CN107834064A - A kind of nickelic small particle nickel cobalt manganese hydroxide and preparation method thereof - Google Patents
A kind of nickelic small particle nickel cobalt manganese hydroxide and preparation method thereof Download PDFInfo
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- CN107834064A CN107834064A CN201711260819.1A CN201711260819A CN107834064A CN 107834064 A CN107834064 A CN 107834064A CN 201711260819 A CN201711260819 A CN 201711260819A CN 107834064 A CN107834064 A CN 107834064A
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- nickel cobalt
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- manganese hydroxide
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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 a kind of nickelic small particle nickel cobalt manganese hydroxide and preparation method thereof, the preparation method comprises the following steps：(1) exist in more mother liquor and under conditions of high complexing agent concentration, be continually fed into nickel cobalt manganese hybrid metal solution, precipitating reagent and complexing agent nucleation, nucleus high degree of dispersion is made by high-speed stirred, into the nucleus growth stage；(2) reaction starts to material to sink, and during D50=1.3~1.5 μm, from the feed liquid of reactor top extraction kettle effective volume 1/6~1/3, when this part feed liquid precipitates completely, pours out supernatant, sediment is returned and continues to react in reactor；(3) operate repeatedly and new crystal seed is introduced with this and increases solid content, to stopping reaction at D50=3 μm.The present invention prepares nickel cobalt manganese hydroxide using the new crystal seed of nucleation and crystallization/introducing, can avoid artificially playing ball, easy to operate without transforming existing reactor, can expanding production；The nickel cobalt manganese hydroxide even particle size distribution of preparation, concentration, do not reunite, tap density is high, good sphericity.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical field, and in particular to a kind of nickelic small particle nickel cobalt manganese hydrogen-oxygen
Compound and preparation method thereof.
Background technology
Lithium ion battery is ground from nineteen ninety by Japanese Sony companies succeed in developing first after because its high voltage, high power capacity
Major advantage, the distinguishing feature have extended cycle life, having a safety feature, be widely used in portable electric appts, electric automobile,
Defense technology and space technology etc., have broad application prospects and potential great economic benefit, rapidly become current
The study hotspot widely paid close attention to.In the structure combination of lithium ion material, the advantages of nickelic positive electrode is due to high power capacity
Extensive attention is received, turns into the emphasis of current research, especially with nickelic just minimum of high-energy, high magnification and high safety performance
Grain attracts attention the most.
The short grained preparation for preparing key and being small particle nickel cobalt manganese hydroxide precursor of nickelic positive pole；Need forerunner
Body good sphericity, particle size distribution are not reunited uniformly, and tap density is high, as matrix, can prepare the nickelic of better performances
Positive pole small-particulate materials.
The content of the invention
The technical problems to be solved by the invention are to overcome the technological deficiency of background technology, there is provided a kind of nickelic small particle nickel
Cobalt manganese hydroxide and preparation method thereof.The present invention high ammonia concn and it is high-revolving under the conditions of, pass through nucleation and crystallization/introducing
New crystal seed and increase solid content, can avoid artificially playing ball；Preparation method of the present invention need not transform existing reactor, operation letter
Just, can expanding production；Nickelic small particle nickel cobalt manganese hydroxide even particle size distribution that the present invention prepares, concentration, do not reunite,
Tap density is high, good sphericity；Nickelic small particle nickel cobalt manganese hydroxide D50=1.5~3 μm, size distribution are 1~10
μm, tap density is 1.6~2.4g/cm3；The lithium-ion electric being prepared by the nickelic small particle nickel cobalt manganese hydroxide of the present invention
Pond positive electrode capacity is high, and tap density is high, and size distribution is concentrated, and monocrystalline pattern is good.
