CN105206827A - Nickel, cobalt and aluminum hydroxide and preparation method thereof and cathode material for lithium ion cell - Google Patents
Nickel, cobalt and aluminum hydroxide and preparation method thereof and cathode material for lithium ion cell Download PDFInfo
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- CN105206827A CN105206827A CN201510546020.3A CN201510546020A CN105206827A CN 105206827 A CN105206827 A CN 105206827A CN 201510546020 A CN201510546020 A CN 201510546020A CN 105206827 A CN105206827 A CN 105206827A
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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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- 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
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
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Abstract
The invention provides a preparation method for nickel, cobalt and aluminum hydroxide. The preparation method comprises the steps that a nickel salt solution and a cobalt salt solution are mixed to obtain a first mixed solution; an aluminum salt solution and a complexing agent are mixed to obtain a second mixed solution; under the action of a precipitant, a coprecipitation reaction is performed on the first mixed solution and the second mixed solution to obtain the nickel, cobalt and aluminum hydroxide, the complexing agent is prepared from aqueous ammonia, ethylene diamine tetraacetic acid and sulfosalicylic acid or glycine, the temperature of the coprecipitation reaction is set at 40 DEG C-65 DEG C, and the pH value of the coprecipitation reaction is set at 10.5-12. By controlling the material adding order, selection of the complexing agent and the temperature and the pH value of the coprecipitation reaction, the prepared nickel, cobalt and aluminum hydroxide has the better spherical appearance and is concentrated in particle size and high in tap density. The invention further provides the nickel, cobalt and aluminum hydroxide prepared through the method and a cathode material for a lithium ion cell.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of nickel cobalt aluminium hydroxide and preparation method thereof and anode material for lithium-ion batteries.
Background technology
In the positive electrode of lithium ion battery, high-energy, high magnification, the positive electrode of high security is the emphasis of positive electrode research always, and the positive electrode of nickelic system receives extensive attention due to the advantage that it has high power capacity.In nickelic system positive electrode, short grained nickel cobalt aluminium positive electrode is with its high-energy, and high rate capability and security performance thereof are widely used in power lithium-ion battery field, as with LiNiO
2for the positive electrode of base material doping Co element system, both there is LiNiO
2the advantage that material discharging specific capacity is high, the crystal stratiform structural stability of this positive electrode is good simultaneously, and the cyclical stability of material is also better; But this positive electrode also exists overcharging resisting ability, poor, that electric discharge irreversible capacity the is higher first defect of thermal stability.For solving the problem, make nickel cobalt material can be applied to commercialization field as early as possible, Chinese scholars has carried out a large amount of doping tests, find that the doping of aluminium element can stablize the crystal structure of nickel cobalt material, increase the diffusion coefficient of lithium ion, exothermic reaction in obvious suppression charge and discharge process, the nickel cobalt material circulation performance of adulterated al and overcharging resisting performance are obtained for and significantly improve.
In the preparation process of short grained nickel cobalt aluminium positive electrode, prepare granule spherical nickel-cobalt aluminium hydroxide particularly important as presoma; A kind of spherical granularity of prior art urgent need is good, granularity is concentrated, and the nickel cobalt aluminium hydroxide that tap density is high, to prepare the nickel cobalt aluminium positive electrode of better performances.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of nickel cobalt aluminium hydroxide and preparation method thereof and anode material for lithium-ion batteries, the spherical granularity of the nickel cobalt aluminium hydroxide that method provided by the invention prepares is good, granularity is concentrated, and tap density is higher.
