CN103746111A - Monocrystal Ni-Co-Mn battery positive pole material and preparing method thereof - Google Patents

Monocrystal Ni-Co-Mn battery positive pole material and preparing method thereof Download PDF

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CN103746111A
CN103746111A CN201410042232.3A CN201410042232A CN103746111A CN 103746111 A CN103746111 A CN 103746111A CN 201410042232 A CN201410042232 A CN 201410042232A CN 103746111 A CN103746111 A CN 103746111A
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positive electrode
nickel cobalt
monocrystal
cobalt manganese
cell positive
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CN103746111B (en
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梁广川
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Heze Jianshu Intelligent Technology Co., Ltd
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TIANJIN XIANZHONG SCIENCE & TECHNOLOGY Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • 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
    • 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
    • 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

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  • Inorganic Chemistry (AREA)
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Abstract

The invention relates to a monocrystal Ni-Co-Mn battery positive pole material and a preparing method thereof and belongs to the technical field of energy materials. The chemical formula of the monocrystal Ni-Co-Mg battery positive pole material is LiNixCoyMn1-x-yO2, wherein 0.3 < x < 0.8, and 0.1 < y < 0.4. The preparing method of the monocrystal Ni-Co-Mn battery positive pole material comprises the following steps: (1) preparation of seed crystals: adding amino water of which the concentration is 0.5-1.5 mol/L to a carbonate or acetate solution of Ni-Co-Mn; then adding a 1-4 mol/L of LiOH solution; standing, filtering and drying; mixing with LiOH.H2O and forging; (2) preparation of a precursor: adding amino water of which the concentration is 0.5-1.5 mol/L to a carbonate or acetate solution of Ni-Co-Mn, and adding a 1-4 mol/L of LiOH solution; standing, ageing and vacuum drying; (3) preparation of the monocrystal Ni-Co-Mn battery positive pole material through sintering: mixing the precursor with a lithium source and the seed crystal according to a stoichiometric ratio, compacting into a block form, sintering, cooling and pulverizing. The monocrystal Ni-Co-Mn battery positive pole material and the preparing method thereof have the advantages of simplicity in operation, easiness in the control of grain size, narrow grain size distribution range, high product purity, excellent circulating performance, excellent safety performance and the like.

Description

A kind of monocrystal nickel cobalt manganese cell positive electrode and preparation method thereof
Technical field
The invention belongs to energy and material technical field, particularly relate to a kind of monocrystal nickel cobalt manganese cell positive electrode and preparation method thereof.
Background technology
At present, the positive electrode of nickel-cobalt-manganese ternary composite oxide powder is mainly used in the positive electrode of lithium ion battery, has the incomparable advantage of other positive electrodes.Cobalt acid lithium is due to expensive, poor safety performance, and toxicity is large and be not suitable as power lithium-ion battery positive electrode.LiFePO4 has cheap, and security performance is good, advantages of environment protection, but its unit volume energy density is low.It is low that LiMn2O4 has cost, and security performance is better, the advantage that environmental pollution is few, but its cycle performance is poor, and unit volume energy density is low.Comparatively speaking, nickel-cobalt-manganese ternary positive electrode has that theoretical specific capacity is higher (can reach 275mAg -1), actual specific capacity can reach 140-180mAg -1the advantages such as cycle performance is good, and tap density is higher, good thermal stability, can overcome the part shortcoming of other materials.Therefore, nickel-cobalt-manganese ternary positive electrode becomes one of preferred material of anode material for lithium-ion batteries.
