CN109037672B - Preparation method of nickel cobalt lithium manganate material for power battery - Google Patents
Preparation method of nickel cobalt lithium manganate material for power battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a nickel cobalt lithium manganate material for a power battery. The preparation method of the nickel cobalt lithium manganate material for the power battery comprises the following steps: 1) putting the nickel cobalt lithium manganate precursor sintering material into an electric field device, then putting the material into a sintering furnace, and introducing protective gas; 2) gradually raising the temperature of the furnace from room temperature to 500-650 ℃, and keeping the temperature constant; 3) loading current to the electric field device, electrifying to process the sintered material, and continuously keeping constant temperature after power failure; 4) firstly introducing oxygen-protective gas mixed gas, then introducing oxygen, continuously heating to 700-950 ℃, and keeping constant temperature to obtain the nickel cobalt lithium manganate material. According to the invention, the nickel cobalt lithium manganate material for the power battery is prepared by adopting an electric field synergistic sintering method, the material sintering is more uniform and compact, and the obtained ternary material has high tap density and good electrical property.
Description
Technical Field
The invention relates to a preparation method of a nickel cobalt lithium manganate material for a power battery.
Background
According to data released by the Ministry of industry and belief, the yield of new energy vehicles in China from 2015 to 2017 is respectively 34.0 thousands, 51.7 thousands and 79.4 thousands, and the sales volume is respectively 33.1 thousands, 50.7 thousands and 77.7 thousands. In recent years, the new energy automobile industry in China is continuously and rapidly developed. The power battery is used as a key part of the new energy automobile, and has the characteristics of good safety, high energy density, long charging and discharging service life and the like.
The lithium nickel cobalt manganese oxide positive electrode material is widely applied according to the high energy density technical route of power batteries in China, and according to the research and statistics of starting points, the yield of the lithium nickel cobalt manganese oxide positive electrode material in 2017 in China is 8.6 ten thousand tons, accounts for 41.0 percent of the total yield of the positive electrode material, and far exceeds the yields of lithium iron phosphate, lithium manganese oxide and lithium cobalt oxide. The performance of the cathode material is a main factor influencing the performance of the battery, and the high-density cathode material is an important way for realizing high-energy-density power.
The traditional solid phase method is a common method for preparing battery materials, and a ternary material is obtained by mixing a ternary precursor with a lithium source in a certain proportion and sintering at high temperature. In the traditional solid phase method, the ternary precursor and the lithium source are mechanically and uniformly mixed, the ternary precursor and the lithium source are difficult to realize complete uniformity, and the sintered material is easy to have local lithium enrichment or lithium deficiency, so that defects are caused, and the performance of the material is influenced. In order to solve the problem of material mixing uniformity, researchers propose a method of mixing, pre-sintering, cooling, secondary mixing and secondary sintering to sinter ternary materials, but the method has the defects of long flow, low efficiency, high energy consumption and the like. Meanwhile, the sintered ternary material produced by the traditional solid phase method has the advantages of loose structure, low density, short service life and small capacity. Wangshanhua et al propose a preparation method of a lithium ion battery anode material (CN107611414A), which is to uniformly mix a precursor material with a lithium source, press the mixture, and sinter the mixture at a low temperature under the condition of applying an electric field. However, the pressing process can destroy the original appearance of the precursor material, even if the spherical precursor material is used as a raw material, the spherical anode material is difficult to obtain after sintering, and the prepared non-spherical anode material has low tap density, small capacity and obvious limitation.
Disclosure of Invention
The invention aims to provide a preparation method of a nickel cobalt lithium manganate material for a power battery.
The technical scheme adopted by the invention is as follows:
a preparation method of a nickel cobalt lithium manganate material for a power battery comprises the following steps:
1) putting the nickel cobalt lithium manganate precursor sintering material into an electric field device, then putting the material into a sintering furnace, and introducing protective gas;
2) gradually raising the temperature of the furnace from room temperature to 500-650 ℃, and keeping the temperature constant;
3) loading current to the electric field device, electrifying to process the sintered material, and continuously keeping constant temperature after power failure;
4) firstly introducing oxygen-protective gas mixed gas, then introducing oxygen, continuously heating to 700-950 ℃, and keeping constant temperature to obtain the nickel cobalt lithium manganate material.
In the preparation method, the electric field device is a crucible boat with platinum sheets at two ends, and the platinum sheets are connected with a direct current device.
