CN105161715A - Lithium nickel cobalt manganese oxide positive electrode precursor and preparation method thereof as well as lithium nickel cobalt manganese oxide positive electrode material and preparation method thereof - Google Patents
Lithium nickel cobalt manganese oxide positive electrode precursor and preparation method thereof as well as lithium nickel cobalt manganese oxide positive electrode material and preparation method thereof Download PDFInfo
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- CN105161715A CN105161715A CN201510686512.2A CN201510686512A CN105161715A CN 105161715 A CN105161715 A CN 105161715A CN 201510686512 A CN201510686512 A CN 201510686512A CN 105161715 A CN105161715 A CN 105161715A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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 lithium nickel cobalt manganese oxide positive electrode precursor, the molecular formula of which is Ni(0.43)Mn(0.3)Co(0.27)(OH)2. The invention also discloses a preparation method of the lithium nickel cobalt manganese oxide positive electrode precursor. The preparation method comprises the following steps: step (1), preparing nickel salt, cobalt salt and manganese salt into a salt mixture solution A according to the mole ratio of Ni to Mn to Co being 0.43 to 0.30 to 0.27, wherein the total concentration of positive ions of the salt mixture solution is 1.5-2.0mol/L; step (2), preparing a mixed base solution B, wherein the concentration of sodium hydroxide is 3.0-4.0mol/L and the concentration of ammonia water is 0.45-1.20mol/L; step (3), adding an ammonia water which is taken as a base solution into a reaction kettle, then pumping the solutions A and B from the bottom of the reaction kettle through a peristaltic pump, and carrying out stirring reaction; step (4), carrying out constant-temperature ageing on overflowing reaction liquid; step (5) carrying out filter pressing on the materials, washing the materials subjected to filter pressing, and drying to obtain the precursor. According to the invention, Li(1+x)Ni(0.43)Mn(0.30)Co(0.27)O2 prepared by Ni(0.43)Mn(0.3)Co(0.27)(OH)2 is taken as the lithium ion positive electrode material, has higher energy density and excellent long cycle performance compared with Li(1+x)Ni(1/3)Co(1/3)O2, and has the equivalent energy density but has the advantages that the cycle life is greatly prolonged compared with Li(1+x)Ni(0.50)Mn(0.30)Co(0.20)O2.
Description
Technical field
The present invention relates to a kind of nickel-cobalt lithium manganate cathode material presoma and preparation method thereof, the invention still further relates to nickel-cobalt lithium manganate cathode material and preparation method thereof.Belong to technical field of lithium-ion battery.
Background technology
Lithium ion battery have energy density high, have extended cycle life, lightweight, memory-less effect, the advantage such as pollution-free, be widely used in the fields such as 3C consumer electronics battery core, electric tool, electric automobile and energy storage.Along with the fast development of smart mobile phone, panel computer, electric automobile, the requirement of people to lithium ion battery is more and more higher, not only require that lithium ion battery has high-energy-density in electric automobile field especially, and possess outstanding cycle performance and safety and stability performance.
In recent years; along with the continuous reinforcement of environmental protection consciousness; haze causes disaster; air contaminant treatment is extremely urgent; advocate Green Travel; development new-energy automobile is one of effective way realizing energy-saving and emission-reduction general objective, so national policy encourages the development of new-energy automobile very much, has put into effect tens of central and local governments' new-energy automobile relevant policies since at the beginning of 2014.Product situation from domestic major impetus lithium battery enterprise: BYD adheres to ferric phosphate lithium cell route all the time, battery cell energy density reaches more than 130Wh/kg, basic close to theoretical limit, company is also at the lithium ferric manganese phosphate material new type power lithium battery that active development energy density is higher; Tianjin power god product based on ferric phosphate lithium cell, at present at small lot batch manufacture ternary material dynamic lithium battery.