The industrial nickel-cobalt-manganese ternary positive electrode LiNi for preparing xco ymn 1-x-yo 2method mainly contain high temperature solid-state method and liquid phase method.High temperature solid-state method advantage be simple and easy to control, be convenient to realize industrialization operation; But its shortcoming is that ion diffusion velocity is slow, and batch mixing is inhomogeneous, there is bigger difference at aspects such as forming structure and particle size distribution in the product of preparation, causes the chemical property of material wayward.The application of liquid phase method in industry is mainly coprecipitation.Coprecipitation method can make material reach molecule or atom level stoichiometric proportion is mixed, thereby can prepare high-quality battery material with lower production cost, is to prepare at present positive electrode to adopt method the most widely.The method can be easy by controlling deposition condition the granularity of control product, but the bulky grain material of preparation is all often spherical microcrystal grain, is not single crystal grain.Due to the particle heterogeneity that a plurality of particles are combined into, particle size distribution is wider, and in being prepared into the process of battery pole piece, many granules also can come off from large particle surface, and the stability of product is poor.In the situation that particularly battery pole piece compacted density is larger, easily spherical microcrystal grain is crushed, cause degradation technical problem under battery quality.
Summary of the invention
The present invention provides a kind of monocrystal nickel cobalt manganese cell positive electrode and preparation method thereof for solving the technical problem existing in known technology.From the angle of materialogy, consider, using monocrystal material is optimal selection.Monocrystal has higher mechanical strength, can effectively improve the pressure of pole piece, and pole piece densification is improved.While monocrystal perfect crystalline, gram volume increases.In order to obtain monocrystal material, can use crystal seed as initial nucleator.In synthetic reaction and calcination reaction, adding crystal seed, is the technology that is applied to Inorganic Non-metallic Materials preparation field, adopts the method that adds crystal seed method to prepare anode material for lithium-ion batteries to apply the novelty that possesses skills.
One of object of the present invention is to provide that a kind of to have product purity high, and stability is high, and particle size distribution is narrow, the monocrystal nickel cobalt manganese cell positive electrode of good cycle performance and the higher features such as security performance.
The technical scheme that monocrystal nickel cobalt manganese cell positive electrode of the present invention is taked is:
A monocrystal nickel cobalt manganese cell positive electrode, is characterized in: the chemical formula of monocrystal nickel cobalt manganese cell positive electrode is LiNi xco ymn 1-x-yo 2, wherein, the span of x is 0.3<x<0.8, the span of y is 0.1<y<0.4.
Two of object of the present invention is to provide a kind of simple to operate, and granular size is easily controlled, and calcining heat is low, energy savings, and product purity is high, particle size distribution, the preparation method of the monocrystal nickel cobalt manganese cell positive electrode of the feature such as function admirable is narrow.
The technical scheme that monocrystal nickel cobalt manganese cell positive electrode of the present invention and preparation method thereof is taked is:
A preparation method for monocrystal nickel cobalt manganese cell positive electrode, is characterized in: the preparation process of monocrystal nickel cobalt manganese cell positive electrode comprises the following steps:
1. prepare crystal seed
The carbonate of nickel cobalt manganese or acetate are mixed with to the aqueous solution of concentration 1-4mol/L; Under nitrogen atmosphere and 40-80 ℃ of temperature, stirring condition, to the ammoniacal liquor that adds concentration 0.5-1.5mol/L in metal salt solution, ammoniacal liquor (NH 3h 2o) molal quantity be transition metal salt molal quantity 0.2-3 doubly, the ammoniacal liquor joining day is 0.5-2h; Then the LiOH solution that adds 1-4mol/L, until pH value reaches 9-11; Standing 12-20h; 80-140 ℃ of vacuumize 2-10 hour after sediment filters; With LiOHH 2o is blended at 450-550 ℃ and calcines 4-10h, obtains required crystal seed;
2. prepare presoma
The carbonate of nickel cobalt manganese or acetate are mixed with to the aqueous solution of concentration 2-4mol/L; Under nitrogen atmosphere and 40-80 ℃, stirring condition, to the ammoniacal liquor that adds concentration 0.5-1.5mol/L in metal salt solution, the addition of ammoniacal liquor is ammoniacal liquor (NH 3h 2o) molal quantity be transition metal salt molal quantity 0.2-3 doubly, after reaction 0.5-2h, to the LiOH solution that adds 1-4mol/L in solution, until pH value reaches 9-11; Then standing 12-20h; After ageing, 80-140 ℃ of vacuumize 2-10 hour, obtains described presoma;
3. sintering makes monocrystal nickel cobalt manganese cell positive electrode
After the crystal seed of the presoma of gained and the lithium source of stoichiometric proportion, 0.1-5% weight ratio mixes after dry, with forcing press, be compacted into bulk, at 850-950 ℃ of temperature lower calcination 14-24h, cooling, pulverize, obtain monocrystal nickel cobalt manganese cell positive electrode.
