CN116093329A - Ternary positive electrode material, preparation method thereof and battery - Google Patents
Ternary positive electrode material, preparation method thereof and battery Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 67
- 238000000576 coating method Methods 0.000 claims abstract description 54
- 239000011248 coating agent Substances 0.000 claims abstract description 50
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 47
- 239000007864 aqueous solution Substances 0.000 claims abstract description 36
- 238000005245 sintering Methods 0.000 claims abstract description 35
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010936 titanium Substances 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 15
- 238000005253 cladding Methods 0.000 claims abstract description 14
- 239000002019 doping agent Substances 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000010406 cathode material Substances 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000010410 layer Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 32
- 229910052759 nickel Inorganic materials 0.000 description 13
- 239000002131 composite material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- -1 titanium ions Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01M4/00—Electrodes
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention discloses a ternary positive electrode material, a preparation method thereof and a battery, and belongs to the technical field of batteries. The preparation method of the ternary positive electrode material comprises the following steps: carrying out wet cladding on a sintered material and a cladding material obtained by mixing a ternary positive electrode material precursor, a lithium source and a doping agent and then carrying out secondary sintering; the coating material is prepared by dissolving an aluminum source and a titanium source in a nano aramid fiber aqueous solution; wherein the aluminum source comprises at least one of aluminum chloride and aluminum phosphate, and the titanium source is titanium tetrachloride. The method not only can make the coating more uniform, but also can make the coating layer circulateIs more stable in the process, and a large number of gaps exist among thin-layer high molecular structure molecules on the surface of the material, so that Li is not influenced + Free passage of ions. The ternary positive electrode material prepared by the method has higher capacity and cycle stability. The corresponding battery also has better electrochemical performance.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a ternary positive electrode material, a preparation method thereof and a battery.
Background
Generally, for the nickel cobalt lithium manganate ternary material positive electrode material, the energy density is improved along with the increase of the nickel content, but the high nickel ternary positive electrode material Ni 2+ /Li + The mixed discharge is serious, and the circulation and multiplying power performance of the materials are affected; and the high-activity surface is easy to react with electrolyte, so that the cycle performance and the safety are reduced.
The surface coating modification is the most commonly used method for improving the circulation performance at present, the proper coating modification can reduce the contact between the anode material and the electrolyte, the storage and circulation performance can be improved while the capacity is kept as much as possible, and the material is protected from being corroded by the electrolyte in the charging and discharging process.
The existing coating method generally adopts the mechanical mixing of metal oxide and positive electrode material, then high-temperature sintering is carried out to achieve the coating effect, the metal oxide has stable structure and can effectively protect the material, but for the small-molecular metal oxide coating agent, the effect of electrolyte is reduced only through surface stacking and reaching a certain thickness, so that the mechanical mixing is difficult to obtain a uniform coating layer, and the coating layer is easy to deform and Li along with the positive electrode material in the circulating process + The release occurs due to the release of the resin, and the cycle performance and the safety are reduced.
In view of this, the present invention has been made.
Disclosure of Invention
One of the objectives of the present invention is to provide a method for preparing a ternary positive electrode material to solve the above technical problems.
The second object of the invention is to provide a ternary positive electrode material prepared by the preparation method.
The third object of the present invention is to provide a battery in which the positive electrode material is the ternary positive electrode material.
The application can be realized as follows:
in a first aspect, the present application provides a method for preparing a ternary positive electrode material, comprising the steps of:
carrying out wet cladding on a sintered material and a cladding material obtained by mixing a ternary positive electrode material precursor, a lithium source and a doping agent and then carrying out secondary sintering;
the coating material is prepared by dissolving an aluminum source and a titanium source in a nano aramid fiber aqueous solution;
wherein the aluminum source comprises at least one of aluminum chloride and aluminum phosphate, and the titanium source is titanium tetrachloride.
In an alternative embodiment, the mass of aluminum element in the aluminum source is 1000-3000ppm of the ternary positive electrode material precursor.
In an alternative embodiment, the mass of titanium element in the titanium source is 1000-3000ppm of the ternary cathode material precursor.
In an alternative embodiment, the mass ratio of the firing material to the nano aramid fiber aqueous solution is 10:1-2, and the mass concentration of the nano aramid fiber in the nano aramid fiber aqueous solution is 0.2-0.3%.
In an alternative embodiment, the mass ratio of the aluminum source, the titanium source and the aqueous solution of the nano-aramid fiber is 7.4:2.44-4.88:50.
