CN107915263A - A kind of preparation method of small particle ternary anode material precursor - Google Patents
A kind of preparation method of small particle ternary anode material precursor Download PDFInfo
- Publication number
- CN107915263A CN107915263A CN201710772952.9A CN201710772952A CN107915263A CN 107915263 A CN107915263 A CN 107915263A CN 201710772952 A CN201710772952 A CN 201710772952A CN 107915263 A CN107915263 A CN 107915263A
- Authority
- CN
- China
- Prior art keywords
- small particle
- liquid
- reaction
- preparation
- anode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
The invention discloses a kind of preparation method of small particle ternary anode material precursor, comprise the following steps：（1）It is raw material to select nickel cobalt manganese liquid, is configured to metal mixed salting liquid, and reaction kettle adds special reaction bottom liquid, metal salt solution and complexing agent and precipitant solution are added in reaction kettle according to stoichiometric number ratio, cocurrent in advance；（2）First time kettle expires the control of D50 particle diameters at 1 ~ 2 μm, and directly from overflow pipe to ready aging reactor overflow after reaction kettle is full, particle size length stops charging immediately to 3.5 4.0 μm in 10 ~ 20h reaction kettles；（3）Washing sieving packaging, you can prepare 3 ~ 4 μm of small particle ternary precursor.The preparation method of the small particle ternary anode material precursor of the present invention has the characteristics that Crystalline Quality is good, sphericity is preferable, cyclicity is preferable, technological operation is simple, can be with continuous production, green energy conservation.
Description
Technical field
The present invention relates to nickel-cobalt-manganese ternary field of material technology, particularly a kind of small particle ternary anode material precursor
Preparation method.
Background technology
On December 30th, 2016, the Ministry of Finance, the Department of Science and Technology, Ministry of Industry and Information and Committee of Development and Reform's issue《Pushed away on adjustment new-energy automobile
The wide notice for applying Chinese Financial Subsidy Policies》Appearance, new-energy automobile promote and apply Chinese Financial Subsidy Policies to power battery energy
The higher of density requirements, enterprise will more use the ternary cell body of energy density higher in order to take more subsidies
System, since country will have decontroled in the end of the year limitation to ternary battery, ternary power battery will welcome outburst in next year.Enterprise of Japan and Korea S leads to
Continuous Promote Technology is crossed with exploitation new material to improve performance of lithium ion battery, is remained in lithium ion battery industry
In superiority of effectiveness with Chinese products, lead status in occupation of high-end lithium ion battery industry.China and Japan and Korea S etc. are national
Still have larger gap, it is impossible to produce high end cells product, exported product is particularly used mainly by cost advantage in power battery
This hot topic with suitable difficulty of anode material for lithium-ion batteries is relatively sluggish with key area development, lacks independent intellectual production
The technical support of power and not yet form industry size.
Small particle LiNixCoyMnzO2 positive electrodes have stable electrochemical property, and cycle performance is excellent, and specific capacity is high, cost
Low advantage, since its particle diameter is small so that the path that lithium ion and electronics migrate abjection/insertion from particle is short, and the time is few, because
This small particle ternary material has the advantages that specific discharge capacity height, good rate capability.
The small particle ternary precursor prepared using coprecipitation, is mainly fired into monocrystalline ternary material, for making height
Voltage lithium cells；Common polycrystalline ternary can also be burnt till to mix with big particle diameter ternary material to improve material compacted density, increased
Its volume and capacity ratio；The ternary battery material of height ratio capacity can also be made, using its powerful characteristic, for power vehicle
Etc. startup power supply.The small particle ternary precursor nucleus sphericity occurred currently on the market is poor, and particle diameter distribution controls poor, center
There is cavitation, tap density is low, causes material poor circulation occur, and stability is poor, and easy self discharge, specific capacity is small, makees high electricity
The problems such as pressure power battery safety is low so that this small particle material cannot preferably be applied.
The content of the invention
The main purpose of the present invention is the provision of a kind of preparation method of small particle ternary anode material precursor, has
Have that Crystalline Quality is good, sphericity is preferable, cyclicity is preferable, technological operation is simple, can be with continuous production, green energy conservation
The characteristics of.