The preparation method of monocrystal nickel cobalt manganese cell positive electrode of the present invention can also adopt following technical scheme:
The preparation method of described monocrystal nickel cobalt manganese cell positive electrode, is characterized in: while preparing crystal seed, after calcining 4-10h, cross 325 mesh sieves, screenings is the required crystal seed obtaining.
The preparation method of described monocrystal nickel cobalt manganese cell positive electrode, is characterized in: when forcing press is compacted into bulk, by be pressed material thickness be 1-5 centimetre, pressure be 10-50 ton/square metre.
The preparation method of described monocrystal nickel cobalt manganese cell positive electrode, is characterized in: when sintering makes monocrystal nickel cobalt manganese cell positive electrode, after pulverizing, cross 100-500 mesh sieve, screenings is the monocrystal nickel cobalt manganese cell positive electrode obtaining.
Advantage and good effect that the present invention has are:
The advantages such as monocrystal nickel cobalt manganese cell positive electrode and preparation method thereof is owing to having adopted the brand-new technical scheme of the present invention, and compared with prior art, the present invention has simple to operate, the easy control of granular size.In sintering process, add crystal seed and exert pressure, thering is remarkable promotion germination and become the effect of monoclinic crystal structure, and adding crystal seed can make the temperature of calcining reduce, energy savings.
Meanwhile, carbonate or acetate that the present invention adopts can decompose completely in sintering process subsequently, can be as sulfate, phosphate the impurity such as residual sulphur, phosphorus.And adopt LiOH as pH value conditioning agent, and can avoid introducing sodium impurity, improve purity and the performance of product.
The nickel-cobalt-manganese ternary battery material of monoclinic crystal structure prepared by the present invention, particle diameter is distributed in 5-20 μ m.In preparing the process of battery pole piece, can prevent that crystal grain fragmentation from coming off with little crystal grain, the stability of material is improved.The present invention has broken the fixedly thoughtcast of people's synthesis of ternary battery material for a long time, adopted the method that adds crystal seed to promote monoclinic crystal structure growth, prepared a kind of more stable than crystallite agglomerated particle, particle size distribution is narrower, and profile is the preparation method of the nickel-cobalt-manganese ternary positive electrode of monoclinic crystal structure.In 3.0V-4.25V voltage range, discharge capacity reaches 160-165mAg first -1, the pole piece compacted density of making can be brought up to 3.8g/cm 3above, there is good cycle performance and higher security performance.18650 lithium ion batteries that in proper order material is made can reach more than 2500mAh capacity (traditional positive electrode make 18650 lithium ion batteries be generally no more than 2200mAh).
Accompanying drawing explanation
Fig. 1 is monocrystalline ternary material microstructure figure of the present invention;
Fig. 2 is traditional ternary material microstructure figure.
Two figure contrast material and the traditional ternary material that visible the present invention makes and have significant difference.
Embodiment
For further understanding summary of the invention of the present invention, Characteristic, hereby exemplify following examples, and be described with reference to the accompanying drawings as follows:
With reference to accompanying drawing 1.
Embodiment 1
A monocrystal nickel cobalt manganese cell positive electrode, this monocrystal nickel cobalt manganese cell positive electrode is the Li (Ni of 111 types 1/3co 1/3mn 1/3) O 2ternary material.
