CN110002515A - A kind of high capacity monocrystalline type tertiary cathode material preparation method - Google Patents

A kind of high capacity monocrystalline type tertiary cathode material preparation method Download PDF

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CN110002515A
CN110002515A CN201910230383.4A CN201910230383A CN110002515A CN 110002515 A CN110002515 A CN 110002515A CN 201910230383 A CN201910230383 A CN 201910230383A CN 110002515 A CN110002515 A CN 110002515A
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reaction
nickel cobalt
cobalt manganese
lithium
monocrystalline
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CN110002515B (en
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顾春芳
王梁梁
朱用
张振兴
许翔
朱涛
叶庆龄
赵亮
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Nantong Jintong Energy Storage Power New Materials Co Ltd
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    • 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
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract

A kind of high capacity monocrystalline type tertiary cathode material preparation method, step are as follows: one, prepare using coprecipitation the nickel cobalt manganese hydroxide precursor of core-shell structure, make core initial stage is passed through quantitative bicarbonate and prepares loose porous kernel by intermittent, making core terminates, loose laminar shell is prepared by significantly lowering revolving speed and improving pH, simultaneously in nucleocapsid conversion stage, dispersing agent is added, revolving speed is effectively prevent to lower the reunion caused between shell；Two, it the presoma of preparation and lithium salts is blended in high temperature under oxygen-enriched atmosphere once calcines and obtain monocrystalline tertiary cathode material.Tertiary cathode material of the present invention is prepared into battery, and lithium ion transport is high-efficient, crystals anisotropy is reduced, and battery has high capacity and good security performance.It is bad to efficiently solve the problems, such as that material capacity caused by monocrystalline ternary material lithium ion transport low efficiency plays.Monocrystalline tertiary cathode material is prepared by once sintered simultaneously, preparation flow is simple, and production cost is low.

Description

A kind of high capacity monocrystalline type tertiary cathode material preparation method
Technical field
The present invention relates to field of lithium ion battery material, and in particular to a kind of system of high capacity monocrystalline type tertiary cathode material Preparation Method.
Background technique
The explosion type development of new-energy automobile has driven the explosive growth of lithium ion battery demand, lithium battery industrial chain It is just being faced with great challenge and opportunity from top to bottom.
Requirement with new-energy automobile to course continuation mileage is higher and higher, the tertiary cathode material of nickelic low cobalt gradually at For one of the Main way of anode material for lithium-ion batteries development.Meanwhile being one to the high safety performance of new-energy automobile and extending Ancient constant pursuit, thus the single crystallization of tertiary cathode material will also become anode material for lithium-ion batteries another is main Developing direction.
Secondary ball particle made of tertiary cathode material is mainly reunited as a nanoparticle at present, battery are being filled, are being put Convergent-divergent to a certain extent, and adding with charge and discharge degree, can occur for the deintercalation positive electrode volume of lithium ion in electric process Acute and cycle-index increase, the volume change of material can also aggravate, this results in following problems: one, due to a nanoparticle There are crystal boundary between son, causes will appear crackle in charge and discharge process between crystal boundary and crystal boundary, seriously affect material electrical property Performance；Two, in the manufacturing process of battery, secondary ball particle is easily crushed, and is aggravated the interfacial reaction of material and electrolyte, is led Cause the electrical property and security performance severe exacerbation of material.
In contrast, monocrystalline type positive electrode can avoid the generation of crackle between crystal boundary, and can reduce between electrolyte Side reaction, and the cycle performance and security performance of material can be improved well.However, monocrystalline ternary material is compared to secondary variole Grain is slightly short of in capacity performance, mainly since the lithium ion transport distance of monocrystal particle is greater than a nanoparticle, and Monocrystal particle nanosizing will sacrifice the volume energy density of battery, therefore how improve the capacity of monocrystal material with very heavy The research significance wanted.Meanwhile the conventional preparation techniques of monocrystal material need higher sintering to require, cause production process it is cumbersome, High production cost, therefore equally have to be solved.