The present invention can be achieved through the following technical solutions：
The invention discloses a kind of preparation method of small particle ternary anode material precursor, comprise the following steps：
（1）It is raw material to select nickel cobalt manganese liquid, is configured to metal mixed salting liquid, and reaction kettle adds special reaction bottom liquid in advance,
Metal salt solution and complexing agent and precipitant solution are added in reaction kettle according to stoichiometric number ratio, cocurrent；Temperature control exists
20~60℃；PH controls are 11 ~ 12；Rotating speed uses 200 ~ 500r/min；Whole reaction carries out under N2 protections；
（2）First time kettle expires the control of D50 particle diameters at 1 ~ 2 μm, is directly overflow after reaction kettle is full from overflow pipe to ready aging reactor
Flow, particle size length stops charging immediately to 3.5-4.0 μm in 10 ~ 20h reaction kettles；
（3）Then reaction kettle slurry is uniformly mixed with aging reactor slurry, stirs 30min, wash through centrifuge, after drying, add
Enter baking oven to dry at 150 DEG C, 200 mesh sieving packaging, you can prepare 3 ~ 4 μm of small particle ternary precursor, pattern is spherical
Or spherical particle, appearance uniform is without agglomerated particle；
The small particle ternary precursor chemical general formula is NixCoyMnz (OH)2, wherein 0.3≤x≤0.95,0.05≤y≤
0.4,0.05≤z≤0.4, x+y+z=1.
Further, the nickel cobalt manganese liquid selects nickel liquid, cobalt liquid, manganese liquid, and controlled concentration is 1.0mol/L ~ 3mol/L, control
Feed temperature processed is at 20-60 DEG C.
Further, the complexing agent selects ammonium hydroxide, and concentration is 2mol/L ~ 10mol/L, and precipitating reagent sodium hydroxide is molten
Liquid, concentration are 2mol/L ~ 10mol/L.
Further, the pure water is compounded into reaction bottom liquid with soluble ammonium, and the soluble ammonium concentration is 3-10g/L,
20 ~ 60 DEG C of bottom liquid temperature degree.
Further, the soluble ammonium selects two kinds of mixtures in ammonium hydroxide, ammonium sulfate, ammonium oxalate, ammonium citrate.
Further, reaction system is made to be in constant pH value by adjusting lye addition speed, pH value control is 10.5
~11。
The preparation method of small particle ternary anode material precursor of the present invention has following beneficial technique effect：
Firstth, the present invention provides a kind of control ternary material particle diameter distribution, reduces material surface residual alkali content, improves crystal structure
Integrality, improves the continuous feed technique of material circulation performance.
Secondth, the present invention provides through unique continuous feed production model, the bottom formed using soluble ammonium and pure water
Liquid, the continuous feed under the drive of high-speed stirred, system is controlled using online pH to prepare 3 ~ 4 μm of small particle presoma, full
Kettle particle diameter D50 can be controlled at 1 ~ 2 μm, and can be accurately controlled in by stopping kettle particle diameter by 3.5 ~ 4.0 μm, so ensure that finished product is not too small
Particle, particle diameter distribution are less than 1.0, and the nucleus sphericity of preparation is preferable, and cyclicity is preferable, can meet power battery requirement, and
Tap density is high, and performance is good, and technological operation simply can be with continuous production, and ammonia nitrogen recycling is easy in waste water, green
It is energy saving.
Brief description of the drawings
Attached drawing 1 is 3 μm of Ni prepared by Application Example 1 of the present invention0.5Co0.2Mn0.3(OH)2Presoma SEM photograph；
Attached drawing 2 is 3 μm of Ni prepared by Application Example 1 of the present invention0.5Co0.2Mn0.3(OH)2Presoma XRD spectrum；
Attached drawing 3 is 3 μm of Ni prepared by Application Example 2 of the present invention0.8Co0.1Mn0.1(OH)2Presoma SEM photograph；
Attached drawing 4 is 3 μm of Ni prepared by Application Example 2 of the present invention0.8Co0.1Mn0.1(OH)2Presoma XRD spectrum.
Embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, with reference to embodiment and to this
Invention product is described in further detail.
Embodiment 1
The invention discloses a kind of preparation method of small particle ternary anode material precursor, comprise the following steps：
（1）It is raw material to select nickel cobalt manganese liquid, is configured to metal mixed salting liquid, and reaction kettle adds special reaction bottom liquid in advance,
Metal salt solution and complexing agent and precipitant solution are added in reaction kettle according to stoichiometric number ratio, cocurrent；Temperature control exists
60℃；PH controls are 11.5；Rotating speed uses 200r/min；Entirely react in N2Protection is lower to be carried out；
（2）First time kettle expires the control of D50 particle diameters at 1 ~ 2 μm, is directly overflow after reaction kettle is full from overflow pipe to ready aging reactor
Flow, particle size length stops charging immediately to 3.5-4.0 μm in 20h reaction kettles；
（3）Then reaction kettle slurry is uniformly mixed with aging reactor slurry, stirs 30min, wash through centrifuge, after drying, add
Enter baking oven to dry at 150 DEG C, 200 mesh sieving packaging, you can prepare 3 ~ 4 μm of small particle ternary precursor, pattern is spherical
Or spherical particle, appearance uniform is without agglomerated particle；
The small particle ternary precursor chemical general formula is NixCoyMnz (OH)2, wherein 0.3≤x≤0.95,0.05≤y≤
0.4,0.05≤z≤0.4, x+y+z=1.