In an alternative embodiment, the wet coating is performed using a rolling fluidized bed, and the spray gas flow rate of the coating is 80-90L/min.
In an alternative embodiment, the secondary sintering is performed at 500-700 ℃ for 8-12 hours;
the sintering atmosphere of the secondary sintering is nitrogen atmosphere or inert gas atmosphere.
In an alternative embodiment, the ternary positive electrode material precursor has a molecular formula of Ni x Co y Mn z (OH) 2 Wherein x=0.7-0.75, y=0.05-0.1, z=1-x-y;
in an alternative embodiment, the ternary positive electrode material precursor includes Ni 0.7 Co 0.1 Mn 0.2 (OH) 2 、Ni 0.72 Co 0.08 Mn 0.2 (OH) 2 And Ni 0.75 Co 0.05 Mn 0.2 (OH) 2 At least one of them.
In an alternative embodiment, the lithium source comprises at least one of lithium carbonate and lithium hydroxide.
In an alternative embodiment, the dopant comprises a doping element comprising at least one of Zr, sr, Y, B and Mg.
In an alternative embodiment, the dopant comprises SrCO 3 、Y 2 O 3 And H 3 BO 3 At least one of them.
In an alternative embodiment, the primary sintering is carried out at 900-960 ℃ for 8-12 hours.
In an alternative embodiment, prior to wet coating with the coating material, the method further comprises crushing a frit to a particle size D 50 =3-4μm。
In a second aspect, the present application provides a ternary positive electrode material prepared by the preparation method of any one of the preceding embodiments.
In a third aspect, the present application provides a battery, wherein the positive electrode material is the ternary positive electrode material of the foregoing embodiment.
The beneficial effects of this application include:
the nanometer aramid fiber aqueous solution that adopts in this application belongs to the polyanion solution, can realize molecular level mixing with trivalent aluminum and tetravalent titanium ion in aqueous solution, then at nanometer aramid fiber surface normal position adsorption ion formation even composite solution, the aluminum forms the complex after loading to nanometer aramid fiber surface, can prevent nanometer aramid fiber's reunion, use composite aqueous solution to carry out wet coating simultaneously and make the whole closely firm cladding of complex at high nickel ternary positive material surface, the coating is difficult to drop and has effectively reduced the activity on high nickel ternary positive material surface. Finally, during secondary sintering, the coating element can partially fill the grain boundary in the sintering process, so as to play a role in reducing the specific surface of the material, thereby improving the capacity and the cycling stability of the material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a ternary positive electrode material obtained in example 1 in a test example;
FIG. 2 is an SEM image of the ternary cathode material obtained in example 2 of the test example;
fig. 3 is an SEM image of the ternary cathode material obtained in comparative example 1 in the test example;
fig. 4 is an SEM image of the ternary cathode material obtained in comparative example 2 in the test example.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The ternary cathode material, the preparation method thereof and the battery provided by the application are specifically described below.
The application provides a preparation method of a ternary positive electrode material, which comprises the following steps:
and carrying out wet cladding on a sintered material and a cladding material obtained by mixing a ternary positive electrode material precursor, a lithium source and a doping agent and then carrying out secondary sintering.
The molecular formula of the ternary positive electrode material precursor is Ni x Co y Mn z (OH) 2 Wherein x=0.7-0.75, y=0.05-0.1, and z=1-x-y.
For example, the ternary positive electrode material precursor may include Ni, for example 0.7 Co 0.1 Mn 0.2 (OH) 2 、Ni 0.72 Co 0.08 Mn 0.2 (OH) 2 And Ni 0.75 Co 0.05 Mn 0.2 (OH) 2 At least one of them.
The lithium source may include at least one of lithium carbonate and lithium hydroxide.
The doping element contained in the dopant may include at least one of Zr, sr, Y, B and Mg.
As an example, the above Zr may be represented by ZrO 2 Provided that Sr can be derived from SrCO 3 Y is provided by Y 2 O 3 Provided, B can be made of H 3 BO 3 Mg is provided by providing MgSO 4 、Mg(NO 3 ) 2 、MgCl 2 Or Mg (CH) 3 COO) 2 Providing.
In some preferred embodiments, the dopant comprises SrCO 3 、Y 2 O 3 And H 3 BO 3 At least one of them.
By reference, one sintering may be performed at 900-960 ℃ (e.g., 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃ or 960 ℃, etc.) for 8-12 hours (e.g., 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, etc.).
