CN111422923A - Lithium ion battery positive active material precursor, preparation method thereof and lithium ion battery positive active material - Google Patents
Lithium ion battery positive active material precursor, preparation method thereof and lithium ion battery positive active material Download PDFInfo
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Abstract
The invention provides a precursor of a lithium ion battery anode active material, a preparation method of the precursor and the lithium ion battery anode active material, and belongs to the technical field of lithium ion battery anode materials. The invention compounds the charged nickel-cobalt composite particles with opposite charges and the difference of Zeta potential of more than 900mV with the charged aluminum compound particles, prepares the precursor of aluminum, nickel and cobalt composite by electrostatic attraction, can prevent the aluminum compound particles from peeling off from the surface of the nickel-cobalt composite particles in the process of compounding treatment, and the formed precursor has larger apparent density.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a lithium ion battery anode active material precursor, a preparation method thereof and a lithium ion battery anode active material.
Background
The lithium ion battery has the advantages of high energy density, high discharge platform, long cycle life, no memory effect and the like, is widely applied to the fields of mobile phones, cameras, notebook computers and the like, and is also widely applied to the fields of power batteries of electric bicycles, electric automobiles and the like.
In the preparation process of the positive electrode active material, a precursor is usually prepared first and then mixed with a lithiated compound to prepare the positive electrode active material, and for the nickel-cobalt lithium aluminate active material, the precursor is a hydroxide mixture of nickel, cobalt and aluminum, but because the nickel hydroxide and the cobalt hydroxide are β type hydroxides and the aluminum hydroxide is α type hydroxides, the nickel-cobalt-aluminum precursor with higher apparent density is difficult to obtain, and the capacity of the lithium ion battery is lower.
Disclosure of Invention
The invention aims to provide a precursor of a lithium ion battery positive electrode active material, a preparation method of the precursor and the lithium ion battery positive electrode active material.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a precursor of a positive active material of a lithium ion battery, which comprises the following steps:
(1) alternately carrying out adsorption treatment on the nickel-cobalt composite particles by using an anionic polyelectrolyte and a cationic polyelectrolyte to obtain charged nickel-cobalt composite particles; the molar ratio of nickel atoms to cobalt atoms in the nickel-cobalt composite particles is 80: 20-95: 5;
(2) alternately carrying out adsorption treatment on aluminum compound particles by using an anionic polyelectrolyte and a cationic polyelectrolyte to obtain charged aluminum compound particles with charges opposite to those of the charged nickel-cobalt composite particles; the difference of the Zeta potentials of the charged nickel-cobalt composite particles and the charged aluminum compound particles is more than or equal to 900 mV;
(3) mixing the charged nickel-cobalt composite particles and the charged aluminum compound particles in water, and carrying out complexing treatment to obtain a precursor; in the precursor, aluminum atoms account for 1-8 mol% of the total amount of nickel atoms, cobalt atoms and aluminum atoms;
the above (1) and (2) are not limited in chronological order.
Preferably, the nickel-cobalt composite particles are nickel-cobalt mixed hydroxide particles, nickel-cobalt mixed oxide particles or nickel-cobalt mixed oxyhydroxide particles, the average particle diameter of the nickel-cobalt composite particles is 7-15 μm, and the specific surface area is 1.0-10.0 m2/g。
Preferably, the aluminum compound particles are aluminum hydroxide particles or aluminum oxide particles, the average particle diameter of the aluminum compound particles is 1/20 or less of the average particle diameter of the nickel-cobalt composite particles, and the specific surface area is 50-180 m2/g。
Preferably, the absolute values of the Zeta potentials of the charged nickel-cobalt composite particles and the charged aluminum compound particles are independently more than or equal to 500 mV.
Preferably, the average molecular weights of the anionic polyelectrolyte and the cationic polyelectrolyte are independently 0.1 × 104～1.0×105(ii) a At 1m2The amount of the anionic polyelectrolyte or the cationic polyelectrolyte used per adsorption treatment was 2.1 × 10 based on the surface area of the nickel-cobalt composite particles or the aluminum compound particles-4～3.6×10-3g/m2。
Preferably, the adsorption treatment in (1) or (2) is specifically an aqueous solution of an anionic polyelectrolyte or an aqueous solution of a cationic polyelectrolyte is added to the slurry of the nickel-cobalt composite particles or the slurry of the aluminum compound particles; adding the anionic polyelectrolyte aqueous solution or the cationic polyelectrolyte aqueous solution at the addition speed of the anionic polyelectrolyte or the cationic polyelectrolyteAcceleration of 1.0 × 10-4～1.3×10-3g/m2·min。
Preferably, the adsorption treatment in (1) or (2) is carried out by adding 70-80% of an aqueous solution of an anionic polyelectrolyte or an aqueous solution of a cationic polyelectrolyte at a rate of 1.0 × 10-4～1.3×10-3g/m2Min to the slurry of the nickel cobalt composite particles or the slurry of the aluminum compound particles, and then the remaining aqueous anionic polyelectrolyte solution or aqueous cationic polyelectrolyte solution at 5.0 × 10-5～1.7×10-4g/m2Min to the slurry of nickel cobalt composite particles or the slurry of aluminum compound particles.