Embodiment 2
The preparation method of the monocrystal nickel cobalt manganese cell positive electrode described in embodiment 1, comprises following processing step:
(1) first prepare crystal seed.Take respectively 19.785g nickelous carbonate (nickel content 0.167mol), 19.824g cobalt carbonate (cobalt content 0.167mol), 19.158g manganese carbonate (manganese content 0.167mol), adding deionized water to solution is 500mL, is mixed with the metal salt solution that concentration is 1mol/L.Under the bath temperature of nitrogen atmosphere and 40 ℃, stirring condition, to ammoniacal liquor (the commercially available ammoniacal liquor that is 11.682g by the quality (NH wherein that adds concentration 0.5mol/L in metal salt solution 3h 2o percentage by weight is 30%) add deionized water and be diluted to 200mL, ammoniacal liquor (NH now 3h 2o) molal quantity is 0.1mol, is 0.2 times of transition metal salt molal quantity (0.5mol)).The ammoniacal liquor joining day adds up to 0.5h.Then in solution, add the LiOH solution of 1mol/L (to the LiOHH of 20.982g 2in O, adding deionized water to solution is 500mL), until pH value reaches 9, stop adding LiOH solution.Then standing 12h.After sediment filters 80 ℃ of vacuumizes 10 hours, with the LiOHH of 20.982g 2o calcines 10h after mixing at 450 ℃, crosses 325 mesh sieves, and screenings is crystal seed of the present invention.
(2) prepare required presoma.Take respectively 39.570g nickelous carbonate (nickel content 0.333mol), 39.647g cobalt carbonate (cobalt content 0.333mol), 38.316g manganese carbonate (manganese content 0.333mol), adding deionized water to solution is 500mL, and being mixed with concentration is the metal salt solution solution of 2mol/L.Under the bath temperature of nitrogen atmosphere and 40 ℃, stirring condition, to the ammoniacal liquor (ammoniacal liquor that is 23.364g by the quality (NH wherein that adds concentration 0.5mol/L in metal salt solution 3h 2o percentage by weight is 30%) add deionized water and be diluted to 400mL), after reaction 0.5h, in solution, add the LiOH solution of 1mol/L (to the LiOHH of 41.964g 2in O, adding deionized water to solution is 1L), until pH value reaches 9, stop adding LiOH solution.Then standing 12h, then 80 ℃ of vacuumize is 10 hours, obtains 91.538g presoma of the present invention.
(3) calcining makes required battery material.After after dry, the 91.538g presoma of gained mixes with 36.946g lithium carbonate, 0.128g crystal seed, (being pressed material thickness is 1 centimetre with forcing press, to be compacted into bulk, pressure is 10 tons/square metre), at 850 ℃ of temperature lower calcination 24h, cooling, pulverize, cross 100 mesh sieves, screenings is positive electrode of the present invention.
Embodiment 3
A monocrystal nickel cobalt manganese cell positive electrode, this monocrystal nickel cobalt manganese cell positive electrode is the Li (Ni of 622 types 0.6co 0.2mn 0.2) O 2ternary material.
Embodiment 4
The preparation method of the monocrystal nickel cobalt manganese cell positive electrode described in embodiment 3, comprises following processing step:
(1) first prepare crystal seed.Take respectively 45.830g nickel acetate (nickel content 0.300mol), 15.300g cobalt acetate (cobalt content 0.100mol), 14.901g manganese acetate (manganese content 0.100mol), adding deionized water to solution is 125mL, and being mixed with concentration is the aqueous solution of 4mol/L.Under the bath temperature of nitrogen atmosphere and 80 ℃, stirring condition, to the ammoniacal liquor (ammoniacal liquor that is 175.228g by the quality (NH wherein that adds concentration 1.5mol/L in metal salt solution 3h 2o percentage by weight is 30%) add deionized water and be diluted to 1L, ammoniacal liquor (NH now 3h 2o) molal quantity is 1.5mol, is 3 times of transition metal salt molal quantity (0.5mol)).The ammoniacal liquor joining day adds up to 2h.Then in solution, add the LiOH solution of 4mol/L (to the LiOHH of 20.982g 2in O, adding deionized water to solution is 125mL), until pH value reaches 11, stop adding LiOH solution.Then standing 20h.After sediment filters 140 ℃ of vacuumizes 10 hours, with the LiOHH of 20.982g 2o calcines 10h after mixing at 550 ℃, crosses 325 mesh sieves, and screenings is crystal seed of the present invention.
