CN111883768A - High-nickel anode material, preparation method thereof and application thereof in lithium ion battery - Google Patents
High-nickel anode material, preparation method thereof and application thereof in lithium ion battery Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 99
- 239000010405 anode material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 91
- 239000002245 particle Substances 0.000 claims abstract description 54
- 239000002243 precursor Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims description 90
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 60
- 239000010406 cathode material Substances 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 26
- 239000010941 cobalt Substances 0.000 claims description 24
- 229910017052 cobalt Inorganic materials 0.000 claims description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 24
- 239000007774 positive electrode material Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000011164 primary particle Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- -1 boria Chemical compound 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 238000005056 compaction Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010902 jet-milling Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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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- 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
- H01M4/50—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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention provides a high-nickel anode material, a preparation method thereof and application thereof in a lithium ion battery. The high-nickel anode material comprises a large-size high-nickel anode material and a small-size high-nickel anode material; the large-size high-nickel anode material accounts for 50-90% of the total mass of the high-nickel anode material. According to the invention, two high-nickel anode materials with different particle sizes are obtained by controlling the particle size and the particle size distribution of the high-nickel hydroxide precursor, and then the two high-nickel anode materials are mixed according to a certain proportion to obtain a final material, wherein the mixed material has higher compaction density, and the volume energy density of the battery can be improved, so that the cost of the battery is reduced. In addition, the selected small-size high-nickel hydroxide precursor does not contain Co element, and the preparation process does not need water washing, so that the cost is very low.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a high-nickel cathode material, a preparation method thereof and application thereof in a lithium ion battery.
Background
Because of the characteristics of higher working voltage, energy density, long service life, environmental friendliness and the like, the lithium ion battery has become a power supply of a new generation of electric vehicles, electric tools and electronic products, and is widely applied to different fields such as energy, traffic, communication and the like at present. In recent years, new requirements are provided for the energy density of the power battery monomer of the new energy automobile, the energy density of the power battery monomer of the new energy automobile is required to be more than 300Wh/kg, the aim of achieving 350Wh/kg is met, and the system specific energy aim of achieving 260 Wh/kg. However, according to the current technical level, the commonly used lithium iron phosphate and low nickel (Nimol% < 70) ternary materials cannot meet the index requirements, and the high nickel (Nimol% > 80) ternary materials are the most ideal anode materials for realizing high energy density due to high specific capacity. In addition, as the subsidy of the state to the lithium ion battery is reduced year by year, the reduction of the production cost of the battery is imperative.
Currently, the positive electrode material accounts for about one third of the total cost of the battery, and therefore, reducing the cost of the positive electrode material is very important to reduce the cost of the battery. For the high-nickel ternary cathode material, the preparation process is complex and the cost is relatively high. In addition, because the cobalt value is high, the cost of the conventional high-nickel ternary material is difficult to be greatly reduced, and with the continuous increase of the Co value, the development of low-Co or Co-free high-nickel materials is a future trend, and meanwhile, the composition of the material is converted from ternary to multi-element.
CN109473652A discloses a method for preparing a high-nickel ternary material for a lithium ion battery, which adopts a high-nickel hydroxide precursor prepared by a continuous coprecipitation method, and the precursor must contain cobalt element. During material preparation, classifying the precursor into large and small particles, and then respectively performing lithium mixing sintering and modification, wherein the large and small particles are prepared by a polycrystalline material preparation process through one-time sintering and all need to be washed; the material prepared by the method has higher cost.
Disclosure of Invention
Based on the problems in the prior art, the invention aims to provide a high-nickel cathode material, a preparation method of the high-nickel cathode material and application of the high-nickel cathode material in preparation of a lithium ion battery.
The purpose of the invention is realized by the following technical means:
in one aspect, the present invention provides a high nickel positive electrode material comprising a large size high nickel positive electrode material and a small size high nickel positive electrode material;
the large-size high-nickel anode material accounts for 50-90% of the total mass of the high-nickel anode material;
wherein the median particle size of the large-size high-nickel anode material is 10-15 μm; the median particle size of the small-size high-nickel anode material is 4-6 mu m.