Technological means is used by the present invention solves above-mentioned technical problem：
A kind of preparation method of nickelic small particle nickel cobalt manganese hydroxide, comprises the following steps：
(1) it is according to formula Ni according to molar ratio needed for nickel cobalt manganese in hydroxide by nickel cobalt manganese soluble-salt1-x- yCoxMny(OH)2, wherein 0.09≤x≤0.12,0.03≤y≤0.05, it is mixed to be configured to first containing tri- kinds of ions of Ni, Co, Mn
Close metal salt solution；Prepare the second mixed solution being made up of precipitating reagent；Prepare the 3rd mixed solution being made up of complexing agent；
(2) pure water of effective volume 80% is added into reactor under agitation, it is mixed to be passed through step (1) described second
Close solution and mother liquor is made in the 3rd mixed solution, and be continually fed into inert gas as protection；
(3) by step (1) first mixed salt solution, the second mixed solution and the 3rd mixed solution cocurrent, hold
It is continuous to be constantly passed through in the reactor of high-speed stirred, it is co-precipitated in the presence of the second mixed solution and the 3rd mixed solution
Reaction, nucleus constantly form, grown up；Continue to feed when granularity is to 1.3~1.5 μm, extract feed liquid out from reactor top, treat this
Supernatant is outwelled after the feed liquid precipitation of part, sediment is refunded into reactor again, takes same method when reactor is full afterwards, with
This introduces new crystal seed, slows down particle growth rate while increasing solid content, can avoid caused little particle group of artificially playing ball
A problem that poly-, stop charging when granularity D50 reaches 2.5~3 μm, terminate reaction；
(4) reaction product that step (3) obtains is aged successively, the slurry after ageing is subjected to alkali cleaning centrifugation, so
Dry afterwards, crush, sieve, obtain nickelic small particle nickel cobalt manganese hydroxide after iron removaling.
Continuous blowing feed back is wanted in above-mentioned technical proposal, in course of reaction, new crystal seed is introduced with this and increase contains admittedly
Amount, can avoid artificially playing ball caused by little particle a problem that reuniting.
Be in above-mentioned technical proposal, in course of reaction it is continual be passed through feed liquid, continuous production, production capacity can't be for it
Reduce.
Preferably, in the step (1), the first mixed salt solution concentration is 1.5~2mol/L.
Preferably, in the step (1), the precipitating reagent is KOH, LiOH, NaOH, Na2CO3In any one or it is several
Kind, more preferably NaOH.
Preferably, in the step (1), the second mixed solution concentration is 2~6mol/L.
Preferably, in the step (1), the complexing agent is ammoniacal liquor, disodium ethylene diamine tetraacetate, sulfosalicylic acid, sweet
Any one or a few in propylhomoserin, more preferably ammoniacal liquor.
Preferably, in the step (1), the 3rd mixed solution concentration is 7~14mol/L.
Preferably, in the step (2), the mother liquor accounts for reactor effective volume more than 80%, and wherein pH value is 12.0
~12.4, ammonia value is 10~12g/L, and temperature is 40~65 DEG C.
Preferably, in the step (2), value of the 3rd mixed solution in reactor system is 8~14g/L.
Preferably, in the step (2), the inert gas is one or both of nitrogen or argon gas.
Preferably, in the step (3), the coprecipitation reaction temperature is 40~65 DEG C.
Preferably, in the step (3), the pH of the coprecipitation reaction is 11.0~12.6.
Preferably, in the step (3), the rotating speed during coprecipitation reaction is 700~1200rpm.
Preferably, in the step (3), the volume for extracting feed liquid out from reactor top accounts for reactor effective volume
1/6~1/3.
It is highly preferred that in the step (3), the volume for extracting feed liquid out from reactor top accounts for reactor effective volume
1/4.
Preferably, in the step (4), the time of the ageing is 45~85min.
Preferably, in the step (4), the temperature of the alkali cleaning is 50~85 DEG C.
Preferably, in the step (4), the temperature of the drying is 100~150 DEG C.
Preferably, in the step (4), the nickelic small particle nickel cobalt manganese hydroxide D50 is 1.5~3 μm.
Preferably, in the step (4), the nickelic small particle nickel cobalt manganese hydroxide size distribution is 1~10 μm, is shaken
Real density is 1.6~2.4g/cm3.
