CN109786731B - Electrode material, lithium ion battery, and preparation method and application thereof - Google Patents
Electrode material, lithium ion battery, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an electrode material, a lithium ion battery, and a preparation method and application thereof. The preparation method comprises the following steps: calcining a mixture of a ternary precursor material, a seed crystal and a lithium ion-containing molten salt in an oxygen-containing atmosphere; wherein the molar ratio of the ternary precursor material to the seed crystal is 2:10-10: 1; the ternary precursor material is nickel-cobalt-manganese hydroxide or nickel-cobalt-aluminum hydroxide. The preparation method can control the average diameter of the obtained electrode material within a proper range, so that the interface side reaction of the electrode material in the battery cycle process is reduced, the capacity retention rate of the battery is further improved, and better rate performance and cycle stability are obtained.
Description
Technical Field
The invention relates to an electrode material, a lithium ion battery, and a preparation method and application thereof.
Background
Lithium cobaltate is the most widely used lithium battery material at present, but cobalt resources are increasingly scarce and expensive, and the utilization of the cobalt is seriously influenced. The nickel cobalt lithium manganate material replaces more than two thirds of cobalt in lithium cobaltate by relatively cheap nickel and manganese, thereby effectively reducing the cost of the material and expanding the source of raw materials, and the nickel cobalt lithium manganate material becomes one of lithium battery materials which are widely concerned and researched by people.
At present, the existing preparation methods of the lithium nickel cobalt manganese oxide material include a solid phase method of directly mixing or mixing and then roasting raw materials, a coprecipitation method of dissolving, mixing and precipitating the raw materials and then drying the raw materials, a suspension method of dispersing and mixing the raw materials by using a solvent, a template method of limiting the arrangement and the orientation of the raw materials by using a template, and the like.
Chinese patent document CN 104868122A discloses a preparation method of a single crystal nickel cobalt lithium manganate material, which adopts a solution method to prepare, wherein the diameter of the prepared nickel cobalt lithium manganate material is about 0.5 μm, and the capacity retention rate of the obtained lithium ion battery is only 86.4-93.1% after the lithium ion battery is cycled for 100 times under 0.2C.
There are also reports related to the preparation of lithium nickel cobalt manganese (aluminum) oxide materials in molten salt in the prior art, and the preparation method is as follows: the hydroxide of nickel cobalt manganese (aluminum) and the molten salt are obtained by calcining. However, the average diameter (less than 2 μm) of the prepared material is smaller by the preparation method, and the capacity retention rate, rate capability and cycling stability of the prepared battery are poor.
Disclosure of Invention
The invention aims to overcome the defects that the average diameter of the material is smaller and the capacity retention rate, the rate capability and the cycling stability of the prepared battery are poorer due to the existing preparation method of the lithium nickel cobalt manganese (aluminum) oxide material, and provides a novel electrode material, a lithium ion battery, and a preparation method and application thereof. According to the preparation method disclosed by the invention, the average diameter of the obtained electrode material can be controlled within a proper range by introducing the seed crystal, so that the interface side reaction of the electrode material in the battery circulation process is reduced, the capacity retention rate of the battery is further improved, and better rate performance and circulation stability are obtained.
The invention solves the technical problems through the following technical scheme:
the invention provides an electrode material, wherein the average diameter of the electrode material is 3-10 microns;
when the electrode material is a lithium nickel cobalt manganese oxide material, the chemical formula of the lithium nickel cobalt manganese oxide material is LiaNix1Cox2Mnx3O2X1 < 1, x2 < 1, x3 < 1, and x1+x2+ x3 is 1, a is 1-1.2;
wherein, when the electrode material is a nickel cobalt lithium aluminate material, the chemical formula of the nickel cobalt lithium aluminate material is LibNiy1Coy2Aly3O2And 0 < y1 < 1, 0 < y2 < 1, 0 < y3 < 1, y1+ y2+ y3 ═ 1, and b is 1 to 1.2.
In the above electrode material, the average diameter of the electrode material is preferably 3 to 6 micrometers, more preferably 3 to 5 micrometers.