The invention provides a kind of preparation method of nickel cobalt aluminium hydroxide, comprising:
By nickel salt solution and cobalt salt solution mixing, obtain the first mixed liquor;
By aluminum salt solution and complexing agent mixing, obtain the second mixed liquor, described complexing agent comprises ammoniacal liquor, disodium ethylene diamine tetraacetate, sulfosalicylic acid or glycine;
Under the effect of precipitation reagent, described first mixed liquor and the second mixed liquor are carried out coprecipitation reaction, obtain nickel cobalt aluminium hydroxide;
The temperature of described coprecipitation reaction is 40 DEG C ~ 65 DEG C,
The pH value of described coprecipitation reaction is 10.5 ~ 12;
Described nickel cobalt aluminium hydroxide is the compound shown in formula I:
Ni
1-x-yco
xal
y(OH)
2+yformula I;
In formula I, 0.1≤x≤0.2,0.03≤y≤0.10.
Preferably, described coprecipitation reaction carries out under the condition stirred, and the speed of described stirring is 150 revs/min ~ 350 revs/min.
Preferably, the concentration in the reaction system that forms at the first mixed liquor, the second mixed liquor and precipitation reagent of described coprecipitation reaction process complexing agent is 5g/L ~ 20g/L.
Preferably, the time of described coprecipitation reaction is 8 hours ~ 24 hours.
Preferably, in described first mixed liquor, the concentration of nickel ion is 0.8mol/L ~ 1.5mol/L;
In described first mixed liquor, the concentration of cobalt ions is 0.1mol/L ~ 0.6mol/L.
Preferably, in described second mixed liquor, aluminum ions concentration is 0.1mol/L ~ 0.5mol/L;
In described second mixed liquor, the mol ratio of aluminium salt and complexing agent is 1:(0.5 ~ 6).
Preferably, described precipitation reagent is NaOH or potassium hydroxide.
Preferably, after described coprecipitation reaction completes, the product obtained is carried out ageing, washing and drying successively, obtain nickel cobalt aluminium hydroxide;
The time of described ageing is 45 minutes ~ 85 minutes;
The temperature of described washing is 50 DEG C ~ 70 DEG C;
The temperature of described drying is 100 DEG C ~ 150 DEG C.
Nickel cobalt aluminium hydroxide provided by the invention makes the pattern of the nickel cobalt aluminium hydroxide prepared be granule spherical morphology by control charging sequence, the selection of complexing agent and the temperature of coprecipitation reaction and pH value, spherical granularity is good, granularity is concentrated, and tap density is high.Experimental result shows, the particle size distribution of the nickel cobalt aluminium hydroxide that method provided by the invention prepares is 2 μm ~ 6 μm; Tap density is 1.5g/cm
3~ 2.0g/cm
3.
In addition, preparation method's technique of nickel cobalt aluminium hydroxide provided by the invention simple, be easy to control.
The nickel cobalt aluminium hydroxide that a kind of method described in technique scheme that the invention provides prepares, the particle size distribution of described nickel cobalt aluminium hydroxide is 2 μm ~ 6 μm;
The tap density of described nickel cobalt aluminium hydroxide is 1.5g/cm
3~ 2.0g/cm
3.
Nickel cobalt aluminium hydroxide provided by the invention prepares for the method described in technique scheme, and this nickel cobalt aluminium hydroxide is granule spherical morphology, and spherical granularity is good, granularity is concentrated and tap density is high.
The invention provides a kind of anode material for lithium-ion batteries, described anode material for lithium-ion batteries is prepared by nickel cobalt aluminium hydroxide; Described nickel cobalt aluminium hydroxide is the nickel cobalt aluminium hydroxide described in technique scheme.