In the above-mentioned high nickel cathode material, preferably, the composition of the large-size high nickel cathode material is LiNix1Coy1Mnz1M1(1-x1-y1-z1)O2Wherein M1 is selected from one or more of Al, Zr, Ti and Mg; x1 is more than or equal to 0.80 and less than 1, y1 is more than 0 and less than or equal to 0.10, z1 is more than 0 and less than or equal to 0.15, and x1+ y1+ z1 is less than 1;
the small-size high-nickel cathode material consists of LiNix2M2y2Mn(1-x2-y2)O2Wherein M2 is selected from one or more of Al, Zr, Ti and Mg; x2 is more than or equal to 0.80 and less than 1, y2 is more than 0 and less than or equal to 0.10, and x2+ y2 is less than 1.
On the other hand, the invention also provides a preparation method of the high-nickel cathode material, which comprises the following steps:
mixing and sintering a large-size high-nickel hydroxide precursor containing cobalt element and lithium hydroxide to obtain a first sintering material; mechanically crushing and sieving the first sintering material, controlling the particle size of sintering material particles to be consistent with that of a cobalt-element-containing large-size high-nickel hydroxide precursor, washing and drying the sintering material particles, then carrying out nano oxide dry coating, and then carrying out secondary sintering to obtain a large-size high-nickel anode material;
mixing and sintering a small-size high-nickel hydroxide precursor without cobalt element and lithium hydroxide to obtain a second sintering material; the second sintering material is respectively subjected to mechanical crushing and airflow crushing, sieved, the particle size of sintering material particles is controlled to be consistent with that of a small-size high-nickel hydroxide precursor without cobalt element, then nano oxide dry coating is carried out, and finally secondary sintering is carried out to obtain a small-size high-nickel anode material;
mixing a large-size high-nickel anode material and a small-size high-nickel anode material to prepare a high-nickel anode material;
the large-size high-nickel anode material accounts for 50-90% of the total mass of the high-nickel anode material.
The dry coating in the above preparation method is a conventional method in the art.
In the preparation method, two high-nickel anode materials with different particle sizes are obtained by controlling the particle size and the particle size distribution of the high-nickel hydroxide precursor, and then are mixed according to a certain proportion to obtain a final material, wherein small particles can fill up pores of large particles, so that the compaction density is improved, therefore, the mixed material has higher compaction density, and the volume energy density of the battery can be improved, thereby reducing the cost of the battery. In addition, the selected small-size high-nickel hydroxide precursor does not contain Co element, and the preparation process does not need water washing, so that the cost is very low.
In the preparation method, in the preparation of the small-size high-nickel cathode material, mechanical crushing and airflow crushing are respectively adopted for the second sintering material, so that the single-crystal granular material can be obtained, and washing is not needed, thereby being beneficial to reducing the cost.
In the preparation method, the median particle diameter D50 of the cobalt-containing large-size high-nickel hydroxide precursor is preferably 10-15 μm, and (D90-D10)/D50 is less than 0.9;
the median particle diameter D50 of the small-size high-nickel hydroxide precursor without cobalt element is 3-5 μm, and (D90-D10)/D50 is less than 1.3.
In the above preparation method, preferably, the cobalt-containing large-size high-nickel hydroxide precursor has a composition of Nix1Coy1Mnz1M1(1-x1-y1-z1)(OH)2(ii) a Wherein M1 is selected from one or more of Al, Zr, Ti and Mg; x1 is more than or equal to 0.80 and less than 1,0＜y1≤0.10，0＜z1≤0.15，x1+y1+z1≤1。
in the above-described production method, preferably, the composition of the small-sized high-nickel hydroxide precursor containing no cobalt element is Nix2M2y2Mn(1-x2-y2)(OH)2(ii) a Wherein M2 is selected from one or more of Al, Zr, Ti and Mg; x2 is more than or equal to 0.80 and less than 1, y2 is more than 0 and less than or equal to 0.10, and x2+ y2 is less than 1.
In the preparation method, the lithium hydroxide is preferably in a micro-powder grade, and the median particle size is 6-20 μm.