In the electrode material, the average diameter is measured by the following method: randomly screening 100 particles in the prepared product, measuring the distance between the farthest two points on each particle by using a scanning microscope, and obtaining an average value, namely the average diameter.
In the above electrode material, x1 is preferably 0.6 to 0.85, more preferably 0.6 to 0.8.
Of the above electrode materials, x2 is preferably 0.1 to 0.2.
In the above electrode material, x3 is preferably 0.05 to 0.2, more preferably 0.1 to 0.2.
In the above electrode material, a is preferably 1 to 1.1.
Of the above electrode materials, y1 is preferably 0.6 to 0.85, more preferably 0.85.
Of the above electrode materials, y2 is preferably 0.1 to 0.2, more preferably 0.1.
Of the above electrode materials, y3 is preferably 0.05 to 0.2, more preferably 0.05.
In the above electrode material, b is preferably 1 to 1.1.
In the above electrode material, the chemical formula of the electrode material is preferably LiNi0.6Co0.2Mn0.2O2。
In the above electrode material, the chemical formula of the electrode material is preferably LiNi0.8Co0.1Mn0.1O2。
In the above electrode material, the chemical formula of the electrode material is preferably LiNi0.85Co0.1Al0.05O2。
The invention also provides a preparation method of the electrode material, which comprises the following steps: calcining a mixture of a ternary precursor material, a seed crystal and a lithium ion-containing molten salt in an oxygen-containing atmosphere; wherein the molar ratio of the ternary precursor material to the seed crystal is 2:10-10: 1; the ternary precursor material is nickel-cobalt-manganese hydroxide or nickel-cobalt-aluminum hydroxide;
when the ternary precursor material is nickel cobalt manganese hydroxide, the chemical formula of the nickel cobalt manganese hydroxide is Nix1Cox2Mnx3(OH)2The chemical formula of the seed crystal is Lia1Nix1Cox2Mnx3O2And 0 < x1 < 1, 0 < x2 < 1, 0 < x3 < 1, x1+ x2+ x3 ═ 1, and a1 is 1 to 1.2;
when the ternary precursor material is nickel cobalt aluminum hydroxide, the chemical formula of the nickel cobalt aluminum hydroxide is Niy1Coy2Aly3(OH)2The chemical formula of the seed crystal is Lib1Niy1Coy2Aly3O2And 0 < y1 < 1, 0 < y2 < 1, 0 < y3 < 1, y1+ y2+ y3 ═ 1, and b1 is 1 to 1.2.
In the above production method, x1 is preferably 0.6 to 0.85, more preferably 0.6 to 0.8.
In the above production method, x2 is preferably 0.1 to 0.2.
In the above production method, x3 is preferably 0.05 to 0.2, more preferably 0.1 to 0.2.
In the above production method, a1 is preferably 1.
In the above preparation method, the chemical formula of the nickel-cobalt-manganese hydroxide can be Ni0.6Co0.2Mn0.2(OH)2The chemical formula of the corresponding seed crystal is LiNi0.6Co0.2Mn0.2O2。
In the above preparation method, the chemical formula of the nickel-cobalt-manganese hydroxide can be Ni0.8Co0.1Mn0.1(OH)2The chemical formula of the corresponding seed crystal is LiNi0.8Co0.1Mn0.1O2。
In the above production method, y1 is preferably 0.6 to 0.85, more preferably 0.85.
In the above production method, y2 is preferably 0.1 to 0.2, more preferably 0.1.
In the above production method, y3 is preferably 0.05 to 0.2, more preferably 0.05.
In the above production method, b1 is preferably 1.
In the above preparation method, the chemical formula of the nickel cobalt aluminum hydroxide can be Ni0.85Co0.1Al0.05(OH)2The chemical formula of the corresponding seed crystal is LiNi0.85Co0.1Al0.05O2。
In the above preparation method, the ternary precursor material may be prepared, for example, by a coprecipitation method.