Such as: existing monocrystalline ternary material preparation mainly realizes monocrystalline ternary material by segmented sintering, addition auxiliary agent The preparation of material, and by the regulation of sintering means not only energy consumption is high, production capacity is low and cannot improve at all the lithium of monocrystalline ternary material from Sub- transmission performance.The monocrystalline tertiary cathode material of patent CN104979546A preparation, the flowers type granular precursor BET of preparation It is excessively high, be unfavorable for filling when sintering, production capacity is low, and this method is by being pre-sintered, double sintering and three times sintering obtain it is final Monocrystalline tertiary cathode material, sintering process is cumbersome, high production cost.
Therefore, above-mentioned the shortcomings of the prior art how is solved, is become as the project of the invention to be researched and solved.
Summary of the invention
The object of the present invention is to provide a kind of high capacity monocrystalline type tertiary cathode material preparation methods.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of high capacity monocrystalline type tertiary cathode material preparation method；Successively the following steps are included:
Step 1: pure water and complexing agent are added into reaction kettle as bottom liquid；And it is continually fed into inert gas, so that in reaction kettle Oxygen concentration holding≤200ppm of entire reaction system, is passed through time >=6h of the inert gas, reaction temperature control 40 ~ 60℃；
Then, it opens stirring and the salting liquid and aqueous slkali and ammonium hydroxide of addition nickel cobalt manganese starts to react into reaction kettle；
The aqueous slkali is added and maintains 11.0 ~ 12.0 with the pH for controlling reaction solution；
The ammonium hydroxide is passed through during reaction makes the ammonia density in reaction solution maintain 0.3 ~ 0.8mol/L；
The bicarbonate solution that concentration is 1 ~ 4mol/L is added every 40 ~ 120min during reaction, each additional amount accounts for The 0.1 ~ 1% of reaction solution volume ratio in reaction kettle, to prepare porous kernel, the diameter of the kernel is at 1 ~ 4 μm, specific surface Product is 10 ~ 30m2/g；
Step 2: stopping liquid feeding pause reaction after 4 ~ 10h of reaction, dispersing agent is put into reaction kettle, additional amount accounts in reaction kettle Then the 0.1 ~ 1% of reaction solution volume ratio is aged 1 ~ 2h；
Step 3: lowering 50 ~ 100rpm on the basis of the revolving speed of step 1 after ageing, then proceeding to that the nickel cobalt is added The reaction was continued for the salting liquid of manganese and the aqueous slkali and the ammonium hydroxide, is continuously added into the aqueous slkali to control reaction solution PH maintains 12.0 ~ 13.0, and being continuously added into the ammonium hydroxide makes the ammonia density in reaction solution in 0.3 ~ 1.0mol/L, and then prepares The shell of loose sheet；
Step 4: the product that step 3 is obtained is aged, washed, dried, kernel is obtained with porous and shell in loose The nickel cobalt manganese hydroxide precursor of sheet；
Step 5: by the obtained presoma of step 4 and lithium salts according to molar ratio 1:(1.0 ~ 1.2) ratio mix Close uniformly, the oxygen content > 90% of sintering system is then made under oxygen-enriched atmosphere, and at a high temperature of 600 ~ 1000 DEG C calcining 6 ~ 20h obtains monocrystalline lithium nickel cobalt manganese oxide, then obtains monocrystalline lithium nickel cobalt manganese oxide after coarse crushing, fine crushing, mistake screen out iron Finished product.
Related content in above-mentioned technical proposal is explained as follows:
1. in above scheme, the preferred ammonium hydroxide of the complexing agent in step 1, make the ammonia density of bottom liquid control 0.05 ~ 1.0mol/L。
2. in above scheme, the inert gas in step 1 as protective gas, including nitrogen or argon gas or helium, Gas flow is controlled in 2 ~ 6m3/h。
3. in above scheme, the bicarbonate in the bicarbonate solution in step 1 is ammonium hydrogencarbonate, bicarbonate At least one of potassium, sodium bicarbonate, calcium bicarbonate and magnesium bicarbonate.