Preferably, the step (3) is to dropwise add the dispersion liquid of the charged nickel-cobalt composite particles into the dispersion liquid of the charged aluminum compound particles under the stirring condition, continue stirring for 8-12 min after dropwise adding, and then stand for 1-1.5 h, wherein the concentration of the dispersion liquid of the charged aluminum compound particles is 10-60 g/L, the concentration of the dispersion liquid of the charged nickel-cobalt composite particles is 200-500 g/L, and the dropwise adding speed is 10-80 m L/min.
A precursor of a lithium ion battery anode active material is obtained by the preparation method of the technical scheme.
The lithium ion battery positive electrode active material is prepared by mixing the lithium ion battery positive electrode active material precursor and a lithiated compound and sintering.
The invention compounds the charged nickel-cobalt composite particles and the charged aluminum compound particles with opposite charges and the difference of Zeta potential of more than 900mV in water, prepares the composite precursor of the nickel-cobalt composite and the aluminum compound by composite treatment through electrostatic attraction, can prevent the aluminum compound particles from being stripped from the surface of the nickel-cobalt composite particles in the subsequent treatment process of preparing the battery by mixing the compounded particles with other treatments, and the formed precursor has higher apparent density.
Drawings
FIG. 1 SEM image of a precursor obtained in example 1 at magnification of 5000;
FIG. 2 SEM image of the precursor obtained in comparative example 1 at 5000 Xmagnification;
FIG. 3 is a graph showing the results of thermal stability tests of the precursors obtained in examples 1 to 2 and comparative example 1.
Detailed Description
The invention provides a preparation method of a precursor of a positive active material of a lithium ion battery, which comprises the following steps:
(1) alternately carrying out adsorption treatment on the nickel-cobalt composite particles by using an anionic polyelectrolyte and a cationic polyelectrolyte to obtain charged nickel-cobalt composite particles; the molar ratio of nickel atoms to cobalt atoms in the nickel-cobalt composite particles is 80: 20-95: 5;
(2) alternately carrying out adsorption treatment on aluminum compound particles by using an anionic polyelectrolyte and a cationic polyelectrolyte to obtain charged aluminum compound particles with charges opposite to those of the charged nickel-cobalt composite particles; the difference of the Zeta potentials of the charged nickel-cobalt composite particles and the charged aluminum compound particles is more than or equal to 900 mV;
(3) mixing the charged nickel-cobalt composite particles and the charged aluminum compound particles in water, and carrying out complexing treatment to obtain a precursor; in the precursor, aluminum atoms account for 1-8 mol% of the total amount of nickel atoms, cobalt atoms and aluminum atoms;
the above (1) and (2) are not limited in chronological order.
Firstly, alternately adsorbing nickel-cobalt composite particles by using anionic polyelectrolyte and cationic polyelectrolyte to obtain charged nickel-cobalt composite particles; the molar ratio of nickel atoms to cobalt atoms in the nickel-cobalt composite particles is 80: 20-95: 5.
In the present invention, the nickel-cobalt composite particles are preferably nickel-cobalt mixed hydroxide particles (i.e., particles obtained by compounding a mixture of nickel hydroxide and cobalt hydroxide), nickel-cobalt mixed oxide particles (i.e., nickel oxide and cobalt oxide)Zirconium mixture composite particles) or nickel-cobalt mixed oxyhydroxide particles (i.e., particles obtained by compounding a mixture of nickel oxyhydroxide and cobalt oxyhydroxide), more preferably nickel-cobalt coprecipitated composite particles (i.e., nickel-cobalt mixed hydroxide particles), wherein the nickel-cobalt composite particles preferably have an average particle diameter of 7 to 15 μm and a specific surface area of 1.0 to 10.0m2(ii) in terms of/g. In the present invention, the above particle size and specific surface area are advantageous for obtaining a suitable particle size of the precursor.
In the present invention, the aluminum compound particles are preferably aluminum hydroxide particles or alumina particles, the average particle diameter of the aluminum compound particles is preferably 1/20 or less, more preferably 1/50 or less, of the average particle diameter of the nickel-cobalt composite particles, and the specific surface area is preferably 50 to 180m2(ii)/g; the average particle diameter of the aluminum compound particles is a secondary particle diameter, and is preferably 120 to 160nm in the embodiment of the present invention.
In the present invention, the average molecular weights of the anionic polyelectrolyte and the cationic polyelectrolyte are preferably independently 0.1 × 104～1.0×105(ii) a The specific types of the anionic polyelectrolyte and the cationic polyelectrolyte are not particularly limited, and the desired Zeta potential can be obtained, specifically, the anionic polyelectrolyte is preferably at least one of polystyrene sulfonic acid (PSS), polyvinyl sulfuric acid (PVS), polyacrylic acid (PAA), polyisobutylene acid (PMA) and polyamic acid, and more preferably is polystyrene sulfonic acid (PSS); the cationic polyelectrolyte is preferably at least one of poly (diallyldimethylammonium chloride) (PDDA), Polyethyleneimine (PEI), Polyvinylamine (PVA), polyallylamine, polydimethybenzoic acid dichloride, polypyrimidinethyne, polypyrrole, polyaniline, polyethyleneimine azole, polydimethylcarbamate, polyimine, poly N-methylimide salt, polyimine salt (CAS number 62238-80-6, trade name PAS-21), and poly (acrylamide-diallyldimethylammonium chloride) (CAS number 26590-05-6), the poly N-methylimide salt is preferably poly N-methylimine hydrochloride (methylidimine hydrochloride polymer, CAS number 29566-78-7, trade name PAS-M-1) or poly N-methylimine sulfate (methylidimine acetate polymer, CAS number 101922-88-7 or95386-45-1, tradename PAS-M-1A); at 1m2The amount of the anionic polyelectrolyte or the cationic polyelectrolyte used per adsorption treatment was 2.1 × 10 based on the surface area of the nickel-cobalt composite particles or the aluminum compound particles-4～3.6×10-3g/m2(i.e., 2.1 × 10 per square meter of surface area of nickel cobalt composite particles or aluminum compound particles is required to be used-4～3.6×10-3g of an anionic polyelectrolyte or a cationic polyelectrolyte), more preferably 1.0 × 10-3～2.6×10-3g/m2. In the present invention, the absolute value of the Zeta potential of the polyelectrolyte in the above molecular weight range is large, which is advantageous for obtaining a desired Zeta potential difference.
