and Fig. 3 C are respectively nickel-cobalt lithium manganate cathode material prepared by the embodiment of the present invention 1 different
Sem test figure under amplification factor.
The button cell that the nickel-cobalt lithium manganate cathode material that Fig. 4 A is prepared by the embodiment of the present invention 1 assembles is at 25 DEG C
Cycle performance test chart, the button cell that the nickel-cobalt lithium manganate cathode material that Fig. 4 B is prepared by the embodiment of the present invention 1 assembles exist
Cycle performance test chart at 60 DEG C.
The button cell that the nickel-cobalt lithium manganate cathode material that Fig. 5 A is prepared by the embodiment of the present invention 1 assembles is at 25 DEG C
High rate performance test chart, the button cell that the nickel-cobalt lithium manganate cathode material that Fig. 5 B is prepared by the embodiment of the present invention 1 assembles exist
High rate performance test chart at 60 DEG C.
The present invention that the following detailed description will be further explained with reference to the above drawings.
Specific embodiment
To better understand the objects, features and advantages of the present invention, with reference to the accompanying drawing and specific real
Applying mode, the present invention will be described in detail.It should be noted that in the absence of conflict, presently filed embodiment and reality
The feature applied in mode can be combined with each other.Many details are explained in the following description in order to fully understand this hair
Bright, described embodiment is only some embodiments of the invention, rather than whole embodiments.Based on the present invention
In embodiment, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Mode shall fall within the protection scope of the present invention.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more
All and arbitrary combinations of relevant listed item.
Referring to Fig. 1, the embodiment of the invention provides a kind of preparation method of nickel-cobalt lithium manganate cathode material, including it is following
Step:
Step S1: preparing includes nickel source, the mixed solution of cobalt source and manganese source, strong base solution and inorganic salts containing ammonium ion
It is quick to be mixed progress by solution simultaneously for the mixed solution, the strong base solution and the inorganic salt solution containing ammonium ion
Coprecipitation reaction, the pH value that control carries out the Rapid coprecipitation reaction is 10-12, obtains the first suspension, separates described the
One suspension obtains sediment；
Step S2: being configured to the second suspension for the sediment, and second suspension is carried out ball milling；
Step S3: the second suspension after ball milling is spray-dried, precursor powder is obtained；
Step S4: the precursor powder is mixed with lithium source, obtains mixture；
Step S5: the mixture is calcined, and obtains the nickel-cobalt lithium manganate cathode material.
In step sl, the nickel source, cobalt source and manganese source are water soluble salt, and the water soluble salt includes sulfate, nitre
At least one of hydrochlorate, chlorate and acetate；The alkali include potassium hydroxide, sodium hydroxide, in lithium hydroxide at least
It is a kind of；The inorganic salts containing ammonium ion include at least one of ammonium hydroxide, ammonium sulfate, ammonium chloride, ammonium fluoride, the ammonium root from
Son is used as complexing agent, and Rapid coprecipitation reaction occurs under alkaline environment in the nickel source, cobalt source and manganese source.
Further, Rapid coprecipitation reaction carries out in protective atmosphere, the protective atmosphere be argon atmosphere or
Person's nitrogen atmosphere；The total mol concentration of nickel contained in the mixed solution, cobalt and manganese Metal ion is 2mol/L-4mol/
The concentration of L, the aqueous slkali are 4mol/L-16mol/L, and the concentration of the inorganic salt solution containing ammonium ion is the metal ion
0.1-0.5 times of molar concentration.
Further, Rapid coprecipitation reaction be low whipping speed be 500-1000r/min, reaction temperature 40
DEG C -60 DEG C, charging rate be 12.5mL/min-30 mL/min, carry out under conditions of the reaction time is 0.5h-2h, obtain institute
State sediment.
Specifically, the mixed solution is nucleated and gradually long great achievement second particle under the alkaline environment containing ammonium ion.
Further, it in Rapid coprecipitation reaction process, since hydroxide ion is constantly consumed, therefore needs persistently to add
Enter aqueous slkali to maintain the pH value of generation Rapid coprecipitation reaction process, makes the Rapid coprecipitation reaction that can continue, stablize
Progress.
