CN118183880A - Preparation method of high-magnification long-circulation type high-nickel ternary positive electrode material - Google Patents
Preparation method of high-magnification long-circulation type high-nickel ternary positive electrode material Download PDFInfo
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- CN118183880A CN118183880A CN202410599710.4A CN202410599710A CN118183880A CN 118183880 A CN118183880 A CN 118183880A CN 202410599710 A CN202410599710 A CN 202410599710A CN 118183880 A CN118183880 A CN 118183880A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 55
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 118
- 238000005245 sintering Methods 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 39
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000002829 reductive effect Effects 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 238000005507 spraying Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 5
- WRSVIZQEENMKOC-UHFFFAOYSA-N [B].[Co].[Co].[Co] Chemical compound [B].[Co].[Co].[Co] WRSVIZQEENMKOC-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 abstract description 14
- 238000005406 washing Methods 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 6
- 239000011247 coating layer Substances 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 49
- 239000002245 particle Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011572 manganese Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- WEZJBAOYGIDDLB-UHFFFAOYSA-N cobalt(3+);borate Chemical compound [Co+3].[O-]B([O-])[O-] WEZJBAOYGIDDLB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a high-multiplying power long-circulation type high-nickel ternary positive electrode material, which comprises the steps of mixing a ternary positive electrode material precursor with battery-level lithium hydroxide micro powder and doping element G, mixing at high speed by a high-speed mixer, sintering, sieving, coating, spraying and secondary calcining the sintered material to obtain the high-nickel ternary positive electrode material, wherein the high-nickel ternary positive electrode material is free from water washing, surface residual alkali is reduced, the sufficient contact between the surface residual alkali and an additive is promoted, a uniform and stable coating layer is formed on the surface of the material after coating and sintering, the investment of processing procedures and fixed assets is reduced, and the processing cost is reduced; the capacity, multiplying power and cycle performance of the nickel ternary positive electrode material are obviously improved, and the powder resistance of the material is reduced.
Description
Technical Field
The invention relates to the field of ternary positive electrode materials of lithium ion batteries, in particular to a preparation method of a high-rate long-circulation type high-nickel ternary positive electrode material.
Background
The lithium ion battery has higher discharge capacity (more than or equal to 180 mAh/g) and voltage platform (more than or equal to 3.6V), so that the lithium ion battery has very wide application in the fields of 3C consumer electronics, electric automobiles and energy storage, with the vigorous development of new energy industry, people have higher requirements on the energy density of the lithium ion battery, and the capacity of a negative graphite material used by the lithium ion battery is about 350mAh/g and is far higher than that of a positive electrode material, so that the development of a ternary positive electrode material with higher energy density is urgently needed, and Ni element in the ternary positive electrode material mainly participates in electrochemical reaction, and the higher the Ni content is, the higher the theoretical capacity of the material is, namely the high-nickel positive electrode material. At present, the production process of the conventional high-nickel ternary cathode material comprises the following steps: primary sintering, crushing, washing, drying, secondary sintering, sieving, deferrization and the like. Because the reaction temperature of the high-nickel ternary cathode material is low (700-850 ℃), the content of Ni 3+ on the surface is high, the material has strong oxidizing property, and is easy to react with H 2O、CO2 in the air, so that residual alkali on the surface of the material is increased, the capacity of the material is reduced, and part of crystal lattice releases oxygen, thereby causing jelly to be produced in the processing process of the material and affecting the normal use of the material. At present, the residual alkali on the surface of the high-nickel material is reduced mainly through a water washing procedure in the production process, but in the water washing process, water can continuously erode the surface of the high-nickel positive electrode material to cause microcracks on the surface of the material, in the subsequent circulation process, especially around 4.2V voltage, the expansion of the microcracks is aggravated by the structural deformation of the ternary positive electrode material H 2 (hexagonal phase) to H 3 (hexagonal phase), new cracks formed on the surface can continue to generate side reaction with electrolyte, irreversible salt rock items are continuously generated, the resistance of the material is increased, the voltage is reduced, the material structure is pulverized, and the performance of the material is greatly influenced.