In the present embodiment, the nickel cobalt manganese liquid selects nickel liquid, cobalt liquid, manganese liquid, and controlled concentration is 1.0mol/L ~ 3mol/
L, control feed temperature is at 60 DEG C.The complexing agent selection ammonium hydroxide, concentration 10mol/L, precipitating reagent sodium hydroxide solution are dense
Spend for 6mol/L.The pure water and soluble ammonium are compounded into reaction bottom liquid, and the soluble ammonium concentration is 3-g/L, bottom liquid temperature degree
60℃.The soluble ammonium selects ammonium hydroxide, two kinds of mixtures of ammonium sulfate.Made by adjusting lye addition speed at reaction system
In constant pH value, pH value control is 10.5 ~ 11.
Embodiment 2
The invention discloses a kind of preparation method of small particle ternary anode material precursor, comprise the following steps：
（1）It is raw material to select nickel cobalt manganese liquid, is configured to metal mixed salting liquid, and reaction kettle adds special reaction bottom liquid in advance,
Metal salt solution and complexing agent and precipitant solution are added in reaction kettle according to stoichiometric number ratio, cocurrent；Temperature control exists
40℃；PH controls are 11；Rotating speed uses 500r/min；Whole reaction carries out under N2 protections；
（2）First time kettle expires the control of D50 particle diameters at 1 ~ 2 μm, is directly overflow after reaction kettle is full from overflow pipe to ready aging reactor
Flow, particle size length stops charging immediately to 3.5-4.0 μm in 15h reaction kettles；
（3）Then reaction kettle slurry is uniformly mixed with aging reactor slurry, stirs 30min, wash through centrifuge, after drying, add
Enter baking oven to dry at 150 DEG C, 200 mesh sieving packaging, you can prepare 3 ~ 4 μm of small particle ternary precursor, pattern is spherical
Or spherical particle, appearance uniform is without agglomerated particle；
The small particle ternary precursor chemical general formula is NixCoyMnz (OH)2, wherein 0.3≤x≤0.95,0.05≤y≤
0.4,0.05≤z≤0.4, x+y+z=1.
In the present embodiment, the nickel cobalt manganese liquid selects nickel liquid, cobalt liquid, manganese liquid, and controlled concentration is 1.0mol/L ~ 3mol/
L, control feed temperature is at 40 DEG C.The complexing agent selection ammonium hydroxide, concentration 2mol/L, precipitating reagent sodium hydroxide solution are dense
Spend for 10mol/L.The pure water and soluble ammonium are compounded into reaction bottom liquid, and the soluble ammonium concentration is 7g/L, bottom liquid temperature degree
20~60℃.The soluble ammonium selects ammonium oxalate, two kinds of mixtures of ammonium citrate.Made instead by adjusting lye addition speed
System is answered to be in constant pH value, pH value control is 10.5 ~ 11.
Embodiment 3
The invention discloses a kind of preparation method of small particle ternary anode material precursor, comprise the following steps：
（1）It is raw material to select nickel cobalt manganese liquid, is configured to metal mixed salting liquid, and reaction kettle adds special reaction bottom liquid in advance,
Metal salt solution and complexing agent and precipitant solution are added in reaction kettle according to stoichiometric number ratio, cocurrent；Temperature control exists
20℃；PH controls are 12；Rotating speed uses 350r/min；Whole reaction carries out under N2 protections；
（2）First time kettle expires the control of D50 particle diameters at 1 ~ 2 μm, is directly overflow after reaction kettle is full from overflow pipe to ready aging reactor
Flow, particle size length stops charging immediately to 3.5-4.0 μm in 10h reaction kettles；
（3）Then reaction kettle slurry is uniformly mixed with aging reactor slurry, stirs 30min, wash through centrifuge, after drying, add
Enter baking oven to dry at 150 DEG C, 200 mesh sieving packaging, you can prepare 3 ~ 4 μm of small particle ternary precursor, pattern is spherical
Or spherical particle, appearance uniform is without agglomerated particle；
The small particle ternary precursor chemical general formula is NixCoyMnz (OH)2, wherein 0.3≤x≤0.95,0.05≤y≤
0.4,0.05≤z≤0.4, x+y+z=1.
In the present embodiment, the nickel cobalt manganese liquid selects nickel liquid, cobalt liquid, manganese liquid, and controlled concentration is 1.0mol/L ~ 3mol/
L, control feed temperature is at 20 DEG C.The complexing agent selection ammonium hydroxide, concentration 10mol/L, precipitating reagent sodium hydroxide solution are dense
Spend for 6mol/L.The pure water and soluble ammonium are compounded into reaction bottom liquid, and the soluble ammonium concentration is 3g/L, bottom liquid temperature degree 20
~60℃.The soluble ammonium selects ammonium hydroxide, two kinds of mixtures of ammonium oxalate.Make reaction system by adjusting lye addition speed
In constant pH value, pH value control is 10.5 ~ 11.
