CN108807976A - Nickel-cobalt-manganese ternary material precursor material of narrow particle diameter distribution and preparation method thereof - Google Patents
Nickel-cobalt-manganese ternary material precursor material of narrow particle diameter distribution and preparation method thereof Download PDFInfo
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- CN108807976A CN108807976A CN201810904508.2A CN201810904508A CN108807976A CN 108807976 A CN108807976 A CN 108807976A CN 201810904508 A CN201810904508 A CN 201810904508A CN 108807976 A CN108807976 A CN 108807976A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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- 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 nickel-cobalt-manganese ternary material precursor materials of a kind of narrow particle diameter distribution and preparation method thereof.The preparation method includes the following steps：S1 prepares metal salt solution, sodium hydroxide solution and ammonia spirit containing Ni, Co, Mn soluble-salt；S2 is separately added into ammonium sulfate as bottom liquid in crystal seed prepares kettle and synthesis reactor, is used in combination and adjusts pH value to 10.5~12.0, and nitrogen formation protective atmosphere is incorporated into synthesis reactor；It is prepared by S3, crystal seed；S4, synthesis step；S5, classification process；S6, aging step：5~10 μm of particle is aged in aging reactor；S7, subsequent processing steps：To be filtered, wash by the particle of ageing, dry after obtain the nickel-cobalt-manganese ternary material precursor material of narrow particle diameter distribution.It applies the technical scheme of the present invention and has achieved the purpose that be precisely controlled product cut size, the efficiency of semi-continuous production is higher.
Description
Technical field
The present invention relates to technical field of lithium batteries, in particular to a kind of nickel-cobalt-manganese ternary material of narrow particle diameter distribution
Persursor material and preparation method thereof.
Background technology
Lithium battery is of wide application, and in addition to traditional 3C small household appliances, lithium battery is also used for waterpower, firepower, wind-force
It is the uninterruptible power supply and electric tool of post and telecommunications, electric bicycle, electronic with the accumulation power supplies system such as solar power station
The multiple fields such as motorcycle, electric vehicle, military equipment, aerospace.
Anode serves not only as electrode material and participates in electrochemical reaction, lithium ion source is also used as, so positive electrode should use up
Amount meets the following conditions：Specific capacity is big, operating voltage is high, the high rate capability of charge and discharge is good, have extended cycle life, safety is good
Deng.Positive electrode occupies 40% or more ratio in the totle drilling cost of lithium battery, and the performance of positive electrode directly affects
The property indices of lithium battery, so lithium electricity positive electrode occupies core status in lithium battery.
Tertiary cathode material has apparent trielement synergistic effect, combines the advantage of nickel, manganese, cobalt respectively, have cost compared with
Low, the advantages that specific capacity is higher, stable cycle performance, chemical property is mainly influenced by persursor material quality.Before
The main performance index for driving body material includes tap density, average grain diameter, particle sphericity etc..It is prepared using coprecipitation
During ternary material precursor, since second particle is made of primary particle, to second particle forming process and formation side
Formula is controlled, on the very big influence of the pattern of second particle.
The granular size of the ternary precursor material of prior art production differs, and particle size distribution span is larger, general range
All 1.2~1.6.Due to polarize in charging process, little particle always excessively de- lithium and it is destructurized, and
The side reaction of the nickelic little particle of Charging state and electrolyte is more violent, will be apparent under high temperature, these result in little particle and follow
The ring service life comparatively fast decays, and exactly the opposite the case where bulky grain.The cycle performance of material entirety is actually to be determined by little particle
Fixed, this is also to restrict an important factor for ternary material cyclicity is further promoted.So it is uniform just to produce particle size
The unanimously ternary material of (particle size distribution span is less than 0.8), to avoid the presence of little particle and bulky grain as far as possible.
According to it has been reported that industrial at present mainly prepare nickel-cobalt-manganese ternary anode using hydroxide coprecipitation step
Then material precursor synthesizes final products with high temperature solid-state method.Various technological parameters are all during hydroxide precipitation reaction
The pattern and particle diameter distribution of particle are affected, such as：Nickel cobalt manganese concentration of salt solution, alkali concentration, ammonia concn, reaction temperature, reaction
Process pH value etc..