Present stage, the cell energy density of LiFePO4 technology was only 110-120Wh/kg, and after being combined into power brick, battery system energy density is less than 90Wh/kg.The energy density of ternary lithium battery is compared LiFePO4 and will be exceeded about 50%, general at 150-180Wh/kg at present.Under ferric phosphate lithium cell theoretical energy density limited circumstances, be lifting vehicle course continuation mileage, the ternary material dynamic lithium battery of high-energy-density is generally had an optimistic view of by market.The technology of electric automobile also development and progressive among, ferric phosphate lithium cell is subject to heat and holds in both hands because of the feature that the life-span is long, fail safe is good before, but solves safety problem along with ternary lithium battery, and ferric phosphate lithium cell is replaced unavoidably.
Cobalt nickel lithium manganate ternary material, with the feature of its high power capacity, high-energy-density, meets the requirement of more and more higher energy density, is subject to more favor.The presoma of the nickel-cobalt lithium manganate cathode material of current commercial type is mainly Ni
1/3mn
1/3co
1/3(OH)
2and Ni
0.5mn
0.3co
0.2(OH)
2this bi-material has superiority in performance.But meet more and more higher energy density to require and cycle life, we also need constantly to research and develop the positive electrode made new advances.
Summary of the invention
For existing problem, the object of the present invention is to provide a kind of new nickel-cobalt lithium manganate cathode material presoma.Another object of the present invention is to provide the preparation method of this kind of presoma, and the third object of the present invention is to provide a kind of nickel-cobalt lithium manganate cathode material and its preparation method.
In order to realize above-mentioned first object, technical scheme of the present invention is such: a kind of nickel-cobalt lithium manganate cathode material presoma, is characterized in that: molecular formula is: Ni
0.43mn
0.3co
0.27(OH)
2.
The second object of the present invention is achieved in that the preparation method of nickel-cobalt lithium manganate cathode material presoma described in a kind of claim 1, it is characterized in that: prepare in accordance with the following steps:
Nickel salt, cobalt salt, manganese salt are the mixing salt solution A that 0.43:0.30:0.27 is mixed with that cation total concentration is 1.5 ~ 2.0mol/L by Ni:Mn:Co mol ratio by step (1);
Step (2), preparation NaOH and ammonia concn are respectively the mixed ammonium/alkali solutions B of 3.0 ~ 4.0mol/L and 0.45 ~ 1.20mol/L;
Step (3), the ammonia spirit of 0.15-0.3mol/L is added as end liquid in the reactor of upper end carry potential overflow mouth, then A, B two kinds of solution are pumped into bottom reactor by peristaltic pump, stirring reaction, in course of reaction, control pH is 11.0 ~ 11.20, reaction temperature 50 ~ 65 DEG C, and the completely rear reactant liquor of still overflows in aging reactor from overfall, the flow velocity pumping into A, B two kinds of solution should be controlled, make the time of the overflow first of the reactant liquor in reactor be greater than 16h;
Step (4), the reactant liquor overflowed is constant temperature ageing 16 ~ 24h at 60 ~ 80 DEG C;
Step (5), material obtains homogeneous Ni by press filtration, washing, drying
0.43mn
0.30co
0.27(OH)
2presoma.
Preparation method of the present invention, adds ammonia spirit in advance as end liquid in reactor, is conducive to primary particle growth, and make particle crystal formation, appearance better, chemical property is good.Be greater than 16h by the flow control reaction time of the A that adds, B solution, ensure primary particle growth, be conducive to the formation of offspring, the primary particle crystal formation of formation is better simultaneously.
In such scheme: in step (1), nickel salt is nickelous sulfate, and cobalt salt is cobaltous sulfate, and manganese salt is manganese sulfate.Sulfate is comparatively common, and cost is low.
In such scheme: in step (3), the addition of ammonia spirit is 1/3rd of reactor volume.Such one side is conducive to the growth of primary particle, on the other hand can not be too much because of end liquid in reactor, thus causes having overflowing liquid to flow out very soon.
In such scheme: in step (3), the total flow that A, B solution pump into reactor is 2-2.5L/h.