At present, modification of the high-nickel positive electrode material is mainly realized by doping and coating means, a nano-level additive is coated on the surface of the material, and a fast ion conductor layer or a passivation layer is generated on the surface of the material by subsequent high-temperature sintering, so that the surface erosion of electrolyte to the positive electrode material can be effectively prevented, the aim of improving the multiplying power performance and the cycle performance of the material is achieved, and therefore, how to improve the electrochemical performance of the high-nickel positive electrode material by a coating modification method and simultaneously reduce the residual alkali on the surface of the high-nickel material, thereby avoiding washing and reducing the processing procedure is an important problem which is urgently needed to be solved in the industry at present.
The Chinese patent publication No. CN114122377A discloses a high-nickel anode material of an embedded coating layer and a preparation method thereof, wherein the high-nickel anode material of the embedded coating layer is obtained by firstly soaking a polycrystalline anode material in an alcohol solution containing cobalt salt, then adding an alcohol solution of sodium borohydride, washing with absolute alcohol after reaction, filtering and drying; the method needs to be protected by introducing inert gas in the whole process, has higher cost, is not beneficial to industrial production popularization, and cobalt boride generated on the surface is difficult to form molecular force on a material interface without high-temperature solid phase reaction, can not play a good role in protecting the material, and also does not solve the problem of higher residual alkali on the surface aiming at the high-nickel positive electrode material.
The Chinese patent publication No. CN105932248A discloses a modified lithium-ion battery lithium-rich manganese-based positive electrode material and a preparation method thereof, wherein the lithium-rich manganese-based positive electrode material is firstly added into a magnesium nitrate solution, and then H 3BO3 solution is dropwise added under the conditions of water bath and stirring to form gel; and finally, drying, grinding and calcining the gel to obtain the magnesium borate coated lithium-rich manganese-based anode material. The method requires longer water bath time, is extremely easy to destroy the surface structure of the material, and is difficult to control the substance content of B and Mg and easy to introduce impurity elements.
The Chinese patent publication No. CN111200120A discloses a ternary positive electrode material and a preparation method thereof, wherein a cobalt source and a lithium source are mixed, a boron source and a cobalt source are mixed, then sintering is carried out in a protective atmosphere to obtain cobalt borate, the cobalt borate and a high-nickel ternary material are mixed, high-speed mixing is carried out in a high-speed mixer, and the mixed material is heated in an oxidizing atmosphere to obtain the ternary positive electrode material. The method has a longer synthesis path, does not limit the particle size (D50/nm) of cobalt boride, easily causes that a coating layer cannot be well and uniformly coated on the surface of a positive electrode material, and in addition, the scheme adopts a high-speed solid mixing method, so that materials are difficult to uniformly mix, a large amount of unevenly distributed residual alkali (lithium hydroxide and lithium carbonate) exists intermittently on the surface of a high-nickel polycrystalline positive electrode and primary particle lattices, cobalt boride cannot fully contact with the residual alkali in the coating process, the residual alkali of a finished product of the material is higher, the surface coating layer of the positive electrode material is discontinuous, and side reactions of electrolyte and the surface of the positive electrode material cannot be effectively prevented.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a high-multiplying power long-circulation type high-nickel ternary positive electrode material, which obviously improves the capacity, multiplying power and circulation performance of the high-nickel ternary positive electrode material and reduces the powder resistance of the material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The invention provides a preparation method of a high-rate long-circulation type high-nickel ternary positive electrode material, which comprises the following steps:
