Patent Application
20240097100
The present disclosure relates to the field of lithium-ion batteries, for example, to a layered positive electrode material and a preparation method therefor and use thereof.
Lithium-ion batteries are widely used in electric vehicles, hybrid vehicles and energy storage systems because of their high capacity and high energy density. As one of the core components of lithium-ion batteries, positive electrode materials have a great influence on the performance of lithium-ion batteries.
Layered positive electrode materials have the advantages of high capacity and low price, and are being used in electric vehicles. However, layered positive electrode materials have the problems of high surface residual alkali (LiOH and Li2CO3) and high pH value, which make positive electrode materials gel during homogenization, hindering their industrial application. At present, the most commonly used method to reduce residual alkali is to wash the positive electrode material and then dry the positive electrode material, which has complicated process and long production period. The process of washing not only causes lithium loss, but also pollutes water resources. Therefore, new processes need to be explored to simplify the process, decrease lithium loss, reduce surface residual alkali and enhance the conductivity of the material.
In one embodiment, the present disclosure provides a preparation method of a layered positive electrode material, and the preparation method includes the following steps:
For example, in the NiaCobMnc(OH)2, a may be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 0.95, etc.; b may be 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11 or 0.12, etc.; c may be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.10, etc.
In the present disclosure, after the primary sintering in the oxygen atmosphere, the sintered material is crushed and screened, and then the secondary sintering is further performed in the sulfur dioxide atmosphere to make full contact and reaction between sulfur dioxide and the primary sintered product, and sulfur dioxide reacts with the residual alkali on the surface of the positive electrode material to produce lithium sulfate, which achieves a purpose of reducing the residual alkali and pH value on the surface of the layered positive electrode material, and at the same time, it is beneficial to improving the processability of the layered positive electrode material, improving the conductivity of the layered positive electrode material and effectively enhancing the electrochemical performance of the battery.
Without crushing and screening after the primary sintering, products after the primary sintering will be agglomerated, which is not conducive to the subsequent full contact and reaction of sulfur dioxide and materials, and it is difficult to achieve the purpose of reducing the residual alkali on the surface of positive electrode materials.
In the secondary sintering of the present disclosure, if the sintering is continue in the oxygen atmosphere instead of in the sulfur dioxide atmosphere, it will not conducive to reducing the residual alkali, and the purpose of introducing sulfur dioxide is to utilize sulfur dioxide to react with the residual alkali on the surface of the positive electrode material.
Compared with a method of removing residual alkali by water washing, a preparation method provided by the present disclosure has the advantages of reducing the residual alkali on the surface of the positive electrode material without losing the capacity of the positive electrode material at the same time (a part of lithium in the positive electrode material will be washed away during the water washing process, which will reduce the capacity of the positive electrode material).
In one embodiment, a molar ratio of the layered nickel-cobalt-manganese hydroxide to lithium in the lithium source in step (1) is 1:(1.02-1.09), such as 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08 or 1:1.09, etc.
In one embodiment, the lithium source includes lithium hydroxide and/or lithium carbonate.
In one embodiment, a flow rate of oxygen in step (1) is 3-10 L/min, such as 3 L/min, 4 L/min, 5 L/min, 6 L/min, 7 L/min, 8 L/min, 9 L/min or 10 L/min, etc.
In one embodiment, a temperature of the primary sintering in step (1) is 850-950° C., such as 850° C., 860° C., 870° C., 880° C., 890° C., 900° C., 910° C., 920° C., 930° C., 940° C. or 950° C., etc.
In one embodiment, a time of the primary sintering in step (1) is 10-18 h, such as 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h or 18 h, etc.
In one embodiment, a flow rate of sulfur dioxide in step (2) is 5-15 L/min, such as 5 L/min, 6 L/min, 7 L/min, 8 L/min, 9 L/min, 10 L/min, 11 L/min, 12 L/min, 13 L/min, 14 L/min or 15 L/min, etc.