4. in above scheme, the salting liquid of the nickel cobalt manganese in step 1 and step 3 is sulfate, the nitre of nickel cobalt manganese At least one of hydrochlorate and chlorate, the concentration of salting liquid are 2 ~ 4mol/L；
The concentration of the aqueous slkali of step 1 and step 3 is 20 ~ 50%, and the concentration of the ammonium hydroxide is 2 ~ 5mol/L.
5. in above scheme, the dispersing agent in step 2 is polyethylene glycol, sodium pyrophosphate, potassium citrate and silicic acid At least one of sodium.
6. in above scheme, the total reaction time of step 1 to three is 40 ~ 100h.
7. in above scheme, the nickel cobalt manganese hydroxide general formula that step 4 obtains is NiXCoYMnZ(OH)2, wherein 0.3≤X≤0.8, X+Y+Z=1.
8. in above scheme, the speed of agitator in step 1 is 150 ~ 300rpm, the speed of agitator in step 3 is 50 ~ 200rpm。
9. in above scheme, the lithium salts in step 5 is lithium carbonate or lithium nitrate or lithium hydroxide.
The working principle of the invention and advantage are as follows:
One, the present invention uses the presoma of core-shell structure, and kernel is loose porous, can increase the infiltration and storage of electrolyte, thus Be conducive to the transmission of lithium ion, improve lithium ion conduction, improve the high rate performance of monocrystal material.It was prepared for before this loose porous Kernel manufactures hole by addition bicarbonate solution, after kernel grows to certain size, stops that bicarbonate is added, passes through It reduces revolving speed and improves pH, form the shell of loose sheet.The items for nickel cobalt manganese hydroxide its crystal structure being prepared The opposite sex is reduced, and is conducive to the radial diffusion of lithium ion, shortens lithium ion transport distance, and the capacity for improving material plays and safety Energy.Meanwhile dispersing agent is added before nucleocapsid changes, change the surface charge of material, shell during effective solution revolving speed is lowered Reunion between shell.
Two, granular precursor specific surface area prepared by the present invention is in 10 ~ 30m2Between/g, connect with conventional secondary ball particle Closely, therefore after mixed lithium loading is constant, and production capacity is higher.
Three, monocrystalline tertiary cathode material, simple production process, energy is prepared by once sintered after mixed lithium in the present invention It is low to reduce production cost.
Detailed description of the invention
Attached drawing 1 is the section SEM photograph of nickel cobalt manganese of embodiment of the present invention hydroxide；
Attached drawing 2 is 10000 times of SEM photograph of nickel cobalt manganese of embodiment of the present invention hydroxide；
Attached drawing 3 is the particle size distribution curve of nickel cobalt manganese of embodiment of the present invention hydroxide；
Attached drawing 4 is 10000 times of SEM photograph of lithium nickel cobalt manganese oxide of the embodiment of the present invention；
Attached drawing 5 is that lithium nickel cobalt manganese oxide of the embodiment of the present invention and commercially available messenger monocrystalline NCM523 tertiary cathode material assemble Curve graph (the 0.1C/0.1C of button cell first charge-discharge；3.0-4.3V).
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment: referring to shown in attached drawing 1 ~ 5, a kind of high capacity monocrystalline type tertiary cathode material preparation method；It successively include following Step:
Step 1: reaction prepares, to reaction kettle (6m3) in pure water (1500L) and complexing agent is added as bottom liquid；And it is continually fed into Inert gas so that in reaction kettle entire reaction system oxygen concentration holding≤200ppm, be passed through the time of the inert gas >=6h, reaction temperature are controlled at 40 ~ 60 DEG C, and preferably 50 DEG C；The preferred ammonium hydroxide of complexing agent controls the ammonia density of bottom liquid 0.05~1.0mol/L.Nitrogen, argon gas, helium etc. may be selected as protective gas in the inert gas, and gas flow is controlled 2 ~6m3/h。
Then, reaction starts, and opens the salting liquid and alkali for stirring and being pumped into reaction kettle by metering pump nickel cobalt manganese Solution and ammonium hydroxide.