S1, mixing a ternary positive electrode material precursor Ni xCoyMn1-x-y（OH）2 with battery-grade lithium hydroxide micro powder and a doping element G, carrying out high-speed mixing by a high-speed mixer, obtaining a material A to be sintered after mixing, putting the material A to be sintered into a sagger, and scribing the material in the sagger by using a patch with the width of 3-5mm according to a cross shape;
In the ternary positive electrode material precursor, x is more than or equal to 0.8 and less than or equal to 0.96,0.03, y is more than or equal to 0.12,8 mu m and D50 is more than or equal to 13 mu m according to the molar ratio;
s2, placing the material A to be sintered into a box furnace for high-temperature sintering, introducing oxygen in the whole process, heating from 25 ℃ according to 3 ℃/min, keeping the temperature for 4 hours at 500 ℃, heating to 700-850 ℃ according to 3 ℃/min after the heat preservation is finished, cooling after constant-temperature sintering for 12 hours, cooling to 300 ℃ according to 5 ℃/min, turning off a power supply, and taking out the material B after the temperature of the material is reduced to room temperature to obtain the material B;
S3, crushing and sieving the material B by using a mechanical mill to obtain a material C to be coated;
S4, nano cobalt boride is calculated according to the mass ratio, and the mass ratio of the nano cobalt boride is as follows: alcohol: mixing deionized water in a ratio of 1:8:1, wherein the temperature of the alcohol and the deionized water is less than or equal to 10 ℃, and stirring the mixed substances at a high speed to obtain a mixed solvent material D;
S5, placing the material C to be coated in a high-speed mixer, carrying out high-speed rotation, atomizing the mixed solvent material D through an atomizer, spraying the atomized material D into the high-speed mixer through the upper part of the high-speed mixer, controlling according to a certain time and a certain weight, and rotating the high-speed mixer for 5min at the same rotating speed after finishing to obtain a coating material E uniformly coated by cobalt boride;
S6, filling the covered material E into a pot, putting the material subjected to pot filling into a box-type furnace for sintering, keeping the oxygen concentration in the furnace to be more than or equal to 96%, heating the material to 500-730 ℃ from room temperature according to 3 ℃/min, performing constant-temperature sintering for 10 hours, cooling the material to 300 ℃ according to 5 ℃/min, turning off a power supply, and taking out the material after the material temperature is cooled to room temperature to obtain the high-nickel ternary cathode material LiNi xCoyMn1-x-yGgO2;
S7, manufacturing the high-nickel ternary positive electrode material into a button cell, and performing relevant detection.
Further, the doping element G is one or more of Zr, W, nb, al, mg, ti.
Further, in the S1, the total content of the doping element G is G in terms of mass ratio, wherein the G is more than or equal to 2000ppm and less than or equal to 4000ppm.
Further, in the S1, the mol ratio of the Li to the ternary positive electrode material precursor is not less than 1.03 and not more than 1.06.
Further, in the step S2, the concentration of the oxygen is not less than 96%, and the concentration of the oxygen is kept consistent in the whole sintering process.
Further, in S4, the cobalt boride is nano: d50 is more than or equal to 30 and less than or equal to 300nm, BET is more than or equal to 140 and less than or equal to 165cm 3/g.
Further, in the step S5, the rotation speed of the high speed mixer is: the rotating speed is more than or equal to 250r/min and less than or equal to 500r/min.
Further, in the step S5, the specific time and the specific weight are as follows: [ M C (kg)/100 (kg)20Min, wherein M C is the mass of the material C to be coated.
The beneficial effects of the invention are as follows: the high-nickel ternary cathode material is not washed by water, so that the surface residual alkali is reduced, the surface residual alkali is promoted to be fully contacted with the additive, a uniform and stable coating layer is formed on the surface of the material after coating and sintering, the investment of processing procedures and fixed assets is reduced, and the processing cost is reduced;
The capacity, multiplying power and cycle performance of the nickel ternary positive electrode material are obviously improved, and the powder resistance of the material is reduced.