In the above preparation method, the molar ratio of the ternary precursor material to the seed crystal is preferably 1:1 to 10: 1.
In the above preparation method, the lithium ion-containing molten salt may be an inorganic salt containing lithium ions, which can dissolve the ternary precursor material and can retain a liquid under the calcination. The lithium ion-containing molten salt may be, for example, Li2SO4One or more of LiF, LiCl and LiOH. The lithium ion-containing molten salt may further contain Na2SO4、K2SO4、Rb2SO4、Cs2SO4、NaCl、KCl、RbCl、CsCl、BaCl2One or more of CaCl, NaOH and KOH. The lithium ion-containing molten salt is more preferably LiOH and NaCl. Wherein, the molar ratio of LiOH to NaCl is preferably 1:10-10:1, more preferably 1:1-1.1: 1.
In the above preparation method, when the lithium ion-containing molten salt is LiOH and NaCl, the molar ratio of the ternary precursor material to the lithium ion-containing molten salt is preferably 0.25:1 to 0.44: 1.
In the above preparation method, before the calcination, the temperature is preferably raised to the calcination temperature at a temperature rise rate of 5 to 30 ℃/min, more preferably at a temperature rise rate of 10 ℃/min.
In the above preparation method, the oxygen-containing atmosphere may be an air atmosphere or an oxygen atmosphere.
In the preparation method, the calcination can realize the reaction of the ternary precursor material with oxygen and lithium ions, and the electrode material is generated on the surface of the seed crystal, and the molar ratio of the ternary precursor material, the oxygen and the lithium ions can satisfy the stoichiometric relationship of the reaction.
In the above preparation method, the calcination temperature may be a calcination temperature conventional in the art, and for example, may be 600-1000 ℃, preferably 900 ℃.
In the above preparation method, the calcination time may be a calcination time conventional in the art, and for example, may be 2 to 48 hours, preferably 10 hours.
In the above preparation method, the calcination is preferably followed by water washing and then drying.
Wherein, after the calcination, the calcination is preferably carried out after cooling to room temperature, and the washing is preferably carried out at the room temperature of 20-30 ℃, and preferably 25 ℃.
Wherein the washing refers to removing the lithium ion-containing molten salt that does not participate in the reaction with water.
Wherein, preferably, the drying treatment is performed under vacuum. The temperature of the drying treatment is preferably 60 to 200 c, more preferably 120 c. The time of the drying treatment is preferably 1 to 12 hours, more preferably 3 hours.
Wherein the drying treatment is preferably followed by a further calcination. The atmosphere for the re-calcination may be an air atmosphere or an oxygen atmosphere. The temperature of the re-calcination is preferably 400-900 deg.C, more preferably 750 deg.C. The calcination time is preferably 1 to 24 hours, for example, 6 hours or 20 hours, more preferably 10 hours. The re-calcination is preferably followed by cooling to room temperature, which is 20-30 c, preferably 25 c.
Wherein, the temperature rise rate of 5-20 ℃/min is preferably increased to the temperature of the re-calcination after the drying treatment, and the temperature rise rate of 10 ℃/min is more preferably increased to the temperature of the re-calcination after the drying treatment.
The invention also provides an electrode material prepared by the preparation method, wherein the average diameter of the electrode material is 3-10 microns, preferably 3-6 microns, and more preferably 3-5 microns.
Compared with the existing lithium nickel cobalt manganese (aluminum) oxide material, the electrode material has the advantages of larger average diameter, smaller specific surface area and specific crystal face morphology.
When the electrode material is a lithium nickel cobalt manganese oxide material, the chemical formula of the lithium nickel cobalt manganese oxide material is LiaNix1Cox2Mnx3O2And 0 < x1 < 1, 0 < x2 < 1, 0 < x3 < 1, x1+ x2+ x3 ═ 1, and a is 1 to 1.2. Wherein a can also be 1-1.1.
Wherein, when the electrode material is a nickel cobalt lithium aluminate material, the chemical formula of the nickel cobalt lithium aluminate material is LibNiy1Coy2Aly3O2And 0 < y1 < 1, 0 < y2 < 1, 0 < y3 < 1, y1+ y2+ y3 ═ 1, and b is 1 to 1.2. Wherein b can also be 1-1.1.