In the preparation method, preferably, in the process of mixing and sintering the cobalt-containing large-size high-nickel hydroxide precursor and lithium hydroxide to obtain the first sintering material, the sintering temperature is 700-800 ℃, and the sintering time is 12-20 h.
In the above preparation method, the molar ratio of the large-size high-nickel hydroxide precursor containing cobalt element to the lithium hydroxide is 1: (1.01-1.05).
In the preparation method, preferably, in the process of obtaining the second sintering material by mixing and sintering the small-size high-nickel hydroxide precursor without cobalt element and lithium hydroxide, the sintering temperature is 750-850 ℃ and the sintering time is 12-20 h.
In the above preparation method, the molar ratio of the small-size high-nickel hydroxide precursor containing no cobalt element to the lithium hydroxide is 1: (1.03-1.07).
In the above preparation method, preferably, when the first sintering material is washed with water, the mass ratio of the water to the first sintering material is (1-3): 1; the washing time is 1-10 min.
In the above preparation method, preferably, the water content of the material after washing and drying is less than 600 ppm.
In the above preparation method, preferably, the nano oxide includes one or more of alumina, zirconia, boria, magnesia and titania.
In the above preparation method, the primary particle diameter of the nano oxide is preferably 10 to 100 nm.
In the above preparation method, preferably, the coating amount of the nano oxide of the first sintering material is 0.1 wt% to 0.5 wt%.
In the above preparation method, preferably, the coating amount of the nano oxide of the second sintering material is 0.2 wt% to 0.5 wt%.
In the preparation method, preferably, the sintering temperature of the second sintering after the first sintering material coats the nano oxide is 200-700 ℃, and the sintering time is 3-10 hours.
In the preparation method, preferably, the sintering temperature of the second sintering material for secondary sintering after the second sintering material coats the nano oxide is 400-700 ℃, and the sintering time is 3-10 hours.
On the other hand, the invention also provides application of the high-nickel cathode material as a cathode material in preparation of a lithium ion battery.
The invention has the beneficial effects that:
(1) the small-size high-nickel hydroxide precursor selected in the preparation process does not contain Co element, and the preparation process does not need water washing, so that the cost is very low.
(2) In the preparation process, two high-nickel anode materials with different particle sizes are obtained by controlling the particle size and the particle size distribution of the high-nickel hydroxide precursor, and are mixed according to a certain proportion to obtain a final material, wherein the mixed material has higher compaction density, and the volume energy density of the battery can be improved, so that the cost of the battery is reduced.
(3) The invention carries out single coating and secondary sintering on the sintering material of the high-nickel hydroxide precursor with the size, determines the coating amount according to the size, can more effectively carry out precise coating on the surface of the high-nickel material, and avoids the influence on the performance caused by too much or too little coating.
Drawings
Fig. 1 is a charge-discharge curve of the high nickel cathode material prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the high nickel cathode material prepared in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
The high nickel hydroxide precursors in the following examples were prepared using methods conventional in the art.
Example 1:
the embodiment provides a high nickel cathode material, and a preparation method of the high nickel cathode material comprises the following steps:
ni, a high-nickel hydroxide precursor having a D50 value of 10 μm and a D90-D10/D50 value of 0.80.85Co0.1Mn0.045Zr0.005(OH)2And micro-powder lithium hydroxide with the D50 of 7 mu m according to the molar ratio of 1:1.03 mixing, and sintering at 770 ℃ for 12h to obtain LiNi0.85Co0.1Mn0.045Zr0.005O2A material;
reacting LiNi0.85Co0.1Mn0.045Zr0.005O2Mechanically crushing and sieving the material, and controlling the particle size of sintered material particles to be consistent with that of the high-nickel hydroxide precursor; washing the sieved material with water at a water-material ratio of 1:1 for 10min, centrifugally dewatering the washed material, drying the material in vacuum with a water content of 400ppm, and coating the dried material with nano ZrO by a dry method2Nano ZrO2The grain diameter of the primary particles is 30nm, the coating amount is 0.2 wt%, the coated material is sintered for the second time at 650 ℃, the sintering time is 5h, and the large-size high-nickel anode material is obtained after the secondary sintering. The median particle size of the large-size high-nickel cathode material is about 10 μm.