In one embodiment, a heating rate of the secondary sintering in step (2) is 2-5° C./min, such as 2° C./min, 3° C./min, 4° C./min or 5° C./min, etc.
In one embodiment, a temperature of the secondary sintering in step (2) is 300-600° C., such as 300° C., 350° C., 400° C., 450° C., 500° C., 550° C. or 600° C., etc.
In one embodiment, a time of the secondary sintering in step (2) is 5-8 h, such as 5 h, 6 h, 7 h or 8 h, etc.
In one embodiment, the preparation method includes the following steps:
In one embodiment, the present disclosure provides a layered positive electrode material, which is prepared by the preparation method of the layered positive electrode material in the first aspect;
wherein, a chemical formula of the layered positive electrode material is Lix(NiaCobMnc)O2, wherein 1.00≤X≤1.12, 0.3≤a≤0.95, 0.03≤b≤0.12, 0.01≤c≤0.10, a+b+c=1.
The positive electrode material provided by the present disclosure has low residual alkali content, strong conductivity and improved electrochemical performance.
In one embodiment, the present disclosure provides a lithium-ion battery, which includes the layered positive electrode material in the second aspect.
In one embodiment, the present disclosure provides a method for preparing a layered positive electrode material, which includes the following steps:
For example, in the NiaCobMnc(OH)2, a may be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 0.95, etc.; b may be 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11 or 0.12, etc.; c may be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.10, etc.
In the present disclosure, after the primary sintering in the oxygen atmosphere, the sintered material is crushed and screened, and then the secondary sintering is further performed in the sulfur dioxide atmosphere to make full contact and reaction between sulfur dioxide and the primary sintered product, and sulfur dioxide reacts with the residual alkali on the surface of the positive electrode material to produce lithium sulfate, which achieves a purpose of reducing the residual alkali and pH value on the surface of the layered positive electrode material, and at the same time, it is beneficial to improving the processability of the layered positive electrode material, improving the conductivity of the layered positive electrode material and effectively enhancing the electrochemical performance of the battery.
In one embodiment, a molar ratio of the layered nickel-cobalt-manganese hydroxide to lithium in the lithium source in step (1) is 1:(1.02-1.09), such as 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08 or 1:1.09, etc.
In one embodiment, the lithium source includes lithium hydroxide and/or lithium carbonate.
In one embodiment, a flow rate of oxygen in step (1) is 3-10 L/min, such as 3 L/min, 4 L/min, 5 L/min, 6 L/min, 7 L/min, 8 L/min, 9 L/min or 10 L/min, etc.
In one embodiment, a temperature of the primary sintering in step (1) is 850-950° C., such as 850° C., 860° C., 870° C., 880° C., 890° C., 900° C., 910° C., 920° C., 930° C., 940° C. or 950° C., etc.
If the temperature of the primary sintering in step (1) is too low, the reaction between the layered nickel-cobalt-manganese hydroxide and the lithium source will be unfavorable, so that the reaction will be insufficient and the synthesized product will have poor performance and even cannot be used in batteries. If the temperature of the primary sintering is too high, particles of the synthesized product will be larger, which is not conducive to the deintercalation of lithium ions and the capacity will be low.
In one embodiment, a time of the primary sintering in step (1) is 10-18 h, such as 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h or 18 h, etc.
In one embodiment, a flow rate of sulfur dioxide in step (2) is 5-15 L/min, such as 5 L/min, 6 L/min, 7 L/min, 8 L/min, 9 L/min, 10 L/min, 11 L/min, 12 L/min, 13 L/min, 14 L/min and 15 L/min, etc.
In one embodiment, a heating rate of the secondary sintering in step (2) is 2-5° C./min, such as 2° C./min, 3° C./min, 4° C./min or 5° C./min, etc.
In a process of the secondary sintering in step (2), too fast a heating rate will result in insufficient reaction between the layered nickel-cobalt-manganese hydroxide and the lithium source, while too slow a heating rate will increase production cost.
