CN115000377A - Low-temperature high-power ternary cathode material and preparation method thereof - Google Patents

Low-temperature high-power ternary cathode material and preparation method thereof Download PDF

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CN115000377A
CN115000377A CN202210721702.3A CN202210721702A CN115000377A CN 115000377 A CN115000377 A CN 115000377A CN 202210721702 A CN202210721702 A CN 202210721702A CN 115000377 A CN115000377 A CN 115000377A
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lithium
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aluminum fluoride
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朱二涛
戴吴月
胡刚刚
吴胜坤
李刚
袁争
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Hefei Rongjie Energy Materials Co ltd
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    • H01M10/05—Accumulators with non-aqueous electrolyte
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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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    • 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
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a low-temperature high-power ternary cathode material and a preparation method thereof, and belongs to the technical field of lithium ion batteries. The preparation method of the low-temperature high-power ternary cathode material comprises the following steps: uniformly mixing the ternary precursor, lithium salt, magnesium chromate and lithium zirconium titanium phosphate to obtain a mixed material; sintering the mixed material in an oxygen-containing atmosphere, and crushing a sintered sample to obtain crushed material; and finally, coating the outer surface of the crushed material layer by layer to form an aluminum fluoride layer and a boron oxide layer, thereby obtaining the target product. According to the invention, by adding magnesium chromate and lithium zirconium titanium phosphate, the low-temperature performance and the rate capability of the material are improved; the invention utilizes the double-layer cladding of boron oxide and aluminum fluoride, which can improve the power of the battery; in addition, the method has simple process preparation and low energy consumption, and is suitable for industrial large-scale production.

Description

Low-temperature high-power ternary cathode material and preparation method thereof
Technical Field
The invention discloses a low-temperature high-power ternary cathode material and a preparation method thereof, and belongs to the technical field of lithium ion batteries.
Background
The new energy automobile is a new industry of national strategy, and with the continuous upgrade of the power battery for the automobile, the lithium ion battery has the advantages of high specific capacity, long cycle life, good safety performance and the like, so the lithium ion battery has received wide attention as energy storage.
The NCM ternary cathode material has the advantages of high capacity, long service life, low cost, rich raw material sources and the like, and is a lithium ion battery material with great application prospect. With the expansion of the application field of lithium batteries, the disadvantage of low-temperature performance is more and more obvious, the temperature in winter in northern areas of China is generally about minus 30 ℃, the performance of the lithium ion battery is greatly influenced by the environment in the charging and discharging process, and particularly the service life of the battery is influenced under the low-temperature condition.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low-temperature high-power ternary cathode material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a ternary cathode material comprises the following steps:
(1) putting the ternary precursor, lithium salt, magnesium chromate and lithium zirconium titanium phosphate into a mixing tank, and uniformly mixing by using a dry method until white points do not exist to obtain a mixed material; preferably, the molecular formula of the ternary precursor is Ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1; the lithium salt is lithium nitrate, lithium carbonate or lithium hydroxide and the like; the molar ratio of the ternary precursor to the lithium salt is 1: (1.01-1.08); the quality of the magnesium chromate in the mixed material is a ternary precursor constitution0.3-1.2 wt% of the amount; the mass of the lithium zirconium titanium phosphate in the mixed material is 0.5-1.5 wt% of that of the ternary precursor.
(2) Placing the obtained mixed material into a sagger, and sintering in an oxygen or air atmosphere to obtain a sintered material; crushing the sintered material in a crusher, sieving the crushed material in a 400-mesh sieve to obtain particles with uniform particle size distribution, and demagnetizing to obtain crushed material; preferably, the sintering process comprises: firstly, heating to 300-600 ℃ at a heating rate of 1-3 ℃/min, and preserving heat for 3-5 h; then heating to 750-960 ℃ at the heating rate of 3-5 ℃/min, and preserving heat for 8-15 h.