The aqueous slkali is added and maintains 11.0 ~ 12.0 to control the pH of reaction solution, and is preferred with 11.5 ± 0.1；It should Step 1 be the core stage processed, for pH control 11.0 ~ 12.0 be because initial reaction stage be a nucleus preparation process, if PH < 11.0, will lead in system that nickel cobalt manganese ion precipitation is incomplete, prepare product nickel cobalt manganese ion ratio and occur to deviate and ion It is unevenly distributed；If pH > 12.0, makes the too fast speed of growth greater than crystal of nucleation rate, system is caused micro mist easily occur, The product sphericity of preparation is bad and the performances shortcoming such as product jolt ramming.
The aqueous slkali can select the water soluble alkalis solution such as sodium hydroxide, potassium hydroxide.
The ammonium hydroxide is passed through during reaction makes the ammonia density in reaction solution maintain 0.3 ~ 0.8mol/L, preferably 0.6mol/L；Ammonium hydroxide reaches an equilibrium relation as complexing agent and pH value, ammonia density influence whether a pattern of particle with And the formation of the loose sheet of shell.
Be preferred during reaction every 40 ~ 120min(with 60min) addition concentration be the preferred 2mol/ of 1 ~ 4mol/L( L bicarbonate solution), each additional amount account for 0.1 ~ 1% of reaction solution volume ratio in reaction kettle, to prepare porous kernel. Reaction process real-time monitoring granularity, kernel granularity (diameter) reach 1 ~ 4 μm (being preferred with 3.5 ~ 4.0 μm) stopping reaction, specific surface Product is 10 ~ 30m2/g.Bicarbonate in the bicarbonate solution is ammonium hydrogencarbonate, saleratus, sodium bicarbonate, bicarbonate At least one of calcium and magnesium bicarbonate.
Step 2: calculating since reaction, stop liquid feeding (i.e. salting liquid, the alkali of stopping addition nickel cobalt manganese after reacting 4 ~ 10h Solution and ammonium hydroxide), into reaction kettle put into dispersing agent (10kg), additional amount account for reaction solution volume ratio in reaction kettle 0.1 ~ 1%, then it is aged 1 ~ 2h；The dispersing agent is at least one of polyethylene glycol, sodium pyrophosphate, potassium citrate and sodium metasilicate. If being added without dispersing agent, the kernel prepared will reunite together after revolving speed is greatly lowered, and be unfavorable for subsequent dredge The leaf package of pine wraps up kernel.And the effect being aged is to dissolve dispersing agent preferably, and makes non-steady in system The particle continued growth of stationary state reaches stable system.
Step 3: lowering 50 ~ 100rpm on the basis of the revolving speed of step 1 after ageing, next proceeding through metering The salting liquid and the aqueous slkali of the pump addition nickel cobalt manganese and the ammonium hydroxide are continuously added into the aqueous slkali to control reaction The pH of solution maintains 12.0 ~ 13.0, and being continuously added into the ammonium hydroxide makes ammonia density in reaction solution in 0.3 ~ 1.0mol/L, into And prepare the shell of loose sheet.Reaction process real-time monitoring materials process D(50), stop reaction when reaching 5.5 ~ 6.0 μm.
The step 3 is the shell stage processed, for pH control 12.0 ~ 13.0 be because be reacted into growth phase, if The speed of growth of pH < 12.0, crystal will be greater than the nucleation rate of nucleus, with can be increasingly between the carry out primary particle of reaction Densification can not form loose sheet, therefore pH needs to control to accelerate the nucleation rate of nucleus, so that particle 12.0 or more Between it is loose；If pH > 13.0, a large amount of nucleus will form, generating a large amount of micro mists causes rate of crystalline growth limited.