A kind of nickelic small particle nickel cobalt manganese hydroxide, is prepared by the above method, the nickelic small particle nickel cobalt manganese
Hydroxide D50=1.5~3 μm, size distribution are 1~10 μm, and tap density is 1.6~2.4g/cm3；The nickelic granule
Footpath nickel cobalt manganese hydroxide good sphericity, even particle size distribution and soilless sticking, tap density are high.
The nickelic small particle nickel cobalt manganese hydroxide is sintered into 24~27h at 700~1000 DEG C, lithium ion battery can be obtained
Positive electrode.
The anode material for lithium-ion batteries capacity is high, and tap density is high, and size distribution is concentrated, and monocrystalline pattern is good.
The general principle of the present invention：
The present invention prepares nickelic small particle hydroxide using the new crystal seed of nucleation and crystallization/introducing：
(1) exist in more mother liquor and under conditions of high complexing agent concentration, be continually fed into nickel cobalt manganese hybrid metal solution, sink
Shallow lake agent and complexing agent nucleation, make nucleus high degree of dispersion, into the nucleus growth stage by high-speed stirred；
(2) reaction starts to material to sink, during D50=1.3~1.5 μm, from the effective body of reactor top extraction kettle
The feed liquid of product 1/4, when this part feed liquid precipitates completely, pours out supernatant, and sediment is returned in reactor and continues to react；
(3) operate repeatedly and new crystal seed is introduced with this and increases solid content, to stopping reaction at D50=3 μm.
Compared with prior art, technical scheme has the following advantages that：
(1) present invention high ammonia concn and it is high-revolving under the conditions of, pass through the new crystal seed of nucleation and crystallization/introducing and increase
Solid content, it can avoid artificially playing ball；
(2) preparation method of the present invention need not transform existing reactor, easy to operate, can expanding production；
(3) present invention prepares nickelic small particle nickel cobalt manganese hydroxide even particle size distribution, concentration, do not reunite, shake
Real density is high, good sphericity；
(4) nickelic small particle nickel cobalt manganese hydroxide D50=1.5~3 μm prepared of the present invention, size distribution is 1~
10 μm, tap density is 1.6~2.4g/cm3；
(5) the anode material for lithium-ion batteries capacity being prepared by the nickelic small particle nickel cobalt manganese hydroxide of the present invention
Height, tap density is high, and size distribution is concentrated, and monocrystalline pattern is good.
Brief description of the drawings
Fig. 1 is the SEM figures for the nickelic small particle nickel cobalt manganese hydroxide that the embodiment of the present invention 1 prepares gained；
Fig. 2 is the nickelic small particle nickel cobalt manganese hydroxide size distribution photo that the embodiment of the present invention 1 prepares gained；
Fig. 3 is the SEM figures for the nickelic small particle nickel cobalt manganese hydroxide that the embodiment of the present invention 2 prepares gained；
Fig. 4 is the nickelic small particle nickel cobalt manganese hydroxide size distribution photo that the embodiment of the present invention 2 prepares gained；
Fig. 5 is the lithium prepared using the nickelic small particle nickel cobalt manganese hydroxide of the preparation gained of the embodiment of the present invention 1 as base material
The SEM figures of ion battery positive electrode.
Embodiment
Content for a better understanding of the present invention, is described further with reference to specific embodiments and the drawings.Ying Li
Solution, these embodiments are only used for that the present invention is further described, rather than limitation the scope of the present invention.In addition, it is to be understood that
After having read present disclosure, person skilled in art makes some nonessential changes or adjustment to the present invention, still belongs to
In protection scope of the present invention.