It should be noted that, in the present application, the ratio of the raw materials related to a sintering material and other preparation conditions of a sintering material may refer to the prior art, and will not be described herein in detail.
Further, before wet coating is carried out on the sintered material and the coating material, crushing is carried out on the sintered material, and sieving is carried out. The particle size of the crushed sintered material is about D 50 =3-4μm。
By crushing into the particle size, a sintered material is formed into particles with proper size, so that the subsequent coating is facilitated.
The coating material used in the application is prepared by dissolving an aluminum source and a titanium source in a nano aramid fiber aqueous solution.
Wherein the aluminum source comprises at least one of aluminum chloride and aluminum phosphate, and the titanium source is titanium tetrachloride.
The coating is assisted by using the high polymer material (nanometer aramid fiber) with excellent mechanical property, so that the coating is more uniform, and the long-chain structure of the high polymer can be better coated on the positive electrode material, so that the coating layer is more stable in the circulating process. In addition, a large number of gaps exist among the thin-layer high-molecular structure molecules on the surface, and Li is not influenced + Free passage of ions.
For reference, the mass of aluminum element in the aluminum source is 1000-3000ppm, such as 1000ppm, 1500ppm, 2000ppm, 2500ppm or 3000ppm, etc., of the ternary positive electrode material precursor, and may be any other value in the range of 1000-3000ppm.
The mass of titanium element in the titanium source can be 1000-3000ppm of ternary positive electrode material precursor, such as 1000ppm, 1500ppm, 2000ppm, 2500ppm or 3000ppm, and can be any other value in the range of 1000-3000ppm.
If the amount of aluminum element or titanium element is too small, coating unevenness is likely to occur.
The mass ratio of the firing material to the nano-aramid fiber aqueous solution can be 10:1-2, such as 10:1, 10:1.2, 10:1.5, 10:1.8 or 10:2, and the like, and can be any other value within the range of 10:1-2.
The mass concentration of the nano aramid fiber in the nano aramid fiber aqueous solution can be 0.2-0.3%, such as 0.2%, 0.22%, 0.25%, 0.28% or 0.3%, and the like, and can be any other value within the range of 0.2-0.3%.
The content of the nanometer aramid fiber in the nanometer aramid fiber aqueous solution is too low, which can lead to low coating efficiency; the content of the nanometer aramid fiber is too high, the nanometer aramid fiber is not easy to disperse in water, and precipitation is easy to generate.
In some specific embodiments, the mass ratio of the aluminum source, the titanium source, and the aqueous solution of the nano-aramid fiber may be 7.4:2.44-4.88:50.
In the present application, the wet coating may be performed, for example, by using a rolling fluidized bed, and the flow rate of the spray gas of the coating material may be about 80 to 90L/min, such as 80L/min, 82L/min, 85L/min, 88L/min, or 90L/min, or any other value within the range of 80 to 90L/min.
In the process, the cladding material is atomized into a gaseous state under the high-speed condition. Because the cladding material has great viscosity in this application, if the flow is too little, lead to the cladding material unable effective atomizing easily, promptly can't effectively realize the cladding promptly.
As a reference, the secondary sintering may be performed at 500-700℃C (e.g., 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, etc.) for 8-12 hours (e.g., 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, etc.).
The sintering atmosphere for the secondary sintering is nitrogen atmosphere or inert gas (such as argon or helium) atmosphere.
By carrying out secondary sintering under nitrogen atmosphere or inert gas (such as argon or helium) atmosphere, the reaction of oxygen and the aqueous solution of the nano aramid fiber at 500-700 ℃ can be prevented, so that most of C is changed into CO after the fiber is decomposed 2 And volatilizing.
On the premise of bearing, the nanometer aramid fiber aqueous solution adopted in the application belongs to a polyanion solution, can realize molecular-level mixing with trivalent aluminum and tetravalent titanium ions in the aqueous solution, then in-situ adsorbs ions on the surface of the nanometer aramid fiber to form a uniform composite solution, aluminum and titanium are loaded on the surface of the nanometer aramid fiber to form a complex, so that agglomeration of the nanometer aramid fiber can be prevented, meanwhile, the complex aqueous solution is used for wet coating to enable the complex to be integrally and tightly coated on the surface of the high-nickel ternary positive electrode material, an Li-Al-Ti-O layer formed after heat treatment can resist corrosion of HF in electrolyte, dissolution of metal ions in an active material is prevented, a coating layer is not easy to fall off, and the activity of the surface of the high-nickel ternary positive electrode material is effectively reduced. Finally, secondary sintering is carried out under nitrogen or inert gas, and the cladding element partially fills the grain boundary in the sintering process, so that the effect of reducing the specific surface of the material is achieved, and the capacity and the cycling stability of the material are improved.