Drawings
FIG. 1 is a flow chart of a method for preparing a high-rate long-cycle high-nickel ternary positive electrode material;
FIG. 2 is an electron microscope image of the first embodiment;
FIG. 3 is an electron microscope image of a second embodiment;
FIG. 4 is an electron microscope image of the third embodiment;
FIG. 5 is an electron microscope image of the fourth embodiment;
FIG. 6 is an electron microscope image of comparative example one;
FIG. 7 is an electron microscope image of comparative example two;
Fig. 8 is an electrical property diagram of the examples and comparative examples.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Referring to fig. 1, a method for preparing a high-rate long-cycle high-nickel ternary cathode material includes the following steps:
S1, mixing a ternary positive electrode material precursor Ni xCoyMn1-x-y（OH）2 with battery-grade lithium hydroxide micro powder and a doping element G, carrying out high-speed mixing by a high-speed mixer, obtaining a material A to be sintered after mixing, putting the material A to be sintered into a sagger, and scribing the material in the sagger by using a patch with the width of 3-5mm according to a cross shape;
In the ternary positive electrode material precursor, x is more than or equal to 0.8 and less than or equal to 0.96,0.03, y is more than or equal to 0.12,8 mu m and D50 is more than or equal to 13 mu m according to the molar ratio;
The size of the ternary polycrystalline positive electrode material is that primary particles are stacked to form secondary spherical particles, gaps exist among the primary particles due to the anisotropic orientation of crystals, lithium sources which do not fully react in the sintering process are easy to adsorb in the gaps to form inactive residual alkali, material jelly is caused in the manufacturing process, the overall performance of the positive electrode material is affected, a washing process is generally adopted on high nickel for eliminating the residual alkali, but the washing process generally has the following disadvantages:
The production flow is prolonged, and the cost is high;
Impurities may be introduced into the deionized water;
water can attack the surface grain boundaries of the positive electrode material, resulting in the generation of microcracks;
The solubility of lithium carbonate in normal-temperature water is small, and the lithium carbonate on the surface of the material is not easy to remove by washing with normal-temperature water.
S2, placing the material A to be sintered into a box furnace for high-temperature sintering, introducing oxygen in the whole process, heating from 25 ℃ according to 3 ℃/min, keeping the temperature for 4 hours at 500 ℃, heating to 700-850 ℃ according to 3 ℃/min after the heat preservation is finished, cooling after constant-temperature sintering for 12 hours, cooling to 300 ℃ according to 5 ℃/min, turning off a power supply, and taking out the material B after the temperature of the material is reduced to room temperature to obtain the material B;
S3, crushing and sieving the material B by using a mechanical mill to obtain a material C to be coated;
S4, nano cobalt boride is calculated according to the mass ratio, and the mass ratio of the nano cobalt boride is as follows: alcohol: mixing deionized water in a ratio of 1:8:1, wherein the temperature of the alcohol and the deionized water is less than or equal to 10 ℃, and stirring the mixed substances at a high speed to obtain a mixed solvent material D;
Wherein, the cobalt boride used as the additive needs to have smaller particle size, the smaller particle size is more easy to form a uniformly distributed coating layer on the surface of the cobalt boride, but the smaller particle size is more easy to agglomerate, and finally the uniform distribution of the additive is not favored,
The low-temperature deionized water and alcohol are characterized in that the solubility of lithium carbonate in water and alcohol is reduced along with the temperature rise, the surface of the material can be obviously dissolved in residual alkali by reducing the water temperature, the solution quantity is reduced, and the subsequent solvent evaporation is facilitated.
S5, placing the material C to be coated in a high-speed mixer, carrying out high-speed rotation, atomizing the mixed solvent material D through an atomizer, spraying the atomized material D into the high-speed mixer through the upper part of the high-speed mixer, controlling according to a certain time and a certain weight, and rotating the high-speed mixer for 5min at the same rotating speed after finishing to obtain a coating material E uniformly coated by cobalt boride;
Because of adding low-temperature liquid, lithium hydroxide and lithium carbonate on the surface of the material and among polycrystalline particles are fully dissolved and fully contacted with the additive after being mixed at high speed;
S6, filling the covered material E into a pot, putting the material subjected to pot filling into a box-type furnace for sintering, keeping the oxygen concentration in the furnace to be more than or equal to 96%, heating the material to 500-730 ℃ from room temperature according to 3 ℃/min, performing constant-temperature sintering for 10 hours, cooling the material to 300 ℃ according to 5 ℃/min, turning off a power supply, and taking out the material after the material temperature is cooled to room temperature to obtain the high-nickel ternary cathode material LiNi xCoyMn1-x-yGgO2;
S7, manufacturing the high-nickel ternary positive electrode material into a button cell, and performing relevant detection.