The invention provides a kind of preparation process of nickelic small particle nickel cobalt manganese hydroxide, including：
(1) it is according to formula Ni according to molar ratio needed for nickel cobalt manganese in hydroxide by nickel cobalt manganese soluble-salt1-x- yCoxMny(OH)2, wherein 0.09≤x≤0.12,0.03≤y≤0.1, are configured to tri- kinds of total ion concentrations of Ni, Co, Mn as 1.5
~2.0mol/L the first mixed salt solution；
It is the second mixed solution to prepare 2~6mol/L of sodium hydroxide pellets agent concentration；
It is that 7~14mol/L is the 3rd mixed solution to prepare ammoniacal liquor complexing agent concentration；
(2) pure water of effective volume 80% is added into reactor under agitation, is passed through complexing agent and precipitating reagent system
Into mother liquor, and certain nitrogen is continually fed into as protection；
(3) configured three kinds of solution cocurrents are continually fed into reactor, entered in the presence of sodium hydroxide and ammoniacal liquor
Row coprecipitation reaction.Continue to feed when granularity is to 1.5 μm, extract 1/4 feed liquid out from reactor top, supernatant is outwelled after to be precipitated
Liquid, material is refunded into reactor again, can take same method when reactor is full afterwards, new crystal seed is introduced with this, increase kettle
Middle system solid content, granularity increases slowly, while can avoid artificially playing ball, and stop charging when granularity D50 reaches 2.5~3 μm,
Terminate reaction；
The coprecipitation reaction temperature is 40~65 DEG C；
The pH of the coprecipitation reaction is 11.0~12.6；
The co-precipitation rotating speed is 700~1200rpm；
The inert gas is one or both of nitrogen or argon gas；
The reaction initial mother liquor accounts for kettle effective volume more than 80%, and wherein pH value is 12.0~12.4, and ammonia value is 10
~12g/L, temperature are 40~65 DEG C；
(4) obtained reaction product is aged, is washed and dried successively, obtain nickelic small particle nickel cobalt manganese hydroxide
Thing；
The time of the ageing is 45~85min；
The temperature of the washing is 50~85 DEG C；
The temperature of the drying is 100~150 DEG C.
Embodiment 1
It is 1.5mol/L's that the dissolving of nickel sulfate, cobaltous sulfate and manganese sulfate water is made into tri- kinds of total ion concentrations of Ni, Co, Mn
Sulfate solution, wherein nickel cobalt manganese ratio are Ni:Co:Mn=0.83:0.12:0.05；Preparation naoh concentration is 4mol/
L is the second mixed solution；It is that 9mol/L is the 3rd mixed solution to prepare ammonia concn；
40L deionized water is added in 50L reactor, is passed through sodium hydroxide solution and ammoniacal liquor, being configured to pH is
12.4th, the mother liquor that ammonia value is 10g/L, temperature is 50 DEG C.It is 900r/min by reactor adjustment of rotational speed, stirring is opened, to reaction
Nitrogen is passed through in kettle and carries out atmosphere protection, and nitrogen is continually fed into whole course of reaction；
Prepare three kinds of solution are passed through reactor by the way that the peristaltic pump of delicate metering is simultaneously continual, carried out brilliant
Karyomorphism is 12.2~12.3 into growth response, control system pH value, and ammonia value is 10~11g/L, reaction time 10h；Charging is anti-
After a period of time, when the feed liquid being discarded in beaker can precipitate completely, pH should be gradually decreased to 12.2 or so；
Continue reaction and during raw meal particle size D50=1.3~1.5 μm, start to extract 1/4 feed liquid out from reactor top into kettle,
Supernatant is outwelled after to be precipitated, material is refunded into reactor again, took same method every two hours afterwards, is introduced with this new
Crystal seed, system solid content increase in kettle, granularity increasess slowly, while can avoid artificially playing ball；When particle size growth is to 2.0 μm,
By adjustment of rotational speed to 1200r/min, system pH is 12.1~12.2, and ammonia value is adjusted to 11~11.5g/L, continues reaction to granularity
D50 stops charging when reaching 2.5 μm or so, continues to stir 1h blowings washing drying and processing；
By separation of solid and liquid after the slurry obtained after co-precipitation ageing 1h, it is 60 DEG C of volumes that cake shape solid is put into temperature
In 1m3 washing kettle, while the caustic soda that concentration is 10mol/L is added, volume ratio is alkali:Water=1:70, centrifuged after washing, in