(2) prepare required presoma.Take respectively 91.660g nickel acetate (nickel content 0.600mol), 30.600g cobalt acetate (cobalt content 0.200mol), 29.801g manganese acetate (manganese content 0.200mol), adding deionized water to solution is 250mL, and being mixed with concentration is the aqueous solution of 4mol/L.Under the bath temperature of nitrogen atmosphere and 80 ℃, stirring condition, to the ammoniacal liquor (ammoniacal liquor that is 350.456g by the quality (NH wherein that adds concentration 1.5mol/L in metal salt solution 3h 2o percentage by weight is 30%) add deionized water and be diluted to 2L), after reaction 2h, in solution, add the LiOH solution of 4mol/L (to the LiOHH of 41.964g 2in O, adding deionized water to solution is 250mL), until pH value reaches 11, stop adding LiOH solution.Then standing 20h.After ageing, 140 ℃ of vacuumize is 10 hours, obtains 92.009g presoma of the present invention.
(3) calcining makes required battery material.The 92.009g presoma of gained and the LiOHH of 20.982g after dry 2after O, 5.650g crystal seed mix, with forcing press, be compacted into bulk (being pressed material thickness is 5 centimetres, and pressure is 50 tons/square metre), at 950 ℃ of temperature lower calcination 14h, cooling, pulverize, cross 500 mesh sieves, screenings is positive electrode of the present invention.
Embodiment 5
A monocrystal nickel cobalt manganese cell positive electrode, this monocrystal nickel cobalt manganese cell positive electrode is the Li (Ni of 523 types 0.5co 0.2mn 0.3) O 2ternary material.
Embodiment 6
The preparation method of the monocrystal nickel cobalt manganese cell positive electrode described in embodiment 5, comprises following processing step:
(1) first prepare crystal seed.Take respectively 29.677g nickelous carbonate (nickel content 0.250mol), 11.894g cobalt carbonate (cobalt content 0.100mol), 17.242g manganese carbonate (manganese content 0.150mol), adding deionized water to solution is 250mL, and being mixed with concentration is the aqueous solution of 2mol/L.Under the bath temperature of nitrogen atmosphere and 60 ℃, stirring condition, to the ammoniacal liquor (ammoniacal liquor that is 20.982g by the quality (NH wherein that adds concentration 1mol/L in metal salt solution 3h 2o percentage by weight is 30%) add deionized water and be diluted to 500mL, ammoniacal liquor (NH now 3h 2o) molal quantity is 0.5mol, is 1 times of transition metal salt molal quantity (0.5mol)).The ammoniacal liquor joining day adds up to after 1h.Then in solution, add the LiOH solution of 2mol/L (to the LiOHH of 20.982g 2in O, adding deionized water to solution is 250mL), until pH value reaches 10, stop adding LiOH solution.Then standing 16h.After sediment filters 100 ℃ of vacuumizes 6 hours, with the LiOHH of 20.982g 2o calcines 6h after mixing at 500 ℃, crosses 325 mesh sieves, and screenings is crystal seed of the present invention.
(2) prepare required presoma.Take respectively 59.355g nickelous carbonate (nickel content 0.500mol), 23.788g cobalt carbonate (cobalt content 0.200mol), 34.484g manganese carbonate (manganese content 0.300mol), adding deionized water to solution is 333mL, and being mixed with concentration is the aqueous solution of 3mol/L.Under the bath temperature of nitrogen atmosphere and 60 ℃, stirring condition, to the ammoniacal liquor (ammoniacal liquor that is 116.189g by quality adds deionized water and is diluted to 1L) that adds concentration 1mol/L in metal salt solution, after reaction 1h, in solution, add the LiOH solution of 2.5mol/L (to the LiOHH of 41.964g 2in O, adding deionized water to solution is 400mL), until pH value reaches 10.5, stop adding LiOH solution.Then standing 18h.After ageing, 120 ℃ of vacuumize is 5 hours, obtains 91.633g presoma of the present invention.