In step s 2, the solid content in second suspension is 20%-35%, and second suspension is placed in
With ball milling 2h-5h under the revolving speed of 200r/min-500r/min in ball grinder, wherein Material quality of grinding balls is in zirconium oxide or agate
At least one, ball grinder material be nylon, polytetrafluoroethylene (PTFE) or agate, material ball ratio (the i.e. matter of the second suspension and abrading-ball
Measure ratio) it is 1:10-15.
In step s3, the second suspension after ball milling is spray-dried in spray dryer, spray drying
Inlet temperature be 200 DEG C -300 DEG C, blowing efficiency 50%-70%, air pressure 0.1MPa-0.5MPa, obtain it is described before
Drive body powder.Since the precipitate particles after ball milling are nano particle, in spray-drying process, the second suspension is being done by spraying
Atomization forms droplet in dry machine, and the sediment containing nano particle in the droplet, under the action of hot-air, the droplet is fast
Speed dries out, and the nanoparticle precipitate object in droplet recombinates to form big second particle, and the second particle is spherical shape, described
Second particle is precursor powder, to realize particle recombination and the pelletizing in spray-drying process, while before also completing
Drive the drying of body powder.
Further, in spray-drying process, micron-sized second particle is gathered by nanoscale primary particle, is had
Conducive to the compacted density for increasing made nickel-cobalt lithium manganate cathode material after calcining, to increase the nickle cobalt lithium manganate
Volume energy density of the positive electrode as lithium ion battery electrode material.
In step s 4, the precursor powder and lithium source are mixed to get mixture in proportion, the lithium source is hydrogen-oxygen
Change at least one of lithium, lithium carbonate, lithium nitrate and lithium acetate, when selecting two kinds and two or more lithium sources, the lithium source
Ratio is arbitrary proportion.Wherein contain three kinds of nickel element, cobalt element and manganese element metallic elements in the precursor powder, it is described
The total mole number of nickel element, cobalt element and manganese element is x, and the molal quantity of the elemental lithium contained in lithium source is y, x:y=1:1.03
~1:1.1.
In step s 5, the calcining includes the first calcination stage and the second calcination stage, and first calcination stage is
By the mixture, first the pre-burning 2h-5h at 450 DEG C -500 DEG C, heating rate are 5-10 DEG C/min, second calcination stage
To be warming up to 750 DEG C -1000 DEG C with the heating rate of 1-3 DEG C/min, 9h-18h is kept the temperature at this temperature.
Further, it is described calcining further include cooling stage, by by the second calcination stage mixture with 5-10 DEG C/
The rate of min is cooled to room temperature.
Further, in the second calcination stage, when the molal quantity of nickel element is less than or equal to the total of three kinds of elements
Molal quantity 50% when, the mixture is calcined in air atmosphere；When the molal quantity of nickel element is greater than described three kinds
The total mole number of element 50% when, the mixture is calcined under oxygen atmosphere.
Further, 300 mesh sievings are carried out to calcined product, obtains the nickel-cobalt lithium manganate cathode material.
The present invention also provides one kind nickel-cobalt lithium manganate cathode material as made from above-mentioned preparation method, the nickle cobalt lithium manganates
The chemical general formula of positive electrode is LiNiaCobMn1-a-bO2, the 0 < a < 1,0 <b < 1, a:b=1:1-8:1；The nickel cobalt mangaic acid
Lithium anode material is made of the second particle that the reunion of nanoscale primary particle is in, and the partial size of the primary particle is
100nm-500nm, the second particle is generally spherical in shape, and the partial size of the second particle is 1 μm -30 μm.
Further, the second particle partial size D50 of the nickel-cobalt lithium manganate cathode material is 12 μm -13 μm (i.e. secondary
There is partial size to account for overall 50% less than 12 μm -13 μm in grain), D10 is 4.0 μm -5.0 μm, and D90 is 30 μm -32 μm, partial size point
Cloth curve is in normal distribution.