20h is dried under the conditions of 130 DEG C reach requirement to moisture in air dry oven；
The nickelic small particle nickel cobalt manganese hydroxide obtained in the embodiment of the present invention 1 is scanned Electronic Speculum detection, detection
It is as a result as shown in Figure 1, it is known that, the nickelic small particle nickel cobalt manganese hydroxide sphericity that the embodiment of the present invention 1 is prepared is preferable,
Even particle size distribution, and soilless sticking；
The nickelic small particle nickel cobalt manganese hydroxide obtained in the embodiment of the present invention 1 is subjected to testing graininess, testing result
As shown in Figure 2, it is known that, the nickelic small particle nickel cobalt manganese hydroxide size distribution that the embodiment of the present invention 1 is prepared concentrates nothing
Reunite, D50 is 2.79 μm；
The nickelic small particle nickel cobalt manganese hydroxide obtained in the embodiment of the present invention 1 is subjected to tap density test, detection
As a result learn that prepared nickelic small particle nickel cobalt manganese hydroxide tap density is 2.24g/cm3, specific surface area 4.5976m2/
g；
Embodiment 2
It is 2.0mol/L's that the dissolving of nickel sulfate, cobaltous sulfate and manganese sulfate water is made into tri- kinds of total ion concentrations of Ni, Co, Mn
Sulfate solution, wherein nickel cobalt manganese ratio are Ni:Co:Mn=0.88:0.09:0.03；Preparation naoh concentration is 6mol/
L is the second mixed solution；It is that 12mol/L is the 3rd mixed solution to prepare ammonia concn；
150L deionized water is added in 200L reactor, is passed through sodium hydroxide solution and ammoniacal liquor, being configured to pH is
12.5th, the mother liquor that ammonia value is 9g/L, temperature is 50 DEG C.It is 700r/min by reactor adjustment of rotational speed, stirring is opened, to reactor
In be passed through nitrogen and carry out atmosphere protection, and be continually fed into nitrogen in whole course of reaction；
Prepare three kinds of solution are passed through reactor by the way that the peristaltic pump of delicate metering is simultaneously continual, carried out brilliant
Karyomorphism is 12.1~12.2 into growth response, control system pH value, and ammonia value is 10~11g/L, reaction time 10h；Charging is anti-
After a period of time, when the feed liquid being discarded in beaker can precipitate completely, pH should be gradually decreased to 12.1 or so；
Continue reaction and during raw meal particle size D50=1.3~1.5 μm, start to extract 1/4 feed liquid out from reactor top into kettle,
Supernatant is outwelled after to be precipitated, material is refunded into reactor again, took same method every two hours afterwards, is introduced with this new
Crystal seed, system solid content increase in kettle, granularity increasess slowly, while can avoid artificially playing ball；When particle size growth is to 2.0 μm,
By adjustment of rotational speed to 900r/min, system pH is 12.0~12.1, and ammonia value is adjusted to 11~11.5g/L, continues reaction to granularity
D50 stops charging when reaching 2.5 μm or so, continues to stir 1h blowings washing drying and processing；
By separation of solid and liquid after the slurry obtained after co-precipitation ageing 1h, it is 60 DEG C of volumes that cake shape solid is put into temperature
In 1m3 washing kettle, while the caustic soda that concentration is 10mol/L is added, volume ratio is alkali:Water=1:70, centrifuged after washing, in
20h is dried under the conditions of 130 DEG C reach requirement to moisture in air dry oven；
The nickelic small particle nickel cobalt manganese hydroxide obtained in the embodiment of the present invention 2 is scanned Electronic Speculum detection, detection
It is as a result as shown in Figure 3, it is known that, the nickelic small particle nickel cobalt manganese hydroxide sphericity that the embodiment of the present invention 2 is prepared is preferable,
Even particle size distribution, and soilless sticking；
The nickelic small particle nickel cobalt manganese hydroxide obtained in the embodiment of the present invention 2 is subjected to testing graininess, testing result
As shown in Figure 4, it is known that, the nickelic small particle nickel cobalt manganese hydroxide size distribution that the embodiment of the present invention 2 is prepared concentrates nothing
Reunite, D50 is 2.82 μm；
The nickelic small particle nickel cobalt manganese hydroxide obtained in the embodiment of the present invention 2 is subjected to tap density test, detection