The third object of the present invention is achieved in that a kind of nickel-cobalt lithium manganate cathode material, it is characterized in that: molecular formula is Li
1+xni
0.43mn
0.3co
0.27o
2.
The preparation method of described nickel-cobalt lithium manganate cathode material is: Ni claim 2 prepared
0.43mn
0.3co
0.27(OH)
2presoma is heat treatment 5-7h at 500-550 DEG C, then mixes with lithium salts, sinters 10-16h and obtain at 900-980 DEG C.
In such scheme, described Ni
0.43mn
0.3co
0.27(OH)
2the mol ratio of presoma and lithium ion is 1:1.09.
In such scheme: described lithium salts is one or more in lithium carbonate, lithium nitrate, lithium acetate, lithium chloride.
The invention has the beneficial effects as follows: compared with prior art:
(1) with Ni obtained by the present invention
0.43mn
0.30co
0.27(OH)
2the Li of precursor power
1+xni
0.43mn
0.30co
0.27o
2as lithium ion anode material, relative Li
1+xni
1/3mn
1/3co
1/3o
2there is higher volume energy density, and have both the long circulating performance of its excellence; Compare Li
1+xni
0.50mn
0.30co
0.20o
2volume energy density is suitable, but significantly improves its cycle life.
(2) with Ni obtained by the present invention
0.43mn
0.30co
0.27(OH)
2the Li of precursor power
1+xni
0.43mn
0.30co
0.27o
2as lithium ion anode material, suitably reduce Ni amount, be conducive to reducing the mixing of Li/Ni ion, reduce and cause the destruction to material structure because of Ni too high levels, promote the Stability Analysis of Structures performance of material, significantly promote material cycle life in battery core.
(3) Ni obtained by the present invention
0.43mn
0.30co
0.27(OH)
2presoma particle size distribution is concentrated, (D
90-D
10)/D
50< 0.8, D50=6 ~ 8 μm, a whisker particle diameter 500 ~ 1000nm, keeps original particle diameter substantially by sinter after in-situ sintering, lattice perfection, is conducive to promoting material circulation performance.
Accompanying drawing explanation
Fig. 1 is that example 1 prepares precursor of lithium ionic cell positive material Ni
0.43mn
0.30co
0.27(OH)
2sEM figure.
Fig. 2 is that example 1 prepares anode material for lithium-ion batteries Li
1+xni
0.43mn
0.30co
0.27o
2sEM figure.
Fig. 3 is that example 1 prepares anode material for lithium-ion batteries Li
1+xni
0.43mn
0.30co
0.27o
2button battery charging and discharging curve chart.
Fig. 4 is that example 1 prepares anode material for lithium-ion batteries Li
1+xni
0.43mn
0.30co
0.27o
2with commercially available Li
1+xni
1/3mn
1/3co
1/3o
2and Li
1+xni
0.50mn
0.30co
0.20o
2circulation comparison diagram.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described:
Example 1
(1) be that 0.43:0.30:0.27 is mixed with the sulfate liquor A mixed by nickelous sulfate, cobaltous sulfate, manganese sulfate by Ni:Mn:Co mol ratio, solution metal total ion concentration 1.5mol/L after mixing.
The concentration preparing NaOH and ammoniacal liquor is again respectively the mixed ammonium/alkali solutions B of 3.0mol/L, 0.45mol/L.In reactor, preparation accounts for the 0.15mol/L ammonia spirit of overall reaction still 1/3 volume as end liquid.Pump into reactor in from the bottom of reactor with B solution by the solution A mixed together with peristaltic pump, in course of reaction, temperature controls at 50 ~ 65 DEG C, and pH value 11.0 ~ 11.20 carries out coprecipitation reaction under stirring condition.The upper end oral area of reactor is provided with overfall, and the completely rear solution of reactor overflows in aging reactor from overfall.Control A, B two kinds of solution pump into the flow velocity in reactor, make the time having liquid to overflow from the overfall of reactor for the first time be greater than 16h.Generally, the total flow that our control A, B solution pump into reactor is 2-2.5L/h, when pumping into, in order to control pH, can regulate the flow velocity of A, B solution.