The doping element G is one or more of Zr, W, nb, al, mg, ti and Zr, W, nb, al, mg, ti.
In the S1, the total content of the doping element G is G in terms of mass ratio, wherein the G is more than or equal to 2000ppm and less than or equal to 4000ppm.
The doping element is generally diffused from the surface of the material to the interior of the material lattice through high temperature, so that a small part of lattice distortion in the lattice is caused, the lattice is firmer, the strength of the material is enhanced, in addition, a bonding bond is formed between the doping element and oxygen atoms, the lattice strength of the material is enhanced, but excessive doping element occupies transition metal positions or lithium positions in the ternary cathode material, and the capacity and the cycle performance of the material are reduced.
In the S1, the mol ratio of Li to ternary positive electrode material precursor is not less than 1.03 and not more than 1.06.
In the step S2, the concentration of the oxygen is more than or equal to 96 percent, and the concentration of the oxygen is kept consistent in the whole sintering process.
In the step S4, nano cobalt boride: d50 is more than or equal to 30 and less than or equal to 300nm, BET is more than or equal to 140 and less than or equal to 165cm 3/g.
In the step S5, the rotation speed of the high speed mixer is: the rotating speed is more than or equal to 250r/min and less than or equal to 500r/min.
In the step S5, the specific time and the specific weight are as follows: [ M C (kg)/100 (kg)20 Min, wherein M C is the mass of the material C to be coated.
Example 1
Ternary precursor Ni 0.83Co0.12Mn0.05（OH）2 with D50 of 10.5 mu m according to the mol ratio of 1:1.06; uniformly mixing battery-grade micro-powder lithium hydroxide and 2000ppm nano-grade ZrO 2, placing the mixture in a box furnace, heating the mixture at the temperature of 25 ℃ from 3 ℃/min to 500 ℃ for 4 hours under the oxygen atmosphere (the concentration is more than or equal to 96%), heating the mixture to 750 ℃ according to 3 ℃/min after the heat preservation is finished, sintering the mixture at the temperature for 12 hours, cooling the mixture to the room temperature of 25 ℃, and mechanically grinding the mixture to obtain a primary sintered material with the D50 particle size of about 10.0-11.0 mu m;
Mixing 20g of nano cobalt boride with 160g of alcohol solvent at 8 ℃ and 20g of deionized water (mass ratio is 1:8:1), and stirring at high speed to obtain a solution; 10kg of primary sintering material (the cladding agent content is 2000 ppm) is added into a high-speed mixer, high-speed mixing is carried out according to the rotating speed of 350r/min, and the solution is sprayed by a spraying device according to 10/100 20 The cobalt boride is sprayed into the high-speed mixer through a spraying port above the high-speed mixer for 2min, the high-speed mixing is continued for 5min after the spraying is finished, and the materials are filled into a box according to the weight of 5 kg/sagger to 330/>330/>Placing the mixture into a sagger with 110mm, sintering the mixture for 10 hours in a box-type furnace at a constant temperature of 600 ℃, and reducing the mixture to room temperature to obtain a first anode material; please refer to fig. 2.
Example two
Uniformly mixing ternary precursor Ni 0.88Co0.09Mn0.03（OH）2 with the D50 of 10 mu m, battery grade micro-powder lithium hydroxide and 2000ppm nano-grade ZrO 2 according to the molar ratio of 1:1.04, placing the mixture in a box furnace, heating the mixture at the temperature of 25 ℃ according to 3 ℃/min under the oxygen atmosphere (the concentration is more than or equal to 96%), heating the mixture to 500 ℃ for 4 hours, heating the mixture to 730 ℃ according to 3 ℃/min after the heat preservation is finished, sintering the mixture at the temperature for 12 hours, cooling the mixture to the room temperature of 25 ℃, and mechanically grinding the mixture to obtain a primary sintered material with the D50 particle size of about 10.0-11.0 mu m;
Mixing 20g of nano cobalt boride with 160g of alcohol solvent at 8 ℃ and 20g of deionized water (mass ratio is 1:8:1), and stirring at high speed to obtain a solution; 10kg of primary sintering material (the cladding agent content is 2000 ppm) is added into a high-speed mixer, high-speed mixing is carried out according to the rotating speed of 350r/min, and the solution is sprayed by a spraying device according to 10/100 20 The cobalt boride is sprayed into the high-speed mixer through a spraying port above the high-speed mixer for 2min, the high-speed mixing is continued for 5min after the spraying is finished, and the materials are filled into a box according to the weight of 5 kg/sagger to 330/>330/>Placing the mixture into a sagger with 110mm, sintering the mixture for 10 hours in a box-type furnace at the constant temperature of 600 ℃, and reducing the mixture to room temperature to obtain a second positive electrode material, see FIG. 3.