Embodiment 4
The invention discloses a kind of preparation method of small particle ternary anode material precursor, comprise the following steps：
（1）It is raw material to select nickel cobalt manganese liquid, is configured to metal mixed salting liquid, and reaction kettle adds special reaction bottom liquid in advance,
Metal salt solution and complexing agent and precipitant solution are added in reaction kettle according to stoichiometric number ratio, cocurrent；Temperature control exists
20~60℃；PH controls are 11 ~ 12；Rotating speed uses 200 ~ 500r/min；Whole reaction carries out under N2 protections；
（2）First time kettle expires the control of D50 particle diameters at 1 ~ 2 μm, is directly overflow after reaction kettle is full from overflow pipe to ready aging reactor
Flow, particle size length stops charging immediately to 3.5-4.0 μm in 10 ~ 20h reaction kettles；
（3）Then reaction kettle slurry is uniformly mixed with aging reactor slurry, stirs 30min, wash through centrifuge, after drying, add
Enter baking oven to dry at 150 DEG C, 200 mesh sieving packaging, you can prepare 3 ~ 4 μm of small particle ternary precursor, pattern is spherical
Or spherical particle, appearance uniform is without agglomerated particle；
The small particle ternary precursor chemical general formula is NixCoyMnz (OH)2, wherein 0.3≤x≤0.95,0.05≤y≤
0.4,0.05≤z≤0.4, x+y+z=1.
In the present embodiment, the nickel cobalt manganese liquid selects nickel liquid, cobalt liquid, manganese liquid, and controlled concentration is 1.0mol/L ~ 3mol/
L, control feed temperature is at 20-60 DEG C.The complexing agent selects ammonium hydroxide, and concentration is 2mol/L ~ 10mol/L, precipitating reagent hydrogen-oxygen
Change sodium solution, concentration is 2mol/L ~ 10mol/L.The pure water is compounded into reaction bottom liquid with soluble ammonium, and the soluble ammonium is dense
Spend for 3-10g/L, 20 ~ 60 DEG C of bottom liquid temperature degree.The soluble ammonium selects two in ammonium hydroxide, ammonium sulfate, ammonium oxalate, ammonium citrate
Kind mixture.Reaction system is set to be in constant pH value by adjusting lye addition speed, pH value control is 10.5 ~ 11.
Application Example 1
3 μm of Ni are prepared using continuous feed0.5Co0.2Mn0.3(OH)2Ternary anode material precursor.
Using nickel sulfate solution, cobalt sulfate solution, manganese sulfate solution, sodium hydroxide, ammonium hydroxide are reaction raw materials, are made into respectively
45 DEG C of 2mol/L nickel cobalt manganese metal salt solutions（Nickel cobalt manganese ratio is 5:2:3）, 8mol/L sodium hydroxide solutions, 6mol/L ammonia
Water.
In 2m3The excessively not upper paddle of pure water is added in pilot scale reaction kettle, adds 6mol/L ammoniacal liquors, ammonium citrate, pure water to blend together stabilization
Reaction bottom liquid, volume accounts for reaction kettle and obtains 50%, and rotating speed 100r/min stirring 30min, into bottom liquid plus 8mol/L sodium hydroxides are molten
PH is adjusted to as 12 by liquid, the whole logical N2 protections of reaction.
Then by nickel cobalt manganese metal salt solution, sodium hydroxide, ammonium hydroxide metering pump according to molar ratio 1:4:2 cocurrents add anti-
To answer in kettle, 50 DEG C of reaction temperature, rotating speed is controlled in 400r/min, and between pH controls are 10.5 ~ 11, reaction feed is carried out continuously,
After reaction kettle is full, it is 1.89 μm to survey full kettle particle diameter D50, overflow pipe is then directly opened to temporary storage kettle overflow, until reaction kettle
Middle particle size length stops charging immediately to 3.7 μm.Then the temporary storage kettle slurry of ageing is mixed with reaction kettle slurry, stirred
30min, through centrifuge lye and pure water, after drying, adds baking oven and is dried at 150 DEG C, 200 mesh sieving packaging, this
Sample can prepare 3 ~ 4 μm of small particle ternary precursor.
The 3 μm of ternary precursors prepared（Ni+Co+Mn）Chemical content 62.5%, S=700ppm, particle diameter distribution Dmin=2.37
μm, D50=3.45 μm, Dmax=4.62 μm, TD=1.75g/cm3,SSA=10.5m2/ g, pattern is spherical or spherical particle, appearance
Uniformly without caking black powder, its corresponding SEM and XRD spectrum are as depicted in figs. 1 and 2.