The reactant liquor overflowed is constant temperature ageing 24h at 60 DEG C, should stir during ageing.Ageing terminates to carry out press filtration to slurry afterwards, and then reaches Separation of Solid and Liquid, solid material through washing, dry after obtain nickel cobalt manganese hydroxide precursor Ni
0.43mn
0.30co
0.27(OH)
2.
(2) above-mentioned nickel cobalt manganese hydroxide powder is carried out 500 DEG C of heat treatment 6h under air conditions, obtain nickel, cobalt and manganese oxide.
(3) above-mentioned nickel, cobalt and manganese oxide and lithium carbonate are pressed nickel cobalt manganese atom sum and lithium atom number than 1:1.09 Homogeneous phase mixing, lithium atom is from lithium carbonate, and under air conditions, at 960 DEG C of calcining 12h, sinter must Li after air-flow crushing crusher machine, screening
1+xni
0.43mn
0.3co
0.27o
2powder A.
After testing, the Li for preparing of the present embodiment
1+xni
0.43mn
0.3co
0.27o
2material primary particle average grain diameter is 0.8 μm, and offspring average grain diameter is 8.5 μm, tap density 2.05g/cm
3.Be assembled into battery testing, materials processing function admirable, gram volume is 150mAh/g, and 1000 times circulation volume conservation rate is 88.0%, battery good thermal stability.
Example 2
(1) be that 0.43:0.30:0.27 is mixed with the sulfate liquor A mixed by nickelous sulfate, cobaltous sulfate, manganese sulfate by Ni:Mn:Co mol ratio, solution metal total ion concentration 2.0mol/L after mixing.
Prepare NaOH again and ammonia concn is respectively 4.0mol/L and 1.20mol/L mixed ammonium/alkali solutions B.In reactor, preparation accounts for the 0.30mol/L ammonia spirit of overall reaction still 1/3 volume as end liquid.
Pump into reactor in from the bottom of reactor with B solution by the solution A mixed together with peristaltic pump, in course of reaction, temperature controls at 50 ~ 65 DEG C, and pH value 11.0 ~ 11.20 carries out coprecipitation reaction under stirring condition.The upper end oral area of reactor is provided with overfall, and the completely rear solution of reactor overflows in aging reactor from overfall.Control AB two kinds of solution pump into the flow velocity in reactor, make the time having liquid to overflow from the overfall of reactor for the first time be greater than 16h.Generally, the total flow that our control A, B solution pump into reactor is 2-2.5L/h, when pumping into, in order to control pH, can regulate the flow velocity of AB solution.
The reactant liquor overflowed is constant temperature ageing 16h at 80 DEG C, should stir during ageing.Ageing terminates to carry out press filtration to slurry afterwards, and then reaches Separation of Solid and Liquid, solid material through washing, dry after obtain nickel cobalt manganese hydroxide precursor Ni
0.43mn
0.30co
0.27(OH)
2.
(2) above-mentioned nickel cobalt manganese hydroxide powder is carried out 500 DEG C of heat treatment 6h under air conditions, obtain nickel, cobalt and manganese oxide.
(3) above-mentioned nickel, cobalt and manganese oxide and lithium carbonate are pressed nickel cobalt manganese atom sum and lithium atom number than 1:1.09 Homogeneous phase mixing, lithium atom is from lithium carbonate, and under air conditions, at 960 DEG C of calcining 12h, sinter must Li after air-flow crushing crusher machine, screening
1+xni0.43Mn
0.3co
0.27o
2powder B.
After testing, nickel-cobalt lithium manganate material primary particle average grain diameter prepared by the present embodiment is 0.8 μm, and offspring average grain diameter is 9.8 μm, tap density 2.08g/cm
3.Be assembled into battery testing, materials processing function admirable, gram volume is 148mAh/g, and 1000 times circulation volume conservation rate is 89.0%, battery good thermal stability.