In the step 1) of the preparation method, the nickel cobalt lithium manganate precursor sintering material is prepared by mixing nickel cobalt manganese hydroxide and a lithium source according to the element molar ratio (Ni + Co + Mn): L i is 1 (1.1-1.3), the ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide is x: y (100-x-y), wherein x is more than or equal to 20 and less than or equal to 80, and y is more than or equal to 0 and less than or equal to 20.
In step 2) of the preparation method, the temperature rise process specifically comprises the following steps: firstly, heating to 120 ℃ at a speed of 0.5-4 ℃/min, and keeping the temperature for 0.5-1 h; then heating to 500-650 ℃ at the speed of 0.5-10 ℃/min, and keeping the temperature for 0.5-1 h.
In the step 3) of the preparation method, the voltage of the electrifying treatment is 6V-9V, the current is 100A-2000A, and the electrifying time is 0.5 h-1 h; and after the power failure, the constant temperature is kept for 1-2 h.
The preparation method comprises the following specific steps in step 4): firstly introducing oxygen-protective gas mixture for 0.5-1 h, then introducing oxygen, continuously heating to 700-950 ℃ at the speed of 1-5 ℃/min, and keeping the temperature for 1-20 h.
In the step 4) of the preparation method, the concentration of oxygen in the oxygen-protective gas mixture is 2 ppm-20 ppm.
In step 1) or step 4) of the preparation method, the protective gas is at least one of nitrogen and inert gas.
A nickel cobalt lithium manganate material for a power battery is prepared by the preparation method.
The positive electrode of the power battery is the nickel cobalt lithium manganate material.
The invention has the beneficial effects that:
according to the invention, the nickel cobalt lithium manganate material for the power battery is prepared by adopting an electric field synergistic sintering method, the material sintering is more uniform and compact, and the obtained ternary material has high tap density and good electrical property.
1. According to the invention, electric field synergistic sintering is adopted, part of lithium source is reduced into metal lithium in the sintering process, the metal lithium with lower melting point is easier to flow and move after being melted, and is automatically and uniformly mixed with the ternary precursor in the sintering process, so that local lithium enrichment or lithium shortage among sintered material particles is avoided. Meanwhile, molten metal lithium is easier to penetrate through the precursor, the consistency of chemical components in the sintered material particles is higher, and the performance of the ternary material is favorably exerted.
2. The invention adopts electric field to sinter, the material is more compact under the action of the electric field, and the material can obtain high tap density after sintering without chemical modification.
3. According to the invention, the precursor and the lithium source are uniformly mixed and then sintered under the condition of applying an electric field, so that the damage of a pressing process to the appearance of the precursor is avoided, spherical nickel cobalt lithium manganate can be obtained after sintering, and the tap density of the material is effectively improved.
Drawings
FIG. 1 is a scanning electron microscope image of a lithium nickel cobalt manganese oxide material prepared in example 1;
FIG. 2 is a charge and discharge graph of examples and comparative examples;
FIG. 3 is a graph of cycle performance for the examples and comparative examples.
Detailed Description
A preparation method of a nickel cobalt lithium manganate material for a power battery comprises the following steps:
1) putting the nickel cobalt lithium manganate precursor sintering material into an electric field device, then putting the material into a sintering furnace, and introducing protective gas;
2) gradually raising the temperature of the furnace from room temperature to 500-650 ℃, and keeping the temperature constant;
3) loading current to the electric field device, electrifying to process the sintered material, and continuously keeping constant temperature after power failure;
4) firstly introducing oxygen-protective gas mixed gas, then introducing oxygen, continuously heating to 700-950 ℃, and keeping constant temperature to obtain the nickel cobalt lithium manganate material.
Preferably, in the preparation method, the electric field device is a crucible boat with platinum sheets arranged at two ends, and the platinum sheets are connected with the direct current device.
Preferably, the crucible boat of the electric field device is made of any one of ceramics, quartz and corundum.
Preferably, in the step 1) of the preparation method, the nickel cobalt lithium manganate precursor sintering material is prepared by mixing nickel cobalt manganese hydroxide and a lithium source according to the element molar ratio (Ni + Co + Mn): L i being 1 (1.1-1.3).
