CN103482711B - A kind of ultrasonic wave added prepares the method for ternary cathode material of lithium ion battery presoma - Google Patents
A kind of ultrasonic wave added prepares the method for ternary cathode material of lithium ion battery presoma Download PDFInfo
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- CN103482711B CN103482711B CN201310400259.0A CN201310400259A CN103482711B CN 103482711 B CN103482711 B CN 103482711B CN 201310400259 A CN201310400259 A CN 201310400259A CN 103482711 B CN103482711 B CN 103482711B
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- sulfate
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- 238000000034 method Methods 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 239000010406 cathode material Substances 0.000 title abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 24
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000975 co-precipitation Methods 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 238000001556 precipitation Methods 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 238000013019 agitation Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- 239000010405 anode material Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 11
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910015645 LiMn Inorganic materials 0.000 description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- 241000080590 Niso Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910017705 Ni Mn Co Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006854 communication Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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 present invention discloses a kind of method that ultrasonic wave added prepares ternary cathode material of lithium ion battery presoma.The present invention is under the protection of inert nitrogen gas; with mechanical agitation dispersion and the mode of ultrasonic assistant; with the nickel cobalt manganese in NaOH and ammoniacal liquor mixed solution continuous co-precipitation metal mixed solution; precipitated product overflows after outgrowth; overflow obtains fresh nickel cobalt manganese composite hydroxide precipitation through washing and filtering, and product obtains good sphericity, nickel cobalt manganese hydroxide precursor that purity is high after the washing of pure water ultrasonic wave added and vacuumize.The precipitation of hydroxide that the present invention adopts the method process of ultrasonic wave added fresh, product is complex hydroxide presoma, and impurity ion content is few; Complex hydroxide presoma has spherical morphology and narrow particle size distribution, tap density advantages of higher.
Description
Technical field
The present invention relates to the preparation method with spheroidization anode material for lithium ion battery presoma, particularly a kind of ultrasonic wave added preparation method of nickel-cobalt-manganternary ternary anode material presoma.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, owing to having high-energy-density, high voltage, good cycle, and the advantage such as small volume, configuration design be flexible and changeable, become the first-selection of increasing portable type electronic product power supply.Lithium ion battery is made up of parts such as positive and negative pole material, barrier film and electrolyte, and wherein positive electrode is the important component part of lithium ion battery.LiCoO
2positive electrode as industrialization the earliest has the advantages such as compacting is high, good cycle, production technology ripe, product is stable, but its actual capacity is only 50% of theoretical capacity, and it is expensive, toxicity is large, security performance existing defects, the requirement of the electrical source of power such as electric vehicle power sources can not be met, need the environmental friendliness new material finding high-performance and low-cost to substitute LiCoO
2, mainly contain LiFePO
4, LiMn
2o
4, LiNiO
2deng, LiFePO
4there is excellent stability and cycle performance, but actual capacity is low, operating voltage is low, electron conduction is poor; LiMn
2o
4cost is low, and security performance is good, but specific capacity is low, and high temperature cyclic performance is poor, structural instability, is difficult to large-scale production; LiNiO
2capacity is high, relative LiCoO
2low price, but its fail safe is low, and preparation difficulty is difficult to realize industrialization.And nickel-cobalt-manganternary ternary anode material nickle cobalt lithium manganate combines LiCoO
2good cycle performance, LiMn
2o
4low cost, high safety performance, LiNiO
2the advantage of height ratio capacity, it is the high performance lithium ion battery anode material with Ni, Co, Mn trielement synergistic effect, have that specific capacity is large, good cycle and the advantage such as operating voltage is high, thermodynamic stability is high, fail safe is good, being easy to realize industrialization, is a kind of novel anode material having market potential.