(3) Firstly, aluminum fluoride and crushed materials are mixed according to the mass ratio (0.004-0.02): 1, uniformly mixing the materials together, preserving the heat for 6 to 8 hours in a muffle furnace at the temperature of between 300 and 650 ℃, and crushing the materials to obtain a material coated with an aluminum fluoride layer; the aluminum fluoride can be uniformly coated on the surface of the material, so that the anode material is prevented from contacting with the electrolyte in the charging and discharging process of the battery, the side reaction on the surface of the material is reduced, and the cycle performance of the material is improved. Then mixing boron oxide with the material coated with the aluminum fluoride layer, preserving heat for 6-8h at the temperature of 300-650 ℃, coating the outer layer of the material to form a boron oxide layer, and crushing to obtain a target product. The boric oxide can absorb moisture in the air more easily to generate boric acid, so that the lithium oxide on the surface of the material is reduced to absorb water and be converted into lithium hydroxide and lithium carbonate, the effect of reducing residual alkali on the surface of the material is achieved, the generated boric acid can further acidify the surface of the material, the corrosion of electrolyte on the surface of the material is reduced, and the cycle performance of the material is further improved.
The invention also provides the ternary cathode material prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, magnesium chromate and lithium zirconium titanium phosphate are added in the preparation of the starting raw material, and in the sintering process, the magnesium chromate is doped with nickel and cobalt elements through a bulk phase, so that the crystal spacing of the material is changed, the particle size can be reduced, the specific surface area of the material is increased, and the low-temperature performance of the material is improved; the doping of the lithium zirconium phosphate reduces the mixing and discharging degree of lithium and nickel, reduces the generation of irreversible phase change in the charging and discharging process, improves the ionic conductivity, reduces the internal resistance of the material, and improves the rate capability of the material. According to the invention, magnesium chromate and lithium titanium zirconium phosphate are added, the two substances are added and sintered at the same time, the melting point of each material is different and is equivalent to the function of a cosolvent, the melting point of the material during reaction can be reduced, the temperature of crystal reaction can be reduced, the processing cost is reduced, the crystal structure can be stabilized by doping zirconium ions in the lithium titanium zirconium phosphate, the lithium ion migration channel can be effectively expanded by doping titanium ions, the migration efficiency is improved, the battery has higher ionic conductivity under the condition of low temperature (minus 20 ℃), and the battery has higher capacity retention rate and excellent rate capability in the long-time circulation process.
(2) The double-layer cladding of boron oxide and aluminum fluoride is utilized, the aluminum fluoride cladding layer is prevented from contacting with electrolyte in the charging and discharging process of the battery, the occurrence of side reaction on the surface of the material is reduced, and the cycle performance of the material is improved. Boric oxide absorbs moisture in the air more easily to generate boric acid, so that lithium oxide on the surface of the material absorbs water and is converted into lithium hydroxide and lithium carbonate, the effect of reducing residual alkali on the surface of the material is achieved, the generated boric acid can acidify the surface of the material, corrosion of electrolyte on the surface of the material is reduced, and the cycle performance of the material is further improved.
(3) The method has simple process preparation and low energy consumption, and is suitable for industrial large-scale production.
Drawings
Fig. 1 is an SEM photograph of 3000 times the pulverized material obtained in step (2) of example 1.
FIG. 2 is a SEM photograph at 3000 times of the final material obtained in step (3) of example 1 of the present invention.
Detailed Description
The invention is further described with reference to the following figures and examples.
Example 1
(1) With Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 Is a ternary precursor, lithium nitrate is lithium salt, and the molar ratio of lithium nitrate to lithium nitrate is 1: 1.05 weighing of Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 And lithium nitrate; by mass of ternary precursorRespectively adding 1 wt% of magnesium chromate and 0.7 wt% of lithium zirconium titanium phosphate as a reference; putting the raw materials into a ball milling tank, and ball milling and mixing for 40min to obtain a required mixed material;
(2) putting the obtained mixed material into a sagger, sintering by using a muffle furnace under the air atmosphere, wherein the sintering temperature is gradient sintering: heating from room temperature to 550 ℃, wherein the sintering time is 3h, and the heating rate is 1.5 ℃/min; then the temperature is increased to 910 ℃, the sintering time is 8h, and the temperature rising rate is 3 ℃/min. The former has a slow heating rate, the crystal can be shaped and grown for a sufficient time, and the latter has a low heating rate and a moderate sintering temperature to prevent the crystal from growing excessively. And after sintering, crushing the sintered material in a universal crusher for 30s, and sieving the crushed material in a 400-mesh sieve to obtain crushed material.