Wherein, in high compact small particle NCM forerunner's preparation that patent CN107640792 is mentioned, crystal seed is introduced
It prepares and drying sieve realizes that material particle size is distributed the diminution of span in two steps.The diameter obtained after 200 mesh sieve after drying
Grain size d10 >=2 micron of nickel cobalt manganese hydroxide, d50=2.5-4 microns, d90≤6 micron, but small size particle can not be again
It utilizes, can only discard.It can also be seen that particle homogeneity increases after screening from the electron microscopic picture that the patent provides, but
Sphericity is bad.
A kind of method preparing spherical small particle NCM presomas is mentioned in patent CN107572603, by controlling pH, is closed
The granular precursor that particle size range is 4~5 μm has been obtained at time and digestion time.The electron microscopic picture and grain size point announced from it
Find out on Butut, although D50 reduces, granular size differs, and homogeneity is bad.
To sum up, it is bad that granular precursor homogeneity exists in the prior art, the shortcomings of preparation process complex procedures.
Invention content
The present invention is intended to provide a kind of nickel-cobalt-manganese ternary material precursor material and preparation method thereof of narrow particle diameter distribution, with
Solve the bad technical problem of granular precursor homogeneity in the prior art.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of nickel cobalt manganese three of narrow particle diameter distribution
The preparation method of first material precursor material.The preparation method includes the following steps：S1 is prepared containing Ni, Co, Mn soluble-salt
Metal salt solution, sodium hydroxide solution and ammonia spirit；S2 is separately added into ammonium sulfate in crystal seed prepares kettle and synthesis reactor
It as bottom liquid, is used in combination and adjusts pH value to 10.5~12.0, nitrogen formation protective atmosphere is incorporated into synthesis reactor；It is prepared by S3, crystal seed：
Metal salt is molten, sodium hydroxide solution and ammonia spirit flow velocity are added to crystal seed and prepare in kettle, form nucleus；S4, synthesis step：
Nucleus is added in synthesis reactor, and metal salt is molten, sodium hydroxide solution and ammonia spirit are added in synthesis reactor and synthesize instead
It answers；S5, classification process：Product after S4 synthesis enters continuously grading plant admittedly, and 1~5 μm of particle is returned to synthesis reactor relaying
Continuous growth, 5~10 μm of particle enter in aging reactor；S6, aging step：5~10 μm of particle is aged in aging reactor, old
The mixing speed for changing kettle is reduced to 200~300r/min, and digestion time is 1~3 hour；S7, subsequent processing steps：Ageing will be passed through
Particle be filtered, wash, dry after obtain the nickel-cobalt-manganese ternary material precursor material of narrow particle diameter distribution.
Further, the total concentration of metal ion is 50~100g/L in metal salt solution.
Further, the molar ratio of Ni, Co, Mn are 5 in metal salt solution：2：3.
Further, a concentration of 80~150g/L of sodium hydroxide solution, a concentration of 30~60g/L of ammonia spirit.
Further, a concentration of 60~100g/L of ammonium sulfate.
Further, in S2, pH value is adjusted to 10.5~12.0 using ammonium hydroxide, and bottom liquid liquid level is prepared higher than crystal seed
The stirrer paddle of kettle and synthesis reactor.
Further, in S3, it is 55~65 DEG C that control crystal seed, which prepares reaction temperature in kettle, and mixing speed is 500~800r/
Min, generated time are 8~10 hours.
Further, in S3, metal salt is molten, the addition molar ratio of sodium hydroxide solution and ammonia spirit is 1：2.5：
0.1；In S4, metal salt is molten, the addition molar ratio of sodium hydroxide solution and ammonia spirit is 1：2.1：0.1.
Further, in S4, by adjusting sodium hydroxide solution flow so that the pH value in synthesis reactor maintains 10.5
~12.0, reaction temperature is 55~65 DEG C, and mixing speed is 600~1000r/min.