Anode material for lithium-ion batteries provided by the invention is prepared by the nickel cobalt aluminium hydroxide described in technique scheme, the spherical granularity of this nickel cobalt aluminium hydroxide is good, granularity is concentrated, tap density is high, and the positive electrode adopting this nickel cobalt manganese hydroxide to prepare has good chemical property.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is the scanning electron microscope (SEM) photograph of the nickel cobalt aluminium hydroxide that the embodiment of the present invention 1 prepares;
Fig. 2 is the particle size distribution figure of the nickel cobalt aluminium hydroxide that the embodiment of the present invention 1 prepares;
Fig. 3 is the scanning electron microscope (SEM) photograph of the nickel cobalt aluminium hydroxide that the embodiment of the present invention 2 prepares;
Fig. 4 is the particle size distribution figure of the nickel cobalt aluminium hydroxide that the embodiment of the present invention 2 prepares.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of preparation method of nickel cobalt aluminium hydroxide, comprising:
By nickel salt solution and cobalt salt solution mixing, obtain the first mixed liquor;
By aluminum salt solution and complexing agent mixing, obtain the second solution, described complexing agent comprises ammoniacal liquor, disodium ethylene diamine tetraacetate, sulfosalicylic acid or glycine;
Under the effect of precipitation reagent, described first mixed liquor and the second mixed liquor are carried out coprecipitation reaction, obtain nickel cobalt aluminium hydroxide;
The temperature of described coprecipitation reaction is 40 DEG C ~ 65 DEG C,
The pH value of described coprecipitation reaction is 10.5 ~ 12;
Described nickel cobalt aluminium hydroxide is the compound shown in formula I:
Ni
1-x-yco
xal
y(OH)
2+yformula I;
In formula I, 0.1≤x≤0.2,0.03≤y≤0.10.
The present invention, by nickel salt solution and cobalt salt solution mixing, obtains the first mixed liquor.In an embodiment of the present invention, described nickel salt solution is nickel salt aqueous solution.In an embodiment of the present invention, the nickel salt in described nickel salt solution comprises the sulfate of nickel, nitrate or chlorate.In an embodiment of the present invention, described cobalt salt solution is cobalt saline solution.In an embodiment of the present invention, the cobalt salt in described cobalt salt solution comprises the sulfate of cobalt, nitrate or chlorate.
In an embodiment of the present invention, in described first mixed liquor, the concentration of nickel ion is 0.8mol/L ~ 1.5mol/L; In other examples, in described first mixed liquor, the concentration of nickel ion is 1mol/L ~ 1.2mol/L.In an embodiment of the present invention, in described first mixed liquor, the concentration of cobalt ions is 0.1mol/L ~ 0.6mol/L; In other examples, in described first mixed liquor, the concentration of cobalt ions is 0.2mol/L ~ 0.5mol/L; In a further embodiment, in described first mixed liquor, the concentration of cobalt ions is 0.3mol/L ~ 0.4mol/L.
The present invention, by aluminum salt solution and complexing agent mixing, obtains the second mixed liquor.In an embodiment of the present invention, described aluminum salt solution is aluminum saline solution.In an embodiment of the present invention, the aluminium salt in described aluminum salt solution comprises the sulfate of aluminium, nitrate or chlorate.In the present invention, described complexing agent comprises ammoniacal liquor, disodium ethylene diamine tetraacetate, sulfosalicylic acid or glycine.In an embodiment of the present invention, described complexing agent is enveloping agent solution.In an embodiment of the present invention, the concentration of described enveloping agent solution is 1mol/L ~ 5mol/L; In other examples, the concentration of described enveloping agent solution is 2mol/L ~ 4mol/L.
In an embodiment of the present invention, in described second mixed liquor, the mol ratio of aluminium salt and complexing agent is 1:(0.5 ~ 6); In other examples, in described second mixed liquor, the mol ratio of aluminium salt and complexing agent is 1:(1 ~ 5); In a further embodiment, in described second mixed liquor, the mol ratio of aluminium salt and complexing agent is 1:(2 ~ 4).
Described first mixed liquor and the second mixed liquor, under the effect of precipitation reagent, are carried out coprecipitation reaction by the present invention, obtain nickel cobalt aluminium hydroxide.In the present invention, the temperature of described coprecipitation reaction is 40 DEG C ~ 65 DEG C; In an embodiment of the present invention, the temperature of described coprecipitation reaction is 45 DEG C ~ 60 DEG C; In other examples, the temperature of described coprecipitation reaction is 50 DEG C ~ 55 DEG C.In the present invention, the pH value of described coprecipitation reaction is 10.5 ~ 12; In an embodiment of the present invention, the pH value of described coprecipitation reaction is 11 ~ 11.5.