As a result learn that prepared nickelic small particle nickel cobalt manganese hydroxide tap density is 1.91g/cm3, specific surface area 6.4874m2/
g；
As seen from the above embodiment, the invention provides a kind of preparation method of nickelic small particle nickel cobalt manganese hydroxide,
More mother liquor exist and high ammonia concn, it is high-revolving under the conditions of, be continually fed into nickel cobalt manganese hybrid metal solution, sodium hydroxide
It is nucleated with ammoniacal liquor, nucleus high degree of dispersion is made by high-speed stirred after nucleation, into the nucleus growth stage, in early growth period, passed through
The means that a part of feed liquid goes its supernatant that sediment is refunded to reactor again are released from reactor, to increase solid content and introduce
New crystal seed, the phenomenon for causing little particle excessively to cause particle agglomeration of artificially playing ball is avoided, finally obtain even particle size distribution, nothing
Reunite and the hydroxide little particle of high D50=1.5~3 μm of good sphericity, tap density.Nickelic granule provided by the invention
Footpath monocrystalline nickel cobalt manganese hydroxide preparation method is by increasing solid content and introducing new crystal seed, in high ammonia concn and high rotating speed
Under conditions of, formation size distribution concentration is not reunited, jolt ramming is high, the nickelic little particle of good sphericity, it is not necessary to is transformed existing anti-
Kettle is answered, it is easy to operate, can expanding production.
Another aspect of the present invention additionally provides a kind of nickelic small particle nickel cobalt manganese hydrogen prepared using the technical scheme of embodiment 1
Oxide is the method that base material prepares anode material for lithium-ion batteries.Lithium source used in the positive electrode preparation is LITHIUM BATTERY hydrogen-oxygen
Change lithium；The anode material for lithium-ion batteries sintering temperature is 700~1000 DEG C, and sintering time is 24~27h；The lithium ion
Cell positive material lithiumation ratio is Li:(Ni+Co+Mn)=1.05；The electric capacity of anode material for lithium-ion batteries 0.1C, 4.3V half
Measure as 215.3mAh/g；
Fig. 5 is above-mentioned anode material for lithium-ion batteries SEM photograph.
Described above is not the limitation to invention, and the present invention is also not limited to the example above.The common skill of the art
Art personnel are in the essential scope of invention, and the variations, modifications, additions or substitutions made should also belong to protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nickelic small particle nickel cobalt manganese hydroxide, it is characterised in that comprise the following steps：
(1) it is according to formula Ni according to molar ratio needed for nickel cobalt manganese in hydroxide by nickel cobalt manganese soluble-salt1-x-yCoxMny
(OH)2, wherein 0.09≤x≤0.12,0.03≤y≤0.05, are configured to the first hybrid metal containing tri- kinds of ions of Ni, Co, Mn
Salting liquid；Prepare the second mixed solution being made up of precipitating reagent；Prepare the 3rd mixed solution being made up of complexing agent；
(2) pure water of effective volume 80% is added into reactor under agitation, it is molten to be passed through step (1) second mixing
Mother liquor is made in liquid and the 3rd mixed solution, and is continually fed into inert gas as protection；
(3) by step (1) first mixed salt solution, the second mixed solution and the 3rd mixed solution cocurrent, continue not
Disconnected is passed through in the reactor of high-speed stirred, carries out being co-precipitated instead in the presence of the second mixed solution and the 3rd mixed solution
Should；Continue to feed when granularity is to 1.3~1.5 μm, feed liquid is extracted out from reactor top, outwelled after this part feed liquid precipitation
Clear liquid, sediment is refunded into reactor again, take same method when reactor is full afterwards, new crystal seed is introduced with this, works as grain
Degree D50 stops charging when reaching 2.5~3 μm, terminates reaction；
(4) reaction product that step (3) obtains is aged successively, the slurry after ageing is subjected to alkali cleaning centrifugation, Ran Hougan
Nickelic small particle nickel cobalt manganese hydroxide is obtained after dry, crushing, sieving, iron removaling.