Contrast test 1
Use commercially available Ni
1/3mn
1/3co
1/3(OH)
2500 DEG C of heat treatment 6h are carried out under air conditions, obtain nickel, cobalt and manganese oxide, then with lithium carbonate press nickel cobalt manganese atom sum and lithium atom number than 1:1.09 Homogeneous phase mixing, under air conditions, carry out 960 DEG C calcining 12h, sinter through Pneumatic crushing machine gaseous broken, screening after nickle cobalt lithium manganate powder C.
Contrast test 2
Use commercially available Ni
0.50mn0.30Co
0.20(OH)
2500 DEG C of heat treatment 6h are carried out under air conditions, obtain nickel, cobalt and manganese oxide, then with lithium carbonate press nickel cobalt manganese atom sum and lithium atom number than 1:1.09 Homogeneous phase mixing, under air conditions, carry out 930 DEG C calcining 12h, sinter through Pneumatic crushing machine gaseous broken, screening after nickle cobalt lithium manganate powder D.
Button battery testing
By prepared that positive electrode A powder body material is active material 9.0g in example 1, add that 0.5gPVDF is binding agent, 0.5gSuper makes conductive agent and 20.0gNMP (1-METHYLPYRROLIDONE) is solvent, on aluminium foil, positive plate is made after mixing, be negative pole with metal lithium sheet in vacuum glove box, take Celgard2300 as barrier film, 1mol/LLiPF
6/ EC/DMC (volume ratio 1:1) is electrolyte, and be assembled into CR2032 and detain battery, charging/discharging voltage scope 3.0-4.20V, 0.1C first discharge specific capacity is 156mAh/g.Fig. 3 is anode material for lithium-ion batteries Li
1+xni
0.43mn
0.30co
0.27o
2button battery charging and discharging curve chart.
Full battery testing
The positive electrode A and contrast test material C and D powder body material of obtaining prepared in example 1 is respectively active material, by active material: PVDF (binding agent): Super (conductive agent)=95.5:2.5:2.0, with NMP (1-METHYLPYRROLIDONE) for solvent, be coated on after being mixed by mechanical agitation on aluminium foil and make positive plate, with C pole piece for negative pole, Celgard2300 is barrier film, 1mol/LLiPF6/EC/DMC (volume ratio 1:1) is electrolyte, be assembled into 063048 box hat battery, charging/discharging voltage scope 3.0-4.20V.
Fig. 4 is that example 1 prepares anode material for lithium-ion batteries Li
1+xni
0.43mn
0.30co
0.27o
2with commercially available Li
1+xni
1/3mn
1/3co
1/3o
2and Li
1+xni
0.50mn
0.30co
0.20o
2circulation comparison diagram.As can be seen from Figure 4, with the Li obtained by the present invention
1+xni
0.43mn
0.30co
0.27o
2as lithium ion anode material, relative Li
1+xni
0.50mn
0.30co
0.20o
2significantly improve its cycle life.The battery energy density that embodiment 1 obtains is 155Wh/kg, and the battery energy density that nickle cobalt lithium manganate powder C and D obtains is respectively 146Wh/kg and 160Wh/kg.
The present invention is not limited to above-mentioned specific embodiment:
As can by as described in lithium salts be changed in lithium nitrate, lithium acetate, lithium chloride one or more.
Nickel salt, cobalt salt, manganese salt can be changed into other salt beyond removing sulfate.
Ni
0.43mn
0.3co
0.27(OH)
2the heat treated temperature of presoma does other selection at 500-550 DEG C, does other selection between heat treatment time 5-7h, and sintering temperature is selected arbitrarily at 900-980 DEG C, and sintering time is selected etc. arbitrarily at 10-16h.Should be appreciated that those of ordinary skill in the art just design according to the present invention can make many modifications and variations without the need to creative work.In a word, all technical staff in the art, all should by the determined protection range of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (9)
1. a nickel-cobalt lithium manganate cathode material presoma, is characterized in that: molecular formula is: Ni
0.43mn
0.3co
0.27(OH)
2.
