CN111276691A - High-voltage single-crystal low-cobalt ternary cathode material and preparation method thereof - Google Patents
High-voltage single-crystal low-cobalt ternary cathode material and preparation method thereof Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 80
- 239000010941 cobalt Substances 0.000 title claims abstract description 80
- 239000013078 crystal Substances 0.000 title claims abstract description 54
- 239000010406 cathode material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 105
- 239000000463 material Substances 0.000 claims abstract description 73
- 239000011521 glass Substances 0.000 claims abstract description 31
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims abstract description 11
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000011247 coating layer Substances 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims description 102
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000007774 positive electrode material Substances 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 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
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910013596 LiOH—H2O Inorganic materials 0.000 claims 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 13
- 239000010405 anode material Substances 0.000 abstract description 9
- 238000004090 dissolution Methods 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910013716 LiNi Inorganic materials 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013172 LiNixCoy Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- H01M4/36—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
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
Abstract
The invention discloses a high-voltage single-crystal low-cobalt ternary cathode material and a preparation method thereof. The high-voltage single-crystal low-cobalt ternary cathode material comprises a matrix and a coating layer coated on the surface of the matrix, wherein the matrix is a low-cobalt ternary cathode material LiNixCoyMn1‑x‑yO2Wherein, 0.6<x<0.8, y is more than or equal to 0.05 and less than or equal to 0.10; the coating layer is made of MBO glass material, wherein M is Li, Ti or Al. The invention adopts a wet coating process to coat the low-cobalt ternary cathode material LiNixCoyMn1‑x‑yO2The surface of the material is coated with the uniform MBO glass material, so that the direct contact between the electrolyte and the surface of the anode material can be effectively prevented in the circulation process,the change of the crystal structure is inhibited, the dissolution of surface metal ions is reduced, and the stability of the material and the electrolyte under high voltage is improved. The preparation process is simple, has strong practicability and can be used for batch production.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-voltage single-crystal low-cobalt ternary cathode material and a preparation method thereof.
Background
The lithium ion battery has the outstanding advantages of high voltage, large energy density, good cycle performance, small self-discharge, no memory effect and the like, and is widely applied to electronic products such as mobile phones, notebook computers, energy storage and the like. The lithium ion battery anode material is a key factor for restricting the capacity and the service life of the lithium battery, so that the lithium ion battery anode material has great significance for the research of the anode material. The high-nickel low-cobalt ternary cathode material has the advantages of high energy density, relatively low cost and the like, and becomes a hotspot for research, development and production in the cathode material of the industrial lithium ion power battery in recent years, but when the material is charged to a higher voltage, the reaction between the material and the electrolyte can occur, so that the rapid deterioration of the cycle stability is caused; the situation of mixed occupation of divalent nickel ions and lithium ions is easy to occur, and the rate capability and the cycle performance of the material are deteriorated. The surface coating is a method for effectively improving the electrochemical performance of the anode material, the direct contact of the electrode material and the electrolyte can be prevented through surface coating modification, the erosion of the electrolyte to the electrode material in the circulating process is inhibited, the side reaction of the electrode material and the electrolyte is reduced, the change of a crystal structure is inhibited, the dissolution of metal ions on the surface of the electrode material is reduced, and the circulating stability of the material and the electrolyte under high voltage is improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-voltage single-crystal low-cobalt ternary cathode material and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a high-voltage single-crystal low-cobalt ternary positive electrode material comprises a substrate and a coating layer coated on the surface of the substrate, wherein the substrate is a low-cobalt ternary positive electrode material LiNixCoyMn1-x-yO2Wherein, 0.6<x<0.8, y is more than or equal to 0.05 and less than or equal to 0.10; the coating layer is made of MBO glass material, wherein M is Li, Ti or Al.
The invention uses low-cobalt ternary anode material LiNixCoyMn1-x-yO2(0.6<x<0.8 and y is more than or equal to 0.05 and less than or equal to 0.10) as a matrix, and the surface of the matrix is coated with an MBO glass material, so that the direct contact between the electrolyte and the surface of the anode material can be effectively prevented in the circulation process, the side reaction of the anode material and the electrolyte is reduced, the change of the crystal structure is inhibited, and the dissolution of metal ions on the surface is reduced, thereby improving the circulation stability of the material and the electrolyte under high voltage.
Preferably, the coating amount of the MBO glass material is low-cobalt ternary cathode material LiNixCoyMn1-x-yO20.2-0.5% of the mass of the lithium iron phosphate, and the prepared high-voltage single-crystal low-cobalt ternary cathode material, in particular LiNi coated with MBO glass material on the surface0.65Co0.07Mn0.28O2The material has better cycling stability under high voltage.
