CN109638251B - Preparation method of gradient sintered gas-phase fluorine-doped modified high-nickel cathode material - Google Patents

Preparation method of gradient sintered gas-phase fluorine-doped modified high-nickel cathode material Download PDF

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CN109638251B
CN109638251B CN201811521420.9A CN201811521420A CN109638251B CN 109638251 B CN109638251 B CN 109638251B CN 201811521420 A CN201811521420 A CN 201811521420A CN 109638251 B CN109638251 B CN 109638251B
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钱飞鹏
马岩华
唐朝辉
赵春阳
李佳军
邓亚烽
陆科炯
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Wuxi Jewel Power & Materials Co ltd
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Abstract

The invention discloses a preparation method of a gradient sintered gas-phase fluorine-doped modified high-nickel anode material, which comprises the following steps of: 1) fully and uniformly mixing a lithium source and high nickel; 2) placing the mixture in an atmosphere furnace, raising the temperature at a high speed to 480-530 ℃, then raising the temperature at a low speed to 700-; 3) then the temperature is reduced to 550-650 ℃, the temperature is kept for 4-8h, high-purity oxygen is closed, high-purity fluorine gas is introduced, and micro-positive pressure is kept in the flow furnace; 4) naturally cooling and closing the air inlet and the air outlet to ensure that no atmosphere flows in the furnace; 5) and taking out the product to obtain a target product after treatment. The surface doping uniformity and consistency are better; adopts the gradient sintering technology to ensure that the Ni is ensured in the sintering process of the high-nickel material2+Can be fully oxidized into Ni3+And the specific capacity and the cycle performance of the material are improved.

Description

Preparation method of gradient sintered gas-phase fluorine-doped modified high-nickel cathode material
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and relates to a preparation method of a gradient sintered surface gas-phase fluorine-doped modified high-nickel anode material.
Background
The lithium ion battery anode material in the current market is mainly lithium cobaltate (LiCoO)2) Lithium manganate (LiMn)2O4) Lithium iron phosphate (LiFePO)4) Ternary materials (lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate). Lithium cobaltate (LiCoO)2) Due to cobalt resourceThe scarcity of sources and the high price limit the development potential of the method; lithium manganate (LiMn)2O4) Although the cost is low and the resources are rich, the large-scale application of the material is limited due to the defects of low energy density, poor high-temperature cycle performance and the like; lithium iron phosphate (LiFePO)4) Although the lithium ion battery has the advantages of good structural stability and cyclicity, wide raw material sources, low price and the like, the development of the lithium ion battery in multiple fields is limited to a certain extent due to the factors of low electronic conductivity, low diffusion rate of lithium ions in the lithium ion battery, low energy density and the like. Due to the advantages of high energy density, excellent cycle performance and the like of ternary materials (lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate), the market share of the ternary materials occupies the leading position of the anode materials.
The ternary material of high nickel series (nickel mol content is more than 80%) has the advantages of high capacity, low price and the like, and is an important development direction of the current ternary cathode material. At present, the mainstream method for synthesizing the high-nickel series ternary material is a high-temperature solid phase method, and sintering is carried out under the high-concentration oxygen atmosphere to synthesize the final product. However, the synthesis process of the high-nickel ternary material is an oxidation reaction, and Ni is required to be reacted2+Oxidation to Ni3+And the reaction is reversible, so that the conventional pure oxygen atmosphere is difficult to completely remove Ni in the material2+Oxidation to Ni3+Thus, the material structure is incomplete, the lithium-nickel mixed discharge is serious, the residual lithium on the surface of the material is high, the spontaneous reaction can occur on the surface of the finished product material particles, and Ni3+Conversion to Ni2+Releasing O2-Thereby causing adverse consequences such as reduction of material capacity and reduction of cycle performance.