In one embodiment, the D50 is 12.3 μm, and D10 is 4.8 μm, and D90 is 30.9 μm.
Further, the valence state of nickel element is+2 and/or+3 in the nickel-cobalt lithium manganate cathode material.
Specifically, the increasing and increase with nickel element content of the nickel element in the nickel-cobalt lithium manganate cathode material containing+trivalent
It is more.
Further, the crystal form of the nickel-cobalt lithium manganate cathode material is hexagonal phase, the nickel-cobalt lithium manganate cathode material
For layer structure, space group is
The embodiment of the present invention also provides a kind of positive plate, and the positive plate includes collector and is set to the afflux body surface
The coating material in face, the coating material include the nickel-cobalt lithium manganate cathode material, conductive material and binder, the nickel cobalt
Manganate cathode material for lithium, conductive material and binder are dispersed in solvent in proportion, are uniformly mixed to get dispersion liquid, then by institute
Dispersion is stated on the collector, dry, slice obtains the positive plate.
The embodiment of the present invention also provides a kind of lithium ion battery, the lithium ion battery include the positive plate, negative electrode tab,
The diaphragm and electrolyte being set between the positive plate and negative electrode tab.
The present invention is specifically described below by embodiment.
Embodiment 1
It is respectively nickel source, cobalt source and manganese source, the nickel sulfate, cobaltous sulfate and sulphur using nickel sulfate, cobaltous sulfate and manganese sulfate
The molar ratio of sour manganese is 8:1:1, and the nickel sulfate, cobaltous sulfate and manganese sulfate are configured to mixed solution, total moles 2mol/
L；Sodium hydroxide is highly basic, is configured to the sodium hydroxide solution of 10mol/L；Ammonium hydroxide is complexing agent, is configured to the ammonia of 0.5mol/L
Aqueous solution, the deionized water of 1L is added into reaction kettle, and suitable sodium hydroxide solution and ammonium hydroxide is added；In stirring speed
Degree is 600r/min, and reaction temperature is 50 DEG C, and will include the nickel sulfate, sulfuric acid in the case where being continually fed into high pure nitrogen
The mixed solution of cobalt and manganese sulfate, sodium hydroxide solution and ammonia spirit be added in reaction kettle simultaneously obtain carry out quickly it is coprecipitated
It forms sediment and reacts, obtain the first suspension, and maintaining the pH value in Rapid coprecipitation reaction process is 11.5, charging rate 15mL/
Min reacts 1h, obtains sediment.
By sediment washing, filtering；Then by the sediment be configured to solid content be 25% it is second suspended
Second suspension is placed in ball grinder by liquid, and agate ball is added, wherein the sediment and agate ball in the second suspension
Mass ratio is 1:10, then the second suspension 3h described in ball milling under the speed of 400r/min.
The second suspension after ball milling is spray-dried, the inlet temperature of the spray drying is 250 DEG C, air blast effect
Rate is 60%, and air pressure 0.3MPa obtains precursor powder after spray drying.
The precursor powder and lithium hydroxide are mixed to get mixture in proportion, wherein x:y=1:1.05.By institute
Mixture is stated under the atmosphere of high pure oxygen, 500 DEG C of heat preservation 5h are warming up to the heating rate of 10 DEG C/min；Then again with 3 DEG C/
The heating rate of min is warming up to 780 DEG C of heat preservation 11h；Room temperature is then cooled to the rate of temperature fall of 5 DEG C/min, finally obtains nickel
Cobalt manganic acid lithium positive electrode.
Embodiment 2
Unlike embodiment: nickel source, cobalt source and manganese source in the present embodiment are respectively nickel chloride, cobalt chloride and chlorination
Manganese, the molar ratio of the nickel chloride, cobalt chloride and manganese chloride are 7:1.5:1.5, and the pH value that Rapid coprecipitation reaction occurs is
11.2, the second calcination stage temperature is 820 DEG C.
Other steps are same as Example 1, are not repeated herein.