Wherein the average diameter is measured as follows: randomly screening 100 particles in the prepared product, measuring the distance between the farthest two points on each particle by using a scanning microscope, and obtaining an average value, namely the average diameter.
The invention also provides an application of the electrode material as a positive electrode material in a lithium ion battery.
The invention also provides a lithium ion battery prepared from the electrode material. The preparation method of the lithium ion battery can be as follows: dissolving 0.9g of the electrode material, 0.05g of acetylene black and 0.05g of PVDF in an NMP solvent, uniformly mixing, coating on an aluminum foil, drying at 80 ℃ for 2 hours and at 120 ℃ for 6 hours to prepare a circular pole piece with the diameter of 1cm, using metal lithium as a counter electrode, and assembling an electrolyte consisting of EC and EMC with the volume ratio of 3:7 and 1M LiPF6 into a 2032 button cell, wherein the 2032 button cell is the lithium ion cell.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the invention provides an electrode material, a lithium ion battery, and a preparation method and application thereof. According to the preparation method disclosed by the invention, the average diameter of the obtained electrode material can be controlled within a proper range by introducing the seed crystal, so that the interface side reaction of the electrode material in the battery circulation process is reduced, the capacity retention rate of the battery is further improved, and better rate performance and circulation stability are obtained.
Drawings
FIG. 1 is a graph of normalized specific capacity as a function of cycle number for the batteries obtained in example 5, example 6 and comparative example 2;
FIG. 2 is a scanning electron micrograph of the product obtained in example 1;
FIG. 3 is a scanning electron micrograph of a product obtained in comparative example 1;
FIG. 4 is a scanning electron micrograph of the product obtained in comparative example 3.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the examples described below, the room temperature is 25 ℃.
In the following examples and comparative examples, precursor materials were prepared by a coprecipitation method.
The average diameters in the following examples and comparative examples were measured as follows: for example, 100 particles of the prepared product are randomly selected, and the distance between the farthest two points on each particle is measured by a scanning microscope to obtain an average value, i.e., an average diameter.
In the following examples and comparative examples, the temperature rise, heating and holding were all performed in an air atmosphere, and the holding process was a calcination process.
Example 1
The precursor (9.2g, 0.1mol) Ni0.6Co0.2Mn0.2(OH)2(9.7g, 0.1mol) seed LiNi0.6Co0.2Mn0.2O2Evenly mixing (4.72g, 0.2mol) LiOH (11.69g, 0.2mol) NaCl, putting the mixture into a corundum crucible, heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 10 hours, naturally cooling the mixture to room temperature, washing the mixture with deionized water for three times to remove molten salt, drying the mixture in vacuum at 120 ℃ for 3 hours, then putting the mixture into the crucible, heating the mixture to 750 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 6 hours, and naturally cooling the mixture to room temperature to obtain a product 1, wherein the chemical formula of the product is LiNi0.6Co0.2Mn0.2O2。
The elemental analysis of the precursor and product 1 of example 1 is as follows.