Ni, a high-nickel hydroxide precursor having a D50 value of 4 μm and a D90-D10/D50 value of 1.00.85Al0.05Mn0.10(OH)2And micro-powder lithium hydroxide with the D50 of 7 mu m according to the molar ratio of 1: 1.05, and sintering at 820 ℃ for 12h to obtain LiNi0.85Al0.05Mn0.10O2A material;
reacting LiNi0.85Al0.05Mn0.10O2Firstly, mechanically crushing the materials, and then carrying out jet milling; coating nano ZrO on crushed material by dry method2Nano ZrO2The primary particle size of the composite is 30nm, the coating amount is 0.3 wt%, the coated material is sintered for the second time at 500 ℃, the sintering time is 5 hours, and the small-size high-nickel anode material is obtained after the secondary sintering. The median particle size of the small-size high-nickel cathode material was about 5 μm.
And (3) respectively crushing and demagnetizing the large-size high-nickel anode material and the small-size high-nickel anode material obtained by secondary sintering, wherein the crushed particle size is consistent with the particle size obtained after primary sintering and crushing, and then fully mixing the large-size high-nickel anode material and the small-size high-nickel anode material according to the mass ratio of 3:1 to obtain the final high-nickel anode material.
The charge and discharge curve of the high nickel cathode material prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that: the capacity of the three materials is in the order of mixed material > large particles > small particles, mainly due to the synergistic effect of the mixed large and small particles.
The SEM image of the high nickel cathode material prepared in this example is shown in fig. 2, and it can be seen from fig. 2 that: the mixed material consists of two kinds of large and small particle materials, wherein the large particles are in a secondary spherical shape, the small particles are in a single crystal shape, and the large particles and the small particles are uniformly dispersed.
Example 2:
the embodiment provides a high nickel cathode material, and a preparation method of the high nickel cathode material comprises the following steps:
ni, a high-nickel hydroxide precursor having a D50 value of 15 μm and a D90-D10/D50 value of 0.80.85Co0.1Mn0.045Zr0.005(OH)2And micro-powder lithium hydroxide with the D50 of 7 mu m according to the molar ratio of 1:1.03 mixing and sintering at 770 ℃ for 12h to obtain LiNi0.85Co0.1Mn0.045Zr0.005O2A material;
reacting LiNi0.85Co0.1Mn0.045Zr0.005O2Mechanically crushing and sieving the material, and controlling the particle size of the crushed and sieved material to be consistent with that of the precursor; sieving the materialWashing with water at a water-to-material ratio of 2:1 for 5min, centrifuging, dewatering, vacuum drying to water content of 500ppm, and dry coating with nano ZrO2Nano ZrO2The grain diameter of the primary particles is 40nm, the coating amount is 0.15 wt%, the coated material is sintered for the second time at 700 ℃, the sintering time is 5h, and the large-size high-nickel anode material is obtained after the secondary sintering. The median particle size of the large-size high-nickel cathode material is about 15 μm.
Ni, a high-nickel hydroxide precursor having a D50 value of 3.5 μm and a D90-D10)/D50 value of 0.90.85Al0.05Mn0.10(OH)2Mixing and sintering the mixture with micro powder lithium hydroxide with the D50 of 6 mu m at 820 ℃ for 12h to obtain LiNi0.85Al0.05Mn0.10O2A material;
reacting LiNi0.85Al0.05Mn0.10O2Firstly, mechanically crushing the materials, and then carrying out jet milling; coating nano ZrO on crushed material by dry method2Nano ZrO2The primary particle size of the composite is 40nm, the coating amount is 0.4 wt%, the coated material is sintered for the second time at 600 ℃, the sintering time is 5 hours, and the small-size high-nickel anode material is obtained after the secondary sintering. The median particle size of the small-size high-nickel cathode material was about 4.5 μm.
And (3) respectively crushing and demagnetizing the large-size high-nickel positive electrode material and the small-size high-nickel positive electrode material obtained by secondary sintering, and fully mixing the large-size high-nickel positive electrode material and the small-size high-nickel positive electrode material according to the mass ratio of 4:1 to obtain the final high-nickel positive electrode material.