Embodiment 3
Unlike embodiment: nickel source, cobalt source and manganese source in the present embodiment are respectively nickel nitrate, cobalt nitrate and nitric acid
Manganese, the molar ratio of the nickel nitrate, cobalt nitrate and manganese nitrate are 6:2:2, and the pH value that Rapid coprecipitation reaction occurs is 11.0,
Second calcination stage temperature is 850 DEG C.
Other steps are same as Example 1, are not repeated herein.
Embodiment 4
Unlike embodiment: nickel source, cobalt source and manganese source in the present embodiment are respectively nickel acetate, cobalt acetate and acetic acid
Manganese, the molar ratio of the nickel acetate, cobalt acetate and manganese acetate are 5:2:3, and the pH value that Rapid coprecipitation reaction occurs is 10.8,
Second calcination stage temperature is 870 DEG C, and the atmosphere of calcining is air.
Other steps are same as Example 1, are not repeated herein.
Embodiment 5
Unlike embodiment: nickel source, cobalt source and manganese source in the present embodiment are respectively nickel sulfate, cobalt chloride and nitric acid
The molar ratio of manganese, the nickel sulfate, cobalt chloride and manganese nitrate is 1:1:1, and complexing agent is ammonium chloride solution, and the ammonium chloride is molten
The concentration of liquid is 0.5mol/L, and the pH value that Rapid coprecipitation reaction occurs is 10.5, and the second calcination stage temperature is 900 DEG C, is forged
The atmosphere of burning is air.
Other steps are same as Example 1, are not repeated herein.
The specific treatment conditions of embodiment 1-5 are as shown in table 1.
The 1 specific treatment conditions of embodiment 1-5 of table
Referring to Fig. 2, XRD test is carried out to nickel-cobalt lithium manganate cathode material made from embodiment 1, due to nickel cobalt mangaic acid
Lithium anode material does not have special standard PDF card matching, usually and LiNiO2Or LiCoO2Standard PDF card carries out
Matching, LiNiO2With LiCoO2Belong to same crystallographic system, therefore the corresponding diffraction peak of its standard PDF card is identical.Selection in Fig. 2
Standard PDF card be LiNiO2, nickel-cobalt lithium manganate cathode material and LiNiO prepared by embodiment 12Characteristic peak all matched
It is good, and there is no other impurity peaks.
Electronic Speculum test, test result such as Fig. 3 A, Fig. 3 B are scanned to nickel-cobalt lithium manganate cathode material prepared by embodiment 1
And shown in Fig. 3 C, Fig. 3 A, Fig. 3 B and Fig. 3 C are the test results under different enlargement ratios, wherein Fig. 3 A, Fig. 3 B and Fig. 3 C
Enlargement ratio be sequentially increased, from Fig. 3 A can the nickel-cobalt lithium manganate cathode material it is substantially spherical in shape, particle diameter distribution is more
Uniformly, the partial size of the second particle of the nickel-cobalt lithium manganate cathode material is 1 μm -20 μm；As can be seen from Figure 3B, each spherical shape
The nickel-cobalt lithium manganate cathode material be all made of lesser primary particle；It can be seen that the primary particle from Fig. 3 C
Particle diameter distribution it is more uniform, about 100nm-500nm.
Nickel-cobalt lithium manganate cathode material obtained by embodiment 1- embodiment 5 is used as anode material for lithium-ion batteries,
It is that 2032 type button cells are assembled into electrode with lithium piece in glove box full of high-purity argon gas.Utilize LANHE CT2001A
Battery test system tests above-mentioned button cell and carries out electrochemical property test under room temperature (25 DEG C) and high temperature (60 DEG C), described
Electrochemical property test includes cycle performance test and high rate performance test.When cycle performance is tested, charge and discharge at room temperature
Voltage range is 2.8-4.5V, and charging/discharging voltage range at high temperature is 2.8-4.3V, the electric current of the cycle performance test
Density is 1C (180 mA/g)；When high rate performance is tested, current density is followed successively by 0.2C, 1C, 2C, 32C, 5C and 10C, each
10 circle of circulation, discharge voltage range are consistent when testing with cycle performance under current density.
Embodiment 1-5 electrochemical property test is in the test result at 25 DEG C and 60 DEG C respectively as shown in table 2 and table 3.