Synthetic method main at present mainly contains high temperature solid-state method, coprecipitation, sol-gel process, spray pyrolysis etc.Traditional high temperature solid-state method due to its operation simple and easy, with low cost, be the common method of synthesis of anode material of lithium-ion battery, but be difficult to obtain uniform composition distribution product.Liquid-phase coprecipitation selects suitable precipitation reagent and metal target salting liquid generation coprecipitation reaction, obtains its hydroxide, carbonate or oxalates complex salt etc., then sinter output tertiary cathode material with Li source compound.The method of current acquisition large-scale production and application is hydroxide coprecipitation steps, the method take ammoniacal liquor as the even synchronous precipitation that complexing agent controls each element, finally obtain spherical hydroxide precursor, but still each component mixing uniformity that there is reacting salt solution is poor, the hydroxide precursor sphericity of synthesis and particle homogeneity is poor, washing afterwards sodium ion and the shortcoming such as sulfate ion content is higher in presoma.
Summary of the invention
The object of the invention is the deficiency overcoming above-mentioned existing synthetic method; a kind of method that ultrasonic wave added prepares ternary cathode material of lithium ion battery presoma is proposed; the shortcomings such as co-precipitation yield is too low, crystal formation integrality is poor, degree of crystallinity is not high are solved; this is that a kind of technique is simple simultaneously; cost is low; administration measure, is conducive to the preparation method of environmental protection, and obtained product has that purity is high, the characteristic of good sphericity, narrow particle size distribution and high-tap density.
The technical solution used in the present invention is in order to achieve the above object: a kind of ultrasonic wave added prepares the method for precursor for ternary anode material of lithium ion battery, it is characterized in that following:
The co-precipitation of A ultrasonic wave added
Be the metal salt solution of sulfuric acid solution preparation containing nickelous sulfate, manganese sulfate and cobaltous sulfate of 2.0-3.0 with pH value in ultrasound environments, metal ion in solution total concentration is 1.0 ~ 4.0mol/L; Prepare the ammonia alkali mixed solution of NaOH and ammoniacal liquor with pure water, wherein the concentration of sodium hydroxide solution is 2.0 ~ 5.0mol/L, and the concentration of ammoniacal liquor is 0.2 ~ 3.0mol/L; Under the protection of nitrogen, make metal salt solution and ammonia alkali mixed solution, in crystallization control reactor, continuous print coprecipitation reaction occur, the mode of mechanical agitation, ultrasonic wave added is adopted in course of reaction, the pH value controlling reaction system is 9.0 ~ 12.0, mechanical agitation speed is 600 ~ 900r/min, supersonic frequency is 40 ~ 70 DEG C in 20 ~ 40kHz, temperature, and product is overflowed with mother liquor;
B overflow washs
The nickel cobalt manganese composite hydroxide precipitation of being overflowed by overfall directly passes in pure water, and is placed in ultrasound environments, separated in time washing suction filtration;
C vacuumize
It is dry that washing is placed in vacuum drying chamber close to neutral nickel cobalt manganese composite precipitation thing, and keep the temperature inside the box to be 50 ~ 120 DEG C, product is nickel cobalt manganese composite hydroxide presoma.
Under the protection of inert nitrogen gas; in the mode that mechanical agitation dispersion and ultrasonic wave added combine; with the nickel cobalt manganese in NaOH and ammoniacal liquor mixed solution continuous co-precipitation metal mixed solution; precipitated product overflows after outgrowth; overflow obtains fresh nickel cobalt manganese composite hydroxide precipitation through washing and filtering, and product obtains good sphericity, nickel cobalt manganese hydroxide precursor that purity is high after the washing of pure water ultrasonic wave added and vacuumize.Ultrasonic wave is a kind of mechanical wave, the vibration that it will cause medium molecule centered by its equilbrium position in liquid medium communication process, the active force that medium is subject to is enough large, intermolecular average distance will increase above critical distance, thus destroy the integrality of liquid structure, cause occurring cavity or hole, but these holes the sound wave malleation come one after the other mutually in will be compressed again, consequently some cavitation bubbles will enter the persistent oscillation stage, and other cavitation bubbles will collapse completely.When these small bubbles burst, produce the high temperature (>5000K) of moment, high pressure (>5 × 10
7pa), formed so-called " focus ", produce strong shock wave, play obvious acceleration to coprecipitation process, make lattice growth complete, the degree of crystallinity obtaining particle is higher; Ultrasonic wave makes liquid occur the mechanical characteristic of turbulent flow on the other hand, reduces diffusional resistance, makes the skin covering of the surface of solid destroy simultaneously, accelerate mass transport process, substantially increase the yield of product.High-energy ultrasonic process better can improve size and the spatial distribution of particle in conjunction with mechanical agitation, and mechanical agitation makes particle macroscopically dispersed, and ultrasonic cavitation and churned mechanically comprehensive function make particle on microcosmic, reach dispersed.