In an embodiment of the present invention, the time of described coprecipitation reaction is 8 hours ~ 24 hours; In other examples, the time of described coprecipitation reaction is 10 hours ~ 20 hours; In a further embodiment, the time of described coprecipitation reaction is 14 hours ~ 16 hours.In an embodiment of the present invention, the concentration of described coprecipitation reaction process complexing agent in the reaction system be made up of the first mixed liquor, the second mixed liquor and precipitation reagent is 5g/L ~ 20g/L; In other examples, the concentration of described coprecipitation reaction process complexing agent in described reaction system is 10g/L ~ 15g/L.
In an embodiment of the present invention, described coprecipitation reaction can be carried out under the condition stirred.In an embodiment of the present invention, the speed of described stirring is 150 revs/min ~ 350 revs/min; In other examples, the speed of described stirring is 200 revs/min ~ 300 revs/min; In a further embodiment, the speed of described stirring is 240 revs/min ~ 260 revs/min.
In an embodiment of the present invention, described precipitation reagent comprises NaOH or potassium hydroxide.In an embodiment of the present invention, described precipitation reagent is precipitant solution.In an embodiment of the present invention, the concentration of described precipitant solution is 5mol/L ~ 10mol/L; In other examples, the concentration of described precipitant solution is 6mol/L ~ 9mol/L; In a further embodiment, the concentration of described precipitant solution is 7mol/L ~ 8mol/L.
In the present invention, the consumption of described first mixed liquor and the second mixed liquor makes the mol ratio of nickel, cobalt and aluminium for (1-x-y): x:y, 0.1≤x≤0.2,0.03≤y≤0.10.In an embodiment of the present invention, described x is 0.12 ~ 0.18; In other examples, described x is 0.14 ~ 0.16.In an embodiment of the present invention, described y is 0.05 ~ 0.08; In other examples, described y is 0.06 ~ 0.07.
In an embodiment of the present invention, after described coprecipitation reaction completes, the product obtained can be carried out ageing, washing and drying successively, obtain nickel cobalt aluminium hydroxide.In an embodiment of the present invention, the time of described ageing is 45 minutes ~ 85 minutes; In other examples, the temperature of described ageing is 50 minutes ~ 80 minutes; In a further embodiment, the temperature of described ageing is 60 minutes ~ 70 minutes.
In an embodiment of the present invention, the reagent of described washing is water; In other examples, the reagent of described washing is deionized water.In an embodiment of the present invention, the temperature of described washing is 50 DEG C ~ 70 DEG C; In other examples, the temperature of described washing is 55 DEG C ~ 65 DEG C.
In an embodiment of the present invention, the temperature of described drying is 100 DEG C ~ 150 DEG C; In other examples, the temperature of described drying is 110 DEG C ~ 140 DEG C; In a further embodiment, the temperature of described drying is 120 DEG C ~ 130 DEG C.In an embodiment of the present invention, the method for described drying is for drying.
The nickel cobalt aluminium hydroxide that method provided by the invention prepares is the compound shown in formula I.In the present invention, x with y in described formula I is consistent with x and y described in technique scheme, does not repeat them here.
The nickel cobalt aluminium hydroxide that a kind of method described in technique scheme that the invention provides prepares, the particle size distribution of described nickel cobalt aluminium hydroxide is 2 μm ~ 6 μm; The tap density of described nickel cobalt aluminium hydroxide is 1.5g/cm
3~ 2.0g/cm
3.