2. a kind of preparation method of nickelic small particle nickel cobalt manganese hydroxide as claimed in claim 1, it is characterised in that described
First mixed salt solution concentration is 1.5~2mol/L, and the second mixed solution concentration is 2~6mol/L, the described 3rd
Mixed solution concentration is 7~14mol/L.
3. a kind of preparation method of nickelic small particle nickel cobalt manganese hydroxide as claimed in claim 1, it is characterised in that described
In step (1), the complexing agent be ammoniacal liquor, disodium ethylene diamine tetraacetate, sulfosalicylic acid, in glycine any one or it is several
Kind.
4. a kind of preparation method of nickelic small particle nickel cobalt manganese hydroxide as claimed in claim 1, it is characterised in that described
In step (2), value of the 3rd mixed solution in reactor system is 8~14g/L.
5. a kind of preparation method of nickelic small particle nickel cobalt manganese hydroxide as claimed in claim 1, it is characterised in that described
In step (2), the mother liquor accounts for reactor effective volume more than 80%, and wherein pH value is 12.0~12.4, and ammonia value is 10~
12g/L, temperature are 40~65 DEG C.
6. a kind of preparation method of nickelic small particle nickel cobalt manganese hydroxide as claimed in claim 1, it is characterised in that described
In step (3), the coprecipitation reaction temperature is 40~65 DEG C, and the pH of the coprecipitation reaction is 11.0~12.6, described common
Rotating speed during precipitation reaction is 700~1200rpm.
7. a kind of preparation method of nickelic small particle nickel cobalt manganese hydroxide as claimed in claim 1, it is characterised in that described
In step (3), the volume for extracting feed liquid out from reactor top accounts for the 1/6~1/3 of reactor effective volume.
8. a kind of preparation method of nickelic small particle nickel cobalt manganese hydroxide as claimed in claim 1, it is characterised in that described
In step (4), the time of the ageing is 45~85min, and the temperature of the alkali cleaning is 50~85 DEG C, and the temperature of the drying is
100~150 DEG C.
9. a kind of nickelic small particle nickel cobalt manganese hydroxide, it is characterised in that using side described in claim 1~8 any one
Method is prepared.
A kind of 10. nickelic small particle nickel cobalt manganese hydroxide as claimed in claim 9, it is characterised in that the nickelic granule
Footpath nickel cobalt manganese hydroxide D50 is 1.5~3 μm, and size distribution is 1~10 μm, and tap density is 1.6~2.4g/cm3.
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| CN108598441A (en) * | 2018-05-29 | 2018-09-28 | 东莞理工学院 | A kind of different grain size narrow ditribution ternary precursor and preparation method thereof |
| CN108807968A (en) * | 2018-08-09 | 2018-11-13 | 中国恩菲工程技术有限公司 | Nickel-cobalt-manganese ternary persursor material and its synthetic method |
| CN109860581A (en) * | 2018-12-25 | 2019-06-07 | 河南科隆新能源股份有限公司 | A kind of preparation method of the ball-shape nickel hydroxide cobalt manganese presoma of narrow particle diameter distribution |
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| CN109950535A (en) * | 2019-03-20 | 2019-06-28 | 兰州金川新材料科技股份有限公司 | A method of filtrate secondary crystallization, which is worn, using hydroxide washing continuously synthesizes presoma |
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| 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 |
| CN110931776A (en) * | 2019-12-24 | 2020-03-27 | 中南大学 | Preparation method of nickel-cobalt-manganese ternary positive electrode material precursor with multi-level distribution of particle sizes |
| CN111547779A (en) * | 2020-05-12 | 2020-08-18 | 宁波容百新能源科技股份有限公司 | Preparation method of ternary precursor with narrow particle size distribution |