Application Example 2
3 μm of Ni are prepared using continuous feed0.8Co0.1Mn0.1(OH)2Ternary anode material precursor.
The 3 μm of Ni prepared0.8Co0.1Mn0.1(OH)2Presoma（Ni+Co+Mn）Chemical content 62.8%, S=500ppm, grain
Footpath is distributed Dmin=2.66 μm, D50=3.16 μm, Dmax=4.75 μm, TD=2.05g/cm3,SSA=9.2m2/ g, pattern is spherical or class
Spheric granules, appearance uniform is without caking brownish-yellow powder.
Using six hydration nickel sulfate, Cobalt monosulfate heptahydrate, Manganous sulfate monohydrate, sodium hydroxide, ammonium hydroxide are reaction raw materials, point
50 DEG C of 2mol/L nickel cobalt manganese metal salt solutions are not made into（Nickel cobalt manganese ratio is 8:1:1）, 8mol/L sodium hydroxide solutions,
6mol/L ammonium hydroxide.In 2m3The excessively not upper paddle of pure water is added in pilot scale reaction kettle, adds certain volume 6mol/L ammoniacal liquors, ammonium citrate, pure
Water blendes together stable reaction bottom liquid, volume accounts for reaction kettle and obtains 50%, and rotating speed 100r/min stirring 30min, 8mol/ is added into bottom liquid
PH is adjusted to as 11.5 by L sodium hydroxide solutions, the whole logical N2 protections of reaction.
Then by nickel cobalt manganese metal salt solution, sodium hydroxide, ammonium hydroxide metering pump according to molar ratio 1:4:3 cocurrents add anti-
To answer in kettle, 60 DEG C of reaction temperature, rotating speed is controlled in 400r/min, and between pH controls are 10.8 ~ 11, reaction feed is carried out continuously,
D50 is 1.95 μm after reaction kettle is full, directly opening overflow pipe to temporary storage kettle overflow, up in reaction kettle particle size grow to
3.5 μm, stop charging immediately.Then the temporary storage kettle slurry of ageing is mixed with reaction kettle slurry, 30min is stirred, through centrifuge
With lye and pure water, after drying, add baking oven and dried at 150 DEG C, 200 mesh sieving packaging, can thus prepare 3
~ 4 μm of small particle ternary precursor, its corresponding SEM and XRD spectrum are as shown in Figure 3 and Figure 4.
The foregoing is only a preferred embodiment of the present invention, not makees limitation in any form to the present invention；It is all
The those of ordinary skill of the industry can be shown in by specification and described above and swimmingly implement the present invention；It is but all familiar
Professional and technical personnel without departing from the scope of the present invention, makes using disclosed above technology contents
A little variation, modification and evolution equivalent variations, be the present invention equivalent embodiment；Meanwhile all realities according to the present invention
Variation, modification and evolution of any equivalent variations that matter technology makees above example etc., still fall within the technology of the present invention
Within the protection domain of scheme.
Claims (6)
1. a kind of preparation method of small particle ternary anode material precursor, it is characterised in that comprise the following steps：
（1）It is raw material to select nickel cobalt manganese liquid, is configured to metal mixed salting liquid, and reaction kettle adds special reaction bottom liquid in advance,
Metal salt solution and complexing agent and precipitant solution are added in reaction kettle according to stoichiometric number ratio, cocurrent, whole reaction exists
N2Protection is lower to be carried out；
（2）First time kettle expires the control of D50 particle diameters at 1 ~ 2 μm, is directly overflow after reaction kettle is full from overflow pipe to ready aging reactor
Flow, particle size length stops charging immediately to 3.5-4.0 μm in 10 ~ 20h reaction kettles；
（3）Then reaction kettle slurry is uniformly mixed with aging reactor slurry, stirs 30min, wash through centrifuge, after drying, add
Enter baking oven to dry at 150 DEG C, 200 mesh sieving packaging, you can prepare 3 ~ 4 μm of small particle ternary precursor, pattern is spherical
Or spherical particle, appearance uniform is without agglomerated particle；
The small particle ternary precursor chemical general formula is NixCoyMnz (OH)2, wherein 0.3≤x≤0.95,0.05≤y≤
0.4,0.05≤z≤0.4, x+y+z=1.
2. the preparation method of small particle ternary anode material precursor according to claim 1, it is characterised in that：The nickel
Cobalt manganese liquid selects nickel liquid, cobalt liquid, manganese liquid, and controlled concentration is 1.0mol/L ~ 3mol/L, and control feed temperature is at 20-60 DEG C.
3. the preparation method of small particle ternary anode material precursor according to claim 1 or 2, it is characterised in that：Institute
State complexing agent and select ammonium hydroxide, concentration be 2mol/L ~ 10mol/L, precipitating reagent sodium hydroxide solution, concentration be 2mol/L ~
10mol/L。
4. the preparation method of small particle ternary anode material precursor according to claim 3, it is characterised in that：It is described pure
Water and soluble ammonium are compounded into reaction bottom liquid, and the soluble ammonium concentration is 3-10g/L, 20 ~ 60 DEG C of bottom liquid temperature degree.