In one embodiment, a temperature of the secondary sintering in step (2) is 300-600° C., such as 300° C., 350° C., 400° C., 450° C., 500° C., 550° C. or 600° C., etc.
If the temperature of the secondary sintering in step (2) is too high, it will lead to the growth of the particles of the positive electrode material, which is not conducive to the deintercalation of lithium ions and reduces the capacity of the positive electrode material. If the temperature is too low, it is difficult to realize the reaction between sulfur dioxide and residual alkali, and the purpose of reducing residual alkali cannot be achieved.
In one embodiment, a time of the secondary sintering in step (2) is 5-8 h, such as 5 h, 6 h, 7 h or 8 h, etc.
In one embodiment, the preparation method includes the following steps:
In one embodiment, the present disclosure provides a layered positive electrode material, which is prepared by the preparation method of the layered positive electrode material in the first aspect;
wherein, a chemical formula of the layered positive electrode material is Lix(NiaCobMnc)O2, wherein 1.00≤X≤1.12, 0.3≤a≤0.95, 0.03≤b≤0.12, 0.01≤c≤0.10, a+b+c=1.
In one embodiment, the present disclosure provides a lithium-ion battery, which includes the layered positive electrode material in the second aspect.
This example provides a layered positive electrode material, and a chemical formula of the layered positive electrode material is Li1.05(Ni0.88Co0.09Mn0.03)O2.
A preparation method of the layered positive electrode material is as follows:
This example differs from Example 1 in that a temperature of the primary sintering was 850° C. in step (1).
The other preparation methods and parameters are the same as in Example 1.
This example provides a layered positive electrode material, and a chemical formula of the layered positive electrode material is Li1.02(Ni0.5Co0.2Mn0.3)O2.
A preparation method of the layered positive electrode material is as follows:
This example provides a layered positive electrode material, and a chemical formula of the layered positive electrode material is Li1.09(Ni1/3Co1/3Mn1/3)O2.
A preparation method of the layered positive electrode material is as follows:
This example differs from Example 1 in that a flow rate of sulfur dioxide was 3 L/min in step (2).
The other preparation methods and parameters are the same as in Example 1.
This example differs from Example 1 in that a temperature of the secondary sintering was 250° C. in step (2).
The other preparation methods and parameters are the same as in Example 1.
This comparative example differs from Example 1 in that step (2) is not performed but only step (1) is performed.
The other preparation methods and parameters are the same as in Example 1.
This comparative example differs from Example 1 in that the primary sintered product was not ground, crushed and screened in step (1).
The other preparation methods and parameters are the same as in Example 1.
This comparative example differs from Example 1 in that a sulfur dioxide atmosphere was replaced by an oxygen atmosphere in step (2).
The other preparation methods and parameters are the same as in Example 1.
The layered positive electrode materials provided by Examples 1-6 and Comparative Examples 1-3 were tested, including the content of lithium hydroxide and lithium carbonate, the content of residual alkali and pH value (lithium carbonate was produced by reacting carbon dioxide in air with residual lithium on the surface of the positive electrode material). The results are shown in Table 1.
As can be seen from Table 1, the data results from Examples 1-6 show that the total residual alkali content of the positive electrode material obtained by the preparation method of the positive electrode material provided in an example of the present disclosure is less than or equal to 0.82%, and the pH value is less than or equal to 11.45. After further adjusting the flow rate of sulfur dioxide and the temperature of the secondary sintering (Examples 1-4), the total residual alkali content of the positive electrode material is less than or equal to 0.46%, and the pH value is less than or equal to 11.06.
It can be seen from the comparison of the data results of Example 1 and Example 5 that when the flow rate of sulfur dioxide is too slow, the reaction between sulfur dioxide and residual alkali on the surface of the positive electrode material is unfavorable, and the purpose of reducing residual alkali is not achieved.