| CN112694139A (en) * | 2020-12-29 | 2021-04-23 | 福建常青新能源科技有限公司 | Preparation method of single crystal NCM ternary positive electrode material precursor |
| 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 |
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| CN108525674A (en) * | 2018-03-27 | 2018-09-14 | 上海倍绿环保科技有限公司 | Couple the cobalt manganese O composite metallic oxide catalyst and preparation method thereof of electrostatic field collaboration removal low-concentration methane gas |
| CN108598441B (en) * | 2018-05-29 | 2021-02-26 | 东莞理工学院 | Different-granularity narrow-distribution ternary precursor and preparation method thereof |
| CN108598441A (en) * | 2018-05-29 | 2018-09-28 | 东莞理工学院 | A kind of different grain size narrow ditribution ternary precursor and preparation method thereof |
| 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 |
| 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 |
| CN108807968A (en) * | 2018-08-09 | 2018-11-13 | 中国恩菲工程技术有限公司 | Nickel-cobalt-manganese ternary persursor material and its synthetic method |
| CN109860581A (en) * | 2018-12-25 | 2019-06-07 | 河南科隆新能源股份有限公司 | A kind of preparation method of the ball-shape nickel hydroxide cobalt manganese presoma of narrow particle diameter distribution |
| CN109860581B (en) * | 2018-12-25 | 2022-05-17 | 河南科隆新能源股份有限公司 | Preparation method of spherical nickel cobalt manganese hydroxide precursor with narrow particle size distribution |
| CN109888242A (en) * | 2019-03-12 | 2019-06-14 | 四川纳创时代新能源科技有限公司 | A kind of high-tap density cobalt nickel lithium manganate ternary material and preparation method thereof |
| CN109950535A (en) * | 2019-03-20 | 2019-06-28 | 兰州金川新材料科技股份有限公司 | A method of filtrate secondary crystallization, which is worn, using hydroxide washing continuously synthesizes presoma |
| CN109950535B (en) * | 2019-03-20 | 2022-04-29 | 兰州金川新材料科技股份有限公司 | Method for continuously synthesizing precursor by washing filter material with hydroxide and secondary crystallization |
| CN110931776A (en) * | 2019-12-24 | 2020-03-27 | 中南大学 | Preparation method of nickel-cobalt-manganese ternary positive electrode material precursor with multi-level distribution of particle sizes |
| 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 |
| CN111547779A (en) * | 2020-05-12 | 2020-08-18 | 宁波容百新能源科技股份有限公司 | Preparation method of ternary precursor with narrow particle size distribution |
| CN111547779B (en) * | 2020-05-12 | 2022-04-05 | 宁波容百新能源科技股份有限公司 | Preparation method of ternary precursor with narrow particle size distribution |
| CN112694139A (en) * | 2020-12-29 | 2021-04-23 | 福建常青新能源科技有限公司 | Preparation method of single crystal NCM ternary positive electrode material precursor |
| CN114804223B (en) * | 2021-01-21 | 2023-11-10 | 中国石油化工股份有限公司 | Continuous and stable preparation method of ternary precursor for lithium ion battery |
| CN114804223A (en) * | 2021-01-21 | 2022-07-29 | 中国石油化工股份有限公司 | Continuous and stable preparation method of ternary precursor for lithium ion battery |
| 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 |
| CN113800577A (en) * | 2021-09-28 | 2021-12-17 | 南通金通储能动力新材料有限公司 | Method for preparing small-particle-size ternary precursor |
| CN114645329A (en) * | 2022-03-30 | 2022-06-21 | 宁波容百新能源科技股份有限公司 | High-nickel low-cobalt fine-whisker nickel-cobalt-manganese hydroxide and preparation method thereof |
| CN115012036A (en) * | 2022-05-31 | 2022-09-06 | 宁波容百新能源科技股份有限公司 | Fine-whisker small-particle-size nickel-cobalt-manganese hydroxide and preparation method thereof |
| CN115012036B (en) * | 2022-05-31 | 2023-10-03 | 宁波容百新能源科技股份有限公司 | Fine whisker small-particle-size nickel cobalt manganese hydroxide and preparation method thereof |
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