In the present invention, described nickel cobalt aluminium hydroxide is consistent with the nickel cobalt aluminium hydroxide described in technique scheme, does not repeat them here.Nickel cobalt aluminium hydroxide provided by the invention is granule spherical morphology, granularity is concentrated, and tap density is high.
The invention provides a kind of anode material for lithium-ion batteries, described anode material for lithium-ion batteries is prepared by nickel cobalt aluminium hydroxide; Described nickel cobalt aluminium hydroxide is the nickel cobalt aluminium hydroxide described in technique scheme, or the nickel cobalt aluminium hydroxide that the method described in technique scheme prepares.Anode material for lithium-ion batteries provided by the invention is prepared by the nickel cobalt aluminium hydroxide described in technique scheme, the spherical granularity of this nickel cobalt aluminium hydroxide is good, granularity is concentrated, tap density is high, and the positive electrode adopting this nickel cobalt manganese hydroxide to prepare has good chemical property.
The preparation method of the present invention to described anode material for lithium-ion batteries does not have special restriction, adopt employing positive electrode material precursor well known to those skilled in the art to prepare the technical scheme of positive electrode, sintering after nickel cobalt aluminium hydroxide and lithium compound mixing is prepared.
Carry out ESEM detection to the nickel cobalt aluminium hydroxide that the present invention prepares, testing result is, nickel cobalt aluminium hydroxide that the present invention prepares is granule spherical morphology.
Adopt Malvern MS2000, the granularity of the nickel cobalt aluminium hydroxide that test the present invention prepares, described granularity is D (50) median particle, namely granularity corresponding when the cumulative particle sizes percentile of nickel cobalt aluminium hydroxide reaches 50%, namely the quantity of the granularity > D (50) of nickel cobalt aluminium hydroxide is the quantity of 50%, < D (50) is also 50%; Test result is, the particle size distribution of the nickel cobalt aluminium hydroxide that method provided by the invention prepares is 2 μm ~ 6 μm.
Adopt tap density meter FZS4-4B, the tap density of nickel cobalt aluminium hydroxide that test the present invention prepares, described tap density refers to the quality of the unit volume that the powder in container is under prescribed conditions measured after jolt ramming.Experimental result shows, the tap density of the nickel cobalt aluminium hydroxide that method provided by the invention prepares is 1.5g/cm
3~ 2.0g/cm
3.
Raw material used by following examples of the present invention is commercial goods.
Embodiment 1
Nickelous sulfate and the water-soluble solution of cobaltous sulfate are made into the first mixed liquor that concentration of metal ions is 1.5mol/L, and in described first mixed liquor, the mol ratio of nickel and cobalt is 8:1;
Aluminum sulfate solution and sulfosalicylic acid are made into by the mol ratio of 1:0.5 the second mixed liquor that aluminium ion concentration is 0.4mol/L;
By the ammoniacal liquor of described first mixed liquor, the second mixed liquor, 9.5mol/L and the sodium hydroxide solution of 6mol/L by measuring pump and stream joins in reaction vessel, under the mixing speed of 55 DEG C, 220 revs/min, carry out continuity coprecipitation reaction, the speed ratio that pumps into of described first mixed liquor and the second mixed liquor is 4.8:1; The speed that pumps into controlling ammoniacal liquor and sodium hydroxide solution makes the ammonia value in coprecipitation process be 14.5, and pH value is 11.6;
By ageing 50min after the coprecipitated product Separation of Solid and Liquid obtained, dry under the condition of 130 DEG C with after the deionized waters washing solid product of 60 DEG C, obtaining chemical formula is Ni
0.80co
0.10al
0.05(OH)
2+0.05nickel cobalt aluminium hydroxide.
The nickel cobalt aluminium hydroxide embodiment of the present invention 1 prepared carries out ESEM detection, testing result as shown in Figure 1, Fig. 1 is the scanning electron microscope (SEM) photograph of the nickel cobalt aluminium hydroxide that the embodiment of the present invention 1 prepares, as shown in Figure 1, the nickel cobalt aluminium hydroxide that the embodiment of the present invention 1 prepares is spheric granules.