In the present invention, in the process of preparing the charged nickel cobalt composite particles, the adsorption treatment is preferably carried out by adding an aqueous solution of an anionic polyelectrolyte or an aqueous solution of a cationic polyelectrolyte to a slurry of the nickel cobalt composite particles, and the addition rate of the aqueous solution of the anionic polyelectrolyte or the aqueous solution of the cationic polyelectrolyte is preferably 1.0 × 10 in terms of the addition rate of the anionic polyelectrolyte or the cationic polyelectrolyte-4～1.3×10-3g/m2Min (i.e., the amount of anionic polyelectrolyte or cationic polyelectrolyte added per minute per square meter of the surface area of the nickel-cobalt composite particle is 1.0 × 10-4～1.3×10-3g) More preferably 2.3 × 10-4～1.29×10-3g/m2·min。
In the present invention, in the preparation process of the charged nickel-cobalt composite particles, it is preferable that the adsorption treatment is performed by adding 70 to 80% of an aqueous solution of an anionic polyelectrolyte or an aqueous solution of a cationic polyelectrolyte at 1.0 × 10 by using an addition velocity of the anionic polyelectrolyte or the cationic polyelectrolyte-4～1.3×10-3g/m2Min, more preferably at 1.0 × 10-4～2.6×10-4g/m2Min into the slurry of nickel cobalt composite particles, and then the remaining aqueous anionic or cationic polyelectrolyte solution was added at 5.0 × 10-5～1.7×10-4g/m2Min, more preferablyIs at 8.5 × 10-5～1.7×10-4g/m2Min to the slurry of nickel cobalt composite particles.
The concentration of the aqueous solution of the anionic polyelectrolyte or the aqueous solution of the cationic polyelectrolyte is not particularly limited in the present invention, and in the embodiment of the present invention, the concentration of the aqueous solution of the anionic polyelectrolyte or the aqueous solution of the cationic polyelectrolyte is independently preferably 4.5 to 13.5 wt%, more preferably 4.8 to 13 wt%.
In the invention, the initial concentration (namely the concentration when no anionic polyelectrolyte or cationic polyelectrolyte is added) of the slurry of the nickel-cobalt composite particles is preferably 0.3-0.5 g/m L, and more preferably 0.4g/m L, in the process of adding, the stirring state of the slurry of the nickel-cobalt composite particles is preferably maintained, after the anionic polyelectrolyte aqueous solution or the cationic polyelectrolyte aqueous solution is added, the stirring is preferably continued for 10min, then the cationic polyelectrolyte aqueous solution or the anionic polyelectrolyte aqueous solution is added, after one adsorption treatment is completed, the next adsorption treatment can be directly carried out, the mixed solution obtained after one adsorption treatment can be filtered, the obtained solid is dispersed in the solvent again, and then the next adsorption treatment is carried out, in the process of adsorption treatment, the appropriate polyelectrolyte concentration is adopted, the particles with the appropriate Zeta potential absolute value are ensured, the waste is avoided, and the addition of 70-80% of the polyelectrolyte aqueous solution is more easily carried out, so that the polyelectrolyte aqueous solution can be more quickly adsorbed than the cationic polyelectrolyte aqueous solution or the anionic polyelectrolyte solution can be more easily subjected to the condensation treatment.
In the present invention, it is preferable that the anionic polyelectrolyte aqueous solution or the cationic polyelectrolyte aqueous solution further includes a surfactant, preferably a cationic surfactant or an anionic surfactant, preferably a 4-order ammonium salt or an N-ethyl alkanamide ammonium halide, preferably at least one of tetramethylammonium chloride, tetraethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, lauryltrimethylammonium bromide and lauryltrimethylammonium chloride, and an anionic surfactant, preferably at least one of a fatty acid salt and a sulfonate, particularly preferably at least one of sodium citrate, sodium oleate, sodium laurate, α -olefin sulfonate, alkyl aromatic hydrocarbon sulfonate, alkyl phosphate (such as sodium lauryl phosphate), alkyl phosphate salt and higher alcohol sulfate salt (such as sodium polyoxymethylene lauryl ether sulfate).
In the invention, the absolute value of the Zeta potential of the charged nickel-cobalt composite particles is preferably more than or equal to 500mV, and more preferably 560-580 mV; the nickel-cobalt composite particles are alternately adsorbed by anionic polyelectrolyte and cationic polyelectrolyte, so that the Zeta potential of the charged nickel-cobalt composite particles can reach the range; the number of cycles of the adsorption treatment performed alternately is not particularly limited, and the Zeta potential can be obtained, and when the number of cycles of the adsorption treatment performed alternately is 0, it means that particles corresponding to the Zeta potential can be obtained by performing the adsorption treatment only once.