(3) calcining makes required battery material.After after dry, the 91.633g presoma of gained mixes with 36.946g lithium carbonate, 2.572g crystal seed, (being pressed material thickness is 2 centimetres with forcing press, to be compacted into bulk, pressure is 30 tons/square metre), at 900 ℃ of temperature lower calcination 16h, cooling, pulverize, cross 300 mesh sieves, screenings is positive electrode of the present invention.
Preparation method described in the present embodiment is simple to operate, and granular size is easily controlled, and calcining heat is low, energy savings; It is high that the nickel-cobalt-manganese ternary battery material of the monoclinic crystal structure of preparation has stability, and product purity is high, and particle size distribution is narrow, good cycle performance and the higher good effects such as security performance.

Claims (5)

1. a monocrystal nickel cobalt manganese cell positive electrode, is characterized in that: the chemical formula of monocrystal nickel cobalt manganese cell positive electrode is LiNi xco ymn 1-x-yo 2, wherein, the span of x is 0.3<x<0.8, the span of y is 0.1<y<0.4.
2. the preparation method of monocrystal nickel cobalt manganese cell positive electrode according to claim 1, is characterized in that: the preparation process of monocrystal nickel cobalt manganese cell positive electrode comprises the following steps:
(1) prepare crystal seed
The carbonate of nickel cobalt manganese or acetate are mixed with to the aqueous solution of concentration 1-4mol/L; Under nitrogen atmosphere and 40-80 ℃ of temperature, stirring condition, to the ammoniacal liquor that adds concentration 0.5-1.5mol/L in metal salt solution, ammoniacal liquor molal quantity be transition metal salt molal quantity 0.2-3 doubly, the ammoniacal liquor joining day is 0.5-2h; Then the LiOH solution that adds 1-4mol/L, until pH value reaches 9-11; Standing 12-20h; 80-140 ℃ of vacuumize 2-10 hour after sediment filters; With LiOHH 2o is blended at 450-550 ℃ and calcines 4-10h, obtains required crystal seed;
(2) prepare presoma
The carbonate of nickel cobalt manganese or acetate are mixed with to the aqueous solution of concentration 2-4mol/L; Under nitrogen atmosphere and 40-80 ℃, stirring condition, to the ammoniacal liquor that adds concentration 0.5-1.5mol/L in metal salt solution, ammoniacal liquor molal quantity be transition metal salt molal quantity 0.2-3 doubly, after reaction 0.5-2h, to the LiOH solution that adds 1-4mol/L in solution, until pH value reaches 9-11; Then standing 12-20h; After ageing, 80-140 ℃ of vacuumize 2-10 hour, obtains described presoma;
(3) sintering makes monocrystal nickel cobalt manganese cell positive electrode
After the crystal seed of the presoma of gained and the lithium source of stoichiometric proportion, 0.1-5% weight ratio mixes after dry, with forcing press, be compacted into bulk, at 850-950 ℃ of temperature lower calcination 14-24h, cooling, pulverize, obtain monocrystal nickel cobalt manganese cell positive electrode.
3. the preparation method of monocrystal nickel cobalt manganese cell positive electrode according to claim 2, is characterized in that: while preparing crystal seed, after calcining 4-10h, cross 325 mesh sieves, screenings is the required crystal seed obtaining.
4. the preparation method of monocrystal nickel cobalt manganese cell positive electrode according to claim 2, is characterized in that: when forcing press is compacted into bulk, being pressed material thickness is 1-5 centimetre, pressure be 10-50 ton/square metre.
5. the preparation method of monocrystal nickel cobalt manganese cell positive electrode according to claim 2, it is characterized in that: when sintering makes monocrystal nickel cobalt manganese cell positive electrode, after pulverizing, cross 100-500 mesh sieve, screenings is the monocrystal nickel cobalt manganese cell positive electrode obtaining.