Disclosure of Invention
The invention aims to overcome the defects of low material capacity and low cycle performance caused by serious lithium-nickel mixed discharge and high residual lithium on the surface of a high-nickel ternary material in the prior art, and provides a preparation method of a gradient sintering surface gas-phase fluorine-doped modified high-nickel anode material.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a gradient sintered gas-phase fluorine-doped modified high-nickel cathode material comprises the following steps:
1) putting a lithium source and a high-nickel precursor into a high-speed mixer, and fully and uniformly mixing;
2) placing the uniformly mixed material in the step 1) in an atmosphere furnace, raising the temperature to 480-530 ℃ at the heating rate of 3-7 ℃/min, raising the temperature to 700-800 ℃ at the heating rate of 0.6-1.5 ℃/min, preserving the temperature for 8-15h, introducing high-purity oxygen in the processes of raising the temperature and preserving the temperature, wherein the flow rate is 5-15L/min, and keeping the micro-positive pressure in the furnace;
3) then, reducing the temperature to 550-650 ℃ at the cooling rate of 2-5 ℃/min, preserving the heat for 4-8h, closing the high-purity oxygen in the processes of cooling and preserving the heat, introducing high-purity fluorine gas at the flow rate of 5-15L/min, and keeping the micro-positive pressure in the furnace;
4) naturally cooling to 90-110 ℃, and closing the air inlet and the air outlet in the cooling process to ensure that no atmosphere flows in the furnace;
5) and taking out the cooled material, crushing and sieving the material to obtain the target product.
Preferably, the molar ratio of the lithium source to the high-nickel precursor in the step 1) is 1-1.05: 1.
Further, in the step 1), the lithium source is battery-grade LiOH, the particle size D50 is 6-10 μm, the high-nickel precursor is nickel-based hydroxide, the molar ratio of nickel is more than 80%, and the D50 is 9-13 μm.
Further, in the step 2), the temperature is increased to 500 ℃ at the temperature increasing speed of 5 ℃/min, and then the temperature is increased to 700 ℃ and 800 ℃ at the temperature increasing speed of 1 ℃/min, and the temperature is maintained for 8-15 h.
Further, the temperature in the step 3) is reduced to 550 ℃ and 650 ℃ at the cooling rate of 3 ℃/min and is kept for 4-8 h.
Further, the purity of the high-purity oxygen in the step 2) and the purity of the high-purity fluorine gas in the step 3) are both more than 99%.
Further, the micro-positive pressure in the furnace in the step 2) and the step 3) is 0.1-1.0 Kpa.
Further, cooling to 100 ℃ in the step 4).
Further, the size of the inner cavity of the atmosphere furnace is 30L.
The invention has the following beneficial effects:
1) because the fluorine doping mode is gas phase doping, the material is fully contacted with fluorine gas in the sintering process, and the surface doping uniformity and consistency are better;
2) and because the gradient sintering technology is adopted, the atmosphere concentration of the oxygen atmosphere heat-preservation platform and the fluorine atmosphere heat-preservation platform can reach more than 95 percent, and Ni of the high-nickel material in the sintering process is ensured2+Can be fully oxidized into Ni3+The structure of the high-nickel material is more complete, the mixed discharging of lithium and nickel is well inhibited, the residual lithium on the surface of the material is well controlled, and the specific capacity and the cycle performance of the material are improved;
3) because the surface of the material is doped with fluorine, the stability of a covalent bond F-M formed by fluorine and metal is stronger than that of a covalent bond O-M formed by oxygen and metal, the F element is doped to replace part of oxygen element, so that the spontaneous oxygen release reaction on the surface of the high nickel material is well inhibited, and the crystal structure of the high nickel material is stabilized, so that the cyclicity and the stability of the high nickel material are improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a cycle chart of example 1 of the present invention and comparative example 1;
fig. 2 is a cycle chart of example 2 and comparative example 2.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1
1) Weighing 462.5g of battery-grade LiOH with the weight of D50 being 6.5 mu m and the weight of D50 being 9.6 mu m according to the mol ratio of 1.03:1, and weighing the high-nickel precursor (Ni)0.835Co0.115Mn0.05)(OH)2The weight is 1000g, the materials are put into a high-efficiency mixer and mixed for 25 minutes at the rotating speed of 1000r/min, and then the materials are discharged;
2) taking 1000g of the mixture in the step 1, putting the mixture in an atmosphere furnace, raising the temperature to 500 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 770 ℃ at a heating rate of 1 ℃/min, and keeping the temperature for 12 hours, wherein high-purity oxygen is introduced in the heating and heat-preservation processes, the flow is 5L/min, the micro-positive pressure is kept in the furnace, and the pressure is 0.1 Kpa;
3) reducing the temperature to 650 ℃ at the cooling rate of 3 ℃/min, preserving the temperature for 6h, closing the high-purity oxygen in the cooling and heat preserving process, introducing high-purity fluorine gas at the flow rate of 5L/min, and keeping the micro-positive pressure in the furnace at the pressure of 0.1 Kpa;
4) naturally cooling to 100 ℃, and closing the air inlet and the air outlet in the cooling process to ensure that no atmosphere flows in the furnace;
5) and taking out the cooled material, crushing and sieving the material to obtain the product.