2. a preparation method for nickel-cobalt lithium manganate cathode material presoma described in claim 1, is characterized in that: prepare in accordance with the following steps:
Nickel salt, cobalt salt, manganese salt are the mixing salt solution A that 0.43:0.30:0.27 is mixed with that cation total concentration is 1.5 ~ 2.0mol/L by Ni:Mn:Co mol ratio by step (1);
Step (2), preparation NaOH and ammonia concn are respectively the mixed ammonium/alkali solutions B of 3.0 ~ 4.0mol/L and 0.45 ~ 1.20mol/L;
Step (3), the ammonia spirit of 0.15-0.3mol/L is added as end liquid in the reactor of upper end carry potential overflow mouth, then A, B two kinds of solution are pumped into bottom reactor by peristaltic pump, stirring reaction, in course of reaction, control pH is 11.0 ~ 11.20, reaction temperature 50 ~ 65 DEG C, and the completely rear reactant liquor of still overflows in aging reactor from overfall, the flow velocity pumping into A, B two kinds of solution should be controlled, make the time of the overflow first of the reactant liquor in reactor be greater than 16h;
Step (4), the reactant liquor overflowed is constant temperature ageing 16 ~ 24h at 60 ~ 80 DEG C;
Step (5), material obtains homogeneous Ni by press filtration, washing, drying
0.43mn
0.30co
0.27(OH)
2presoma.
3. the preparation method of nickel-cobalt lithium manganate cathode material presoma according to claim 1, it is characterized in that: in step (1), nickel salt is nickelous sulfate, and cobalt salt is cobaltous sulfate, and manganese salt is manganese sulfate.
4. the preparation method of nickel-cobalt lithium manganate cathode material presoma according to claim 2, it is characterized in that: in step (3), the addition of ammonia spirit is 1/3rd of reactor volume.
5. the preparation method of nickel-cobalt lithium manganate cathode material presoma according to any one of claim 2-4, it is characterized in that: in step (3), the total flow that A, B solution pump into reactor is 2-2.5L/h.
6. a nickel-cobalt lithium manganate cathode material, is characterized in that: molecular formula is Li
1+xni
0.43mn
0.3co
0.27o
2.
7. a preparation method for nickel-cobalt lithium manganate cathode material described in claim 6, is characterised in that: Ni claim 2 prepared
0.43mn
0.3co
0.27(OH)
2presoma is heat treatment 5-7h at 500-550 DEG C, then mixes with lithium salts, sinters 10-16h and obtain at 900-980 DEG C.
8. the preparation method of nickel-cobalt lithium manganate cathode material according to claim 7, is characterized in that: Ni
0.43mn
0.3co
0.27(OH)
2the mol ratio of presoma and lithium ion is 1:1.09.
9. the preparation method of nickel-cobalt lithium manganate cathode material according to claim 8, is characterized in that: described lithium salts is one or more in lithium carbonate, lithium nitrate, lithium acetate, lithium chloride.