Further preferably, in the step 1) of the preparation method, the nickel cobalt manganese acid lithium precursor sintering material is obtained by mixing nickel cobalt manganese hydroxide and a lithium source according to the element molar ratio (Ni + Co + Mn): L i being 1 (1.1-1.3), adding an auxiliary grinding agent according to the solid-liquid ratio 1 (0.01-0.2), and carrying out ball milling for 1-10 h.
Preferably, in the nickel cobalt manganese acid lithium precursor sintering material, the ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide is x: y: (100-x-y), wherein x is more than or equal to 20 and less than or equal to 80, and y is more than or equal to 0 and less than or equal to 20.
Preferably, in the nickel cobalt lithium manganate precursor sintering material, the lithium source is at least one of lithium carbonate, lithium nitrate, lithium hydroxide, lithium oxide, lithium oxalate and lithium acetate; more preferably, the lithium source is at least one of lithium carbonate and lithium hydroxide.
Preferably, in the nickel cobalt lithium manganate precursor sintering material, the grinding aid is at least one of water, ethanol, propanol and acetone.
Preferably, in step 2) of the preparation method, the temperature rise process specifically comprises: firstly, heating to 120 ℃ at a speed of 0.5-4 ℃/min, and keeping the temperature for 0.5-1 h; then heating to 500-650 ℃ at the speed of 0.5-10 ℃/min, and keeping the temperature for 0.5-1 h.
Preferably, in the step 3) of the preparation method, the voltage of the electrifying treatment is 6V-9V, the current is 100A-2000A, and the electrifying time is 0.5 h-1 h; and after the power failure, the constant temperature is kept for 1-2 h.
Preferably, in step 4) of the preparation method, the method specifically comprises the following steps: firstly introducing oxygen-protective gas mixture for 0.5-1 h, then introducing oxygen, continuously heating to 700-950 ℃ at the speed of 1-5 ℃/min, and keeping the temperature for 1-20 h.
Preferably, in step 4) of the preparation method, the concentration of oxygen in the oxygen-shielding gas mixture is 2ppm to 20 ppm.
Preferably, in step 1) or step 4) of the preparation method, the protective gas is at least one of nitrogen and inert gas; further preferably, the protective gas is at least one of nitrogen and argon; still more preferably, the protective gas in step 1) is argon; the oxygen-protective gas mixed gas in the step 4) is oxygen-argon gas mixed gas.
Preferably, the preparation method further comprises a step 5) of crushing the lithium nickel cobalt manganese oxide material, and controlling the particle size D50 to be 2-20 μm to obtain the lithium nickel cobalt manganese oxide positive electrode material.
Preferably, in the preparation method, the sintering furnace is a closed sintering furnace, the sintering furnace is provided with an air inlet and an air outlet, and the air outlet is provided with a check valve.
A nickel cobalt lithium manganate material for a power battery is prepared by the preparation method.
The positive electrode of the power battery is the nickel cobalt lithium manganate material.
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
Example 1:
a preparation method of power type lithium nickel cobalt manganese oxide comprises the following specific steps:
and S1, mixing the nickel-cobalt-manganese hydroxide and lithium carbonate according to the element molar ratio (Ni + Co + Mn): L i is 1:1.1, adding ethanol, and performing ball milling for 4 hours to obtain the material to be sintered, wherein the molar ratio of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide is 55:20: 25.
S2: and putting the material to be sintered into a ceramic crucible boat, respectively inserting platinum sheets at two ends of the crucible boat, putting the crucible boat into a closed sintering furnace, and introducing argon gas from a gas inlet.
S3: heating from room temperature to 120 deg.C at 0.5 deg.C/min, holding the temperature for 0.5h, and continuing heating to 550 deg.C at 0.5 deg.C/min, and holding the temperature for 1 h.
S4: and (3) loading direct current on the platinum sheet, wherein the voltage is 6V, the current is 100A, and the platinum sheet is electrified for 1 h. And continuously keeping the constant temperature for 1h after power failure.
S5: at the temperature, oxygen-argon mixed gas with the oxygen concentration of 2ppm is introduced, and the introducing time is 1 h. And introducing oxygen, continuously heating to 800 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1h to obtain the nickel cobalt lithium manganate.
S6: the above lithium nickel cobalt manganese oxide was crushed, and the particle size was controlled to 10 μm in D50, to obtain the lithium nickel cobalt manganese oxide positive electrode material of example 1. The SEM image of the lithium nickel cobalt manganese oxide cathode material of the example 1 can be seen in the attached figure 1.