Comparative example 1
1) Weighing 462.5g of battery-grade LiOH with the weight of D50 being 6.5 mu m and the weight of D50 being 9.6 mu m according to the mol ratio of 1.03:1, and weighing the high-nickel precursor (Ni)0.835Co0.115Mn0.05)(OH)2The weight is 1000g, the materials are put into a high-efficiency mixer and mixed for 25 minutes at the rotating speed of 1000r/min, and then the materials are discharged;
2) taking 1000g of the mixture in the step 1, putting the mixture in an atmosphere furnace, raising the temperature to 500 ℃ at a heating rate of 5 ℃/min, then raising the temperature to 770 ℃ at a heating rate of 1 ℃/min, and keeping the temperature for 12 hours, wherein high-purity oxygen is introduced in the heating and heat-preservation processes, the flow is 5L/min, the micro-positive pressure is kept in the furnace, and the pressure is 0.1 Kpa;
3) then, reducing the temperature to 650 ℃ at a cooling speed of 3 ℃/min, and preserving the temperature for 6h, wherein high-purity oxygen is introduced in the cooling and heat preserving process, the flow is 5L/min, the micro-positive pressure is kept in the furnace, and the pressure is 0.1 Kpa;
4) naturally cooling to 100 ℃, and closing the air inlet and the air outlet in the cooling process to ensure that no atmosphere flows in the furnace;
5) and taking out the cooled materials, crushing and sieving the materials to obtain the product.
Example 2:
1) weighing 445.8g of D50-8.2 mu m battery-grade LiOH and 12.5 mu m high-nickel precursor (Ni) according to a molar ratio of 1.02:1, wherein D50 is0.88Co0.09Al0.03)(OH)2Weight 1000g, placed in a high efficiency mixerMixing at 1000r/min for 25 min, and discharging;
2) taking 1000g of the mixture in the step 1, putting the mixture in an atmosphere furnace, raising the temperature to 500 ℃ at a heating rate of 5 ℃/min, raising the temperature to 750 ℃ at a heating rate of 1 ℃/min, and preserving the temperature for 10 hours, wherein high-purity oxygen is introduced in the heating and heat preservation processes, the flow is 15L/min, the micro-positive pressure is kept in the furnace, and the pressure is 0.5 Kpa;
3) reducing the temperature to 550 ℃ at the cooling rate of 3 ℃/min, preserving the temperature for 6h, closing high-purity oxygen in the cooling and heat preserving process, introducing high-purity fluorine gas at the flow rate of 15L/min, and keeping micro-positive pressure in the furnace at the pressure of 0.5 Kpa;
4) naturally cooling to 100 ℃, and closing the air inlet and the air outlet in the cooling process to ensure that no atmosphere flows in the furnace;
5) and taking out the cooled material, crushing and sieving the material to obtain the product.
Comparative example 2:
1) weighing 445.8g of D50-8.2 mu m battery-grade LiOH and 12.5 mu m high-nickel precursor (Ni) according to a molar ratio of 1.02:1, wherein D50 is0.88Co0.09Al0.03)(OH)2The weight is 1000g, the materials are put into a high-efficiency mixer and mixed for 25 minutes at the rotating speed of 1000r/min, and then the materials are discharged;
2) taking 1000g of the mixture in the step 1, putting the mixture in an atmosphere furnace, raising the temperature to 500 ℃ at a heating rate of 5 ℃/min, raising the temperature to 750 ℃ at a heating rate of 1 ℃/min, and preserving the temperature for 10 hours, wherein high-purity oxygen is introduced in the heating and heat preservation processes, the flow is 15L/min, the micro-positive pressure is kept in the furnace, and the pressure is 0.5 Kpa;
3) reducing the temperature to 550 ℃ at the cooling rate of 3 ℃/min, and preserving the temperature for 6h, wherein high-purity oxygen is introduced in the cooling and heat preserving process, the flow is 15L/min, the micro-positive pressure is kept in the furnace, and the pressure is 0.5 Kpa;
4) naturally cooling to 100 ℃, and closing the air inlet and the air outlet in the cooling process to ensure that no atmosphere flows in the furnace;
5) and taking out the cooled material, crushing and sieving the material to obtain the product.
And (3) testing results:
1. EDS tests were carried out on the products of example 1 and example 2 and comparative example 1 and comparative example 2, respectively, and the contents of elements F and O were analyzed, with the results shown in Table 1:
table 1 EDS test results
Figure BDA0001902138330000041
Figure BDA0001902138330000051
As can be seen from table 1, both examples 1 and 2 had the F element, and comparative examples 1 and 2 had no F element.