The method comprises the following steps of (1) alternately carrying out adsorption treatment on aluminum compound particles by using an anionic polyelectrolyte and a cationic polyelectrolyte to obtain charged aluminum compound particles with charges opposite to those of the charged nickel-cobalt composite particles; the steps are not limited in sequence with the steps for preparing the charged nickel-cobalt composite particles.
In the present invention, the adsorption treatment method in the preparation process of the charged aluminum compound particles is the same as the adsorption treatment method in the preparation process of the charged nickel-cobalt composite particles, and thus the description thereof is omitted, and in the preparation process of the charged aluminum compound particles, the initial concentration of the slurry of the aluminum compound particles (i.e., the concentration when no anionic polyelectrolyte or cationic polyelectrolyte is added) is preferably 0.01155 to 0.01375g/m L.
In the present invention, the absolute value of the Zeta potential of the charged aluminum compound particles is preferably not less than 500mV, more preferably 530 to 550 mV; the Zeta potential of the charged aluminum compound particles can reach the range by alternately carrying out adsorption treatment on the aluminum compound particles by using anionic polyelectrolyte and cationic polyelectrolyte; in the present invention, the number of cycles of the adsorption treatment performed alternately is not particularly limited, and the Zeta potential may be obtained.
In the present invention, the charged nickel-cobalt composite particles and the charged aluminum compound particles may be separated from the slurry after the alternate adsorption treatment and then carried out in the next step, or may be directly carried out in the next step without separation, and those skilled in the art may select them according to the circumstances. In the embodiment of the present invention, it is preferable that the slurry after the alternate adsorption treatment is filtered to obtain the charged nickel-cobalt composite particles and the charged aluminum compound particles, and then the charged nickel-cobalt composite particles and the charged aluminum compound particles are dispersed in water to obtain the charged nickel-cobalt composite particle dispersion liquid and the charged aluminum compound particle dispersion liquid with desired concentrations, and then the composite treatment is performed.
After the charged nickel-cobalt composite particles and the charged aluminum compound particles are obtained, the charged nickel-cobalt composite particles and the charged aluminum compound particles are mixed in water and subjected to complexing treatment to obtain a precursor; in the precursor, aluminum atoms account for 1-8 mol% of the total amount of nickel atoms, cobalt atoms and aluminum atoms.
In the invention, the specific process of preparing the precursor by the composite treatment is preferably that the dispersion liquid of the charged nickel-cobalt composite particles is dripped into the dispersion liquid of the charged aluminum compound particles under the stirring condition, after the dripping is finished, the stirring is continued for 8-12 min, then the standing is carried out for 1-1.5 h, and the precursor is obtained in the dispersion liquid, wherein the concentration of the dispersion liquid of the charged aluminum compound particles is preferably 10-60 g/L, the concentration of the dispersion liquid of the charged nickel-cobalt composite particles is preferably 200-500 g/L, and the dripping speed is preferably 10-80 m L/min.
After obtaining the precursor in the dispersion, the invention preferably performs solid-liquid separation, washing, drying and sieving on the obtained dispersion in sequence to obtain the precursor; the solid-liquid separation is preferably performed by filtration.
In the present invention, the washing is not particularly limited, and a conventional washing method may be employed, and the washing detergent is preferably water.
The drying is not particularly limited in the present invention, and a constant weight product can be obtained, and in the embodiment of the present invention, the drying is preferably oven drying, fluidized bed drying or spray drying.
In the present invention, the mesh number of the screen used for the screening is preferably 250 mesh.
The invention also provides a precursor of the lithium ion battery anode active material, which is obtained by the preparation method of the technical scheme.
The invention also provides a lithium ion battery anode active material, which is prepared by mixing the lithium ion battery anode active material precursor and a lithiated compound and sintering.
The preparation method of the lithium ion battery anode active material is not particularly limited, and the conventional preparation method in the field can be adopted.