Correspondingly, the application also provides a ternary positive electrode material which is prepared by the preparation method. The ternary positive electrode material has higher capacity and cycle stability.
In addition, the application also provides a battery, and the positive electrode material of the battery is the ternary positive electrode material. The battery has better electrochemical performance.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
Ni is added with 0.7 Co 0.1 Mn 0.2 (OH) 2 500g of precursor, 197g of lithium carbonate and doping agent (SrCO) 3 0.59g、Y 2 O 3 0.79g and H 3 BO 3 0.92 g) are evenly mixed, and then are heated to 930 ℃ at a heating rate of 3 ℃/min for 12 hours of heat preservation, and the high nickel material LiNi is obtained after one-time firing 0.7 Co 0.1 Mn 0.2 O 2 (i.e., a frit) is pulverized with an air mill at a classification frequency of 120Hz and then sieved (D) 50 3-4 μm) for later use.
7.4g of aluminum chloride and 4.88g of titanium tetrachloride are dissolved in 50g of a nano aramid fiber aqueous solution with the mass fraction of 0.2wt% to prepare a coating material, and the coating material is sprayed onto the surface of a sintering material (500 g) in a wet coating mode by using a rolling fluidized bed, wherein the spraying gas flow rate is 80L/min.
And then carrying out secondary sintering under nitrogen atmosphere, wherein the secondary sintering temperature is 550 ℃, and the heat preservation time is 8 hours, so as to obtain the nano aramid fiber-based-Al/Ti composite high-nickel ternary anode material.
Example 2
This embodiment differs from embodiment 1 in that: the coating material was obtained by dissolving 7.4g of aluminum chloride and 2.44g of titanium tetrachloride in 50g of a 0.2wt% aqueous solution of a nano-aramid fiber.
Example 3
This embodiment differs from embodiment 1 in that: the coating material is prepared by dissolving 7.4g of aluminum chloride and 4.88g of titanium tetrachloride in 50g of a nano aramid fiber aqueous solution with the mass fraction of 0.3 wt%.
The flow rate of the spraying gas in the wet coating process is 90L/min.
Example 4
Ni is added with 0.7 Co 0.1 Mn 0.2 (OH) 2 500g of precursor, 197g of lithium carbonate and doping agent (SrCO) 3 0.59g、Y 2 O 3 0.79g and H 3 BO 3 0.92 g) and then heating to 900 ℃ at a heating rate of 3 ℃/min for 10h, and obtaining the high nickel material LiNi after primary combustion 0.7 Co 0.1 Mn 0.2 O 2 (namely, a burned material) is crushed by using an air mill with 120Hz grading frequency and then is sieved by a 400-mesh sieve for standby.
Aluminum chloride and titanium tetrachloride are dissolved in a nano aramid fiber aqueous solution with the mass fraction of 0.2wt% to prepare a coating material. Wherein the mass of aluminum element in aluminum chloride is 1000ppm of ternary positive electrode material precursor; the mass of titanium element in the titanium tetrachloride is 3000ppm of ternary positive electrode material precursor. The coating material is sprayed onto the surface of a firing material (the mass ratio of the firing material to the nano aramid fiber aqueous solution is 10:2) in a wet coating mode by using a rolling fluidized bed, and the flow rate of spraying gas is 85L/min.
And then carrying out secondary sintering under argon atmosphere, wherein the secondary sintering temperature is 500 ℃, and the heat preservation time is 12 hours, so as to obtain the nano aramid fiber-Al/Ti composite high-nickel ternary anode material.
Example 5
Ni is added with 0.7 Co 0.1 Mn 0.2 (OH) 2 500g of precursor, 197g of lithium carbonate and doping agent (SrCO) 3 0.59g、Y 2 O 3 0.79g and H 3 BO 3 0.92 g) and then heating to 960 ℃ at a heating rate of 3 ℃/min, preserving heat for 8 hours, and obtaining the high nickel material LiNi after primary combustion 0.7 Co 0.1 Mn 0.2 O 2 (namely, a burned material) is crushed by using an air mill with 120Hz grading frequency and then is sieved by a 400-mesh sieve for standby.