Example 2:
a preparation method of power type lithium nickel cobalt manganese oxide comprises the following specific steps:
s1, mixing the nickel-cobalt-manganese hydroxide and the lithium hydroxide according to the element molar ratio (Ni + Co + Mn): L i is 1.2, adding ethanol, and carrying out ball milling for 1h to obtain the material to be sintered, wherein the molar ratio of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide is 20:20: 60.
S2: and (3) putting the material to be sintered into a quartz crucible boat, respectively inserting platinum sheets at two ends of the crucible boat, putting the crucible boat into a closed sintering furnace, and introducing argon gas from a gas inlet.
S3: heating from room temperature to 120 deg.C at 2 deg.C/min, holding the temperature for 1h, heating to 650 deg.C at 3 deg.C/min, and holding the temperature for 0.7 h.
S4: and (3) loading direct current on the platinum sheet, wherein the voltage is 8V, the current is 500A, and the power is supplied for 0.7 h. And continuously keeping the constant temperature for 1.5h after power failure.
S5: at the temperature, oxygen-argon mixed gas with the oxygen concentration of 10ppm is introduced, and the introducing time is 0.7 h. And introducing oxygen, continuously heating to 700 ℃ at the speed of 3 ℃/min, and keeping the temperature for 8 hours to obtain the nickel cobalt lithium manganate.
S6: and crushing the nickel cobalt lithium manganate, and controlling the particle size until the D50 is 20 mu m to obtain the nickel cobalt lithium manganate positive electrode material of example 2.
Example 3:
a preparation method of power type lithium nickel cobalt manganese oxide comprises the following specific steps:
s1, mixing the nickel-cobalt-manganese hydroxide and the lithium hydroxide according to the element molar ratio (Ni + Co + Mn): L i is 1.3, adding ethanol, and carrying out ball milling for 10 hours to obtain the material to be sintered, wherein the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese hydroxide is 80:5: 15.
S2: and (3) putting the material to be sintered into a corundum crucible boat, respectively inserting platinum sheets at two ends of the crucible boat, putting the crucible boat into a closed sintering furnace, and introducing argon from an air inlet.
S3: heating from room temperature to 120 deg.C at 4 deg.C/min, holding the temperature for 0.8h, and continuing heating to 500 deg.C at 10 deg.C/min, and holding the temperature for 0.5 h.
S4: and (3) loading direct current on the platinum sheet, wherein the voltage is 9V, the current is 2000A, and the power is supplied for 0.5 h. And continuously keeping the constant temperature for 2 hours after power failure.
S5: at the temperature, oxygen-argon mixed gas with the oxygen concentration of 20ppm is introduced, and the introducing time is 0.5 h. And introducing oxygen, continuously heating to 950 ℃ at the speed of 5 ℃/min, and keeping the temperature for 20 hours to obtain the nickel cobalt lithium manganate.
S6: and crushing the nickel cobalt lithium manganate, and controlling the particle size until the D50 is 2 microns to obtain the nickel cobalt lithium manganate positive electrode material of example 3.
Example 4:
a preparation method of power type lithium nickel cobalt manganese oxide comprises the following specific steps:
and S1, mixing the nickel-cobalt-manganese hydroxide and lithium carbonate according to the element molar ratio (Ni + Co + Mn): L i is 1:1.1, adding ethanol, and performing ball milling for 2 hours to obtain the material to be sintered, wherein the molar ratio of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide is 55:15: 30.
S2: and putting the material to be sintered into a ceramic crucible boat, respectively inserting platinum sheets at two ends of the crucible boat, putting the crucible boat into a closed sintering furnace, and introducing argon gas from a gas inlet.
S3: heating from room temperature to 120 deg.C at 1 deg.C/min, holding the temperature for 0.5h, and continuing heating to 600 deg.C at 0.5 deg.C/min, and holding the temperature for 0.8 h.
S4: and (3) loading direct current on the platinum sheet, wherein the voltage is 7V, the current is 100A, and the platinum sheet is electrified for 1 h. And continuously keeping the constant temperature for 1h after power failure.
S5: at the temperature, oxygen-argon mixed gas with the oxygen concentration of 2ppm is introduced, and the introducing time is 1 h. And introducing oxygen, continuously heating to 750 ℃ at the speed of 1 ℃/min, and keeping the temperature for 5 hours to obtain the nickel cobalt lithium manganate.