Example 3:
the embodiment provides a high nickel cathode material, and a preparation method of the high nickel cathode material comprises the following steps:
ni, a high-nickel hydroxide precursor having a D50 value of 10 μm and a D90-D10/D50 value of 0.80.9Co0.05Mn0.045Zr0.005(OH)2Mixing with fine powder lithium hydroxide with the D50 being 7 mu m according to the mol ratio of 1:1.03, and carrying out mixed sintering at 730 ℃ for 12h to obtain LiNi0.9Co0.05Mn0.045Zr0.005O2A material;
reacting LiNi0.9Co0.05Mn0.045Zr0.005O2Crushing and sieving the material, and controlling the particle size of sintered material particles to be consistent with that of the high-nickel hydroxide precursor; washing the sieved material with water at a water-material ratio of 1:2 for 1min, centrifugally dewatering the washed material, drying the material in vacuum with a water content of 300ppm, and coating the dried material with nano ZrO by a dry method2Nano ZrO2The grain diameter of the primary particles is 30nm, the coating amount is 0.2 wt%, the coated material is sintered for the second time at 650 ℃, the sintering time is 5h, and the large-size high-nickel anode material is obtained after the secondary sintering. The median particle size of the large-size high-nickel cathode material is about 10 μm.
Ni, a high-nickel hydroxide precursor having a D50 value of 4 μm and a D90-D10/D50 value of 1.00.9Al0.05Mn0.05(OH)2And micro-powder lithium hydroxide with the D50 of 7 mu m according to the molar ratio of 1: 1.05, and then mixed and sintered for 12 hours at 820 ℃ to obtain LiNi0.9Al0.05Mn0.05O2A material;
reacting LiNi0.9Al0.05Mn0.05O2Firstly, mechanically crushing the materials, and then carrying out jet milling; coating nano ZrO on crushed material by dry method2Nano ZrO2The primary particle size of the composite is 30nm, the coating amount is 0.3 wt%, the coated material is sintered for the second time at 500 ℃, the sintering time is 5 hours, and the small-size high-nickel anode material is obtained after the secondary sintering. The median particle size of the small-size high-nickel cathode material was about 5 μm.
And (3) respectively crushing and demagnetizing the large-size high-nickel positive electrode material and the small-size high-nickel positive electrode material obtained by secondary sintering, and fully mixing the large-size high-nickel positive electrode material and the small-size high-nickel positive electrode material according to the mass ratio of 3:1 to obtain the final high-nickel positive electrode material.
Claims (10)
1. A high nickel positive electrode material comprises a large-size high nickel positive electrode material and a small-size high nickel positive electrode material;
the large-size high-nickel anode material accounts for 50-90% of the total mass of the high-nickel anode material;
wherein the median particle size of the large-size high-nickel anode material is 10-15 μm; the median particle size of the small-size high-nickel anode material is 4-6 mu m.
2. The high nickel positive electrode material according to claim 1, wherein the composition of the large-size high nickel positive electrode material is LiNix1Coy1Mnz1M1(1-x1-y1-z1)O2Wherein M1 is selected from one or more of Al, Zr, Ti and Mg; x1 is more than or equal to 0.80 and less than 1, y1 is more than 0 and less than or equal to 0.10, z1 is more than 0 and less than or equal to 0.15, and x1+ y1+ z1 is less than 1;
the small-size high-nickel cathode material consists of LiNix2M2y2Mn(1-x2-y2)O2Wherein M2 is selected from one or more of Al, Zr, Ti and Mg; x2 is more than or equal to 0.80 and less than 1, y2 is more than 0 and less than or equal to 0.10, and x2+ y2 is less than 1.