Step 4: the product that step 3 is obtained carries out ageing 2h, centrifuge washing is to material neutrality, finally at 150 DEG C It is dry complete, obtain nickel cobalt manganese hydroxide precursor of the kernel with porous and shell in loose sheet；The obtained nickel Cobalt manganese hydroxide general formula is NiXCoYMnZ(OH)2, wherein 0.3≤X≤0.8, X+Y+Z=1.Time for being wherein aged, washing Mode and requirement, dry temperature and time are the standing procedure in industry, be will appreciate that by those skilled in the art, by In and be not the invention point of the case, therefore do not repeat.
It can be seen that gained nickel-cobalt-manganese ternary granular precursor sample is core-shell structure in conjunction with Fig. 1 and Fig. 2, chemical formula is Ni0.5Co0.2Mn0.3(OH)2.The core-shell structure is made of core and shell, and core is consistent with the nickel cobalt manganese molar ratio of shell, and the kernel is Porosity and looseness, interior nuclear diameter is at 1 ~ 4 μm, 10 ~ 30m of specific surface area2/g；The shell is in loose sheets shape, the vibration of the particle Real density is 1.64g/cm3, specific surface area 15.56m2/g。
Step 5: by the obtained Ni of step 40.5Co0.2Mn0.3(OH)2Nickel-cobalt-manganese ternary presoma and lithium salts are according to rubbing You are than 1:(1.0 ~ 1.2) ratio carry out uniformly mixed, then preferably 1:1.05 makes the oxygen of sintering system under oxygen-enriched atmosphere Content > 90%, and 6 ~ 20h(preferred 10h is calcined at a high temperature of 600 ~ 1000 DEG C (preferably 900 DEG C)) obtain monocrystalline lithium nickel cobalt manganese Oxide (i.e. LiNi0.5Co0.2Mn0.3O2Monocrystalline tertiary cathode material), then list is obtained after coarse crushing, fine crushing, mistake screen out iron Brilliant lithium nickel cobalt manganese oxide finished product.Wherein the lithium salts is lithium carbonate or lithium nitrate or lithium hydroxide.And coarse crushing, fine crushing and sieving It except the mode of iron and requirement are the standing procedure in industry, will appreciate that by those skilled in the art, due to being not this case Inventive point, therefore do not repeat.
Step 4: step 5 is post-processing step.
Wherein, the salting liquid of the nickel cobalt manganese in step 1 and step 3 be the sulfate of nickel cobalt manganese, nitrate and At least one of chlorate, the concentration of salting liquid are 2 ~ 4mol/L；The concentration of the aqueous slkali of step 1 and step 3 It is 20 ~ 50%, the concentration of the ammonium hydroxide is 2 ~ 5mol/L.Metallic nickel in the salting liquid of the nickel cobalt manganese, cobalt, manganese molar ratio be 5:2:3.
The total reaction time of step 1 to three is 40 ~ 100h, is preferred with 50h.
Wherein, the speed of agitator in step 1 is 150 ~ 300rpm, preferably 240rpm；Speed of agitator in step 3 is 50 ~ 200rpm, preferably 100rpm.
Wherein, the LiNi prepared by embodiment0.5Co0.2Mn0.3O2Monocrystalline tertiary cathode material and commercially available same model NCM523 monocrystalline ternary material is mixed with conductive agent, binder according to the ratio of 8:1:1 respectively, and it is mixed that a certain amount of binder is added Anode pole piece is prepared after closing uniformly, then battery cathode is assembled into button cell using lithium piece and carries out on blue electrical testing cabinet electrically It can test, the discharge capacity under different multiplying is tested under the voltage of 3.0 ~ 4.3V, specific data are shown in Table 1, it can be seen that different The high rate performance of embodiment is better than the material of commercially available same type under multiplying power.Meanwhile from fig. 5, it can be seen that commercially available same type material It is 192.5/171.6mAh/g that material, which is assembled into battery in the charge/discharge capacity of 0.1C, and head effect is 89.14%；The preparation of the present embodiment The discharge capacity for the first time that material is assembled into battery is higher, and under the voltage of 3.0 ~ 4.3V, the charge/discharge capacity of 0.1C is 194.9/ 174.3mAh/g, head effect are 89.43%, and discharge capacity improves 2.7mAh/g for the first time.