2. The products of example 1 and example 2, and comparative example 1 and comparative example 2 were subjected to surface residual lithium test, and the content of LiOH and Li2CO3 were analyzed, and the results are shown in table 2:
table 2: test results for surface residual lithium
Sample/residual lithium LiOH％ Li2CO3％ Total Li%
Example 1 0.2961 0.2610 0.1349
Comparative example 1 0.4916 0.4119 0.2199
Example 2 0.4182 0.1456 0.1486
Comparative example 2 0.5224 0.3766 0.2226
3. Full cell tests are respectively carried out on the products of example 1 and example 2 and the products of comparative example 1 and comparative example 2, the test voltage range is 2.75V-4.2V, the rate is 1C, charging and discharging are carried out, and the full cell tests are respectively cycled for 50 weeks. The capacity retention rate after 50 cycles of the embodiment 1 is 94.5%, the capacity retention rate after 50 cycles of the comparative example 1 is 80.6%, the capacity retention rate after 50 cycles of the embodiment 2 is 95.3%, and the capacity retention rate after 50 cycles of the comparative example 2 is 85.2%, which shows that the F element doping modification improves the cycle performance of the material.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A preparation method of a gradient sintered gas-phase fluorine-doped modified high-nickel cathode material is characterized by comprising the following steps of:
1) putting a lithium source and a high-nickel precursor into a high-speed mixer, and fully and uniformly mixing;
2) placing the uniformly mixed material in the step 1) in an atmosphere furnace, raising the temperature to 480-530 ℃ at the heating rate of 3-7 ℃/min, raising the temperature to 700-800 ℃ at the heating rate of 0.6-1.5 ℃/min, preserving the temperature for 8-15h, introducing high-purity oxygen in the processes of raising the temperature and preserving the temperature, wherein the flow rate is 5-15L/min, and keeping the micro-positive pressure in the furnace;
3) then, reducing the temperature to 550-650 ℃ at the cooling rate of 2-5 ℃/min, preserving the heat for 4-8h, closing the high-purity oxygen in the processes of cooling and preserving the heat, introducing high-purity fluorine gas at the flow rate of 5-15L/min, and keeping the micro-positive pressure in the furnace;
4) naturally cooling to 90-110 ℃, and closing the air inlet and the air outlet in the cooling process to ensure that no atmosphere flows in the furnace;
5) and taking out the cooled material, crushing and sieving the material to obtain the target product.
2. The preparation method of the gradient sintering gas-phase fluorine-doped modified high-nickel cathode material as claimed in claim 1, wherein the molar ratio of the lithium source to the high-nickel precursor in the step 1) is 1-1.05: 1.
3. The method for preparing the gradient sintering gas-phase fluorine-doped modified high-nickel cathode material as claimed in claim 2, wherein in the step 1), the lithium source is battery-grade LiOH, the particle size D50 is 6-10 μm, the high-nickel precursor is nickel-based hydroxide, the molar ratio of nickel is more than 80%, and D50 is 9-13 μm.
4. The method for preparing a gradient sintered gas-phase fluorine-doped modified high-nickel cathode material as claimed in claim 1, wherein the temperature in the step 2) is raised to 500 ℃ at a temperature-raising rate of 5 ℃/min, and then raised to 800 ℃ at a temperature-raising rate of 1 ℃/min, and the temperature is maintained for 8-15 h.
5. The method for preparing a gradient sintered gas-phase fluorine-doped modified high-nickel cathode material as claimed in claim 1, wherein the temperature in the step 3) is reduced to 550-650 ℃ at a cooling rate of 3 ℃/min and is kept for 4-8 h.
6. The method for preparing the gradient sintered gas-phase fluorine-doped modified high-nickel cathode material as claimed in claim 1, wherein the purity of the high-purity oxygen in the step 2) and the purity of the high-purity fluorine gas in the step 3) are both more than 99%.
7. The method for preparing the gradient sintered gas-phase fluorine-doped modified high-nickel cathode material according to claim 6, wherein the micro-positive pressure in the furnace in the step 2) and the step 3) is 0.1 to 1.0 Kpa.
8. The method for preparing the gradient sintered gas-phase fluorine-doped modified high-nickel cathode material as claimed in claim 1, wherein the temperature in the step 4) is reduced to 100 ℃.
9. The method for preparing the gradient sintering gas-phase fluorine-doped modified high-nickel cathode material as claimed in claim 1, wherein the size of the inner cavity of the atmosphere furnace is 30L.
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