According to another aspect of the present invention, a kind of nickel-cobalt-manganese ternary material precursor material of narrow particle diameter distribution is provided.
Any of the above-described kind of preparation method is prepared the nickel-cobalt-manganese ternary material precursor material through the invention.
Further, the chemical formula for the nickel cobalt manganese hydroxide for including in nickel-cobalt-manganese ternary material precursor material is
NixCoyMnz(OH)2, x+y+z=1 in formula.
Further, the tap density of nickel-cobalt-manganese ternary material precursor material is 1.9g/cm3More than, D50 is 45~10
μm, particle size distribution span≤1.1.
It applies the technical scheme of the present invention, nickel-cobalt-manganese ternary material precursor material existing in the prior art can be solved
The problems such as grain particle size distribution span is big, and median is larger, and tap density is relatively low, and reached and product cut size is precisely controlled
Purpose, the efficiency of semi-continuous production is higher.
Description of the drawings
The accompanying drawings which form a part of this application are used to provide further understanding of the present invention, and of the invention shows
Meaning property embodiment and its explanation are not constituted improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Fig. 1 shows the preparation of the nickel-cobalt-manganese ternary material precursor material of the narrow particle diameter distribution of an embodiment of the present invention
Method flow schematic diagram；And
Fig. 2 shows the nickel-cobalt-manganese ternary material precursor materials of the preparation narrow particle diameter distribution of an embodiment of the present invention
Apparatus structure schematic diagram.
Wherein, above-mentioned attached drawing includes the following drawings label：
Metal salt solution accumulator tank 11, sodium hydroxide solution accumulator tank 12, ammonium hydroxide accumulator tank 13, crystal seed prepare kettle 20, close
At kettle 30, admittedly grading plant 40, aging reactor 50, filtration wash unit 60 and drying device 70.
Specific implementation mode
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
The shortcomings that in view of the prior art, if granular precursor homogeneity is bad, the shortcomings of preparation process complex procedures, this hair
It is bright to solve the problems, such as being overcome the deficiencies in the prior art, it is preferred that a kind of small particle, narrow particle diameter distribution nickel cobalt manganese three are provided
The preparation method of first material precursor, the nickel cobalt manganese hydroxide median of gained is small, tap density is high, particle is uniform.
According to a kind of typical embodiment of the present invention, a kind of nickel-cobalt-manganese ternary material precursor of narrow particle diameter distribution is provided
The preparation method of material.The preparation method includes the following steps：S1, prepare metal salt solution containing Ni, Co, Mn soluble-salt,
Sodium hydroxide solution and ammonia spirit；S2 is separately added into ammonium sulfate as bottom liquid in crystal seed prepares kettle and synthesis reactor, and
With pH value is adjusted to 10.5~12.0, nitrogen formation protective atmosphere is incorporated into synthesis reactor；It is prepared by S3, crystal seed：Metal salt is molten,
Sodium hydroxide solution and ammonia spirit flow velocity are added to crystal seed and prepare in kettle, form nucleus；S4, synthesis step：Nucleus is added
In synthesis reactor, and metal salt is molten, sodium hydroxide solution and ammonia spirit are added in synthesis reactor and carry out synthetic reaction；S5, classification
Process：Product after S4 synthesis enters continuously grading plant admittedly, and 1~5 μm of particle is returned to continued growth in synthesis reactor, 5~
10 μm of particle enters in aging reactor；S6, aging step：5~10 μm of particle is aged in aging reactor, the stirring of aging reactor
Speed is reduced to 200~300r/min, and digestion time is 1~3 hour.S7, subsequent processing steps：Particle by ageing is carried out
Be filtered, washed, dry after obtain the nickel-cobalt-manganese ternary material precursor material of narrow particle diameter distribution.
It applies the technical scheme of the present invention, nickel-cobalt-manganese ternary material precursor material existing in the prior art can be solved
The problems such as grain particle size distribution span is big, and median is larger, and tap density is relatively low, and reached and product cut size is precisely controlled
Purpose, the efficiency of semi-continuous production is higher.