5. the preparation method of small particle ternary anode material precursor according to claim 4, it is characterised in that：It is described can
Dissolubility ammonium selects two kinds of mixtures in ammonium hydroxide, ammonium sulfate, ammonium oxalate, ammonium citrate.
6. the preparation method of small particle ternary anode material precursor according to claim 5, it is characterised in that：Pass through tune
Section lye, which adds speed, makes reaction system be in constant pH value, and pH value control is 10.5 ~ 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710772952.9A CN107915263B (en) | 2017-08-31 | 2017-08-31 | Preparation method of small-particle-size ternary cathode material precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710772952.9A CN107915263B (en) | 2017-08-31 | 2017-08-31 | Preparation method of small-particle-size ternary cathode material precursor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107915263A true CN107915263A (en) | 2018-04-17 |
| CN107915263B CN107915263B (en) | 2020-01-14 |
Family
ID=61898799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710772952.9A Active CN107915263B (en) | 2017-08-31 | 2017-08-31 | Preparation method of small-particle-size ternary cathode material precursor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107915263B (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878866A (en) * | 2018-06-28 | 2018-11-23 | 山东理工大学 | The method for preparing ternary material precursor using waste and old lithium ion battery tertiary cathode material and recycling lithium |
| CN108946827A (en) * | 2018-07-03 | 2018-12-07 | 华友新能源科技（衢州）有限公司 | A kind of ultra-small grain size nickel cobalt manganese hydroxide and preparation method thereof |
| CN109037670A (en) * | 2018-07-10 | 2018-12-18 | 湖南鸿捷新材料有限公司 | A kind of method of continuity preparation little particle ternary precursor material |
| CN109225069A (en) * | 2018-08-29 | 2019-01-18 | 广东佳纳能源科技有限公司 | The preparation facilities and its production method of a kind of small particle, high jolt ramming ternary precursor |
| CN109305698A (en) * | 2018-09-03 | 2019-02-05 | 广东佳纳能源科技有限公司 | A kind of preparation method of unformed lithium ion anode material presoma |
| CN109817906A (en) * | 2018-12-29 | 2019-05-28 | 深圳市卓能新能源股份有限公司 | Anode coating, battery anode slice and lithium ion battery |
| CN109830654A (en) * | 2018-12-29 | 2019-05-31 | 深圳市卓能新能源股份有限公司 | Anode coating, battery anode slice and lithium ion battery |
| CN110028112A (en) * | 2019-04-23 | 2019-07-19 | 金川集团股份有限公司 | A kind of method of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor |
| CN110364714A (en) * | 2019-07-17 | 2019-10-22 | 中国恩菲工程技术有限公司 | The method for preparing nickel-cobalt-manganese ternary material precursor |
| CN110739447A (en) * | 2018-07-20 | 2020-01-31 | 河南科隆新能源股份有限公司 | Preparation method capable of controlling particle size distribution of lithium ion battery precursors |
| CN111129485A (en) * | 2019-12-20 | 2020-05-08 | 中南大学 | Single-crystal high-nickel ternary cathode material and preparation method thereof |
| WO2021073583A1 (en) | 2019-10-17 | 2021-04-22 | 中国石油化工股份有限公司 | Lithium battery positive electrode material precursor, preparation method therefor and use thereof |
| CN113130886A (en) * | 2019-12-30 | 2021-07-16 | 荆门市格林美新材料有限公司 | Preparation method and application of superfine high-nickel ternary precursor |
| CN113161536A (en) * | 2021-04-15 | 2021-07-23 | 华友新能源科技（衢州）有限公司 | Method for preparing layered precursor with various proportions |
| CN113461073A (en) * | 2021-07-01 | 2021-10-01 | 广东佳纳能源科技有限公司 | Ternary precursor and preparation method and application thereof |
| CN113735194A (en) * | 2021-08-26 | 2021-12-03 | 池州西恩新材料科技有限公司 | pH control method for ternary precursor reaction kettle |
| CN114804232A (en) * | 2022-05-16 | 2022-07-29 | 南通金通储能动力新材料有限公司 | Hollow ternary positive electrode material precursor and preparation method thereof |
| WO2022242596A1 (en) | 2021-05-19 | 2022-11-24 | 中国石油化工股份有限公司 | Lithium battery positive electrode material precursor, preparation method therefor and application thereof |
| CN115771914A (en) * | 2021-09-07 | 2023-03-10 | 浙江海创锂电科技有限公司 | Preparation method of doped small-particle-size high-nickel precursor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253717A (en) * | 2013-04-23 | 2013-08-21 | 宁夏东方钽业股份有限公司 | Method for preparing small-size nickel-cobalt lithium manganate precursor |