S6: and crushing the nickel cobalt lithium manganate, and controlling the particle size until the D50 is 4 mu m to obtain the nickel cobalt lithium manganate positive electrode material of example 4.
Example 5:
a preparation method of power type lithium nickel cobalt manganese oxide comprises the following specific steps:
and S1, mixing the nickel-cobalt-manganese hydroxide and lithium carbonate according to the element molar ratio (Ni + Co + Mn): L i is 1:1.1, adding ethanol, and performing ball milling for 8 hours to obtain the material to be sintered, wherein the molar ratio of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide is 55:12: 33.
S2: and putting the material to be sintered into a ceramic crucible boat, respectively inserting platinum sheets at two ends of the crucible boat, putting the crucible boat into a closed sintering furnace, and introducing argon gas from a gas inlet.
S3: heating from room temperature to 120 deg.C at 3 deg.C/min, holding the temperature for 0.5h, and continuing heating to 550 deg.C at 0.5 deg.C/min, and holding the temperature for 0.6 h.
S4: and (3) loading direct current on the platinum sheet, wherein the voltage is 6V, the current is 100A, and the platinum sheet is electrified for 1 h. And continuously keeping the constant temperature for 1h after power failure.
S5: at the temperature, oxygen-argon mixed gas with the oxygen concentration of 2ppm is introduced, and the introducing time is 1 h. And introducing oxygen, continuously heating to 850 ℃ at the speed of 1 ℃/min, and keeping the temperature for 15 hours to obtain the nickel cobalt lithium manganate.
S6: the nickel cobalt lithium manganate is crushed, and the particle size is controlled to be 14 μm in D50, so that the nickel cobalt lithium manganate positive electrode material of example 5 is obtained.
Comparative example 1:
respectively mixing nickel-cobalt-manganese hydroxide (the ratio of nickel, cobalt and manganese elements is 55:20: 25) and lithium carbonate according to the element molar ratio (Ni + Co + Mn) of L i is 1:1, adding ethanol, carrying out ball milling for 4h, drying in an oven at 120 ℃, putting the obtained powder in a muffle furnace, sintering in oxygen at 800 ℃ for 8h, and obtaining a nickel-cobalt-manganese acid lithium comparative sample of comparative example 1. comparative example 2:
the preparation method of the nickel cobalt lithium manganate positive electrode material of the comparative example 2 comprises the following specific steps:
and S1, mixing the nickel-cobalt-manganese hydroxide and lithium carbonate according to the element molar ratio (Ni + Co + Mn): L i is 1:1.1, adding ethanol, carrying out ball milling for 4 hours, and drying to obtain the material to be sintered, wherein the molar ratio of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide is 55:20: 25.
S2: and putting the material to be sintered into a mould, respectively inserting platinum sheets into two ends of the mould, pressing, and putting the pressed material and the mould into a ceramic crucible boat.
S3: heating from room temperature to 120 deg.C at a rate of 0.5 deg.C/min under argon atmosphere, holding the temperature for 0.5h, continuing heating at a rate of 0.5 deg.C/min to 550 deg.C, and holding the temperature for 1 h.
S4: and (3) loading direct current on the platinum sheet, wherein the voltage is 6V, the current is 100A, and the platinum sheet is electrified for 1 h. And continuously keeping the constant temperature for 1h after power failure.
S5: at the temperature, oxygen-argon mixed gas with the oxygen concentration of 2ppm is introduced, and the introducing time is 1 h. And introducing oxygen, keeping the temperature constant for 1 hour, and crushing after cooling to obtain the nickel cobalt lithium manganate positive electrode material of the comparative example 2.
And (3) performance detection:
tap density tests were performed on the lithium nickel cobalt manganese oxides obtained in examples 1 to 5 and the lithium nickel cobalt manganese oxides obtained in comparative examples 1 to 2, and the results are shown in Table 1. The result shows that the tap density of the nickel cobalt lithium manganate prepared in the examples 1-5 is far higher than that of the comparative examples 1-2.