(3) The method comprises the following steps of coating an aluminum fluoride layer and a boron oxide layer on the outer surface of a crushed material in a layered manner: aluminum fluoride and crushed materials are mixed according to a mass ratio of 0.015: 1, then placing the mixture in a muffle furnace to sinter the mixture for 8 hours at 650 ℃, crushing the material in a universal crusher for 30s after sintering, and sieving the crushed material in a 400-mesh sieve to obtain the material coated with the aluminum fluoride layer; mixing boron oxide and a material coated with an aluminum fluoride layer in a mass ratio of 0.015: 1, then placing the mixture in a muffle furnace to sinter for 8 hours at 650 ℃, after sintering, placing the material in a universal pulverizer to pulverize for 30s, and screening by a 400-mesh screen to obtain a final product.
SEM examination was performed on the materials obtained in step (2) and step (3) of example 1, and the results are shown in FIG. 1 and FIG. 2, respectively. The figure shows that the primary particle size of the sintering material particles is small, the crystal structure is complete and has no defects, the crystal structure is optimized, a layer of coating material is attached to the surface of the coated material to prevent the corrosion of electrolyte, and the cycle performance and the capacity retention rate of the material are improved.
Example 2
(1) With Ni 0.6 Co 0.1 Mn 0.3 (OH) 2 Is a ternary precursor, lithium nitrate is lithium salt, and the molar ratio of lithium nitrate to lithium nitrate is 1: 1.05 weighing of Ni 0.6 Co 0.1 Mn 0.3 (OH) 2 And lithium nitrate(ii) a Respectively adding 1 wt% of magnesium chromate and 0.7 wt% of lithium zirconium titanium phosphate based on the mass of the ternary precursor; putting the raw materials into a mixing tank, and uniformly mixing the raw materials by using a dry method without white spots to obtain a required mixed material;
(2) putting the obtained mixed material into a sagger, and sintering under an air atmosphere, wherein the sintering temperature is gradient sintering: heating from room temperature to 600 ℃, and keeping the temperature for 3h, wherein the heating rate is 1.5 ℃/min; then heating to 910 ℃ and preserving the heat for 8h, wherein the heating rate is 3 ℃/min. And after sintering, crushing the sintered material in a crusher, and sieving the crushed material in a 400-mesh sieve to obtain crushed material.
(3) The aluminum fluoride layer and the boron oxide layer are coated on the outer surface of the crushed material layer by layer, and the method comprises the following steps: aluminum fluoride and crushed materials are mixed according to a mass ratio of 0.015: 1, then placing the mixture in a muffle furnace to sinter the mixture for 8 hours at 650 ℃, crushing the material in a universal crusher for 30s after sintering, and sieving the crushed material in a 400-mesh sieve to obtain the material coated with the aluminum fluoride layer; mixing boron oxide and a material coated with an aluminum fluoride layer in a mass ratio of 0.015: 1, then placing the mixture in a muffle furnace to sinter for 8 hours at 650 ℃, after sintering, placing the material in a universal pulverizer to pulverize for 30s, and screening by a 400-mesh screen to obtain the final product.
Example 3
(1) With Ni 0.6 Co 0.1 Mn 0.3 (OH) 2 Is a ternary precursor, lithium nitrate is lithium salt, and the molar ratio is 1: 1.01 weighing Ni 0.6 Co 0.1 Mn 0.3 (OH) 2 And lithium nitrate; respectively adding 0.3 wt% of magnesium chromate and 0.5 wt% of lithium zirconium titanium phosphate based on the mass of the ternary precursor; putting the raw materials into a mixing tank, and uniformly mixing the raw materials by using a dry method without white spots to obtain a required mixed material;
(2) putting the obtained mixed material into a sagger, and sintering under an air atmosphere, wherein the sintering temperature is gradient sintering: heating from room temperature to 600 ℃, and keeping the temperature for 4h, wherein the heating rate is 1.5 ℃/min; then heating to 910 ℃ and preserving the heat for 15h, wherein the heating rate is 3 ℃/min. And after sintering, crushing the sintered material in a crusher, and sieving the crushed material in a 400-mesh sieve to obtain crushed material.