| CN103545504A (en) * | 2013-10-17 | 2014-01-29 | 江西赣锋锂业股份有限公司 | Preparation method of ternary anode material precursor |
| CN105161715A (en) * | 2015-10-21 | 2015-12-16 | 重庆特瑞电池材料股份有限公司 | Lithium nickel cobalt manganese oxide positive electrode precursor and preparation method thereof as well as lithium nickel cobalt manganese oxide positive electrode material and preparation method thereof |
| CN105934409A (en) * | 2014-01-31 | 2016-09-07 | 住友金属矿山株式会社 | Nickel-manganese composite hydroxide particles, method for producing same, positive electrode active material for nonaqueous electrolyte secondary batteries, method for producing positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery |
| CN106252730A (en) * | 2016-08-04 | 2016-12-21 | 陈永林 | A kind of preparation method of energy-density lithium ion battery |
-
2017
- 2017-08-31 CN CN201710772952.9A patent/CN107915263B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253717A (en) * | 2013-04-23 | 2013-08-21 | 宁夏东方钽业股份有限公司 | Method for preparing small-size nickel-cobalt lithium manganate precursor |
| CN103545504A (en) * | 2013-10-17 | 2014-01-29 | 江西赣锋锂业股份有限公司 | Preparation method of ternary anode material precursor |
| CN105934409A (en) * | 2014-01-31 | 2016-09-07 | 住友金属矿山株式会社 | Nickel-manganese composite hydroxide particles, method for producing same, positive electrode active material for nonaqueous electrolyte secondary batteries, method for producing positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery |
| CN105161715A (en) * | 2015-10-21 | 2015-12-16 | 重庆特瑞电池材料股份有限公司 | Lithium nickel cobalt manganese oxide positive electrode precursor and preparation method thereof as well as lithium nickel cobalt manganese oxide positive electrode material and preparation method thereof |
| CN106252730A (en) * | 2016-08-04 | 2016-12-21 | 陈永林 | A kind of preparation method of energy-density lithium ion battery |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878866A (en) * | 2018-06-28 | 2018-11-23 | 山东理工大学 | The method for preparing ternary material precursor using waste and old lithium ion battery tertiary cathode material and recycling lithium |
| WO2020007176A1 (en) * | 2018-07-03 | 2020-01-09 | 华友新能源科技（衢州）有限公司 | Ultra-small particle size nickel-cobalt-manganese hydroxide, and preparation method therefor |
| CN108946827A (en) * | 2018-07-03 | 2018-12-07 | 华友新能源科技（衢州）有限公司 | A kind of ultra-small grain size nickel cobalt manganese hydroxide and preparation method thereof |
| CN108946827B (en) * | 2018-07-03 | 2020-09-29 | 华友新能源科技（衢州）有限公司 | Ultra-small particle size nickel-cobalt-manganese hydroxide and preparation method thereof |
| CN109037670A (en) * | 2018-07-10 | 2018-12-18 | 湖南鸿捷新材料有限公司 | A kind of method of continuity preparation little particle ternary precursor material |
| CN110739447A (en) * | 2018-07-20 | 2020-01-31 | 河南科隆新能源股份有限公司 | Preparation method capable of controlling particle size distribution of lithium ion battery precursors |
| CN109225069A (en) * | 2018-08-29 | 2019-01-18 | 广东佳纳能源科技有限公司 | The preparation facilities and its production method of a kind of small particle, high jolt ramming ternary precursor |
| CN109305698A (en) * | 2018-09-03 | 2019-02-05 | 广东佳纳能源科技有限公司 | A kind of preparation method of unformed lithium ion anode material presoma |
| CN109830654A (en) * | 2018-12-29 | 2019-05-31 | 深圳市卓能新能源股份有限公司 | Anode coating, battery anode slice and lithium ion battery |
| CN109817906A (en) * | 2018-12-29 | 2019-05-28 | 深圳市卓能新能源股份有限公司 | Anode coating, battery anode slice and lithium ion battery |
| CN110028112B (en) * | 2019-04-23 | 2021-09-28 | 金川集团股份有限公司 | Method for synthesizing nickel-cobalt-aluminum cathode material precursor with wide particle size distribution through continuous coprecipitation |
| CN110028112A (en) * | 2019-04-23 | 2019-07-19 | 金川集团股份有限公司 | A kind of method of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor |
| CN110364714A (en) * | 2019-07-17 | 2019-10-22 | 中国恩菲工程技术有限公司 | The method for preparing nickel-cobalt-manganese ternary material precursor |
| WO2021073583A1 (en) | 2019-10-17 | 2021-04-22 | 中国石油化工股份有限公司 | Lithium battery positive electrode material precursor, preparation method therefor and use thereof |
| CN111129485A (en) * | 2019-12-20 | 2020-05-08 | 中南大学 | Single-crystal high-nickel ternary cathode material and preparation method thereof |
| CN113130886A (en) * | 2019-12-30 | 2021-07-16 | 荆门市格林美新材料有限公司 | Preparation method and application of superfine high-nickel ternary precursor |