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CN104051709A (en) * 2014-06-10 2014-09-17 奇瑞汽车股份有限公司 Preparation method of lithium ion battery positive electrode material
CN104868122A (en) * 2015-05-15 2015-08-26 北京理工大学 Preparation method of single-crystal Li(NiCoMn)O2 ternary cathode material
CN106910882A (en) * 2017-04-01 2017-06-30 济南大学 A kind of lithium ion battery preparation method of large single crystal layered cathode material
CN107394201A (en) * 2016-05-09 2017-11-24 日亚化学工业株式会社 The manufacture method of nickel cobalt complex hydroxide and the manufacture method of positive electrode active material for nonaqueous electrolyte secondary battery
CN109216687A (en) * 2018-10-16 2019-01-15 桑顿新能源科技有限公司 A kind of preparation method of monocrystalline trielement composite material and a kind of lithium ion battery
CN109244549A (en) * 2018-09-03 2019-01-18 江西理工大学 Method for preparing garnet electrolyte sheet with high density and high conductivity by guiding crystal growth
WO2019037459A1 (en) 2017-08-25 2019-02-28 湖南杉杉能源科技股份有限公司 High-voltage lithium nickel manganese cobalt oxide precursor, preparation method therefor, and high-voltage lithium nickel manganese cobalt oxide positive electrode material
CN109786731A (en) * 2018-12-12 2019-05-21 上海紫剑化工科技有限公司 Electrode material, lithium ion battery and preparation method thereof, application
CN110422892A (en) * 2019-08-08 2019-11-08 青岛新正锂业有限公司 A kind of preparation process of micron order monocrystalline primary particle tertiary cathode material
CN110690447A (en) * 2019-10-15 2020-01-14 合肥国轩高科动力能源有限公司 Ternary cathode material and preparation method and application thereof
CN111354926A (en) * 2018-12-22 2020-06-30 中天新兴材料有限公司 Nickel cobalt lithium manganate composite material and preparation method thereof
CN112366308A (en) * 2020-11-11 2021-02-12 江西普瑞美新材料科技有限公司 Method for rapidly synthesizing nickel-cobalt-manganese positive electrode material precursor
CN112391671A (en) * 2020-10-30 2021-02-23 中南大学 Method for reconstructing ternary single crystal material from waste ternary polycrystalline material
CN113206241A (en) * 2021-04-22 2021-08-03 湖北融通高科先进材料有限公司 Preparation method of single crystal nickel cobalt lithium manganate ternary material
CN113299905A (en) * 2021-05-21 2021-08-24 湖北融通高科先进材料有限公司 Preparation method of single crystal nickel cobalt lithium manganate ternary material
CN113651372A (en) * 2021-10-19 2021-11-16 金驰能源材料有限公司 Discontinuous growth preparation method of high-sphericity twinning-particle-free precursor
CN113871562A (en) * 2021-09-28 2021-12-31 武汉科技大学 Processing method and production line of lithium battery positive electrode material
CN114141990A (en) * 2021-11-19 2022-03-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of high-compaction lithium iron phosphate pole piece
CN114695878A (en) * 2022-06-01 2022-07-01 四川新能源汽车创新中心有限公司 Single crystal ternary cathode material and preparation method and application thereof

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CN104051709A (en) * 2014-06-10 2014-09-17 奇瑞汽车股份有限公司 Preparation method of lithium ion battery positive electrode material
CN104868122A (en) * 2015-05-15 2015-08-26 北京理工大学 Preparation method of single-crystal Li(NiCoMn)O2 ternary cathode material
CN107394201A (en) * 2016-05-09 2017-11-24 日亚化学工业株式会社 The manufacture method of nickel cobalt complex hydroxide and the manufacture method of positive electrode active material for nonaqueous electrolyte secondary battery
CN106910882A (en) * 2017-04-01 2017-06-30 济南大学 A kind of lithium ion battery preparation method of large single crystal layered cathode material