Aluminum chloride and titanium tetrachloride are dissolved in a nano aramid fiber aqueous solution with the mass fraction of 0.2wt% to prepare a coating material. Wherein the mass of aluminum element in aluminum chloride is 3000ppm of ternary positive electrode material precursor; the mass of titanium element in the titanium tetrachloride is 1000ppm of the ternary cathode material precursor. The coating material is sprayed onto the surface of a sintering material (the mass ratio of the sintering material to the nano aramid fiber aqueous solution is 10:1.5) in a wet coating mode by using a rolling fluidized bed, and the flow rate of spraying gas is 85L/min.
And then carrying out secondary sintering under helium atmosphere, wherein the secondary sintering temperature is 700 ℃, and the heat preservation time is 10 hours, so as to obtain the nano aramid fiber-Al/Ti composite high-nickel ternary anode material.
Example 6
This embodiment differs from embodiment 1 in that: the aluminum source is aluminum phosphate.
Example 7
This embodiment differs from embodiment 1 in that: the lithium source is lithium hydroxide.
Example 8
This embodiment differs from embodiment 1 in that: the dopant consisted of 3.63g of MgSO 4 ZrO 1.35g 2 Composition is prepared.
Comparative example 1
The difference between this comparative example and example 1 is that:
the coating material was obtained by dissolving 7.4g of aluminum chloride and 4.88g of titanium tetrachloride in an aqueous solution.
The flow rate of the spraying gas in the wet coating process is 80L/min.
Comparative example 2
The difference between this comparative example and example 1 is that:
the coating material consists of 7.4g of aluminum chloride and 4.88g of titanium tetrachloride, and the coating process is to mechanically coat the coating material and a sintering material at 600r/min for 15 minutes.
The secondary sintering is performed under an air atmosphere.
Comparative example 3
The difference between this comparative example and example 1 is that: the coating material is prepared by dissolving 7.4g of aluminum chloride in 50g of a nano aramid fiber aqueous solution with the mass fraction of 0.2 wt%.
I.e., the coating does not contain titanium tetrachloride.
Comparative example 4
The difference between this comparative example and example 1 is that: the coating material is prepared by dissolving 4.88g of titanium tetrachloride in 50g of a nano aramid fiber aqueous solution with the mass fraction of 0.2 wt%.
I.e. the coating is free of aluminium chloride.
Comparative example 5
The difference between this comparative example and example 1 is that: the mass of aluminum element in the aluminum source is 500ppm of the ternary cathode material precursor.
Comparative example 6
The difference between this comparative example and example 1 is that: the mass of aluminum element in the aluminum source is 3500ppm of ternary positive electrode material precursor.
Comparative example 7
The difference between this comparative example and example 1 is that: the mass of titanium element in the titanium source is 500ppm of the ternary cathode material precursor.
Comparative example 8
The difference between this comparative example and example 1 is that: the mass of titanium element in the titanium source is 3500ppm of ternary positive electrode material precursor.
Comparative example 9
The difference between this comparative example and example 1 is that: the mass ratio of the firing material to the nano aramid fiber aqueous solution is 10:0.5.
Comparative example 10
The difference between this comparative example and example 1 is that: the mass ratio of the firing material to the nano aramid fiber aqueous solution is 10:2.5.
Comparative example 11
The difference between this comparative example and example 1 is that: the mass concentration of the nanometer aramid fiber in the nanometer aramid fiber aqueous solution is 0.1 percent.
Comparative example 12
The difference between this comparative example and example 1 is that: the mass concentration of the nanometer aramid fiber in the nanometer aramid fiber aqueous solution is 0.4 percent.
Comparative example 13
The difference between this comparative example and example 1 is that: the spray gas flow of the coating material was 60L/min.
Test examples
(1) Scanning electron microscope observation was performed on the obtained ternary cathode materials, taking examples 1-2 and comparative examples 1-2 as examples, and SEM images are shown in fig. 1 to 4, respectively.
As can be seen from fig. 1 to 4: the nanometer aramid fiber aqueous solution is used for assisting in wet coating, so that the whole composite is tightly and firmly coated on the surface of the high-nickel ternary cathode material, agglomeration of the coating layer in the traditional mechanical coating method can be slowed down, and the coating layer is more uniform and stable.