The invention also provides a preparation method of the high-voltage single-crystal low-cobalt ternary cathode material, which comprises the following steps of:
1) adding the M-containing coating and the B-containing coating into absolute ethyl alcohol and stirring until the M-containing coating and the B-containing coating are completely dispersed;
2) the low-cobalt ternary positive electrode material LiNixCoyMn1-x-yO2Adding the mixture into the solution obtained in the step 1), continuously stirring, and heating to 60-70 ℃ to completely volatilize ethanol to obtain a coated material;
3) and (3) carrying out low-temperature oxygen-enriched sintering on the material coated in the step 2), heating to 350-600 ℃ at the speed of 3-7 ℃/min, preserving the heat for 8-12h, and cooling to room temperature to obtain the high-voltage single-crystal low-cobalt ternary cathode material coated with the MBO glass material on the surface.
The invention selects the technological parameters through a wet coating process and selects the technological parameters to obtain the low-cobalt ternary cathode material LiNixCoyMn1-x-yO2The surface of the MBO glass material is uniformly coated, the preparation process is simple, the practicability is high, and the MBO glass material can be produced in batches.
Preferably, in the step 1), the molar ratio of the M-containing coating to the B-containing coating is 1:1-1:5, more preferably 1:2, which is beneficial to improving the holding capacity of the material and the cycling stability under high voltage.
Preferably, the M-containing coating is nano LiOH & H2O, nano Li2O, nano Ti (OH)4TiO 2 nanoparticles2Nano Al (OH)3Or nano Al2O3。
Preferably, the B-containing coating is nano B2O3Or nano H3BO3。
Preferably, in the step 3), the low-temperature oxygen-enriched sintering adopts a roller furnace or a push plate furnace, and the oxygen flow rate is 0.5-1.0m3/h。
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a wet coating process to coat the low-cobalt ternary cathode material LiNixCoyMn1-x-yO2The uniformly coated MBO glass material can effectively prevent the electrolyte from directly contacting the surface of the anode material in the circulating process, inhibit the change of a crystal structure, reduce the dissolution of metal ions on the surface, improve the stability of the material and the electrolyte under high voltage, and the prepared material has good circulating performance. The preparation process is simple, has strong practicability and can be used for batch production.
Drawings
FIG. 1 is a scanning electron microscope image of a high voltage single crystal low cobalt ternary positive electrode material of example 1;
FIG. 2 is a scanning electron microscope image of the high voltage single crystal low cobalt ternary positive electrode material of example 2;
FIG. 3 is a scanning electron micrograph of a high voltage single crystal low cobalt ternary positive electrode material of example 3;
FIG. 4 is a scanning electron microscope image of the high voltage single crystal low cobalt ternary positive electrode material of comparative example 3;
FIG. 5 is a scanning electron microscope image of the high voltage single crystal low cobalt ternary positive electrode material of comparative example 4;
table 1 shows the comparison of the capacitance values of the high voltage single crystal low cobalt ternary positive electrode materials of examples 1-5 and comparative examples 1-4.
FIG. 6 is a graph comparing cycle performance of high voltage single crystal low cobalt ternary positive electrode materials of examples 1-5 and comparative examples 1-4.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
Example 1
A preparation method of a high-voltage single-crystal low-cobalt ternary cathode material comprises the following steps:
1) and adding the M-containing coating and the B-containing coating into absolute ethyl alcohol and stirring until the M-containing coating and the B-containing coating are completely dispersed to obtain the MBO coating. Wherein the mol ratio of the coating containing M to the coating containing B is 1:1, and the coating containing M is nano LiOH. H2O, B-containing coating is nano H3BO3；
2) The low-cobalt ternary positive electrode material LiNi0.65Co0.07Mn0.28O2Adding the solution obtained in the step 1), continuously stirring, heating to 60 ℃ to completely volatilize ethanol to obtain a coated material, wherein the coating amount of the MBO glass material is low-cobalt ternary cathode material LiNi0.65Co0.07Mn0.28O20.3% of the mass of (c);
3) putting the material coated in the step 2) into a roller furnace for low-temperature oxygen-enriched sintering, wherein the oxygen flow is 0.5m3And h, heating to 500 ℃ at the speed of 5 ℃/min, preserving the heat for 10h, and cooling to room temperature to obtain the high-voltage single-crystal low-cobalt ternary cathode material with the surface coated with the MBO glass material.