(3) The aluminum fluoride layer and the boron oxide layer are coated on the outer surface of the crushed material layer by layer, and the method comprises the following steps: aluminum fluoride and crushed material in a mass ratio of 0.004: 1, then placing the mixture in a muffle furnace to sinter the mixture for 6 hours at 300 ℃, crushing the material in a universal crusher for 30s after sintering, and sieving the crushed material in a 400-mesh sieve to obtain the material coated with the aluminum fluoride layer; mixing boron oxide and a material coated with an aluminum fluoride layer in a mass ratio of 0.004: 1, then placing the mixture in a muffle furnace to sinter for 60 hours at 300 ℃, after sintering, placing the material in a universal pulverizer to pulverize for 30s, and screening by a 400-mesh screen to obtain the final product.
Example 4
(1) With Ni 0.6 Co 0.1 Mn 0.3 (OH) 2 Is a ternary precursor, lithium nitrate is lithium salt, and the molar ratio of lithium nitrate to lithium nitrate is 1: 1.08 weighing of Ni 0.6 Co 0.1 Mn 0.3 (OH) 2 And lithium nitrate; respectively adding 1.2 wt% of magnesium chromate and 1.5 wt% of lithium zirconium titanium phosphate based on the mass of the ternary precursor, and putting the raw materials into a mixing tank to be uniformly mixed by a dry method without white spots to obtain a required mixed material;
(2) putting the obtained mixed material into a sagger, and sintering under an air atmosphere, wherein the sintering temperature is gradient sintering: heating from room temperature to 600 ℃, and keeping the temperature for 3h, wherein the heating rate is 1.5 ℃/min; then heating to 910 ℃ and preserving the heat for 10h, wherein the heating rate is 3 ℃/min. And after sintering, crushing the sintered material in a crusher, and sieving the crushed material in a 400-mesh sieve to obtain crushed material.
(3) The aluminum fluoride layer and the boron oxide layer are coated on the outer surface of the crushed material layer by layer, and the method comprises the following steps: aluminum fluoride and crushed materials are mixed according to the mass ratio of 0.02: 1, then placing the mixture in a muffle furnace to be sintered for 8 hours at 500 ℃, crushing the material in a universal crusher for 30s after sintering, and sieving the crushed material in a 400-mesh sieve to obtain the material coated with the aluminum fluoride layer; boron oxide and the material coated with the aluminum fluoride layer are mixed according to the mass ratio of 0.02: 1, then placing the mixture in a muffle furnace to sinter for 8 hours at 500 ℃, after sintering, placing the material in a universal pulverizer to pulverize for 30s, and screening by a 400-mesh screen to obtain the final product.
Comparative example 1
This comparative example differs from example 1 in that: the step (1) was carried out in the same manner as in example 1 except that magnesium chromate and lithium zirconium titanium phosphate were not added.
Comparative example 2
This comparative example differs from example 1 in that: the coating with aluminum fluoride and boron oxide was not performed, that is, the step (3) was not performed, and other steps were the same as in example 1.
Comparative example 3
This comparative example differs from example 1 in that: the step (1) was carried out in the same manner as in example 1 except that no magnesium chromate was added.
Comparative example 4
This comparative example differs from example 1 in that: the procedure of step (1) was the same as in example 1 except that lithium zirconium titanium phosphate was not added.
Comparative example 5
This comparative example differs from example 1 in that: the aluminum fluoride coating was not performed in the step (3), and the other steps were the same as in example 1.
Comparative example 6
This comparative example differs from example 1 in that: the boron oxide coating was not performed in step (3), and the other steps were the same as in example 1.
The materials obtained in the above examples and comparative examples were subjected to characterization and performance tests, and the test results are shown in table 1.