1 embodiment of table and commercially available same type NCM523 monocrystal material high rate performance compare
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art's energy The solution contents of the present invention much of that are simultaneously implemented accordingly, and it is not intended to limit the scope of the present invention.It is all spiritual according to the present invention Equivalent change or modification made by essence, should be covered by the protection scope of the present invention.

Claims (10)

1. a kind of high capacity monocrystalline type tertiary cathode material preparation method；It is characterized by:
Successively the following steps are included:
Step 1: pure water and complexing agent are added into reaction kettle as bottom liquid；And it is continually fed into inert gas, so that in reaction kettle Oxygen concentration holding≤200ppm of entire reaction system, is passed through time >=6h of the inert gas, reaction temperature control 40 ~ 60℃；
Then, it opens stirring and the salting liquid and aqueous slkali and ammonium hydroxide of addition nickel cobalt manganese starts to react into reaction kettle；
The aqueous slkali is added and maintains 11.0 ~ 12.0 with the pH for controlling reaction solution；
The ammonium hydroxide is passed through during reaction makes the ammonia density in reaction solution maintain 0.3 ~ 0.8mol/L；
The bicarbonate solution that concentration is 1 ~ 4mol/L is added every 40 ~ 120min during reaction, each additional amount accounts for The 0.1 ~ 1% of reaction solution volume ratio in reaction kettle, to prepare porous kernel, the diameter of the kernel is at 1 ~ 4 μm, specific surface Product is 10 ~ 30m2/g；
Step 2: stopping liquid feeding pause reaction after 4 ~ 10h of reaction, dispersing agent is put into reaction kettle, additional amount accounts in reaction kettle Then the 0.1 ~ 1% of reaction solution volume ratio is aged 1 ~ 2h；
Step 3: lowering 50 ~ 100rpm on the basis of the revolving speed of step 1 after ageing, then proceeding to that the nickel cobalt is added The salting liquid of manganese and the aqueous slkali and the ammonium hydroxide continue to react, and it is molten to control reaction to be continuously added into the aqueous slkali The pH of liquid maintains 12.0 ~ 13.0, and being continuously added into the ammonium hydroxide makes the ammonia density in reaction solution in 0.3 ~ 1.0mol/L, in turn Prepare the shell of loose sheet；
Step 4: the product that step 3 is obtained is aged, washed, dried, kernel is obtained with porous and shell in loose The nickel cobalt manganese hydroxide precursor of sheet；
Step 5: by the obtained presoma of step 4 and lithium salts according to molar ratio 1:(1.0 ~ 1.2) ratio mix Close uniformly, the oxygen content > 90% of sintering system is then made under oxygen-enriched atmosphere, and at a high temperature of 600 ~ 1000 DEG C calcining 6 ~ 20h obtains monocrystalline lithium nickel cobalt manganese oxide, then obtains monocrystalline lithium nickel cobalt manganese oxide after coarse crushing, fine crushing, mistake screen out iron Finished product.
2. according to the method described in claim 1, it is characterized by: the preferred ammonium hydroxide of the complexing agent in step 1, makes bottom liquid Ammonia density control in 0.05 ~ 1.0mol/L.
3. according to the method described in claim 1, it is characterized by: the inert gas in step 1 as protective gas, Including nitrogen or argon gas or helium, gas flow is controlled in 2 ~ 6m3/h。
4. according to the method described in claim 1, it is characterized by: bicarbonate in the bicarbonate solution in step 1 Salt is at least one of ammonium hydrogencarbonate, saleratus, sodium bicarbonate, calcium bicarbonate and magnesium bicarbonate.