In the present invention, the lithiated compound is preferably at least one of lithium hydroxide, a lithium salt, and lithium oxide, and the lithium salt is preferably lithium carbonate; the molar ratio of the lithium element in the lithiated compound to the total amount of metal ions in the precursor of the positive electrode active material of the lithium ion battery is preferably 1: 0.99-1.09, and the ratio range can avoid residual unreacted metal ions and excessive lithiated compound to generate residual alkali; in a specific production process, the preparation method of the lithium ion battery anode material specifically comprises the following steps: premixing a lithium compound and a precursor of a lithium ion battery anode active material, then mixing the lithium compound and the precursor of the lithium ion battery anode active material with a PVA binder solution, re-granulating to obtain granular matters, drying the granular matters, then sintering under an oxygen-enriched condition, and crushing to obtain the lithium ion battery anode active material; in the embodiment of the invention, the preparation method can adopt the following steps due to the small preparation amount: mixing the precursor of the positive active material of the lithium ion battery with a lithiated compoundSintering to obtain the lithium ion battery anode material; the sintering process is preferably to heat the mixture from room temperature to 480 ℃ within 2.5h, keep the temperature for 2h, then heat the mixture to 745 ℃ within 1h, keep the temperature for 15h, and then cool the mixture to below 150 ℃ within 4.5 h; the lithium ion battery positive electrode active material is a hexagonal system, the average particle size is preferably 5.0-15 mu m, and the specific surface area is preferably 0.2-0.7 m2/g。
In the embodiment of the invention, the lithium ion battery positive active material is preferably mixed with a conductive material and a binder to prepare a positive electrode, carbon or aluminum foil is used as a negative electrode, the positive electrode is assembled with a diaphragm and an electrolyte to obtain a button battery, the conductive material is preferably black acetylene or carbon black, the binder is preferably Polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF), the diaphragm is preferably a microporous film made of polyethylene or polypropylene, and the solute of the electrolyte is preferably L iPF6、LiClO4、LiBF4、LiCF3SO3、LiCnF2n+1SO3(n≥1)、LiCF3CO2、LiN(CF3SO2)2、LiC(CF3SO2)3、LiAsF6、LiSbF6And lithium carboxylate which is a lower fatty acid, wherein the solvent is preferably an organic solvent, more preferably at least one of Polycarbonate (PC), Ethylene Carbonate (EC), 4-ethyl-1, 3-dioxan-2-one, dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), gamma-butyrolactone (GB L), ethylene glycol dimethyl ether (DME), Tetrahydrofuran (THF), 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane (DO L), formamide, N-Dimethylformamide (DMF), acetonitrile, nitromethane, methyl formate, methyl acetate, trimethyl phosphate (TMP), trimethyl orthoacetate, 1, 2-trimethoxyethane, sulfolane, 3-methyl-2-oxazolidinone, and 1, 3-propanesultone, and the concentration of the solute is preferably 0.2 to 3 mol/L.
The lithium ion battery positive electrode active material precursor, the preparation method thereof, and the lithium ion battery positive electrode active material provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
100g of a specific surface area of 5.47m2Ni-Co mixed hydroxide (i.e., particles of a mixture of nickel hydroxide and cobalt hydroxide, Ni: Co molar ratio 84:16) having an average particle diameter of 10.1 μm was dispersed in 250m L distilled water, and 12m L containing 0.63g of Ni having an average molecular weight of 2.0 × 10 was added under stirring at a speed of 200rpm4The aqueous solution of cationic polyelectrolyte (poly-N-methylimidate) was added within 5min, followed by stirring for 10min, and 12m of L containing 1.3g of a polymer having an average molecular weight of 3.0 × 104The water solution of the anionic polyelectrolyte (polystyrene sulfonic acid) is added within 5min, and then stirred for 10min, the obtained mixed solution is filtered, and then the obtained solid is dispersed in water of 250m L, thus obtaining nickel-cobalt composite particle slurry with the Zeta potential of-580 mV;
2.75g of fine alumina powder (specific surface area 130 m)2(ii)/g, the average particle diameter (i.e., secondary particle diameter) is 120nm, the primary particle diameter is 20 to 30nm) is dispersed in 200m L distilled water, 6m L is added under stirring at 80rpm, and 0.92g of the mixture having an average molecular weight of 4.0 × 103After the addition of the aqueous solution of the anionic polyelectrolyte (polystyrenesulfonic acid) within 2min, stirring was continued for 10 minutes, and 6m L containing 0.38g of the anionic polyelectrolyte (polystyrenesulfonic acid) and having an average molecular weight of 3.0 × 10 was added thereto4Filtering the obtained mixed solution, drying to obtain a solid which is charged alumina powder, and adding the charged alumina powder into 250m L distilled water to prepare alumina micropowder slurry with a Zeta potential of +550 mV;
the nickel-cobalt composite particle slurry with the Zeta potential of-580 mV is dripped into alumina micro powder slurry with the Zeta potential of +550mV under stirring at the speed of 10m L/min while stirring at the rotating speed of 200rpm, after the dripping is finished, the stirring is continued for 10 minutes, then the mixture is kept stand for 1 hour, clear liquid is separated, then the filtration is carried out, the obtained solid is dried for 2 hours at the temperature of 120 ℃ after being washed, the obtained dried powder is screened by a 250-mesh screen, and the undersize is used as a precursor.
The precursor obtained in the example was tested to have an average particle diameter of 11.2 μm and a specific surface area of 28.3m2/g。
Fig. 1 shows an SEM image of the precursor obtained in this example at 5000 x magnification. In FIG. 1, the translucent structure near the particle interface is alumina fine powder, and it can be seen from the state of locally thick adhesion that the surface of the Ni-Co mixed hydroxide is coated. From the EDX detection results of the center particles, it was found that the fine alumina powder was substantially uniformly distributed even in the absence of the fine alumina powder, that is, the fine alumina powder was uniformly distributed, and the black dots were portions not covered with the fine alumina powder.