Example 2
A preparation method of a high-voltage single-crystal low-cobalt ternary cathode material comprises the following steps:
1) and adding the M-containing coating and the B-containing coating into absolute ethyl alcohol and stirring until the M-containing coating and the B-containing coating are completely dispersed to obtain the MBO coating. Wherein the mol ratio of the coating containing M to the coating containing B is 1:2, and the coating containing M is nano LiOH. H2O, B-containing coating is nano H3BO3；
2) The low-cobalt ternary positive electrode material LiNi0.65Co0.07Mn0.28O2Adding the solution obtained in the step 1), continuously stirring, heating to 60 ℃ to completely volatilize ethanol to obtain a coated material, wherein the coating amount of the MBO glass material is low-cobalt ternary cathode material LiNi0.65Co0.07Mn0.28O20.3% of the mass of (c);
3) putting the material coated in the step 2) into a roller furnace for low-temperature oxygen-enriched sintering, wherein the oxygen flow is 0.5m3And h, heating to 500 ℃ at the speed of 5 ℃/min, preserving the heat for 10h, and cooling to room temperature to obtain the high-voltage single-crystal low-cobalt ternary cathode material with the surface coated with the MBO glass material.
Example 3
A preparation method of a high-voltage single-crystal low-cobalt ternary cathode material comprises the following steps:
1) adding the M-containing coating and the B-containing coating into absolute ethyl alcohol and stirring until the M-containing coating and the B-containing coating are completely dispersed to obtain the MBO bagAnd (4) covering. Wherein the mol ratio of the coating containing M to the coating containing B is 1:5, and the coating containing M is nano LiOH. H2O, B-containing coating is nano H3BO3；
2) The low-cobalt ternary positive electrode material LiNi0.65Co0.07Mn0.28O2Adding the solution obtained in the step 1), continuously stirring, heating to 60 ℃ to completely volatilize ethanol to obtain a coated material, wherein the coating amount of the MBO glass material is low-cobalt ternary cathode material LiNi0.65Co0.07Mn0.28O20.3% of the mass of (c);
3) putting the material coated in the step 2) into a roller furnace for low-temperature oxygen-enriched sintering, wherein the oxygen flow is 0.5m3And h, heating to 500 ℃ at the speed of 5 ℃/min, preserving the heat for 10h, and cooling to room temperature to obtain the high-voltage single-crystal low-cobalt ternary cathode material with the surface coated with the MBO glass material.
Example 4
A preparation method of a high-voltage single-crystal low-cobalt ternary cathode material comprises the following steps:
1) and adding the M-containing coating and the B-containing coating into absolute ethyl alcohol and stirring until the M-containing coating and the B-containing coating are completely dispersed to obtain the MBO coating. Wherein the mol ratio of the coating containing M to the coating containing B is 1:2, and the coating containing M is nano LiOH. H2O, B-containing coating is nano H3BO3；
2) The low-cobalt ternary positive electrode material LiNi0.65Co0.07Mn0.28O2Adding the solution obtained in the step 1), continuously stirring, heating to 60 ℃ to completely volatilize ethanol to obtain a coated material, wherein the coating amount of the MBO glass material is low-cobalt ternary cathode material LiNi0.65Co0.07Mn0.28O20.2% of the mass of (c);
3) putting the material coated in the step 2) into a roller furnace for low-temperature oxygen-enriched sintering, wherein the oxygen flow is 0.5m3And h, heating to 500 ℃ at the speed of 5 ℃/min, preserving the heat for 10h, and cooling to room temperature to obtain the high-voltage single-crystal low-cobalt ternary cathode material with the surface coated with the MBO glass material.
Example 5
A preparation method of a high-voltage single-crystal low-cobalt ternary cathode material comprises the following steps:
1) and adding the M-containing coating and the B-containing coating into absolute ethyl alcohol and stirring until the M-containing coating and the B-containing coating are completely dispersed to obtain the MBO coating. Wherein the mol ratio of the coating containing M to the coating containing B is 1:2, and the coating containing M is nano LiOH. H2O, B-containing coating is nano H3BO3；
2) The low-cobalt ternary positive electrode material LiNi0.65Co0.07Mn0.28O2Adding the solution obtained in the step 1), continuously stirring, heating to 60 ℃ to completely volatilize ethanol to obtain a coated material, wherein the coating amount of the MBO glass material is low-cobalt ternary cathode material LiNi0.65Co0.07Mn0.28O20.5% of the mass of (c);
3) putting the material coated in the step 2) into a roller furnace for low-temperature oxygen-enriched sintering, wherein the oxygen flow is 0.5m3And h, heating to 500 ℃ at the speed of 5 ℃/min, preserving the heat for 10h, and cooling to room temperature to obtain the high-voltage single-crystal low-cobalt ternary cathode material with the surface coated with the MBO glass material.