2 embodiment 1-5 of table electrochemical property test result at 25 DEG C
3 embodiment 1-5 of table electrochemical property test result at 60 DEG C
To account for nickel source, cobalt source and manganese source total moles quality higher and higher for the molal weight of nickel source from embodiment 1-5 in table 1,
That is the content of the nickel element of nickel-cobalt lithium manganate cathode material prepared by from embodiment 1 to embodiment 5 is lower and lower.From table 2 and
Table 3 is as can be seen that the content with nickel element reduces, and the capacity retention ratio after 25 DEG C and 60 DEG C respectively 100 circle of circulation is gradually
Increase, this is because the content with nickel element reduces, the content of cobalt element and manganese element increases, and the nickle cobalt lithium manganate of preparation is just
The stability of pole material is higher and higher.
As the content of nickel element reduces, the reversible capacity under reversible capacity and 10C is gradually decreased for the first time, this is because
In nickel-cobalt lithium manganate cathode material, nickel element is the component of electro-chemical activity, is played by the redox reaction of nickel element
Capacity, so nickel element content is lower, the charging and discharging capacity of nickel-cobalt lithium manganate cathode material is also lower.
Please referring to Fig. 4 A and Fig. 4 B, Fig. 4 A and Fig. 4 B is respectively nickel-cobalt lithium manganate cathode material group prepared by embodiment 1
The button cell of dress carries out cycle performance test at 25 DEG C and 60 DEG C, 100 circle of circulation in the case where current density is 180mA/g.Please
Refering to Fig. 4 A, under 25 DEG C of test condition, button cell prepared by embodiment 1 is after the circle of circulation 100, and discharge specific volume
Amount is 173mAh/g, capacity retention ratio 93.34%；Fig. 4 B is please referred to, under 60 DEG C of test condition, specific discharge capacity is
177mAh/g, capacity retention ratio 93.29%；Illustrate the nickel-cobalt lithium manganate cathode material of the preparation of embodiment 1 as lithium-ion electric
Pond electrode material has good cyclical stability and preferable high temperature circulation stability.
Please referring to Fig. 5 A and Fig. 5 B, Fig. 5 A and Fig. 5 B is respectively nickel-cobalt lithium manganate cathode material group prepared by embodiment 1
The button cell of dress carries out high rate performance test at 25 DEG C and 60 DEG C, after the charge-discharge test of excessive multiplying power (10C), then
Charging and discharging capacity when small multiplying power (0.2C) charge-discharge test is returned to, can still be tested with original small multiplying power (0.2C)
When phase same level, illustrate that nickel-cobalt lithium manganate cathode material prepared by embodiment 1 can be subjected to the charge and discharge cycles of big multiplying power
Test.
The preparation method of nickel-cobalt lithium manganate cathode material provided by the present invention is based on Rapid coprecipitation and combines spray drying
Technology obtains having high sphericity and the uniform nickel-cobalt lithium manganate cathode material of particle diameter distribution, the preparation method is conducive to contract
The generated time of short precursor of nickel-cobalt-lithium-manganese-oxide, and the reaction time of Rapid coprecipitation process is short, simple process, cost is relatively low,
Suitable for produce in enormous quantities, have it is huge can industrialization production value.Simultaneously preparation method provided by the present invention according to nickel,
The difference of the composition ratio of three kinds of elements of cobalt and manganese, can prepare the different nickel-cobalt lithium manganate cathode material of performance.The present invention
The nickel-cobalt lithium manganate cathode material of offer has high charging and discharging capacity, high voltage and high temperature circulation stability and good
High rate performance.
Embodiment of above is only used to illustrate the technical scheme of the present invention and not to limit it, although referring to the above preferable embodiment party
Formula describes the invention in detail, those skilled in the art should understand that, it can be to technical solution of the present invention
It modifies or equivalent replacement should not all be detached from the spirit and scope of technical solution of the present invention.