A kind of ultrasonic wave added of the present invention prepares the method for ternary cathode material of lithium ion battery presoma, specific embodiment and technological parameter as follows:
1 solution preparation
Be the mixed salt solution of sulfuric acid solution preparation containing nickelous sulfate, manganese sulfate and cobaltous sulfate of 2.0-3.0 with pH value in ultrasound environments, wherein the mol ratio of nickel, cobalt and manganese is preferably 3-5:3:2-3, and metal ion in solution total concentration is 1.0 ~ 4.0mol/L; Prepare the mixed solution of NaOH and ammoniacal liquor with pure water, wherein the concentration of sodium hydroxide solution is 2.0 ~ 5.0mol/L, and the concentration of ammoniacal liquor is 0.2 ~ 3.0mol/L.
2 ultrasonic wave added co-precipitation
Under the protection of nitrogen, make metal salt solution and ammonia alkali mixed solution that continuous print coprecipitation reaction occurs in synthesis reaction vessel; adopt mechanical agitation in conjunction with ultrasonic wave added in process; the pH value controlling reaction system is 9.0 ~ 12.0, mixing speed is 600 ~ 900r/min, supersonic frequency is 40 ~ 70 DEG C in 20 ~ 40kHz, temperature; product is overflowed rear washing and filtering and is namely obtained fresh nickel cobalt manganese composite hydroxide precipitation, and the chemical reaction that co-precipitation occurs is as follows:
Me
2++ 2OH
-=M (OH)
2↓ (Me is Ni, Co and Mn).
3 overflow washings
The fresh hydrooxidation thing precipitation of being overflowed by overfall directly passes in pure water, and through ultrasonic wave added, separated in time washing suction filtration.
4 vacuumizes
It is dry that washing is placed in vacuum drying chamber close to neutral composite precipitation thing, and keep the temperature inside the box to be 50 ~ 120 DEG C, product is nickel cobalt manganese composite hydroxide presoma.
Described manganese sulfate, nickelous sulfate, cobaltous sulfate, NaOH, ammoniacal liquor, nitrogen are electron level, and pure electrical conductivity of water is less than 0.055us/cm.
Every physical index of presoma (nickel cobalt manganese composite hydroxide) prepared by described method is respectively, and granularity D50 is 8 ~ 12 μm, tap density>=2.2g/cm
3.
The invention has the advantages that:
1. adopt ultrasonic scattering method configuration salting liquid, three kinds of salt are fully dissolved, and in product, the ratio of each component is closer to ideal value;
2. adopt crystallization control technology, in conjunction with mechanical agitation and ultrasonic wave added, synthesizing spherical degree be good, the ternary anode material precursor of narrow particle size distribution and high-tap density;
3. adopt the precipitation of hydroxide that the method process of ultrasonic wave added washing is fresh, product is complex hydroxide presoma, and impurity ion content is few;
4. adopt the precipitation of hydroxide of vacuum drying method dry composite, obtaining dry metal state is the hydroxide precursor of divalence.
Present invention process is simple, controlled, and cost is low, easily realizes large-scale production.The tertiary cathode material adopting product of the present invention to prepare has excellent stability, and specific capacity is high, tap density is large, good cycle.
Accompanying drawing explanation
Fig. 1 is present invention process schematic flow sheet.
Fig. 2 is the SEM figure of ternary cathode material of lithium ion battery presoma of the present invention.