5. according to the method described in claim 1, it is characterized by: the salting liquid of the nickel cobalt manganese in step 1 and step 3 For at least one of the sulfate, nitrate and chlorate of nickel cobalt manganese, the concentration of salting liquid is 2 ~ 4mol/L；
The concentration of the aqueous slkali of step 1 and step 3 is 20 ~ 50%, and the concentration of the ammonium hydroxide is 2 ~ 5mol/L.
6. according to the method described in claim 1, it is characterized by: the dispersing agent in step 2 is polyethylene glycol, burnt phosphorus At least one of sour sodium, potassium citrate and sodium metasilicate.
7. according to the method described in claim 1, it is characterized by: the total reaction time of step 1 to three is 40 ~ 100h.
8. according to the method described in claim 1, it is characterized by: the nickel cobalt manganese hydroxide general formula that step 4 obtains is NiXCoYMnZ(OH)2, wherein 0.3≤X≤0.8, X+Y+Z=1.
9. according to the method described in claim 1, it is characterized by: the speed of agitator in step 1 is 150 ~ 300rpm, step Speed of agitator in three is 50 ~ 200rpm.
10. according to the method described in claim 1, it is characterized by: the lithium salts in step 5 is lithium carbonate or lithium nitrate Or lithium hydroxide.
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CN110589903A (en) * 2019-07-24 2019-12-20 南通金通储能动力新材料有限公司 Large-particle nickel-cobalt-manganese hydroxide and preparation method thereof
CN111276680A (en) * 2020-02-13 2020-06-12 荆门市格林美新材料有限公司 Precursor cathode material with hollow interior and core-shell structure and preparation method thereof
CN111384382A (en) * 2020-03-25 2020-07-07 四川大学 Doping and coating dual-regulation nickel-based multi-element positive electrode material and preparation method thereof
CN112047399A (en) * 2020-09-07 2020-12-08 厦门厦钨新能源材料股份有限公司 Precursor with reticular structure, composite oxide powder, preparation method and application thereof
CN112174227A (en) * 2020-09-30 2021-01-05 厦门厦钨新能源材料股份有限公司 Single crystal material precursor and composite oxide powder, and preparation method and application thereof
CN112531155A (en) * 2019-09-17 2021-03-19 湖南杉杉新能源有限公司 Preparation method of positive electrode material precursor and preparation method of positive electrode material
CN113060777A (en) * 2021-04-01 2021-07-02 南通瑞翔新材料有限公司 Preparation method of high-compaction ternary single crystal material
CN113415830A (en) * 2021-08-24 2021-09-21 金驰能源材料有限公司 Preparation method of lithium ion battery anode material precursor
CN113921789A (en) * 2021-10-08 2022-01-11 合肥国轩高科动力能源有限公司 Preparation method of carbon quantum dot modified NCM ternary cathode material and prepared NCM ternary cathode material
CN114408987A (en) * 2022-03-30 2022-04-29 宜宾锂宝新材料有限公司 Nickel-cobalt-manganese precursor, ternary cathode material and preparation method thereof
CN114744188A (en) * 2022-06-13 2022-07-12 河南科隆新能源股份有限公司 Lithium ion battery anode material with non-hollow porous structure and preparation method and application thereof
CN114804229A (en) * 2022-04-24 2022-07-29 南通金通储能动力新材料有限公司 High-nickel ternary precursor and preparation method thereof
CN115353153A (en) * 2022-07-29 2022-11-18 宁夏中色金辉新能源有限公司 High-specific-surface-area nickel-cobalt-manganese ternary precursor and preparation method thereof
CN115477332A (en) * 2022-09-21 2022-12-16 广东佳纳能源科技有限公司 Nickel-manganese binary precursor and preparation method thereof, nickel-manganese positive electrode material and battery
CN115710024A (en) * 2022-10-24 2023-02-24 天津巴莫科技有限责任公司 Core-shell structure precursor and preparation method and application thereof
WO2023040358A1 (en) * 2021-09-18 2023-03-23 宁德时代新能源科技股份有限公司 Ternary precursor and preparation method therefor, ternary positive electrode material, and electric device