According to the method described in technique scheme, detect the granularity of the nickel cobalt aluminium hydroxide that the embodiment of the present invention 1 prepares, as shown in Figure 2, as shown in Figure 2, the granularity of the aluminium hydroxide that the embodiment of the present invention 1 prepares is 2.71 μm to testing result.
According to the method described in technique scheme, detect the tap density of the nickel cobalt aluminium hydroxide that the embodiment of the present invention 1 prepares, testing result is, the tap density of the nickel cobalt aluminium hydroxide that the embodiment of the present invention 1 prepares is 1.78g/cm
3.
Embodiment 2
Nickelous sulfate and the water-soluble solution of cobaltous sulfate are made into the first mixed liquor that concentration of metal ions is 1.5mol/L, and in described first mixed liquor, the mol ratio of nickel and cobalt is 8.45:1.55;
Aluminum sulfate solution and sulfosalicylic acid are made into by the mol ratio of 1:3 the second mixed liquor that aluminium ion concentration is 0.4mol/L;
By the ammoniacal liquor of described first mixed liquor, the second mixed liquor, 9.5mol/L and the sodium hydroxide solution of 6mol/L by measuring pump and stream joins in reaction vessel, under the mixing speed of 45 DEG C, 270 revs/min, carry out continuity coprecipitation reaction, the speed ratio that pumps into of described first mixed liquor and the second mixed liquor is 7.3:1; The speed that pumps into controlling ammoniacal liquor and sodium hydroxide solution makes the ammonia value in coprecipitation process be 16.5, and pH value is 11.3;
By ageing 50min after the coprecipitated product Separation of Solid and Liquid obtained, dry under the condition of 130 DEG C with after the deionized waters washing solid product of 60 DEG C, obtaining chemical formula is Ni
0.815co
0.
15al
0.035(OH)
2+0.035nickel cobalt aluminium hydroxide.
The nickel cobalt aluminium hydroxide embodiment of the present invention 2 prepared carries out ESEM detection, testing result as shown in Figure 3, Fig. 3 is the scanning electron microscope (SEM) photograph of the nickel cobalt aluminium hydroxide that the embodiment of the present invention 2 prepares, as shown in Figure 3, the nickel cobalt aluminium hydroxide that the embodiment of the present invention 2 prepares is spheric granules.
According to the method described in technique scheme, detect the granularity of the nickel cobalt aluminium hydroxide that the embodiment of the present invention 2 prepares, as shown in Figure 4, as shown in Figure 4, the granularity of the aluminium hydroxide that the embodiment of the present invention 2 prepares is 3.23 μm to testing result.
According to the method described in technique scheme, detect the tap density of the nickel cobalt aluminium hydroxide that the embodiment of the present invention 2 prepares, testing result is, the tap density of the nickel cobalt aluminium hydroxide that the embodiment of the present invention 2 prepares is 1.88g/cm
3.
As seen from the above embodiment, the invention provides a kind of preparation method of nickel cobalt aluminium hydroxide, comprising: by nickel salt solution and cobalt salt solution mixing, obtain the first mixed liquor; By aluminum salt solution and complexing agent mixing, obtain the second mixed liquor; Under the effect of precipitation reagent, described first mixed liquor and the second mixed liquor are carried out coprecipitation reaction, obtain nickel cobalt aluminium hydroxide, described complexing agent comprises ammoniacal liquor, disodium ethylene diamine tetraacetate, sulfosalicylic acid or glycine, the temperature of described coprecipitation reaction is 40 DEG C ~ 65 DEG C, and the pH value of described coprecipitation reaction is 10.5 ~ 12.By controlling charging sequence, the selection of complexing agent and the temperature of coprecipitation reaction and pH value, nickel cobalt aluminium hydroxide provided by the invention makes that the nickel cobalt aluminium hydroxide prepared has good spherical morphology, granularity is concentrated and tap density is high.