100g of the precursor obtained in this example and 44.86g of lithium hydroxide (average particle size 28.6 μm) were mixed in such a manner that the molar ratio of the lithium element to the total amount of metal elements in the precursor was 1: 1.06, using a magnesia sagger for sintering, heating the mixture from room temperature to 480 ℃ within 2.5h under the atmosphere of oxygen, preserving the heat for 2h, then heating the mixture to 745 ℃ within 1h, preserving the heat for 15h, cooling the mixture to 100 ℃ within 4.5h, discharging the mixture, and crushing the mixture to obtain the cathode active material, wherein the average particle size of the cathode active material is 12.5 mu m, and the specific surface area of the cathode active material is 0.28m2/g。
Preparing button cell, mixing 45mg of the above positive electrode active material with 10.5mg of black acetylene and 4.5mg of PTFE to obtain paste, coating the paste on an aluminum net with the diameter of 18mm, performing over-pressure forming under the pressure of 200MPa, performing vacuum drying on the obtained formed product in a vacuum drying oven at the temperature of 120 ℃ to obtain a positive electrode, taking an aluminum foil as a negative electrode, and using 1M L iPF as electrolyte6Two polyethylene porous membranes having a thickness of 25 μm were stacked as separators in an equal amount of a mixed solution of EC and DMC as electrolytes, and assembled in a glove box under an argon atmosphere to obtain a button cell.
After the button cell is placed for hours and the open loop voltage OCV (open Circuit Voltage) is stable, the current density corresponding to the positive electrode is 0.2mA/cm2And charging to a cut-off voltage of 4.2V. The capacity at this time was the first cycle charge capacity, and the capacity discharged to a cut-off voltage of 2.5V after leaving it for 30 minutes was the first cycle discharge capacity. Under the same conditions as aboveThe maintenance rate a of the discharge capacity at the 50 th cycle was obtained by the following formula (1) after repeated charge and discharge tests. The results are shown in Table 1.
A (50 th cycle discharge capacity)/(first cycle discharge capacity) × 100% formula (1)
Example 2
1.0kg of a specific surface area of 5.8m2(ii)/g Ni-Co mixed hydroxide (i.e., particles of a mixture of nickel hydroxide and cobalt hydroxide, Ni: Co molar ratio: 87.5:12.5) having an average particle diameter of 11.3 μm was dispersed in 2.5L distilled water, and 6.5g of Ni-Co mixed hydroxide having an average molecular weight of 2.0 × 10 was added to 120m L at 400rpm under stirring4The aqueous solution of cationic polyelectrolyte (polyimine) of (1) was added in two stages, first 90m L at a rate of 11.5m L/min and the remaining 30m L at a rate of 6m L/min, after the addition was completed, stirring was carried out for 10min, then filtration was carried out, the resulting solid was dispersed in 2.5L distilled water, stirred uniformly at a stirring speed of 400rpm, and then 120m L containing 13.5g of a polymer having an average molecular weight of 2.0 × 10 was added4The aqueous solution of the anionic polyelectrolyte (polystyrene sulfonic acid) is added in a way that the first 90m L is added at the speed of 18m L/min, the remaining 30m L is added at the speed of 6m L/min, and after the addition is finished, the mixture is stirred for 10min, the obtained mixed solution is filtered, and then the obtained solid is dispersed in 2.5L water to obtain the slurry of the nickel-cobalt composite particles with the Zeta potential of-560 mV;
23.1g of fine alumina powder (specific surface area 100 m)2(ii)/g, the average particle diameter (i.e., secondary particle diameter) is 160nm, the primary particle diameter is 20 to 30nm) is dispersed in 2.01L distilled water, 60m L is added under stirring at a rotation speed of 300rpm, and 7.9g of the mixture having an average molecular weight of 6.0 × 104The aqueous solution of anionic polyelectrolyte (polystyrenesulfonic acid) was added at a rate of 4.5m L/min for the first 45m L and 1.5m L/min for the remaining 15m L, after the addition was completed, stirring was continued for 10 minutes, followed by filtration, the resulting solid powder was added to 2.01L distilled water and stirred uniformly at 300rpm, and then 60m L containing 3.3g of an average molecular weight of 5.0 × 10 was added3The aqueous solution of the cationic polyelectrolyte (poly (acrylamide-diallyldimethylammonium chloride)) is added at the speed of 4.5m L/min for the first 45m L and the restAdding 15m L at the speed of 3m L/min, stirring for 10 minutes after the addition is finished, filtering the obtained mixed solution, drying to obtain a solid which is charged alumina powder, and adding the charged alumina powder into 2.5L distilled water to prepare alumina micropowder slurry with the Zeta potential of +530 mV;
the nickel-cobalt composite particle slurry with the Zeta potential of-560 mV is dripped into the alumina micro powder slurry with the Zeta potential of +530mV under stirring at the speed of 33m L/min while stirring at the rotating speed of 400rpm, after the dripping is finished, the stirring is continued for 10 minutes, then the mixture is kept stand for 1 hour, clear liquid is separated, then the filtration is carried out, the obtained solid is washed by water and dried for 4 hours at the temperature of 120 ℃, the obtained dried powder is screened by a 250-mesh screen, and the undersize is used as a precursor.
The precursor obtained in the example was tested to have an average particle size of 12.1 μm and a specific surface area of 27.9m2/g。
A positive electrode active material was prepared by the method of example 1, and it was tested that the positive electrode active material obtained in this example had an average particle diameter of 13.1 μm and a specific surface area of 0.27m2/g。
Comparative example 1
100g of a specific surface area of 5.47m2Ni-Co mixed hydroxide (Ni: Co molar ratio 84:16) having an average particle diameter of 10.1 μm/g was added to 250m L distilled water, and the mixture was stirred at 200rpm and added at a rate of 10m L/min to 200m L to contain 2.75g of alumina fine powder (specific surface area 130 m)2And/g, the average particle size (namely the secondary particle size) is 120nm, the primary particle size is 20-30 nm), the alumina suspension is kept in a stirring state, after the addition is finished, the stirring is continued for 10 minutes, the standing is carried out for 1 hour, the obtained mixed solution is filtered, the solid obtained by the filtering is washed, the dried product is dried for 2 hours at the temperature of 120 ℃, and then the dried product passes through a 250-mesh screen, and the undersize product is a precursor.