Comparative example 1
A preparation method of a high-voltage single-crystal low-cobalt ternary cathode material comprises the following steps:
1) and adding the M-containing coating and the B-containing coating into absolute ethyl alcohol and stirring until the M-containing coating and the B-containing coating are completely dispersed to obtain the MBO coating. Wherein the mol ratio of the coating containing M to the coating containing B is 1:2, and the coating containing M is nano LiOH. H2O, B-containing coating is nano H3BO3；
2) The low-cobalt ternary positive electrode material LiNi0.65Co0.07Mn0.28O2Adding the solution obtained in the step 1), continuously stirring, heating to 60 ℃ to completely volatilize ethanol to obtain a coated material, wherein the coating amount of the MBO glass material is low-cobalt ternary cathode material LiNi0.65Co0.07Mn0.28O20.1% of the mass of (c);
3) putting the material coated in the step 2) into a roller furnace for low-temperature oxygen-enriched sinteringOxygen flow of 0.5m3And h, heating to 500 ℃ at the speed of 5 ℃/min, preserving the heat for 10h, and cooling to room temperature to obtain the high-voltage single-crystal low-cobalt ternary cathode material with the surface coated with the MBO glass material.
Comparative example 2
A preparation method of a high-voltage single-crystal low-cobalt ternary cathode material comprises the following steps:
1) and adding the M-containing coating and the B-containing coating into absolute ethyl alcohol and stirring until the M-containing coating and the B-containing coating are completely dispersed to obtain the MBO coating. Wherein the mol ratio of the coating containing M to the coating containing B is 1:2, and the coating containing M is nano LiOH. H2O, B-containing coating is nano H3BO3；
2) The low-cobalt ternary positive electrode material LiNi0.65Co0.07Mn0.28O2Adding the solution obtained in the step 1), continuously stirring, heating to 60 ℃ to completely volatilize ethanol to obtain a coated material, wherein the coating amount of the MBO glass material is low-cobalt ternary cathode material LiNi0.65Co0.07Mn0.28O20.6% of the mass of (c);
3) putting the material coated in the step 2) into a roller furnace for low-temperature oxygen-enriched sintering, wherein the oxygen flow is 0.5m3And h, heating to 500 ℃ at the speed of 5 ℃/min, preserving the heat for 10h, and cooling to room temperature to obtain the high-voltage single-crystal low-cobalt ternary cathode material with the surface coated with the MBO glass material.
Comparative example 3
A preparation method of a high-voltage single-crystal low-cobalt ternary cathode material comprises the following steps:
1) nano H3BO3Adding into absolute ethyl alcohol and stirring until the mixture is completely dispersed to obtain the BO coating material.
2) The low-cobalt ternary positive electrode material LiNi0.65Co0.07Mn0.28O2Adding the mixture into the solution obtained in the step 1), continuously stirring, heating to 60 ℃ to completely volatilize ethanol to obtain a coated material, wherein the coating amount of BO coating is low-cobalt ternary cathode material LiNi0.65Co0.07Mn0.28O20.3% of the mass of (c);
3) putting the material coated in the step 2) into a roller furnace for low-temperature oxygen-enriched sintering, wherein the oxygen flow is 0.5m3And h, heating to 500 ℃ at the speed of 5 ℃/min, preserving the heat for 10h, and cooling to room temperature to obtain the high-voltage single-crystal low-cobalt ternary cathode material with the surface coated with the BO material.
Comparative example 4
A preparation method of a high-voltage single-crystal low-cobalt ternary cathode material comprises the following steps:
mixing LiNi as a raw material0.65Co0.07Mn0.28O2Placing into a roller furnace for low-temperature oxygen-enriched sintering, wherein the oxygen flow is 0.5m3And h, heating to 500 ℃ at the speed of 5 ℃/min, preserving the heat for 10h, and cooling to room temperature to obtain the high-voltage single-crystal low-cobalt ternary cathode material without the surface coating material.
Fig. 1 to 5 are SEM images of particles of the high voltage single crystal low cobalt ternary positive electrode materials obtained in examples 1 to 3 and comparative examples 3 to 4.
Electrochemical performance tests were performed on the high voltage single crystal low cobalt ternary positive electrode materials of examples 1-5 and comparative examples 1-4 according to the following methods: mixing the obtained material, acetylene black serving as a conductive agent and PVDF serving as a binder in 12ml of NMP according to the mass ratio of 9.2:0.5:0.3, fully stirring to form slurry, then coating the slurry on the surface of an aluminum foil through a coating machine, drying, cutting into a proper size, assembling a button cell by taking a lithium sheet as a negative electrode and a lithium hexafluorophosphate solution as an electrolyte in a glove box protected by argon through adopting a 2032 type button cell case, and then carrying out electrochemical performance test at the temperature of 25 ℃ at 3.0-4.45V.