Example III
Uniformly mixing ternary precursor Ni 0.90Co0.05Mn0.05（OH）2 with the D50 of 10 mu m, battery grade micro-powder lithium hydroxide and 2000ppm nano-grade ZrO 2 with the D50 of 1000ppm nano-grade Nb 2O5 according to the molar ratio of 1:1.04, placing the mixture in a box furnace, heating the mixture at the temperature of 25 ℃ according to the speed of 3 ℃/min to 500 ℃ for 4 hours under the oxygen atmosphere (the concentration is more than or equal to 96%), heating the mixture to 719 ℃ according to the speed of 3 ℃/min after the heat preservation is finished, sintering the mixture at the temperature for 12 hours, cooling the mixture to the room temperature of 25 ℃, and mechanically grinding and crushing the mixture to obtain a primary sintered material with the D50 particle size of about 10.0-11.0 mu m;
Mixing 20g of nano cobalt boride with 160g of alcohol solvent at 8 ℃ and 20g of deionized water (mass ratio is 1:8:1), and stirring at high speed to obtain a solution; 10kg of primary sintering material (the cladding agent content is 2000 ppm) is added into a high-speed mixer, high-speed mixing is carried out according to the rotating speed of 350r/min, and the solution is sprayed by a spraying device according to 10/100 20 The cobalt boride is sprayed into the high-speed mixer through a spraying port above the high-speed mixer for 2min, the high-speed mixing is continued for 5min after the spraying is finished, and the materials are filled into a box according to the weight of 5 kg/sagger to 330/>330/>Placing the mixture into a sagger with 110mm, sintering the mixture for 10 hours in a box-type furnace at a constant temperature of 450 ℃, and reducing the mixture to room temperature to obtain a cathode material III, see fig. 4.
Example IV
Uniformly mixing ternary precursor Ni 0.92Co0.05Mn0.03（OH）2 with the D50 of 10.0 mu m, battery grade micro-powder lithium hydroxide and 2000ppm nano-grade ZrO 2 with 1000ppm nano-grade Nb 2O5 according to the molar ratio of 1:1.05, placing in a box furnace, heating the mixture to 500 ℃ from 3 ℃/min at the temperature of 25 ℃ under the oxygen atmosphere (the concentration is more than or equal to 96%), preserving the heat for 4 hours, heating to 710 ℃ at the temperature of 3 ℃/min after the heat preservation is finished, sintering the mixture for 12 hours at the temperature, cooling to the room temperature of 25 ℃, and mechanically grinding and crushing the mixture to obtain a primary sintered material with the D50 particle size of about 10.0-11.0 mu m;
Mixing 20g of cobalt boride with 160g of an alcohol solvent at 8 ℃ and 20g of deionized water (mass ratio is 1:8:1), and stirring at a high speed to obtain a solution; 10kg of primary sintering material (the cladding agent content is 2000 ppm) is added into a high-speed mixer, high-speed mixing is carried out according to the rotating speed of 350r/min, and the solution is sprayed by a spraying device according to 10/100 20 The cobalt boride is sprayed into the high-speed mixer through a spraying port above the high-speed mixer for 2min, the high-speed mixing is continued for 5min after the spraying is finished, and the materials are filled into a box according to the weight of 5 kg/sagger to 330/>330/>Placing the mixture into a sagger with 110mm, sintering the mixture for 10 hours in a box-type furnace at a constant temperature of 450 ℃, and reducing the mixture to room temperature to obtain a cathode material IV, see FIG. 5.