Fig. 3 is the XRD figure of ternary cathode material of lithium ion battery presoma of the present invention.
Embodiment
Embodiment 1:
By NiSO
4, MnSO
4, CoSO
4ni: Mn: Co=4:3:3 ratio pH value is the sulfuric acid solution ultrasonic wave added dissolving preparation nickel manganese cobalt mixed solution of 2.1 in molar ratio, total concentration is 2.0 mol/L, be mixed with the sodium hydroxide solution of 2.5 mol/L, compound concentration is the ammonia spirit of 0.5 mol/L, respectively with measuring pump nickel cobalt-manganese salt solution, sodium hydroxide solution, ammonia spirit is input in the reactor of the 1L volume adding liquid of certain end in advance and carries out stirring and ultrasonic wave added coprecipitation reaction.Under nitrogen protection condition; controlling temperature of reaction kettle is 50 DEG C; pH value 11.5; speed of agitator is 600r/min; supersonic frequency is 200W at 40kHz, power; to reactor, feed liquid is naturally overflowed and is entered collecting tank; the precipitation obtained; namely the washing of complex hydroxide deionized water ultrasonic wave added is less than 8.0 to washings pH value; use Buchner funnel suction filtration, then vacuumize 6h at 100 DEG C in vacuum drying chamber, product nickel manganese cobalt composite oxide presoma pattern is spherical in shape; narrow particle size distribution D50 is 10.83 μm, and tap density is 2.30g/cm
3.In the present embodiment, the supersonic frequency of ultrasonic wave added is 200W at 40kHz, power.
Embodiment 2:
By NiSO
4, MnSO
4, CoSO
4ni: Mn: Co=3:3:3 ratio pH value is the sulfuric acid solution ultrasonic wave added dissolving preparation nickel manganese cobalt mixed solution of 2.0 in molar ratio, total concentration is 1.0 mol/L, be mixed with the sodium hydroxide solution of 2 mol/L, compound concentration is the ammonia spirit of 3 mol/L, respectively with measuring pump nickel cobalt-manganese salt solution, sodium hydroxide solution, ammonia spirit is input in the reactor of the 1L volume adding liquid of certain end in advance and carries out stirring and ultrasonic wave added coprecipitation reaction.Under nitrogen protection condition; controlling temperature of reaction kettle is 45 DEG C, pH value 9.0, and speed of agitator is 700r/min; supersonic frequency is 500W at 30kHz, power; to reactor, feed liquid is naturally overflowed and is entered collecting tank, the precipitation obtained, and namely the washing of complex hydroxide deionized water ultrasonic wave added is less than 8 to washings pH value; use Buchner funnel suction filtration; then vacuumize 6h at 120 DEG C in vacuum drying chamber, product nickel manganese cobalt composite oxide presoma pattern is spherical in shape, narrow particle size distribution D
50be 10.8 μm, tap density is 2.28g/cm
3.In the present embodiment, the supersonic frequency of ultrasonic wave added is 500W at 30kHz, power.
Embodiment 3:
By NiSO
4, MnSO
4, CoSO
4ni: Mn: Co=5:2:3 ratio pH value is the sulfuric acid solution ultrasonic wave added dissolving preparation nickel manganese cobalt mixed solution of 2.0 in molar ratio, total concentration is 3.0 mol/L, be mixed with the sodium hydroxide solution of 5 mol/L, compound concentration is the ammonia spirit of 2.0 mol/L, respectively with measuring pump nickel cobalt-manganese salt solution, sodium hydroxide solution, ammonia spirit is input in the reactor of the 1L volume adding liquid of certain end in advance and carries out stirring and ultrasonic wave added coprecipitation reaction.Under nitrogen protection condition; controlling temperature of reaction kettle is 60 DEG C, pH value 10.5, and speed of agitator is 900r/min; supersonic frequency is 800W at 20kHz, power; to reactor, feed liquid is naturally overflowed and is entered collecting tank, the precipitation obtained, and namely the supersound washing of complex hydroxide deionized water is less than 8.0 to washings pH value; use Buchner funnel suction filtration; then vacuumize 8h at 70 DEG C in vacuum drying chamber, product nickel manganese cobalt composite oxide presoma pattern is spherical in shape, narrow particle size distribution D
50be 9.52 μm, tap density is 2.32g/cm
3.In the present embodiment, the supersonic frequency of ultrasonic wave added is 800W at 20kHz, power.