3. A method for producing the high nickel positive electrode material according to claim 1 or 2, comprising the steps of:
mixing and sintering a large-size high-nickel hydroxide precursor containing cobalt element and lithium hydroxide to obtain a first sintering material; mechanically crushing and sieving the first sintering material, controlling the particle size of sintering material particles to be consistent with that of a cobalt-element-containing large-size high-nickel hydroxide precursor, washing and drying the sintering material particles, then carrying out nano oxide dry coating, and then carrying out secondary sintering to obtain a large-size high-nickel anode material;
mixing and sintering a small-size high-nickel hydroxide precursor without cobalt element and lithium hydroxide to obtain a second sintering material; the second sintering material is respectively subjected to mechanical crushing and airflow crushing, sieved, the particle size of sintering material particles is controlled to be consistent with that of a small-size high-nickel hydroxide precursor without cobalt element, then nano oxide dry coating is carried out, and finally secondary sintering is carried out to obtain a small-size high-nickel anode material;
mixing a large-size high-nickel anode material and a small-size high-nickel anode material to prepare a high-nickel anode material;
the large-size high-nickel anode material accounts for 50-90% of the total mass of the high-nickel anode material.
4. The preparation method according to claim 3, wherein the cobalt-containing large-size high nickel hydroxide precursor has a median particle diameter D50 of 10 to 15 μm and (D90-D10)/D50 < 0.9;
the median particle diameter D50 of the small-size high-nickel hydroxide precursor without cobalt element is 3-5 μm, and (D90-D10)/D50 is less than 1.3.
5. The production method according to claim 3, wherein the cobalt-containing large-size high-nickel hydroxide precursor has a composition of Nix1Coy1Mnz1M1(1-x1-y1-z1)(OH)2(ii) a Wherein M1 is selected from one or more of Al, Zr, Ti and Mg; x1 is more than or equal to 0.80 and less than 1, y1 is more than 0 and less than or equal to 0.10, z1 is more than 0 and less than or equal to 0.15, and x1+ y1+ z1 is less than or equal to 1;
preferably, the composition of the small-size high-nickel hydroxide precursor without cobalt element is Nix2M2y2Mn(1-x2-y2)(OH)2(ii) a Wherein M2 is selected from one or more of Al, Zr, Ti and Mg; x2 is more than or equal to 0.80 and less than 1, y2 is more than 0 and less than or equal to 0.10, and x2+ y2 is less than 1;
preferably, the lithium hydroxide is in a micro-powder grade, and the median particle size is 6-20 microns.
6. The preparation method according to claim 3, wherein in the process of mixing and sintering the cobalt-containing large-size high-nickel hydroxide precursor and lithium hydroxide to obtain the first sintering material, the sintering temperature is 700-800 ℃, and the sintering time is 12-20 h;
preferably, the molar ratio of the cobalt-containing large-size high-nickel hydroxide precursor to the lithium hydroxide is 1: (1.01-1.05);
preferably, in the process of obtaining a second sintering material by mixing and sintering a small-size high-nickel hydroxide precursor without cobalt element and lithium hydroxide, the sintering temperature is 750-850 ℃, and the sintering time is 12-20 h;
preferably, the molar ratio of the small-sized high nickel hydroxide precursor free of cobalt element to the lithium hydroxide is 1: (1.03-1.07).
7. The preparation method according to claim 3, wherein when the first sintering material is washed with water, the mass ratio of the water to the first sintering material is (1-3): 1; the washing time is 1-10 min;
preferably, the water content of the material after washing and drying is less than 600 ppm.
8. The production method according to claim 3, wherein the nano-oxide comprises a combination of one or more of alumina, zirconia, boria, magnesia and titania;
preferably, the primary particle size of the nano oxide is 10-100 nm;
preferably, the coating amount of the nano oxide of the first sintering material is 0.1 wt% to 0.5 wt%;
preferably, the coating amount of the nano oxide of the second sintering material is 0.2 wt% to 0.5 wt%.
9. The preparation method according to claim 3, wherein the sintering temperature of the first sintering material for secondary sintering after coating the nano oxide is 200-700 ℃, and the sintering time is 3-10 h;
preferably, the sintering temperature of the second sintering material for secondary sintering after the second sintering material coats the nano oxide is 400-700 ℃, and the sintering time is 3-10 h.
10. Use of the high nickel positive electrode material of claim 1 or 2 as a positive electrode material in the preparation of lithium ion batteries.
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