Results of elemental analysis (ICP)
| Example 1 | Li | Ni | Co | Mn |
| Precursor body | 0 | 0.5949 | 0.2002 | 0.2050 |
| Product 1 | 1.03 | 0.5950 | 0.2000 | 0.2046 |
Example 2
The precursor (9.2g, 0.1mol) Ni0.6Co0.2Mn0.2(OH)2(0.97g, 0.01mol) seed LiNi0.6Co0.2Mn0.2O2Evenly mixing (2.9g, 0.121mol) LiOH (6.43g, 0.11mol) NaCl, putting the mixture into a corundum crucible, heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 10 hours, naturally cooling the mixture to room temperature, washing the mixture with deionized water for three times to remove molten salt, drying the mixture in vacuum at 120 ℃ for 3 hours, then putting the mixture into the crucible, heating the mixture to 750 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 6 hours, and naturally cooling the mixture to room temperature to obtain a product 2, wherein the chemical formula of the product is LiNi0.6Co0.2Mn0.2O2。
Example 3
The precursor (9.2g, 0.1mol) Ni0.8Co0.1Mn0.1(OH)2(9.7g, 0.1mol) seed LiNi0.8Co0.1Mn0.1O2Evenly mixing (4.72g, 0.2mol) LiOH (11.69g, 0.2mol) NaCl, putting the mixture into a corundum crucible, heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 10 hours, naturally cooling the mixture to room temperature, washing the mixture with deionized water for three times to remove molten salt, drying the mixture in vacuum at 120 ℃ for 3 hours, then putting the mixture into the crucible, heating the mixture to 750 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 6 hours, naturally cooling the mixture to room temperature to obtain a product 3, wherein the chemical formula of the product is LiNi0.8Co0.1Mn0.1O2。
Example 4
The precursor (9.1g, 0.1mol) Ni0.85Co0.1Al0.05(OH)2(9.6g, 0.1mol) seed LiNi0.85Co0.1Al0.05O2(4.72g, 0.2mol) LiOH, (11.69g, 0.2mol) NaCl are mixed evenly and put into a corundum crucibleHeating to 900 ℃ at the heating rate of 10 ℃/min, keeping for 10 hours, naturally cooling to room temperature, washing the mixture with deionized water for three times to remove molten salt, vacuum-drying at 120 ℃ for 3 hours, then placing the mixture into a crucible, heating to 750 ℃ at the heating rate of 10 ℃/min, keeping for 6 hours, and naturally cooling to room temperature to obtain a product 4 with the chemical formula of LiNi0.85Co0.1Al0.05O2。
Example 5
0.9g of product 1, 0.05g of acetylene black and 0.05g of PVDF were dissolved in NMP solvent, mixed uniformly, coated on an aluminum foil, dried at 80 ℃ for 2 hours and at 120 ℃ for 6 hours. A circular pole piece with the diameter of 1cm is manufactured, metal lithium is used as a counter electrode, and a 2032 button cell is assembled by using an electrolyte (EC/EMC: 3/7 volume ratio, 1MLiPF 6).
Example 6
0.9g of product 2, 0.05g of acetylene black and 0.05g of PVDF were dissolved in NMP solvent, mixed uniformly, coated on an aluminum foil, dried at 80 ℃ for 2 hours and at 120 ℃ for 6 hours. A circular pole piece with the diameter of 1cm is manufactured, metal lithium is used as a counter electrode, and a 2032 button cell is assembled by using an electrolyte (EC/EMC: 3/7 volume ratio, 1MLiPF 6).
Comparative example 1
Precursor Ni (18.4g, 0.2mol)0.6Co0.2Mn0.2(OH)2The preparation method comprises the following steps of (4.79g, 0.2mol) LiOH, (11.69g, 0.2mol) NaCl is uniformly mixed, the mixture is placed into a corundum crucible, heated to 900 ℃ at the heating rate of 10 ℃/min, kept for 10 hours, naturally cooled to room temperature, the mixture is washed three times by deionized water, dried in vacuum at 120 ℃ for 3 hours, then placed into the crucible, heated to 750 ℃ at the heating rate of 10 ℃/min, kept for 6 hours, and naturally cooled to room temperature, and a product 5 is obtained.
Comparative example 2
0.9g of product 5, 0.05g of acetylene black and 0.05g of PVDF were dissolved in NMP solvent, mixed uniformly, coated on an aluminum foil, dried at 80 ℃ for 2 hours and at 120 ℃ for 6 hours. A circular pole piece with the diameter of 1cm is manufactured, metal lithium is used as a counter electrode, and a 2032 button cell is assembled by using an electrolyte (EC/EMC: 3/7 volume ratio, 1MLiPF 6).