CN106910882B (en) * 2017-04-01 2019-04-23 济南大学 A kind of preparation method of lithium ion battery large single crystal layered cathode material
KR20200041978A (en) 2017-08-25 2020-04-22 후난 산산 에너지 테크놀로지 컴퍼니 리미티드 High voltage lithium nickel cobalt manganese oxide precursor, manufacturing method thereof, and high voltage lithium nickel cobalt manganese oxide cathode material
WO2019037459A1 (en) 2017-08-25 2019-02-28 湖南杉杉能源科技股份有限公司 High-voltage lithium nickel manganese cobalt oxide precursor, preparation method therefor, and high-voltage lithium nickel manganese cobalt oxide positive electrode material
CN109244549A (en) * 2018-09-03 2019-01-18 江西理工大学 Method for preparing garnet electrolyte sheet with high density and high conductivity by guiding crystal growth
CN109244549B (en) * 2018-09-03 2021-08-03 江西理工大学 Method for preparing garnet electrolyte sheet with high density and high conductivity by guiding crystal growth
CN109216687A (en) * 2018-10-16 2019-01-15 桑顿新能源科技有限公司 A kind of preparation method of monocrystalline trielement composite material and a kind of lithium ion battery
CN109786731B (en) * 2018-12-12 2021-12-10 上海紫剑化工科技有限公司 Electrode material, lithium ion battery, and preparation method and application thereof
CN109786731A (en) * 2018-12-12 2019-05-21 上海紫剑化工科技有限公司 Electrode material, lithium ion battery and preparation method thereof, application
CN111354926A (en) * 2018-12-22 2020-06-30 中天新兴材料有限公司 Nickel cobalt lithium manganate composite material and preparation method thereof
CN110422892A (en) * 2019-08-08 2019-11-08 青岛新正锂业有限公司 A kind of preparation process of micron order monocrystalline primary particle tertiary cathode material
CN110690447B (en) * 2019-10-15 2021-08-27 合肥国轩高科动力能源有限公司 Ternary cathode material and preparation method and application thereof
CN110690447A (en) * 2019-10-15 2020-01-14 合肥国轩高科动力能源有限公司 Ternary cathode material and preparation method and application thereof
CN112391671A (en) * 2020-10-30 2021-02-23 中南大学 Method for reconstructing ternary single crystal material from waste ternary polycrystalline material
CN112391671B (en) * 2020-10-30 2021-12-14 中南大学 Method for reconstructing ternary single crystal material from waste ternary polycrystalline material
CN112366308A (en) * 2020-11-11 2021-02-12 江西普瑞美新材料科技有限公司 Method for rapidly synthesizing nickel-cobalt-manganese positive electrode material precursor
CN112366308B (en) * 2020-11-11 2021-12-07 江西普瑞美新材料科技有限公司 Method for rapidly synthesizing nickel-cobalt-manganese positive electrode material precursor
CN113206241A (en) * 2021-04-22 2021-08-03 湖北融通高科先进材料有限公司 Preparation method of single crystal nickel cobalt lithium manganate ternary material
CN113299905A (en) * 2021-05-21 2021-08-24 湖北融通高科先进材料有限公司 Preparation method of single crystal nickel cobalt lithium manganate ternary material
CN113871562A (en) * 2021-09-28 2021-12-31 武汉科技大学 Processing method and production line of lithium battery positive electrode material
CN113651372A (en) * 2021-10-19 2021-11-16 金驰能源材料有限公司 Discontinuous growth preparation method of high-sphericity twinning-particle-free precursor
CN113651372B (en) * 2021-10-19 2021-12-21 金驰能源材料有限公司 Discontinuous growth preparation method of high-sphericity twinning-particle-free precursor
CN114141990A (en) * 2021-11-19 2022-03-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of high-compaction lithium iron phosphate pole piece
CN114141990B (en) * 2021-11-19 2024-02-13 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of high-compaction lithium iron phosphate pole piece
CN114695878A (en) * 2022-06-01 2022-07-01 四川新能源汽车创新中心有限公司 Single crystal ternary cathode material and preparation method and application thereof

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