Preferably, the total concentration of metal ion is 50~100g/L in metal salt solution, can be protected in this concentration range
Demonstrate,prove preferable granule-morphology and reaction rate etc..In order to advanced optimize granule-morphology and reaction rate etc., it is preferred that metal salt
The molar ratio of Ni, Co, Mn are 5 in solution：2：3.Preferably, a concentration of 80~150g/L of sodium hydroxide solution, ammonia spirit
A concentration of 30~60g/L, can ensure preferable amount of solution in this concentration range, be unlikely to since concentration is too low, solution
Amount is big, increases subsequent treating capacity.Preferably, a concentration of 60~100g/L of ammonium sulfate.Preferably, in S2, using ammonia
Water adjusts pH value to 10.5~12.0, and bottom liquid liquid level prepares the stirrer paddle of kettle and synthesis reactor higher than crystal seed.To ensure
The entire reaction system of Co deposited synthesis ternary material precursor is all alkaline, promotes the progress of reaction.
Preferably, in S3, it is 55~65 DEG C that control crystal seed, which prepares reaction temperature in kettle, and mixing speed is 500~800r/
Min, generated time are 8~10 hours.At this point in the reaction, the particle growth rate prepared is suitable, and physical quality is preferable.
In order to optimize industrialized production, ensure that reaction speed does not waste raw material again, it is preferred that in S3, metal salt is molten, hydrogen-oxygen
The addition molar ratio for changing sodium solution and ammonia spirit is 1:2.5:0.1；In S4, metal salt is molten, sodium hydroxide solution and ammonium hydroxide
The addition molar ratio of solution is 1:2.1:0.1.
Preferably, in S4, by adjusting sodium hydroxide solution flow so that the pH value in synthesis reactor maintain 10.5~
12.0, reaction temperature is 55~65 DEG C, and mixing speed is 600~1000r/min.Temperature and pH value could protect within the scope of this
The progress of synthetic reaction is demonstrate,proved, mixing speed is big, is conducive to solid-liquid two-phase and uniformly contacts, and the practical physical quality of synthesis is higher.
According to a kind of typical embodiment of the present invention, as shown in Figure 1, the preparation method includes the following steps：Preparation contains
Nickel sulfate, the metal salt solution of cobaltous sulfate and manganese sulfate, sodium hydroxide solution and ammonia spirit；Kettle and synthesis reactor are prepared in crystal seed
In be separately added into ammonium sulfate and be added to crystal seed as bottom liquid, metal salt is molten, sodium hydroxide solution and ammonia spirit flow velocity
It prepares in kettle, forms nucleus；Nucleus is added in synthesis reactor, and metal salt is molten, sodium hydroxide solution and ammonia spirit are added
Synthetic reaction is carried out in synthesis reactor；Product after synthesis enters continuously grading plant progress gradation admittedly, will meet the requirements
Particle enter in aging reactor and be aged：To be filtered, wash by the particle of ageing, dry after obtain narrow particle diameter distribution
Nickel-cobalt-manganese ternary material precursor material.
According to a kind of typical embodiment of the present invention, a kind of nickel-cobalt-manganese ternary material precursor of narrow particle diameter distribution is provided
Material.The nickel-cobalt-manganese ternary material precursor material of the narrow particle diameter distribution is prepared by any of the above-described kind of preparation method.
Preferably, the chemical formula for the nickel cobalt manganese hydroxide for including in nickel-cobalt-manganese ternary material precursor material is
NixCoyMnz(OH)2, x+y+z=1 in formula.
Preferably, the tap density of nickel-cobalt-manganese ternary material precursor material is 1.9g/cm3More than, D50 is 5~10 μm,
Particle size distribution span≤1.1.