Comparative example 3
The precursor (9.2g, 0.1mol) Ni0.6Co0.2Mn0.2(OH)2(0.49g, 0.005mol) seed LiNi0.6Co0.2Mn0.2O2Uniformly mixing (4.79g, 0.2mol) LiOH (11.69g, 0.2mol) NaCl, putting the mixture into a corundum crucible, heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 10 hours, naturally cooling the mixture to room temperature, washing the mixture with deionized water for three times to remove molten salt, carrying out vacuum drying at 120 ℃ for 3 hours, then putting the mixture into the crucible, heating the mixture to 750 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 6 hours, and naturally cooling the mixture to room temperature to obtain a product 5 with the chemical formula of LiNi0.6Co0.2Mn0.2O2。
Effect example 1 cycle test
1. And (3) testing conditions are as follows: the voltage range is 2.8-4.3V, the current circulation of 0.1C multiplying factor is performed for 3 times, and then the current circulation of 1C multiplying factor is performed for 300 times.
As a result: as can be seen from fig. 1, the capacity retention rates of the batteries obtained in comparative example 2, example 5 and example 6 were 74.6%, 87.5% and 82.93%, respectively, after 300 cycles. Therefore, with the addition of the seed crystal, the cycling stability of the battery prepared from the nickel cobalt lithium manganate which is the final product is obviously improved.
2. And (3) testing conditions are as follows: the voltage range is 2.8-4.3V, and the current is circulated for 100 times at 0.2C multiplying power.
As a result: the capacity retention rates of the batteries obtained in example 5 and example 6 were 96.3% and 92.8%, respectively.
3. And (3) testing conditions are as follows: the voltage range is 2.8-4.3V, and the current is circulated for 100 times at 1C multiplying power.
As a result: the capacity retention rates of the batteries obtained in example 5 and example 6 were 94.7% and 89.5%, respectively.
Effect example 2 Rate test
The test conditions are that the voltage range is 2.8-4.3V, the charging current is 0.2C multiplying power, the discharging current is 0.2C, and the cycle is 5 times; then, the discharge current is 1C, and the cycle is performed for 5 times; discharging current is 3C, and circulating for 5 times; the discharge current is 5C, and the cycle is 5 times; the discharge current is 10C, and the cycle is 5 times; the discharge current is 20C, and the cycle is 5 times; wherein, the specific capacities of 5 times are respectively taken, and the average value of the obtained specific capacities of 5 times is the average specific capacity in the following table.
TABLE 1 average specific capacity (unit (mAh/g)) of battery obtained in rate test
| 0.2C | 1C | 3C | 5C | 10C | 20C | |
| Comparative example 2 | 173 | 166 | 156 | 145 | 136 | 128 |
| Example 5 | 178 | 170 | 163 | 151 | 144 | 132 |
| Example 6 | 175 | 168 | 160 | 149 | 141 | 130 |
As can be seen from table 1, the rate performance of the battery obtained in example 5 is the best, and the rate performance of example 6 times is better than that of comparative example 2.
Effect example 3 Observation by scanning Electron microscope
As can be seen from FIGS. 2 and 3, the average diameter of the product obtained in example 1 was 3 to 5 μm, and the average diameter of the product obtained in comparative example 1 was 1 to 2 μm. Therefore, the average diameter of the product obtained in example 1 is obviously larger than that of comparative example 1, and the inventor finds that the specific surface area of the product obtained in example 1 is smaller, the interface side reaction is less, and the battery prepared by the product has better capacity retention rate, rate capability and cycling stability. That is, the performance of the battery obtained in example 5 was superior to that of the battery obtained in comparative example 2.