TABLE 1 tap density of lithium nickel cobalt manganese oxide materials
| Sample (I) | Tap density (g/cm)3) |
| Examples1 | 2.6 |
| Example 2 | 2.6 |
| Example 3 | 2.5 |
| Example 4 | 2.6 |
| Example 5 | 2.5 |
| Comparative example 1 | 2.2 |
| Comparative example 2 | 1.8 |
The lithium nickel cobaltate prepared in example 1 and comparative examples 1-2 was used as a positive electrode and metallic lithium was used as a negative electrode, respectively, to assemble a battery. The first discharge test was performed on each of the prepared batteries at a rate of 1C, and the results are shown in fig. 2. The result shows that under the rate of 1C, the first discharge specific capacity of the power type nickel cobalt lithium manganate positive electrode material of the example 1 is higher than that of the comparative example 1 of the common solid phase method, the specific capacity of the example 1 is 185.4mAh/g, while the specific capacity of the comparative example 1 is only 172.2mAh/g, and the specific capacity of the comparative example 2 is only 175.2 mAh/g.
The results of 1000 charge-discharge cycle tests at 0.5C rate are shown in fig. 3. The result shows that the specific capacity of the nickel cobalt lithium manganate positive electrode material is higher than that of the common solid phase method after 1000 cycles, the capacity retention rate of example 1 is 93.6%, and the capacity retention rate of comparative example 1 is only 85.5%. Example 1 is also higher than comparative example 2 with the addition of the pressing process, and comparative example 2 has a capacity retention of only 87.4%.
Claims (8)
1. A preparation method of a nickel cobalt lithium manganate positive electrode material for a power battery is characterized by comprising the following steps: the method comprises the following steps:
1) putting the nickel cobalt lithium manganate precursor sintering material into an electric field device without pressing, then putting the material into a sintering furnace, and introducing protective gas;
2) gradually raising the temperature of the furnace from room temperature to 500-650 ℃, and keeping the temperature constant;
3) loading current to the electric field device, electrifying to process the sintered material, and continuously keeping constant temperature after power failure;
4) introducing oxygen-protective gas mixed gas, introducing oxygen, continuously heating to 700-950 ℃, and keeping constant temperature to obtain a nickel cobalt lithium manganate positive electrode material;
in the step 1), the nickel cobalt lithium manganate precursor sintering material is prepared by mixing nickel cobalt manganese hydroxide and a lithium source according to the element molar ratio (Ni + Co + Mn): L i is 1 (1.1-1.3);
in the step 3), the voltage of the electrifying treatment is 6-9V, the current is 100-2000A, and the electrifying time is 0.5-1 h; keeping the constant temperature for 1-2 h after power failure;
in the step 4), the method specifically comprises the following steps: firstly introducing oxygen-protective gas mixture for 0.5-1 h, then introducing oxygen, continuously heating to 700-950 ℃ at the speed of 1-5 ℃/min, and keeping the temperature for 1-20 h.
2. The preparation method of the nickel cobalt lithium manganate positive electrode material for the power battery according to claim 1, characterized in that: the electric field device is a crucible boat with platinum sheets arranged at two ends, and the platinum sheets are connected with the direct current device.
3. The preparation method of the nickel cobalt lithium manganate positive electrode material for the power battery according to claim 1, characterized in that: in the step 1), the molar ratio of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide is x: y: (100-x-y), wherein x is more than or equal to 20 and less than or equal to 80, y is more than 0 and less than or equal to 20, and x + y is less than 100.
4. The preparation method of the nickel cobalt lithium manganate positive electrode material for the power battery according to claim 1, characterized in that: in the step 2), the temperature rise process specifically comprises the following steps: firstly, heating to 120 ℃ at a speed of 0.5-4 ℃/min, and keeping the temperature for 0.5-1 h; then heating to 500-650 ℃ at a speed of 0.5-10 ℃/min, and keeping the temperature for 0.5-1 h.
5. The preparation method of the nickel cobalt lithium manganate positive electrode material for the power battery according to claim 1, characterized in that: in the step 4), the concentration of oxygen in the oxygen-protective gas mixed gas is 2 ppm-20 ppm.
6. The preparation method of the nickel cobalt lithium manganate positive electrode material for power batteries according to claim 1 or 5, characterized in that: the protective gas is at least one of nitrogen and inert gas.
7. The utility model provides a lithium nickel cobalt manganese oxide cathode material for power battery which characterized in that: is prepared by the preparation method of any one of claims 1 to 6.
8. A power battery, characterized by: the positive electrode is the nickel cobalt lithium manganate positive electrode material of claim 7.
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| CN112079396A (en) * | 2020-08-25 | 2020-12-15 | 北方奥钛纳米技术有限公司 | Nickel-containing cathode material, preparation method thereof and lithium ion battery comprising nickel-containing cathode material |
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