According to the present invention, a kind of typically embodiment there is provided a kind of nickel-cobalt-manganese ternary materials preparing narrow particle diameter distribution
The device of persursor material.The device includes：Solution storage unit inputs solution for being prepared in kettle and synthesis reactor to crystal seed；
The crystal seed prepared for crystal seed prepares kettle, is provided with crystal seed outlet；Synthesis reactor, be provided with crystal seed be added mouth, crystal seed be added mouth with
The crystal seed outlet that crystal seed prepares kettle is connected, and synthesis reactor is used for the synthesis of nickel-cobalt-manganese ternary material precursor material；Gu Gu classification
Device is arranged in the downstream of synthesis reactor, has large-size particles outlet and small size particle outlet, little particle outlet and crystal seed system
The feed inlet of standby kettle is connected；Aging reactor is provided with aging reactor feed inlet, and phase is exported with the large-size particles of grading plant admittedly
Connection；And after-treatment device, for being filtered, washed, drying the material exported from aging reactor.The device be in order to realize on
The device that method corresponds to invention is stated, the effect of each component corresponds to each step in the above method.
Preferably, solution storage unit includes metal salt accumulator tank, sodium hydroxide accumulator tank and ammonium hydroxide accumulator tank, metal salt
The exit of solution storage slot, sodium hydroxide solution accumulator tank and ammonium hydroxide accumulator tank is respectively arranged with flow control valve, crystal seed system
It is both provided with agitating element in standby kettle and synthesis reactor, further, synthesis reactor is additionally provided with nitrogen input unit.It is furthermore preferred that
Prepared by crystal seed is both provided with pH monitoring elements in kettle and synthesis reactor.Preferably, admittedly the achievable series classification of grading plant admittedly, and
Can realize classification to particle by adjusting wash water speed and charging rate, further, after-treatment device include filter element,
Washing unit and drying unit.
According to a kind of typical embodiment of the present invention, as shown in Fig. 2, preparing the nickel-cobalt-manganese ternary material of narrow particle diameter distribution
The device of persursor material includes：Solution storage unit (including metal salt solution accumulator tank 11, sodium hydroxide solution accumulator tank 12
With ammonium hydroxide accumulator tank 13), input solution for being prepared in kettle and synthesis reactor to crystal seed；The crystal seed prepared for crystal seed prepares kettle
20, it is provided with crystal seed outlet；Synthesis reactor 30 is provided with crystal seed and mouth is added, and the crystal seed outlet that mouth prepares kettle with crystal seed is added in crystal seed
It is connected, synthesis reactor is used for the synthesis of nickel-cobalt-manganese ternary material precursor material；Admittedly Gu grading plant 40, is arranged in synthesis reactor
There is large-size particles outlet and small size particle outlet, the feed inlet that little particle outlet prepares kettle with crystal seed to be connected in downstream；
Aging reactor 50 is provided with aging reactor feed inlet, is connected with the large-size particles outlet of grading plant admittedly；And post-processing dress
(filtration wash unit 60 and drying device 70) is set, for being filtered, washed, drying the material exported from aging reactor.
The advantageous effect further illustrated the present invention below in conjunction with embodiment.
Embodiment 1
It is 5 according to molar ratio:2:The total concentration of 3 configuration Ni, Co, Mn soluble-salt mixed solutions, metal ion is 80g/
L, configuration concentration of sodium hydroxide solution are 100g/L, a concentration of 50g/L of ammonia spirit.
A concentration of 80g/L ammonium sulfates are added in crystal seed prepares kettle and synthesis reactor as bottom liquid, bottom liquid liquid level
Stirrer paddle need to be higher than, ammonium hydroxide is used in combination to adjust pH value to 11.0, nitrogen formation protective atmosphere is incorporated into synthesis reactor.
With mixing salt solution, sodium hydroxide solution and the ammonia spirit that will configure with molar ratio for 1:2.1:0.1 is added crystalline substance
Kind is prepared in kettle, and controlling reaction temperature is 60 DEG C, mixing speed 600r/min, and generated time is 8 hours, forms nucleus.
Crystal seed is added in synthesis reactor, and synthesis reactor is added according to certain flow rate in the every solution configured in step (1)
In, it adjusts the flow of sodium hydroxide and maintains 11.0 with the pH value ensured in kettle, reaction temperature is 60 DEG C, and mixing speed is
800r/min。
Product after synthesis enters continuously grading plant admittedly, and the particle by grain size less than 3 μm returns to be continued in synthesis reactor
Growth, satisfactory particle enter in aging reactor.