As shown in fig. 2, the SEM image of the precursor obtained in the present comparative example was magnified 5000 times. As is clear from fig. 2, the precursor obtained in the present comparative example formed aggregates, and alumina was present in the gaps between the particles of the nickel cobalt hydroxide particles, forming aggregates.
Button cells were prepared from the precursors obtained in example 2 and comparative example 1 by the method of example 1, and the first cycle specific discharge capacity and the 50 th cycle specific discharge capacity were measured, and the results are shown in table 1. As can be seen from table 1, the precursors obtained in examples 1 to 2 have higher first cycle discharge capacity, smaller first cycle irreversible capacity, and discharge maintenance rates of 50 th cycle are all above 80%, which indicates that the precursors obtained by the preparation method provided by the present invention not only have excellent rate performance, but also have more excellent cycle stability.
TABLE 1 results of testing cycling stability of button cell prepared from precursors obtained in examples 1-2 and comparative example 1
Thermal stability test in the method of example 1, the precursors obtained in examples 1 to 2 and comparative example 1 were prepared into a positive electrode material, and then a button cell was prepared in the method of example 1, the test cell CV-CC was charged to 4.2V and decomposed under the condition of 0.1mA of cutoff current, and then an active material (i.e., a positive electrode plate) in an internally charged state was taken out, and the positive electrode plate was taken out, washed with ethylene glycol dimethyl ether, and vacuum-dried at 60 ℃ to prepare a sample for thermal analysis, and 35mg of a positive electrode mixture (i.e., a positive electrode active material, black acetylene and PTFE) and 5mg of an electrolyte solution 1M L iPF were charged in a stainless steel container for detection6EC/DME, differential thermal analysis at a heating rate of 5 ℃/min. The results of the detection are shown in FIG. 3.
As can be seen from fig. 3, the precursor obtained in comparative example 1 has a large calorific value (peak area) and high reaction initiation temperature and decomposition initiation temperature because the solid solution in the active material to alumina is incomplete (i.e., alumina distribution is not uniform). In example 1, since the solid solution of alumina is relatively uniform (i.e., the alumina distribution is uniform), the reaction between the precursor and the electrolyte is suppressed, and the temperature shifts to the side where the reaction start temperature is high, and the amount of heat generation also decreases. In example 2, since the Ni content is high, the heat generation amount becomes large as a whole, and a large difference occurs in the decomposition start temperature. The safety is improved compared with comparative example 1. Therefore, the precursor prepared by the method has better thermal stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a precursor of a positive electrode active material of a lithium ion battery is characterized by comprising the following steps:
(1) alternately carrying out adsorption treatment on the nickel-cobalt composite particles by using an anionic polyelectrolyte and a cationic polyelectrolyte to obtain charged nickel-cobalt composite particles; the molar ratio of nickel atoms to cobalt atoms in the nickel-cobalt composite particles is 80: 20-95: 5;
(2) alternately carrying out adsorption treatment on aluminum compound particles by using an anionic polyelectrolyte and a cationic polyelectrolyte to obtain charged aluminum compound particles with charges opposite to those of the charged nickel-cobalt composite particles; the difference of the Zeta potentials of the charged nickel-cobalt composite particles and the charged aluminum compound particles is more than or equal to 900 mV;
(3) mixing the charged nickel-cobalt composite particles and the charged aluminum compound particles in water, and carrying out complexing treatment to obtain a precursor; in the precursor, aluminum atoms account for 1-8 mol% of the total amount of nickel atoms, cobalt atoms and aluminum atoms;
the above (1) and (2) are not limited in chronological order.
2. The method according to claim 1, wherein the nickel-cobalt composite particles are nickel-cobalt mixed hydroxide particles, nickel-cobalt mixed oxide particles, or nickel-cobalt mixed oxyhydroxide particles, and have an average particle diameter of 7 to 15 μm and a specific surface area of 1.0 to 10.0m2/g。
3. According to the rightThe method according to claim 1, wherein the aluminum compound particles are aluminum hydroxide particles or aluminum oxide particles, the average particle diameter of the aluminum compound particles is 1/20 or less of the average particle diameter of the nickel-cobalt composite particles, and the specific surface area is 50 to 180m2/g。
4. The production method according to any one of claims 1 to 3, wherein the absolute values of the Zeta potentials of the charged nickel-cobalt composite particles and the charged aluminum compound particles are independently 500mV or more.