Comparative example:
Comparative example one:
Ternary precursor Ni 0.83Co0.12Mn0.05（OH）2 with D50 of 10.5 mu m according to the mol ratio of 1:1.06; uniformly mixing battery-grade micro-powder lithium hydroxide and 2000ppm nano-grade ZrO 2, placing the mixture in a box furnace, heating the mixture at the temperature of 25 ℃ from 3 ℃/min to 500 ℃ for 4 hours under the oxygen atmosphere (the concentration is more than or equal to 96%), heating the mixture to 750 ℃ according to 3 ℃/min after the heat preservation is finished, sintering the mixture at the temperature for 12 hours, cooling the mixture to the room temperature of 25 ℃, and mechanically grinding the mixture to obtain a primary sintered material with the D50 particle size of about 10.0-11.0 mu m;
Mixing 20g of nano cobalt boride with 10kg of the materials, putting the mixture into a high-speed mixer, mixing at a high speed of 350r/min, mixing at a high speed for 10min, and loading the materials into a box according to 5 kg/min to 330 330/>Placing the mixture into a sagger with 110mm, sintering the mixture for 10 hours in a box-type furnace at a constant temperature of 600 ℃, and reducing the mixture to room temperature to obtain a comparative anode material I, see FIG. 6.
Comparative example two
Uniformly mixing ternary precursor Ni 0.92Co0.05Mn0.03（OH）2 with the D50 of 10.0 mu m, battery grade micro-powder lithium hydroxide and 2000ppm nano-grade ZrO 2 with 1000ppm nano-grade Nb 2O5 according to the molar ratio of 1:1.03, placing in a box furnace, heating the mixture to 500 ℃ from 3 ℃/min under the oxygen atmosphere (the concentration is more than or equal to 96%), keeping the temperature for 4 hours at the temperature of 500 ℃, heating to 710 ℃ at the temperature of 3 ℃/min after the heat preservation is finished, sintering the mixture for 12 hours at the temperature, cooling the mixture to the room temperature of 25 ℃, and mechanically grinding the mixture to obtain a primary sintered material with the D50 particle size of about 10.0-11.0 mu m;
Adding 20g of cobalt boride and 10kg of primary sintering material (the content of a coating agent is 2000 ppm) into a high-speed mixer, mixing at a high speed of 350r/min for 10min, and loading the material into a box according to 5 kg/min after the high-speed mixing is finished 330/>110Mm sagger, sintering in a box furnace at 450 deg.c for 10 hr, and cooling to room temperature to obtain the second comparative example, see fig. 7.
Other performance related data are shown in tables 1, 2 and fig. 8.
Table 1 shows the performance of examples and comparative examples
Table 2 shows the performance of the examples and comparative examples
The foregoing examples merely illustrate embodiments of the invention and are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present patent is to be determined by the appended claims.