| CN113161536A (en) * | 2021-04-15 | 2021-07-23 | 华友新能源科技（衢州）有限公司 | Method for preparing layered precursor with various proportions |
| CN113161536B (en) * | 2021-04-15 | 2023-03-21 | 华友新能源科技（衢州）有限公司 | Method for preparing layered precursor with various proportions |
| WO2022242596A1 (en) | 2021-05-19 | 2022-11-24 | 中国石油化工股份有限公司 | Lithium battery positive electrode material precursor, preparation method therefor and application thereof |
| CN113461073A (en) * | 2021-07-01 | 2021-10-01 | 广东佳纳能源科技有限公司 | Ternary precursor and preparation method and application thereof |
| CN113735194A (en) * | 2021-08-26 | 2021-12-03 | 池州西恩新材料科技有限公司 | pH control method for ternary precursor reaction kettle |
| CN115771914A (en) * | 2021-09-07 | 2023-03-10 | 浙江海创锂电科技有限公司 | Preparation method of doped small-particle-size high-nickel precursor |
| CN114804232A (en) * | 2022-05-16 | 2022-07-29 | 南通金通储能动力新材料有限公司 | Hollow ternary positive electrode material precursor and preparation method thereof |
| CN114804232B (en) * | 2022-05-16 | 2023-11-14 | 南通金通储能动力新材料有限公司 | Hollow ternary positive electrode material precursor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107915263B (en) | 2020-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107915263A (en) | A kind of preparation method of small particle ternary anode material precursor | |
| CN109037644B (en) | Preparation method of coated lithium ion battery ternary cathode material | |
| CN102569781B (en) | High-voltage lithium ion battery cathode material and preparation method thereof | |
| CN102683645A (en) | Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery | |
| CN106745336A (en) | A kind of precursor of nickel-cobalt-lithium-manganese-oxide of nanometer sheet reunion second particle and preparation method thereof | |
| CN104201367A (en) | High-density small-particle-size nickel-cobalt-manganese hydroxide and preparing method thereof | |
| CN107324405A (en) | A kind of lithium nickel cobalt manganese oxide precursor and preparation method thereof and the lithium ion battery prepared by the presoma | |
| CN107565121A (en) | A kind of preparation method of lithium battery modified anode material | |
| CN101304090A (en) | Method for synthesizing lithium ion battery anode material LiNixCoyMn(1-x-y)O2 | |
| CN107910531A (en) | A kind of preparation method of high Ni-based tertiary cathode material | |
| CN105118981A (en) | High-capacity nickel-cobalt-lithium manganate precursor and preparation method thereof | |
| CN112537802B (en) | Preparation method of high-voltage lithium battery precursor doped with cobalt hydroxide | |
| CN103165878A (en) | Preparation method of spherical nickel-manganese binary material | |
| CN103178263A (en) | Method for preparing nickel cobalt lithium aluminate cathode material | |
| CN103715424A (en) | Core-shell structured cathode material and preparation method thereof | |
| CN102569780A (en) | Method for preparing lithium ion battery cathode material with layered structure | |
| CN102208607A (en) | Synthesis and surface modification method of lithium excessive laminar oxide anode material | |
| CN101269849A (en) | High-density spherical lithium nickel cobalt manganese oxygen and method for preparing the same | |
| CN104810521A (en) | Preparing method of nickel cobalt lithium manganate ternary positive electrode material | |
| CN104966820A (en) | Lithium-ion battery precursor material, composite positive electrode material and preparation method thereof | |
| CN104916837A (en) | Preparation method of aluminum element doped ternary positive electrode material | |
| CN106587170A (en) | Preparation method of cobaltosic oxide with rare earth element doped body phase | |
| CN103035905B (en) | A kind of preparation method of polynary positive pole material of lithium ion cell spherical precursor | |
| CN105016394B (en) | A kind of industrial production process of lithium ion battery manganate cathode material for lithium | |
| CN104600285A (en) | Method for preparing spherical lithium nickel manganese oxide positive pole material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210409 Address after: 513000 Qingtang Town, Yingde City, Qingyuan City, Guangdong Province Patentee after: GUANGDONG JIANA ENERGY TECHNOLOGY Co.,Ltd. Address before: 513000 Qingtang Town, Yingde City, Qingyuan City, Guangdong Province Patentee before: GUANGDONG JIANA ENERGY TECHNOLOGY Co.,Ltd. Patentee before: HUNAN JIANA ENERGY TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right |