Claims (10)
1. a preparation method for nickel cobalt aluminium hydroxide, comprising:
By nickel salt solution and cobalt salt solution mixing, obtain the first mixed liquor;
By aluminum salt solution and complexing agent mixing, obtain the second mixed liquor, described complexing agent comprises ammoniacal liquor, disodium ethylene diamine tetraacetate, sulfosalicylic acid or glycine;
Under the effect of precipitation reagent, described first mixed liquor and the second mixed liquor are carried out coprecipitation reaction, obtain nickel cobalt aluminium hydroxide;
The temperature of described coprecipitation reaction is 40 DEG C ~ 65 DEG C;
The pH value of described coprecipitation reaction is 10.5 ~ 12;
Described nickel cobalt aluminium hydroxide is the compound shown in formula I:
Ni
1-x-yco
xal
y(OH)
2+yformula I;
In formula I, 0.1≤x≤0.2,0.03≤y≤0.10.
2. method according to claim 1, is characterized in that, described coprecipitation reaction carries out under the condition stirred, and the speed of described stirring is 150 revs/min ~ 350 revs/min.
3. method according to claim 1, is characterized in that, the concentration in the reaction system that described coprecipitation reaction process complexing agent forms at the first mixed liquor, the second mixed liquor and precipitation reagent is 5g/L ~ 20g/L.
4. method according to claim 1, is characterized in that, the time of described coprecipitation reaction is 8 hours ~ 24 hours.
5. method according to claim 1, is characterized in that, in described first mixed liquor, the concentration of nickel ion is 0.8mol/L ~ 1.5mol/L;
In described first mixed liquor, the concentration of cobalt ions is 0.1mol/L ~ 0.6mol/L.
6. method according to claim 1, is characterized in that, in described second mixed liquor, aluminum ions concentration is 0.1mol/L ~ 0.5mol/L.
7. method according to claim 1, is characterized in that, described precipitation reagent is NaOH or potassium hydroxide.
8. method according to claim 1, is characterized in that, after described coprecipitation reaction completes, also comprises: the product obtained is carried out ageing, washing and drying successively, obtains nickel cobalt aluminium hydroxide;
The time of described ageing is 45 minutes ~ 85 minutes;
The temperature of described washing is 50 DEG C ~ 70 DEG C;
The temperature of described drying is 100 DEG C ~ 150 DEG C.
9. the nickel cobalt aluminium hydroxide that the method in claim 1 ~ 8 described in any one prepares, the particle size distribution of described nickel cobalt aluminium hydroxide is 2 μm ~ 6 μm;
The tap density of described nickel cobalt aluminium hydroxide is 1.5g/cm
3~ 2.0g/cm
3.
10. a positive electrode for lithium ion battery, the positive electrode of described lithium ion battery is prepared by nickel cobalt aluminium hydroxide; Described nickel cobalt aluminium hydroxide is nickel cobalt aluminium hydroxide according to claim 9.