Claims (8)
1. The preparation method of the high-magnification long-circulation type high-nickel ternary positive electrode material is characterized by comprising the following steps of:
S1, mixing a ternary positive electrode material precursor Ni xCoyMn1-x-y（OH）2 with battery-grade lithium hydroxide micro powder and a doping element G, carrying out high-speed mixing by a high-speed mixer, obtaining a material A to be sintered after mixing, putting the material A to be sintered into a sagger, and scribing the material in the sagger by using a patch with the width of 3-5mm according to a cross shape;
In the ternary positive electrode material precursor, x is more than or equal to 0.8 and less than or equal to 0.96,0.03, y is more than or equal to 0.12,8 mu m and D50 is more than or equal to 13 mu m according to the molar ratio;
s2, placing the material A to be sintered into a box furnace for high-temperature sintering, introducing oxygen in the whole process, heating from 25 ℃ according to 3 ℃/min, keeping the temperature for 4 hours at 500 ℃, heating to 700-850 ℃ according to 3 ℃/min after the heat preservation is finished, cooling after constant-temperature sintering for 12 hours, cooling to 300 ℃ according to 5 ℃/min, turning off a power supply, and taking out the material B after the temperature of the material is reduced to room temperature to obtain the material B;
S3, crushing and sieving the material B by using a mechanical mill to obtain a material C to be coated;
S4, nano cobalt boride is calculated according to the mass ratio, and the mass ratio of the nano cobalt boride is as follows: alcohol: mixing deionized water in a ratio of 1:8:1, wherein the temperature of the alcohol and the deionized water is less than or equal to 10 ℃, and stirring the mixed substances at a high speed to obtain a mixed solvent material D;
S5, placing the material C to be coated in a high-speed mixer, carrying out high-speed rotation, atomizing the mixed solvent material D through an atomizer, spraying the atomized material D into the high-speed mixer through the upper part of the high-speed mixer, controlling according to a certain time and a certain weight, and rotating the high-speed mixer for 5min at the same rotating speed after finishing to obtain a coating material E uniformly coated by cobalt boride;
S6, filling the covered material E into a pot, putting the material subjected to pot filling into a box-type furnace for sintering, keeping the oxygen concentration in the furnace to be more than or equal to 96%, heating the material to 500-730 ℃ from room temperature according to 3 ℃/min, performing constant-temperature sintering for 10 hours, cooling the material to 300 ℃ according to 5 ℃/min, turning off a power supply, and taking out the material after the material temperature is cooled to room temperature to obtain the high-nickel ternary cathode material LiNi xCoyMn1-x-yGgO2;
S7, manufacturing the high-nickel ternary positive electrode material into a button cell, and performing relevant detection.
2. The method for preparing the high-rate long-circulation type high-nickel ternary positive electrode material, which is disclosed in claim 1, is characterized in that: the doping element G is one or more of Zr, W, nb, al, mg, ti and Zr, W, nb, al, mg, ti.
3. The method for preparing the high-rate long-circulation type high-nickel ternary positive electrode material, which is disclosed in claim 2, is characterized in that: in the S1, the total content of the doping element G is G in terms of mass ratio, wherein the G is more than or equal to 2000ppm and less than or equal to 4000ppm.
4. The method for preparing the high-rate long-circulation type high-nickel ternary positive electrode material according to claim 3, which is characterized by comprising the following steps of: in the S1, the mol ratio of Li to ternary positive electrode material precursor is not less than 1.03 and not more than 1.06.
5. The preparation method of the high-rate long-circulation type high-nickel ternary positive electrode material is characterized by comprising the following steps of: in the step S2, the concentration of the oxygen is more than or equal to 96 percent, and the concentration of the oxygen is kept consistent in the whole sintering process.
6. The preparation method of the high-rate long-circulation type high-nickel ternary positive electrode material is characterized by comprising the following steps of: in the step S4, nano cobalt boride: d50 is more than or equal to 30 and less than or equal to 300nm, BET is more than or equal to 140 and less than or equal to 165cm 3/g.
7. The method for preparing the high-rate long-circulation type high-nickel ternary positive electrode material, which is disclosed in claim 6, is characterized in that: in the step S5, the rotation speed of the high speed mixer is: the rotating speed is more than or equal to 250r/min and less than or equal to 500r/min.
8. The preparation method of the high-rate long-circulation type high-nickel ternary positive electrode material is characterized by comprising the following steps of: in the step S5, the specific time and the specific weight are as follows: [ M C (kg)/100 (kg)20Min, wherein M C is the mass of the material C to be coated.
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Address after: 1618 Xinqi Street, Muye District, Xinxiang City, Henan Province, 453000 Patentee after: Tianli Lithium Energy Group Co.,Ltd. Country or region after: China Address before: Southeast corner of the intersection of Xinqi Street and Weiqi Road in Xinxiang Chemical and Physical Power Industrial Park, Muye District, Xinxiang City, Henan Province Patentee before: XINXIANG TIANLI LITHIUM ENERGY CO.,LTD. Country or region before: China |