It can be seen from the comparison of the data results of Example 1 and Example 6 that when the temperature of the secondary sintering is too low, the reaction of sulfur dioxide with the positive electrode material is insufficient
It can be seen from the comparison of the data results of Example 1 and Comparative Example 1 that the residual alkali and pH on the surface of the layered positive electrode materials are obviously reduced after introducing sulfur dioxide.
It can be seen from the comparison of the data results of Example 1 and Comparative Example 2 that without crushing and screening the product after the primary sintering, the contact reaction between sulfur dioxide and the residual alkali on the surface of the positive electrode material is unfavorable, and the reduction of the residual alkali is unfavorable.
It can be seen from the comparison of the data results of Example 1 and Comparative Example 3 that the reduction of residual alkali on the surface of the positive electrode material cannot be achieved by replacing sulfur dioxide with oxygen.
The layered positive electrode materials provided in Examples 1-6 and Comparative Examples 1-3 are prepared into batteries, and a preparation process is as follows.
The preparation of button battery used the lithium nickel manganate positive electrode materials prepared in examples and comparative examples, respectively. The positive electrode material, a carbon black conductive agent and a binder PVDF (a solid content of 6.25%) were weighed in a weight ratio of 92:4:4, and NMP was added to adjust a solid content of a slurry to 49%, and mixed uniformly to obtain a positive electrode slurry. The positive electrode slurries prepared above were coated on an aluminum foil with a thickness of 20 μm, vacuum dried and rolled to prepare positive electrode sheets. The positive electrode sheet was used as a positive electrode, a lithium metal sheet was used as a negative electrode sheet, and an electrolyte containing 1 mol/L LiPF6/EC:DMC (a volume ratio of 2:3) was used to assemble a button battery.
The batteries provided in Examples 1-6 and Comparative Examples 1-3 are subjected to electrochemical performance tests under the following test conditions.
the electrical performance of the materials were tested at 25° C. using Blue Electric Battery Test System with a voltage range of 3.0-4.3 V; an initial discharge capacity, an initial discharge efficiency and a capacity retention rate after 50 cycles were tested.
The results are shown in Table 2
As can be seen from Table 2, the data results from Examples 1-6 show that the button battery assembled with the positive electrode material obtained by the preparation method of the positive electrode material provided in an example of the present disclosure can have a discharge capacity of more than or equal to 208.5 mAh/g at 0.1 C, an initial efficiency of more than or equal to 88.56%, and a capacity retention rate after 50 cycles of more than or equal to 88.98%. After further adjusting a rate of sulfur dioxide and a temperature of the secondary sintering (Examples 1-4), the discharge capacity of the battery can have a discharge capacity of more than or equal to 211.8 mAh/g at 0.1 C, an initial efficiency of more than or equal to 90.24%, and a capacity retention rate after 50 cycles of more than or equal to 97.79%.
It can be seen from the comparison of the data results of Example 1 and Example 5 that when the flow rate of sulfur dioxide is too slow, the reduction of residual alkali is unfavorable, and the electrochemical performance of the positive electrode material is affected.
It can be seen from the comparison of the data results of Example 1 and Example 6 that when the temperature of the secondary sintering is too low, the reaction of sulfur dioxide with the positive electrode material is insufficient, which will also affect the electrochemical performance of the positive electrode material.
It can be seen from the comparison of the data results of Example 1 and Comparative Example 1 that the residual alkali and pH on the surface of layered positive electrode materials are obviously reduced after introducing sulfur dioxide.
It can be seen from the comparison of the data results of Example 1 and Comparative Example 2 that without crushing and screening the product after the primary sintering, sulfur dioxide is not conducive to reacting with the residual alkali on the surface of the positive electrode material, resulting in a decrease of the electrochemical performance of the positive electrode material.
It can be seen from the comparison of the data results of Example 1 and Comparative Example 3 that the purpose of reducing the residual alkali and reducing the residual alkali of the positive electrode material cannot be achieved by replacing sulfur dioxide with oxygen.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202110875613.X | Jul 2021 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/081681 | 3/18/2022 | WO |