Claims (10)
1. a kind of preparation method of nickel-cobalt lithium manganate cathode material, which comprises the following steps:
It prepares including nickel source, the mixed solution of cobalt source and manganese source, strong base solution and inorganic salt solution containing ammonium ion, it will be described
Mixed solution, the strong base solution and the inorganic salt solution containing ammonium ion mix simultaneously carries out Rapid coprecipitation reaction,
The pH value that control carries out the Rapid coprecipitation reaction is 10-12, obtains the first suspension, separates first suspension and obtains
Sediment；
The sediment is configured to the second suspension, second suspension is subjected to ball milling；
The second suspension after ball milling is spray-dried, precursor powder is obtained；
The precursor powder is mixed with lithium source, obtains mixture；And
The mixture is calcined, the nickel-cobalt lithium manganate cathode material is obtained.
2. the preparation method of nickel-cobalt lithium manganate cathode material according to claim 1, which is characterized in that the nickel source, cobalt
Source and manganese source are water soluble salt, and the water soluble salt includes at least one in sulfate, nitrate, chlorate and acetate
Kind, the highly basic includes at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide；The packet of inorganic salts containing ammonium ion
At least one of ammonium hydroxide, ammonium sulfate, ammonium chloride, ammonium fluoride are included, the lithium source is lithium hydroxide, lithium carbonate, lithium nitrate and second
At least one of sour lithium.
3. the preparation method of nickel-cobalt lithium manganate cathode material according to claim 1, which is characterized in that the precursor
The total mole number of nickel element, cobalt element and manganese element is x in end, and the molal quantity of the elemental lithium in lithium source is y, the x:y=1:
1.03~1:1.1.
4. the preparation method of nickel-cobalt lithium manganate cathode material according to claim 1, which is characterized in that the calcining includes
First calcination stage and the second calcination stage, first calcination stage are that the mixture is first pre- at 450 DEG C -500 DEG C
2h-5h is burnt, heating rate is 5-10 DEG C/min, and second calcination stage is to be warming up to 750 with the heating rate of 1-3 DEG C/min
DEG C -1000 DEG C, 9h-18h is kept the temperature at this temperature.
5. the preparation method of nickel-cobalt lithium manganate cathode material according to claim 4, which is characterized in that calcine rank second
Duan Shi, when the molal quantity of nickel element is less than or equal to the 50% of the total mole number of the nickel element, cobalt element and manganese element,
The mixture is calcined under air atmosphere；When the molal quantity of nickel element is greater than the 50% of the total mole number, in oxygen
The mixture is calcined under gas atmosphere.
6. the preparation method of nickel-cobalt lithium manganate cathode material according to claim 1, which is characterized in that described quickly coprecipitated
The condition reacted of forming sediment includes that mixing speed is 500-1000r/min, and reaction temperature is 40 DEG C -60 DEG C, charging rate 12.5mL/
Min-30mL/min, reaction time 0.5h-2h.
7. a kind of nickel-cobalt lithium manganate cathode material, which is characterized in that the chemical general formula of the nickel-cobalt lithium manganate cathode material is
LiNiaCobMn1-a-bO2, the 0 < a < 1,0 <b < 1, a:b=1:1-8:1；The nickel-cobalt lithium manganate cathode material is by nanoscale
The second particle composition that is agglomerated into of primary particle, the partial size of the primary particle is 100nm-500nm, and the second particle is big
It causes to be spherical, the partial size of the second particle is 1 μm -30 μm.
8. nickel-cobalt lithium manganate cathode material according to claim 7, which is characterized in that the nickel-cobalt lithium manganate cathode material
Second particle partial size D50 be 12 μm -13 μm, D10 is 4.0 μm -5.0 μm, and D90 is 30 μm -32 μm, and grading curve is in just
State distribution.
9. a kind of positive plate, which is characterized in that the positive plate includes collector and the coating for being set to the collection liquid surface
Material, the coating material include nickel-cobalt lithium manganate cathode material, the conductive material as described in claim 7 or 8 any one
And binder.
10. a kind of lithium ion battery, which is characterized in that including positive plate as claimed in claim 9, negative electrode tab, be set to institute
State the diaphragm and electrolyte between positive plate and negative electrode tab.
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