Satisfactory granular precursor slurry enters in ageing stirred tank, and mixing speed is reduced to 200r/min, time 2
Hour.
Obtained granular precursor grain size is 6.0 μm (D50), tap density 1.9g/cm3, particle size distribution span 0.9.
Embodiment 2
It is 5 according to molar ratio：2：The total concentration of 3 configuration Ni, Co, Mn soluble-salt mixed solutions, metal ion is 100g/
L, configuration concentration of sodium hydroxide solution are 90g/L, a concentration of 40g/L of ammonia spirit.
A concentration of 80g/L ammonium sulfates are added in crystal seed prepares kettle and synthesis reactor as bottom liquid, bottom liquid liquid level
Stirrer paddle need to be higher than, ammonium hydroxide is used in combination to adjust pH value to 11.2, nitrogen formation protective atmosphere is incorporated into synthesis reactor.
By the mixing salt solution, sodium hydroxide solution and ammonia spirit of configuration with molar ratio for 1:2.1:0.1 is added crystal seed
It prepares in kettle, controlling reaction temperature is 55 DEG C, mixing speed 800r/min, and generated time is 9 hours, forms nucleus.
Crystal seed is added in synthesis reactor, and synthesis reactor is added according to certain flow rate in the every solution configured in step (1)
In, it adjusts the flow of sodium hydroxide and maintains 11.50 with the pH value ensured in kettle, reaction temperature is 60 DEG C, and mixing speed is
1000r/min。
Product after synthesis enters continuously grading plant admittedly, and the particle by grain size less than 5 μm returns to be continued in synthesis reactor
Growth, satisfactory particle enter in aging reactor.
Satisfactory granular precursor slurry enters in ageing stirred tank, and mixing speed is reduced to 200r/min, and the time is
2.5 hour.Obtained granular precursor grain size is 8.0 μm (D50), tap density 2.1g/cm3, particle size distribution span 1.0.
Embodiment 3
It is 5 according to molar ratio:2:The total concentration of 3 configuration Ni, Co, Mn soluble-salt mixed solutions, metal ion is 90g/
L, configuration concentration of sodium hydroxide solution are 150g/L, a concentration of 60g/L of ammonia spirit.
A concentration of 80g/L ammonium sulfates are added in crystal seed prepares kettle and synthesis reactor as bottom liquid, bottom liquid liquid level
Stirrer paddle need to be higher than, ammonium hydroxide is used in combination to adjust pH value to 12, nitrogen formation protective atmosphere is incorporated into synthesis reactor.
With by mixing salt solution, sodium hydroxide solution and ammonia spirit with molar ratio be 1:2.1:0.1, which is added crystal seed, prepares
In kettle, controlling reaction temperature is 65 DEG C, mixing speed 900r/min, and generated time is 10 hours, forms nucleus.
Crystal seed is added in synthesis reactor, and synthesis reactor is added according to certain flow rate in the every solution configured in step (1)
In, it adjusts the flow of sodium hydroxide and maintains 11.80 with the pH value ensured in kettle, reaction temperature is 65 DEG C, and mixing speed is
800r/min。
Product after synthesis enters continuously grading plant admittedly, and the particle by grain size less than 5 μm returns to be continued in synthesis reactor
Growth, satisfactory particle enter in aging reactor.
Satisfactory granular precursor slurry enters in ageing stirred tank, and mixing speed is reduced to 200r/min, time 3
Hour.
Obtained granular precursor grain size is 10.0 μm (D50), tap density 2.2g/cm3, particle size distribution span 1.1.