The results of the capacitance values of the high voltage single crystal low cobalt ternary positive electrode materials of examples 1-5 and comparative examples 1-4 are shown in table 1. Fig. 6 is a graph comparing the cycling performance of the high voltage single crystal low cobalt ternary positive electrode materials of examples 1-5 and comparative examples 1-4.
TABLE 1 comparison of the capacitance drop of the high voltage single crystal low cobalt ternary positive electrode materials of examples 1-5 and comparative examples 1-4
Examples 1-5 were prepared by coating LiNi with BO material on the surface and comparative example 3 with no coating material on the surface0.65Co0.07Mn0.28O2The surface is coated with the MBO glass material, so that the buckling capacity of the material and the cycling stability under high voltage can be improved.
From the results of examples 1 to 3, it is known that the high voltage single crystal low cobalt ternary positive electrode material prepared has higher holding capacity and cycling stability when the molar ratio of the M cladding to the B-containing cladding is 1:1 to 1: 5.
As is apparent from the results of examples 2, 4-5 and comparative examples 1-2, too low or too high a coating amount of the MBO glass material causes a decrease in the holding capacity of the material and the cycle stability at high voltage, and therefore, the coating amount of the MBO glass material of the present invention is preferably 0.2 to 0.5% by mass of the low-cobalt ternary positive electrode material.
The low-cobalt ternary cathode material applicable to the present invention is not limited to the LiNi of the above embodiment0.65Co0.07Mn0.28O2LiNi of the above example0.65Co0.07Mn0.28O2Replacing the material with other low-cobalt ternary cathode material LiNixCoyMn1-x-yO2，0.6<x<Y is more than or equal to 0.8 and less than or equal to 0.05 and less than or equal to 0.10, and the cycle stability of the material under high voltage can be improved to a certain extent by adjusting the coating amount of the MBO glass material.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The high-voltage single-crystal low-cobalt ternary cathode material is characterized by comprising a matrix and a coating layer coated on the surface of the matrix, wherein the matrix is a low-cobalt ternary cathode material LiNixCoyMn1-x-yO2Wherein, 0.6<x<0.8，0.05≤y≤0.10；The coating layer is made of MBO glass material, wherein M is Li, Ti or Al.
2. The high-voltage single-crystal low-cobalt ternary cathode material according to claim 1, wherein the coating amount of the MBO glass material is LiNixCoyMn1-x-yO20.2-0.5% of the mass of (A).
3. The preparation method of the high-voltage single-crystal low-cobalt ternary cathode material as claimed in claim 1 or 2, characterized by comprising the following steps:
1) adding the M-containing coating and the B-containing coating into absolute ethyl alcohol and stirring until the M-containing coating and the B-containing coating are completely dispersed;
2) the low-cobalt ternary positive electrode material LiNixCoyMn1-x-yO2Adding the mixture into the solution obtained in the step 1), continuously stirring, and heating to 60-70 ℃ to completely volatilize ethanol to obtain a coated material;
3) and (3) carrying out low-temperature oxygen-enriched sintering on the material coated in the step 2), heating to 350-600 ℃ at the speed of 3-7 ℃/min, preserving the heat for 8-12h, and cooling to room temperature to obtain the high-voltage single-crystal low-cobalt ternary cathode material coated with the MBO glass material on the surface.
4. The method for preparing the high-voltage single-crystal low-cobalt ternary cathode material as claimed in claim 3, wherein in the step 1), the molar ratio of the M-containing coating to the B-containing coating is 1:1-1: 5.
5. The method for preparing the high-voltage single-crystal low-cobalt ternary cathode material as claimed in claim 4, wherein the molar ratio of the M-containing coating to the B-containing coating in the step 1) is 1: 2.
6. The method for preparing a high voltage single crystal low cobalt ternary positive electrode material according to claim 3, wherein the M-containing coating is nano LiOH-H2O, nano Li2O, nano Ti (OH)4TiO 2 nanoparticles2Sodium and sodiumRice Al (OH)3Or nano Al2O3。
7. The method for preparing a high-voltage single-crystal low-cobalt ternary cathode material according to claim 3, wherein the B-containing coating is nano B2O3Or nano H3BO3。
8. The method for preparing the high-voltage single-crystal low-cobalt ternary cathode material as claimed in claim 3, wherein in the step 3), a roller furnace or a push plate furnace is used for low-temperature oxygen-enriched sintering, and the oxygen flow rate is 0.5-1.0m3/h。
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