TABLE 1 analysis results of physical properties of products prepared in each example and comparative example
Figure BDA0003711563320000051
Figure BDA0003711563320000061
The products prepared in the examples and the comparative examples are used as positive active materials, graphite is used as a negative electrode to assemble a soft package battery, a battery performance tester is used for testing the electrical performance of the battery, the charge-discharge cut-off voltage is 3-4.35V, and the charge-discharge cycle is 1C, and the results are shown in table 2.
Table 2 electrical property test results of batteries composed of products prepared in each example and comparative example
Figure BDA0003711563320000062
As can be seen from tables 1 and 2: the magnesium chromate and the lithium titanium zirconium phosphate additive are added, so that the granularity of the material is obviously reduced, the specific surface area is increased, the contact area of the electrolyte and the material can be increased by the larger specific surface area, the lithium ion migration path is reduced, and the low temperature and rate capability of the material are improved. The aluminum fluoride and boron oxide coating layers obviously improve the cycle performance of the material, and the cycle performance is the best when the aluminum fluoride and boron oxide are coated in a double-layer mode. And the material is doped with magnesium chromate and lithium zirconium titanium phosphate, and is subjected to double-layer coating of aluminum fluoride and boron oxide, so that the comprehensive performance is optimal.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. A preparation method of a ternary cathode material is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing the ternary precursor, lithium salt, magnesium chromate and lithium titanium zirconium phosphate to obtain a mixed material;
(2) sintering the mixed material in an oxygen-containing atmosphere, and crushing a sintered sample to obtain crushed material;
(3) mixing the crushed materials with aluminum fluoride, preserving heat for 6-8h at the temperature of 300-650 ℃, and crushing to obtain a material coated with an aluminum fluoride layer; mixing boron oxide with the material coated with the aluminum fluoride layer, preserving heat for 6-8h at the temperature of 300-650 ℃, and crushing to obtain a target product.
2. The method for producing a ternary positive electrode material according to claim 1, characterized in that: in the step (1), the molecular formula of the ternary precursor is Ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1.
3. The method for producing a ternary positive electrode material according to claim 1, characterized in that: in the step (1), the lithium salt is lithium nitrate, lithium carbonate or lithium hydroxide.
4. The method for producing a ternary positive electrode material according to claim 1, characterized in that: in the step (1), the molar ratio of the ternary precursor to the lithium salt is 1: (1.01-1.08); the mass of the magnesium chromate in the mixed material is 0.3-1.2 wt% of that of the ternary precursor; the mass of the lithium zirconium titanium phosphate in the mixed material is 0.5-1.5 wt% of that of the ternary precursor.
5. The method for producing a ternary positive electrode material according to claim 1, characterized in that: in the step (2), the oxygen-containing atmosphere is oxygen or air atmosphere.
6. The method for producing a ternary cathode material according to claim 1, characterized in that: in the step (2), the sintering process comprises the following steps: firstly, heating to 600 ℃ at a heating rate of 1-3 ℃/min, and preserving heat for 3-5 h; then heating to 750-960 ℃ at the heating rate of 3-5 ℃/min, and preserving heat for 8-15 h.
7. The method for producing a ternary positive electrode material according to claim 1, characterized in that: in the step (3), the mass ratio of the aluminum fluoride to the crushed materials is (0.004-0.02): 1; the mass ratio of the boron oxide to the crushed materials is (0.004-0.02): 1.
8. a ternary positive electrode material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 7.
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CN104681809A (en) * 2015-02-12 2015-06-03 长沙矿冶研究院有限责任公司 Method for modifying lithium-rich manganese-based cathode material
CN108417797A (en) * 2018-02-09 2018-08-17 山东丰元化学股份有限公司 Nickelic tertiary cathode composite material and preparation method
CN111606362A (en) * 2020-05-27 2020-09-01 惠州亿纬锂能股份有限公司 Method for preparing high-nickel ternary material with assistance of fluxing agent, obtained product and application
CN112993259A (en) * 2021-05-12 2021-06-18 蜂巢能源科技有限公司 Coated ternary cathode material, preparation method thereof and lithium ion battery

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