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| CN106058244A (en) * | 2016-06-30 | 2016-10-26 | 广东省稀有金属研究所 | Preparation method and device of nickel-cobalt-aluminum anode material precursor |
| CN106299347A (en) * | 2016-08-08 | 2017-01-04 | 天津巴莫科技股份有限公司 | Nickel cobalt aluminum ternary precursor and preparation method thereof and the positive electrode prepared and method |
| CN106532038A (en) * | 2017-01-18 | 2017-03-22 | 宁波金和锂电材料有限公司 | Lithium nickel and cobalt aluminate anode material and preparation method and lithium ion battery thereof |
| CN107681143A (en) * | 2017-09-30 | 2018-02-09 | 赣南师范大学 | A kind of nickel cobalt lithium aluminate cathode material and preparation method thereof |
| CN107742703A (en) * | 2017-09-25 | 2018-02-27 | 济宁市无界科技有限公司 | The method for preparing lithium ion battery lithium nickel cobalt aluminium composite oxide positive electrode |
| CN108011095A (en) * | 2017-11-17 | 2018-05-08 | 中国科学院青岛生物能源与过程研究所 | It is a kind of to be suitable for power-type lithium ion battery, the preparation method of high circulation stability NCA positive electrodes |
| CN108281648A (en) * | 2017-01-06 | 2018-07-13 | 河南科隆新能源股份有限公司 | A kind of small particle ball-shape nickel hydroxide cobalt aluminium presoma and preparation method thereof |
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| CN106299347B (en) * | 2016-08-08 | 2018-07-24 | 天津巴莫科技股份有限公司 | Nickel cobalt aluminium ternary precursor and preparation method thereof and the positive electrode prepared and method |
| CN108281648A (en) * | 2017-01-06 | 2018-07-13 | 河南科隆新能源股份有限公司 | A kind of small particle ball-shape nickel hydroxide cobalt aluminium presoma and preparation method thereof |
| CN106532038A (en) * | 2017-01-18 | 2017-03-22 | 宁波金和锂电材料有限公司 | Lithium nickel and cobalt aluminate anode material and preparation method and lithium ion battery thereof |
| CN107742703A (en) * | 2017-09-25 | 2018-02-27 | 济宁市无界科技有限公司 | The method for preparing lithium ion battery lithium nickel cobalt aluminium composite oxide positive electrode |
| CN107681143A (en) * | 2017-09-30 | 2018-02-09 | 赣南师范大学 | A kind of nickel cobalt lithium aluminate cathode material and preparation method thereof |
| CN107681143B (en) * | 2017-09-30 | 2020-04-21 | 赣南师范大学 | Nickel-cobalt lithium aluminate cathode material and preparation method thereof |
| CN108011095B (en) * | 2017-11-17 | 2020-05-05 | 中国科学院青岛生物能源与过程研究所 | Preparation method of NCA (negative polarity anodic oxidation) cathode material with high cycle stability suitable for power type lithium ion battery |
| CN108011095A (en) * | 2017-11-17 | 2018-05-08 | 中国科学院青岛生物能源与过程研究所 | It is a kind of to be suitable for power-type lithium ion battery, the preparation method of high circulation stability NCA positive electrodes |
| CN108767218A (en) * | 2018-05-21 | 2018-11-06 | 金川集团股份有限公司 | A kind of post-processing approach that battery is prepared with nickel cobalt aluminium hydroxide |
| CN111661879A (en) * | 2020-06-09 | 2020-09-15 | 深圳市贝特瑞纳米科技有限公司 | Nickel-cobalt-tungsten oxide, preparation method thereof and lithium ion battery |
| CN111661879B (en) * | 2020-06-09 | 2023-01-17 | 深圳市贝特瑞纳米科技有限公司 | Nickel-cobalt-tungsten oxide, preparation method thereof and lithium ion battery |
| CN111717938A (en) * | 2020-06-22 | 2020-09-29 | 华友新能源科技（衢州）有限公司 | Narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide and preparation method thereof |
| CN111717938B (en) * | 2020-06-22 | 2022-10-14 | 华友新能源科技（衢州）有限公司 | Narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide and preparation method thereof |
| US20220223831A1 (en) * | 2021-01-08 | 2022-07-14 | Semiconductor Energy Laboratory Co., Ltd. | Secondary battery and manufacturing method of positive electrode active material |
| CN115893515A (en) * | 2022-10-14 | 2023-04-04 | 宜宾光原锂电材料有限公司 | Novel positive electrode material precursor and preparation method thereof |
| CN115893515B (en) * | 2022-10-14 | 2024-03-26 | 宜宾光原锂电材料有限公司 | Preparation method of nickel-cobalt-containing hydroxide positive electrode material precursor |
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