5. The method according to claim 1, wherein the average molecular weights of the anionic polyelectrolyte and the cationic polyelectrolyte are independently 0.1 × 104～1.0×105(ii) a At 1m2The amount of the anionic polyelectrolyte or the cationic polyelectrolyte used per adsorption treatment was 2.1 × 10 based on the surface area of the nickel-cobalt composite particles or the aluminum compound particles-4～3.6×10-3g/m2。
6. The method according to any one of claims 1 to 3 and 5, wherein the adsorption treatment in (1) or (2) is carried out by adding an aqueous solution of an anionic polyelectrolyte or an aqueous solution of a cationic polyelectrolyte to the slurry of the nickel-cobalt composite particles or the slurry of the particles of the aluminum compound, wherein the rate of addition of the aqueous solution of the anionic polyelectrolyte or the aqueous solution of the cationic polyelectrolyte is 1.0 × 10 in terms of the rate of addition of the anionic polyelectrolyte or the cationic polyelectrolyte-4～1.3×10-3g/m2·min。
7. The method according to any one of claims 1 to 3 and 5, wherein the adsorption treatment in (1) or (2) is carried out by adding 70 to 80% of an aqueous solution of an anionic polyelectrolyte or an aqueous solution of a cationic polyelectrolyte at 1.0 × 10 based on the addition rate of the anionic polyelectrolyte or the cationic polyelectrolyte-4～1.3×10-3g/m2Speed of minAdded to the slurry of the nickel-cobalt composite particles or the slurry of the aluminum compound particles, and then the remaining aqueous anionic polyelectrolyte solution or aqueous cationic polyelectrolyte solution is added at 5.0 × 10-5～1.7×10-4g/m2Min to the slurry of nickel cobalt composite particles or the slurry of aluminum compound particles.
8. The preparation method according to claim 1, wherein the step (3) is specifically carried out by dropwise adding the dispersion liquid of the charged nickel-cobalt composite particles into the dispersion liquid of the charged aluminum compound particles under stirring, continuously stirring for 8-12 min after the dropwise adding is finished, and then standing for 1-1.5 h, wherein the concentration of the dispersion liquid of the charged aluminum compound particles is 10-60 g/L, the concentration of the dispersion liquid of the charged nickel-cobalt composite particles is 200-500 g/L, and the dropwise adding speed is 10-80 m L/min.
9. A precursor of a positive electrode active material of a lithium ion battery, which is obtained by the preparation method of any one of claims 1 to 8.
10. The lithium ion battery positive electrode active material is characterized by being prepared by mixing the lithium ion battery positive electrode active material precursor according to claim 9 with a lithiated compound and then sintering the mixture.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114883546A (en) * | 2022-05-19 | 2022-08-09 | 江苏正力新能电池技术有限公司 | Silicon-carbon composite active material, preparation method thereof, negative plate and secondary battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2469367A1 (en) * | 2004-05-28 | 2005-11-28 | Nippon Chemical Industrial Co., Ltd | Lithium cobalt oxide, method for manufacturing the same, and nonaqueous electrolyte secondary battery |
| CN101262061A (en) * | 2008-04-14 | 2008-09-10 | 天津巴莫科技股份有限公司 | Spherical aluminum-doped nickel cobalt lithium for lithium ion battery and its making method |
| CN104143633A (en) * | 2014-07-31 | 2014-11-12 | 深圳市振华新材料股份有限公司 | Anode material made through element microemulsion coating method, manufacturing method and application |
| CN104362305A (en) * | 2014-08-18 | 2015-02-18 | 香港应用科技研究院有限公司 | Composite material and production method thereof |
| CN106684361A (en) * | 2017-01-19 | 2017-05-17 | 新乡天力锂能股份有限公司 | Preparation method of Ni-Co-Al precursor |
| CN107565112A (en) * | 2017-08-29 | 2018-01-09 | 湖南长远锂科有限公司 | A kind of preparation method of graphene coated lithium ion secondary battery anode material |
| CN108336350A (en) * | 2018-02-05 | 2018-07-27 | 天津理工大学 | The preparation method of anode material for lithium-ion batteries laminar nano nickel cobalt lithium aluminate |
-
2020
- 2020-03-30 CN CN202010236722.2A patent/CN111422923A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2469367A1 (en) * | 2004-05-28 | 2005-11-28 | Nippon Chemical Industrial Co., Ltd | Lithium cobalt oxide, method for manufacturing the same, and nonaqueous electrolyte secondary battery |
| CN101262061A (en) * | 2008-04-14 | 2008-09-10 | 天津巴莫科技股份有限公司 | Spherical aluminum-doped nickel cobalt lithium for lithium ion battery and its making method |
| CN104143633A (en) * | 2014-07-31 | 2014-11-12 | 深圳市振华新材料股份有限公司 | Anode material made through element microemulsion coating method, manufacturing method and application |
| CN104362305A (en) * | 2014-08-18 | 2015-02-18 | 香港应用科技研究院有限公司 | Composite material and production method thereof |
| CN106684361A (en) * | 2017-01-19 | 2017-05-17 | 新乡天力锂能股份有限公司 | Preparation method of Ni-Co-Al precursor |
| CN107565112A (en) * | 2017-08-29 | 2018-01-09 | 湖南长远锂科有限公司 | A kind of preparation method of graphene coated lithium ion secondary battery anode material |
| CN108336350A (en) * | 2018-02-05 | 2018-07-27 | 天津理工大学 | The preparation method of anode material for lithium-ion batteries laminar nano nickel cobalt lithium aluminate |
Non-Patent Citations (2)
| Title |
|---|
| 戴遐明: "《超微陶瓷粉体实用化处理技术》", 30 September 2009, 北京：国防工业出版社 * |
| 郑春满等: "《高等合成化学 方法与实践》", 30 September 2018, 北京：国防工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114883546A (en) * | 2022-05-19 | 2022-08-09 | 江苏正力新能电池技术有限公司 | Silicon-carbon composite active material, preparation method thereof, negative plate and secondary battery |
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