It can be seen from the above description that the above embodiments of the present invention realize following technique effect：
1) technological process of the invention is simple, and technological parameter stabilization is, it can be achieved that semicontinuous operation；
2) the ternary precursor material that the present invention can be prepared both has small median, and particle diameter distribution is narrow, granular size
It is uniform；
3) present invention realizes the size tunable of ternary product, can prepare the forerunner of different-grain diameter according to different requirements
Body material；
4) what the present invention used returns crystal seed mode, and crystal growth is fine and close, and tap density is high.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (12)
1. a kind of preparation method of the nickel-cobalt-manganese ternary material precursor material of narrow particle diameter distribution, which is characterized in that including following
Step：
S1 prepares metal salt solution, sodium hydroxide solution and ammonia spirit containing Ni, Co, Mn soluble-salt；
S2 is separately added into ammonium sulfate as bottom liquid in crystal seed prepares kettle and synthesis reactor, be used in combination adjust pH value to 10.5~
12.0, nitrogen formation protective atmosphere is incorporated into the synthesis reactor；
It is prepared by S3, crystal seed：By the metal salt, molten, sodium hydroxide solution and ammonia spirit flow velocity are added to the crystal seed and prepare kettle
In, form nucleus；
S4, synthesis step：The nucleus is added in synthesis reactor, and molten, sodium hydroxide solution and ammonium hydroxide are molten by the metal salt
Liquid is added in synthesis reactor and carries out synthetic reaction；
S5, classification process：Product after the S4 synthesis enters continuously grading plant admittedly, and 1~5 μm of particle is returned to synthesis reactor
Middle continued growth, 5~10 μm of particle enter in aging reactor；
S6, aging step：5~10 μm of the particle is aged in the aging reactor, the mixing speed drop of the aging reactor
For 200~300r/min, digestion time is 1~3 hour；
S7, subsequent processing steps：To be filtered, wash by the particle of ageing, dry after obtain the narrow grain size point
The nickel-cobalt-manganese ternary material precursor material of cloth.
2. preparation method according to claim 1, which is characterized in that the total concentration of metal ion in the metal salt solution
For 50~100g/L.
3. preparation method according to claim 1, which is characterized in that the molar ratio of Ni, Co, Mn in the metal salt solution
It is 5：2：3.
4. preparation method according to claim 1, which is characterized in that a concentration of the 80 of the sodium hydroxide solution~
150g/L, a concentration of 30~60g/L of the ammonia spirit.
5. preparation method according to claim 1, which is characterized in that a concentration of 60~100g/ of the ammonium sulfate
L。
6. preparation method according to claim 1, which is characterized in that in the step S2, using ammonium hydroxide adjust pH value to
10.5~12.0, and bottom liquid liquid level prepares the stirrer paddle of kettle and synthesis reactor higher than crystal seed.
7. preparation method according to claim 1, which is characterized in that in the step S3, control the crystal seed and prepare kettle
Middle reaction temperature is 55~65 DEG C, and mixing speed is 500~800r/min, and generated time is 8~10 hours.
8. preparation method according to claim 1, which is characterized in that in the step S3, the metal salt is molten, hydroxide
The addition molar ratio of sodium solution and ammonia spirit is 1:2.5：0.1；In the step S4, the metal salt is molten, sodium hydroxide
The addition molar ratio of solution and ammonia spirit is 1:2.1:0.1.
9. preparation method according to claim 1, which is characterized in that in the step S4, by adjusting the hydroxide
The flow of sodium solution is so that the pH value in the synthesis reactor maintains 10.5~12.0, and reaction temperature is 55-65 DEG C, mixing speed
For 600~1000r/min.
10. a kind of nickel-cobalt-manganese ternary material precursor material of narrow particle diameter distribution, which is characterized in that pass through such as claim 1 to 9
Any one of described in preparation method be prepared.
11. nickel-cobalt-manganese ternary material precursor material according to claim 10, which is characterized in that the nickel-cobalt-manganese ternary
The chemical formula for the nickel cobalt manganese hydroxide for including in material precursor material is NixCoyMnz(OH)2, x+y+z=1 in formula.
12. nickel-cobalt-manganese ternary material precursor material according to claim 11, which is characterized in that the nickel-cobalt-manganese ternary
The tap density of material precursor material is 1.9g/cm3More than, D50 is 5~10 μm, particle size distribution span≤1.1.
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