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| CN106252730A (en) * | 2016-08-04 | 2016-12-21 | 陈永林 | A kind of preparation method of energy-density lithium ion battery |
| CN106241894A (en) * | 2016-07-20 | 2016-12-21 | 湘潭大学 | A kind of preparation method of nanometer spinel type nickle cobalt lithium manganate |
| CN107915263A (en) * | 2017-08-31 | 2018-04-17 | 广东佳纳能源科技有限公司 | A kind of preparation method of small particle ternary anode material precursor |
| CN107959022A (en) * | 2017-10-31 | 2018-04-24 | 华南理工大学 | A kind of solvent-thermal method prepares tertiary cathode material and preparation method thereof |
| CN109037673A (en) * | 2018-10-18 | 2018-12-18 | 珠海嘉志科技咨询有限公司 | A kind of environmentally friendly, efficiently preparation nickel-cobalt-manganternary ternary anode material presoma method |
| CN109160545A (en) * | 2018-07-24 | 2019-01-08 | 格林美股份有限公司 | A kind of precursor of nickel-cobalt-lithium-manganese-oxide synthesizer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1964103A (en) * | 2005-11-09 | 2007-05-16 | 比亚迪股份有限公司 | A method to manufacture precursor of nickel-cobalt-lithium-manganese-oxide of lithium ion cell anode material |
| CN102092798A (en) * | 2010-12-01 | 2011-06-15 | 兰州金川新材料科技股份有限公司 | Method for continuously synthesizing precursor of lithium ion battery positive material |
| CN102569781A (en) * | 2012-03-27 | 2012-07-11 | 天津理工大学 | High-voltage lithium ion battery cathode material and preparation method thereof |
| CN103762355A (en) * | 2014-01-26 | 2014-04-30 | 中南大学 | Method for synthesizing lithium, nickel, manganese and cobalt composite oxide powder material |
| CN103950997A (en) * | 2014-02-13 | 2014-07-30 | 宁波金和新材料股份有限公司 | High voltage positive electrode material precursor, lithium battery positive electrode material prepared from high voltage positive electrode material precursor, and preparation methods of high voltage positive electrode material precursor and lithium battery positive electrode material |
-
2015
- 2015-10-21 CN CN201510686512.2A patent/CN105161715A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1964103A (en) * | 2005-11-09 | 2007-05-16 | 比亚迪股份有限公司 | A method to manufacture precursor of nickel-cobalt-lithium-manganese-oxide of lithium ion cell anode material |
| CN102092798A (en) * | 2010-12-01 | 2011-06-15 | 兰州金川新材料科技股份有限公司 | Method for continuously synthesizing precursor of lithium ion battery positive material |
| CN102569781A (en) * | 2012-03-27 | 2012-07-11 | 天津理工大学 | High-voltage lithium ion battery cathode material and preparation method thereof |
| CN103762355A (en) * | 2014-01-26 | 2014-04-30 | 中南大学 | Method for synthesizing lithium, nickel, manganese and cobalt composite oxide powder material |
| CN103950997A (en) * | 2014-02-13 | 2014-07-30 | 宁波金和新材料股份有限公司 | High voltage positive electrode material precursor, lithium battery positive electrode material prepared from high voltage positive electrode material precursor, and preparation methods of high voltage positive electrode material precursor and lithium battery positive electrode material |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106241894A (en) * | 2016-07-20 | 2016-12-21 | 湘潭大学 | A kind of preparation method of nanometer spinel type nickle cobalt lithium manganate |
| CN106252730A (en) * | 2016-08-04 | 2016-12-21 | 陈永林 | A kind of preparation method of energy-density lithium ion battery |
| CN107915263A (en) * | 2017-08-31 | 2018-04-17 | 广东佳纳能源科技有限公司 | A kind of preparation method of small particle ternary anode material precursor |
| CN107915263B (en) * | 2017-08-31 | 2020-01-14 | 广东佳纳能源科技有限公司 | Preparation method of small-particle-size ternary cathode material precursor |
| CN107959022A (en) * | 2017-10-31 | 2018-04-24 | 华南理工大学 | A kind of solvent-thermal method prepares tertiary cathode material and preparation method thereof |
| CN109160545A (en) * | 2018-07-24 | 2019-01-08 | 格林美股份有限公司 | A kind of precursor of nickel-cobalt-lithium-manganese-oxide synthesizer |
| CN109160545B (en) * | 2018-07-24 | 2021-01-05 | 格林美股份有限公司 | Nickel cobalt lithium manganate precursor synthesizer |
| CN109037673A (en) * | 2018-10-18 | 2018-12-18 | 珠海嘉志科技咨询有限公司 | A kind of environmentally friendly, efficiently preparation nickel-cobalt-manganternary ternary anode material presoma method |
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