As can be seen from fig. 4, the average diameter of the product obtained in comparative example 3 is 0.4 μm, the specific surface area thereof is larger than that of examples 1 and 2, the interfacial side reaction increases, and thus the capacity retention rate, rate capability and cycle stability of the battery obtained therefrom are inferior to those of the batteries obtained in examples 1 and 2. That is, the performance of the battery obtained from the product of comparative example 3 was inferior to that of the batteries obtained from examples 5 and 6.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (11)
1. A preparation method of an electrode material is characterized by comprising the following steps: calcining a mixture of a ternary precursor material, a seed crystal and a lithium ion-containing molten salt in an oxygen-containing atmosphere; wherein the molar ratio of the ternary precursor material to the seed crystal is 1:1-10: 1;
the ternary precursor material is nickel-cobalt-manganese hydroxide, and the chemical formula of the nickel-cobalt-manganese hydroxide is Ni0.6Co0.2Mn0.2(OH)2The chemical formula of the seed crystal is LiNi0.6Co0.2Mn0.2O2；
The lithium ion-containing molten salt is LiOH and NaCl, and the molar ratio of the LiOH to the NaCl is 1:1-1.1: 1;
the molar ratio of the ternary precursor material to the lithium ion-containing molten salt is 0.25:1-0.44: 1;
the average diameter of the electrode material is 3-5 microns.
2. The method of claim 1, wherein the ternary precursor material is prepared by a co-precipitation method.
3. The method for preparing an electrode material according to claim 1, wherein, prior to the calcining, the temperature is raised to the calcining temperature at a temperature rise rate of 5 to 30 ℃/min;
and/or the oxygen-containing atmosphere is an air atmosphere or an oxygen atmosphere;
and/or the temperature of the calcination is 600-1000 ℃;
and/or the calcining time is 2-48 h.
4. The method for preparing an electrode material according to claim 3, wherein, prior to the calcining, the temperature is raised to the calcining temperature at a temperature rise rate of 10 ℃/min;
and/or, the temperature of the calcination is 900 ℃;
and/or the calcining time is 10 h.
5. The method for preparing an electrode material according to claim 1, wherein the calcination is followed by water washing and drying.
6. The method for preparing the electrode material according to claim 5, wherein the calcining is followed by cooling to room temperature and then washing, wherein the room temperature is 20-30 ℃;
and/or, the drying process is carried out under vacuum;
and/or the temperature of the drying treatment is 60-200 ℃;
and/or the drying treatment time is 1-12 h;
and/or, the drying treatment is followed by a further calcination;
and/or, after the drying treatment, the temperature is increased to the temperature of the secondary calcination at a temperature rising rate of 5-20 ℃/min.
7. The method for preparing an electrode material according to claim 6, wherein the calcination is followed by cooling to 25 ℃ and then by the washing;
and/or the temperature of the drying treatment is 120 ℃;
and/or the drying treatment time is 3 h;
and/or the atmosphere of the secondary calcination is an air atmosphere or an oxygen atmosphere;
and/or the temperature of the secondary calcination is 400-900 ℃;
and/or the time for the secondary calcination is 1-24 h;
and/or, after said re-calcination, cooling to 20-30 ℃;
and/or, after the drying treatment, the temperature is increased to the temperature of the re-calcination at a temperature increasing rate of 10 ℃/min.
8. The method for preparing an electrode material according to claim 7, wherein the temperature of the re-calcination is 750 ℃;
and/or the time for the secondary calcination is 10 h;
and/or, after said re-calcination, cooling to 25 ℃.
9. An electrode material produced by the production method according to any one of claims 1 to 8, wherein the electrode material has an average diameter of 3 to 5 μm;
the electrode material is a lithium nickel cobalt manganese oxide material, and the chemical formula of the lithium nickel cobalt manganese oxide material is LiNi0.6Co0.2Mn0.2O2。
10. Use of the electrode material according to claim 9 as a positive electrode material in a lithium ion battery.
11. A lithium ion battery, characterized in that it is made of the electrode material according to claim 9.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811518320.0A CN109786731B (en) | 2018-12-12 | 2018-12-12 | Electrode material, lithium ion battery, and preparation method and application thereof |
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| CN113299905B (en) * | 2021-05-21 | 2023-05-16 | 湖北融通高科先进材料集团股份有限公司 | Preparation method of monocrystal nickel cobalt lithium manganate ternary material |
| CN115084506B (en) * | 2022-05-18 | 2024-07-09 | 广东邦普循环科技有限公司 | Large-particle-size monocrystal ternary positive electrode material, and preparation method and application thereof |
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