(2) The ternary cathode materials obtained in examples 1 to 8 and comparative examples 1 to 13 were made into 2025 type button cells and subjected to electrochemical performance tests, and the preparation and test methods were as follows: ternary positive electrode: carbon black: pvdf=90: 5:5, a step of; the negative electrode was lithium metal, the electrolyte was new state battery (M10), the charge-discharge voltage range was 2.8 to 4.35V, and after 1 charge-discharge at different rates of 0.1C, 0.2C, 0.5C, and 1C, the capacity and cycle performance of 1C were finally tested at normal temperature, and the results are shown in table 1.
Table 1 test results
| Buckling capacity (mAh/g) | 1C cycle 50 week retention (%) | |
| Example 1 | 187.3 | 96.4 |
| Example 2 | 186.6 | 95.5 |
| Example 3 | 186.1 | 96.3 |
| Example 4 | 185.7 | 95.5 |
| Example 5 | 185.9 | 96.4 |
| Example 6 | 186.7 | 94.2 |
| Example 7 | 185.6 | 96 |
| Example 8 | 186.5 | 95.2 |
| Comparative example 1 | 182.0 | 93.3 |
| Comparative example 2 | 181.2 | 91.3 |
| Comparative example 3 | 183.8 | 92.5 |
| Comparative example 4 | 184.4 | 93.9 |
| Comparative example 5 | 183.5 | 92.9 |
| Comparative example 6 | 181.2 | 91.3 |
| Comparative example 7 | 183.4 | 93.6 |
| Comparative example 8 | 185.0 | 93.4 |
| Comparative example 9 | 185.3 | 93.5 |
| Comparative example 10 | 181.8 | 93.2 |
| Comparative example 11 | 182.0 | 93.7 |
| Comparative example 12 | 181.4 | 93.4 |
| Comparative example 13 | 180.9 | 93.6 |
As can be seen from table 1, the ternary cathode materials obtained in examples 1 to 8 can more advantageously improve the buckling capacity and cycle retention rate of the battery than the ternary cathode materials obtained in comparative examples 1 to 13. And among examples 1 to 8, the combination effect of example 1 was the best.
In conclusion, the preparation method provided by the application can effectively improve the capacity and the cycle stability of the material.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the ternary positive electrode material is characterized by comprising the following steps of:
carrying out wet cladding on a sintered material and a cladding material obtained by mixing a ternary positive electrode material precursor, a lithium source and a doping agent and then carrying out secondary sintering;
the coating material is prepared by dissolving an aluminum source and a titanium source in a nano aramid fiber aqueous solution;
wherein the aluminum source comprises at least one of aluminum chloride and aluminum phosphate, and the titanium source is titanium tetrachloride.
2. The preparation method according to claim 1, wherein the mass of aluminum element in the aluminum source is 1000-3000ppm of the ternary cathode material precursor;
and/or the mass of titanium element in the titanium source is 1000-3000ppm of the ternary cathode material precursor;
and/or the mass ratio of the first firing material to the nano aramid fiber aqueous solution is 10:1-2, and the mass concentration of the nano aramid fiber in the nano aramid fiber aqueous solution is 0.2-0.3%.
3. The method according to claim 2, wherein the mass ratio of the aluminum source, the titanium source and the aqueous solution of the nano-aramid fiber is 7.4:2.44-4.88:50.
4. The method according to claim 1, wherein the wet coating is performed by using a rolling fluidized bed, and the spray gas flow rate of the coating is 80-90L/min.
5. The method according to claim 1, wherein the secondary sintering is performed at 500 to 700 ℃ for 8 to 12 hours;
the sintering atmosphere of the secondary sintering is nitrogen atmosphere or inert gas atmosphere.
6. The method of any one of claims 1-5, wherein the ternary positive electrode material precursor has a molecular formula of Ni x Co y Mn z (OH) 2 Wherein x=0.7-0.75, y=0.05-0.1, z=1-x-y;
and/or, the lithium source comprises at least one of lithium carbonate and lithium hydroxide;
and/or the doping element contained in the dopant includes at least one of Zr, sr, Y, B and Mg.
7. The method according to claim 1, wherein the primary sintering is carried out at 900-960 ℃ for 8-12 hours.
8. The method of claim 1, further comprising crushing the frit to a particle size D prior to wet coating with the coating material 50 =3-4μm。
9. A ternary cathode material prepared by the method of any one of claims 1-8.
10. A battery, characterized in that the positive electrode material of the battery is the ternary positive electrode material of claim 9.
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