CN116462243A (en) * 2023-06-19 2023-07-21 宜宾光原锂电材料有限公司 Battery, ternary positive electrode material thereof, precursor thereof and preparation method

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CN110589903A (en) * 2019-07-24 2019-12-20 南通金通储能动力新材料有限公司 Large-particle nickel-cobalt-manganese hydroxide and preparation method thereof
CN112531155A (en) * 2019-09-17 2021-03-19 湖南杉杉新能源有限公司 Preparation method of positive electrode material precursor and preparation method of positive electrode material
CN111276680B (en) * 2020-02-13 2021-06-15 荆门市格林美新材料有限公司 Precursor cathode material with hollow interior and core-shell structure and preparation method thereof
CN111276680A (en) * 2020-02-13 2020-06-12 荆门市格林美新材料有限公司 Precursor cathode material with hollow interior and core-shell structure and preparation method thereof
CN111384382A (en) * 2020-03-25 2020-07-07 四川大学 Doping and coating dual-regulation nickel-based multi-element positive electrode material and preparation method thereof
CN111384382B (en) * 2020-03-25 2021-07-13 四川大学 Doping and coating dual-regulation nickel-based multi-element positive electrode material and preparation method thereof
CN112047399A (en) * 2020-09-07 2020-12-08 厦门厦钨新能源材料股份有限公司 Precursor with reticular structure, composite oxide powder, preparation method and application thereof
CN112174227A (en) * 2020-09-30 2021-01-05 厦门厦钨新能源材料股份有限公司 Single crystal material precursor and composite oxide powder, and preparation method and application thereof
CN112174227B (en) * 2020-09-30 2022-05-24 厦门厦钨新能源材料股份有限公司 Single crystal material precursor and composite oxide powder, and preparation method and application thereof
CN113060777A (en) * 2021-04-01 2021-07-02 南通瑞翔新材料有限公司 Preparation method of high-compaction ternary single crystal material
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CN113415830A (en) * 2021-08-24 2021-09-21 金驰能源材料有限公司 Preparation method of lithium ion battery anode material precursor
CN113415830B (en) * 2021-08-24 2021-11-05 金驰能源材料有限公司 Preparation method of lithium ion battery anode material precursor
WO2023040358A1 (en) * 2021-09-18 2023-03-23 宁德时代新能源科技股份有限公司 Ternary precursor and preparation method therefor, ternary positive electrode material, and electric device
CN113921789B (en) * 2021-10-08 2022-12-09 合肥国轩高科动力能源有限公司 Preparation method of carbon quantum dot modified NCM ternary cathode material and prepared NCM ternary cathode material
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CN114408987B (en) * 2022-03-30 2022-06-21 宜宾锂宝新材料有限公司 Nickel-cobalt-manganese precursor, ternary cathode material and preparation method thereof
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CN114804229B (en) * 2022-04-24 2023-11-14 南通金通储能动力新材料有限公司 High-nickel ternary precursor and preparation method thereof
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CN114744188A (en) * 2022-06-13 2022-07-12 河南科隆新能源股份有限公司 Lithium ion battery anode material with non-hollow porous structure and preparation method and application thereof
CN115353153A (en) * 2022-07-29 2022-11-18 宁夏中色金辉新能源有限公司 High-specific-surface-area nickel-cobalt-manganese ternary precursor and preparation method thereof
CN115477332A (en) * 2022-09-21 2022-12-16 广东佳纳能源科技有限公司 Nickel-manganese binary precursor and preparation method thereof, nickel-manganese positive electrode material and battery
CN115477332B (en) * 2022-09-21 2024-04-30 广东佳纳能源科技有限公司 Nickel-manganese binary precursor, preparation method thereof, nickel-manganese positive electrode material and battery
CN115710024A (en) * 2022-10-24 2023-02-24 天津巴莫科技有限责任公司 Core-shell structure precursor and preparation method and application thereof
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