Physical and chemical index/the % of table 1 nickel cobalt manganese hydroxide precursor
| NO. D 50/ μm tap density/g.cm -3Specific area/m 2.g -1Ni Mn Co Na moisture |
| Embodiment 1 10.8 2.28 2.72 26.41 23.73 25.86 0.001 0.28 embodiment 2 10.83 2.30 3.98 29.65 20.13 21.28 0.002 0.30 embodiment 3 9.52 2.32 3.61 35.81 13.37 20.52 0.002 0.30 |
Repeatability production result shows, presoma physical index prepared by the method is consistent, chemical composition is even.
Claims (2)
1. ultrasonic wave added prepares a method for precursor for ternary anode material of lithium ion battery, it is characterized in that
Below:
The co-precipitation of A ultrasonic wave added
Be the metal salt solution of sulfuric acid solution preparation containing nickelous sulfate, manganese sulfate and cobaltous sulfate of 2.0-3.0 with pH value in ultrasound environments, metal ion in solution total concentration is 1.0 ~ 4.0mol/L; Prepare the ammonia alkali mixed solution of NaOH and ammoniacal liquor with pure water, wherein the concentration of sodium hydroxide solution is 2.0 ~ 5.0mol/L, and the concentration of ammoniacal liquor is 0.2 ~ 3.0mol/L; Under the protection of nitrogen, make metal salt solution and ammonia alkali mixed solution, in crystallization control reactor, continuous print coprecipitation reaction occur, the mode of mechanical agitation, ultrasonic wave added is adopted in course of reaction, the pH value controlling reaction system is 9.0 ~ 12.0, mechanical agitation speed is 600 ~ 900r/min, supersonic frequency is 40 ~ 70 DEG C in 20 ~ 40kHz, temperature, and product is overflowed with mother liquor;
B overflow washs
The nickel cobalt manganese composite hydroxide precipitation of being overflowed by overfall directly passes in pure water, and is placed in ultrasound environments, separated in time washing suction filtration;
C vacuumize
It is dry that washing is placed in vacuum drying chamber close to neutral nickel cobalt manganese composite precipitation thing, keeps the temperature inside the box to be 50 ~ 120 DEG C, and product is has that purity is high, the nickel cobalt manganese composite hydroxide presoma of good sphericity, narrow particle size distribution;
Described manganese sulfate, nickelous sulfate, cobaltous sulfate, NaOH, ammoniacal liquor, nitrogen are electron level, and pure electrical conductivity of water is less than 0.055 μ S/cm;
It is 8 ~ 12 μm that every physical index of described nickel cobalt manganese composite hydroxide presoma is respectively granularity D50, tap density>=2.2g/cm
3;
Described containing in the metal salt solution of nickelous sulfate, manganese sulfate and cobaltous sulfate, the mol ratio of nickel, cobalt and manganese is 3-5:3:2-3.
2. ultrasonic wave added according to claim 1 prepares the method for precursor for ternary anode material of lithium ion battery, it is characterized in that: ultrasonic power is 100 ~ 800W.
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| CN104201368B (en) * | 2014-04-18 | 2017-03-08 | 宁夏东方钽业股份有限公司 | Lithium battery ternary material precursor nickel cobalt manganese hydroxide and preparation method thereof |
| CN105304864A (en) * | 2014-07-15 | 2016-02-03 | 北京当升材料科技股份有限公司 | Preparation and treatment method for low-sulfur manganese cobalt nickel hydroxide |
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| CN109205685B (en) * | 2017-07-03 | 2022-04-26 | 东莞东阳光科研发有限公司 | Continuous preparation method of high-nickel ternary precursor for lithium ion battery |
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