CN113328083A - Preparation method of lithium metaaluminate coated nickel-cobalt-manganese ternary positive electrode material - Google Patents
Preparation method of lithium metaaluminate coated nickel-cobalt-manganese ternary positive electrode material Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 41
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 38
- 239000010406 cathode material Substances 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 238000003837 high-temperature calcination Methods 0.000 claims description 11
- 238000007873 sieving Methods 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 claims description 2
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 claims description 2
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 claims description 2
- 229910015150 Ni1/3Co1/3Mn1/3(OH)2 Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 239000010405 anode material Substances 0.000 abstract description 10
- 229910010093 LiAlO Inorganic materials 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000009283 thermal hydrolysis Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 24
- 239000011572 manganese Substances 0.000 description 18
- 229910013716 LiNi Inorganic materials 0.000 description 17
- 229910010092 LiAlO2 Inorganic materials 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 12
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000904 FeC2O4 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/50—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
-
- 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
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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
- 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 provides a preparation method of a lithium metaaluminate coated nickel-cobalt-manganese ternary positive electrode material, which comprises the steps of mixing a nickel-cobalt-manganese ternary precursor with a lithium source, sintering at a high temperature to prepare the nickel-cobalt-manganese ternary positive electrode material, preparing the nickel-cobalt-manganese ternary positive electrode material by using aluminum isopropoxide through a hydro-thermal hydrolysis method, filtering and drying after the hydro-thermal reaction is finished, and grinding the nickel-cobalt-manganese ternary positive electrode material into powder; and placing the dried powder in a box-type calcining furnace, and calcining at high temperature to obtain the lithium metaaluminate coated nickel-cobalt-manganese ternary cathode material. The preparation method does not need to additionally add a lithium source, but takes lithium residues on the surface of the cathode material as the original materialThe material can remove lithium residue on the surface of the anode material and coat a layer of LiAlO on the surface of the anode material2The material is protected, so that the rate capability and the cycling stability of the anode material are improved.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery anode materials, in particular to a preparation method of a lithium metaaluminate coated nickel-cobalt-manganese ternary anode material.
Background
In recent years, nickel-cobalt-manganese ternary cathode materials are receiving much attention, have high specific capacity, energy density and power density and good cycling stability, and are hot cathode materials for producing lithium ion power batteries at present. Among them, the NCM622 type and NCM811 type positive electrode materials have higher specific capacity due to the increase of nickel content, and are more promising positive electrode materials for next-generation lithium ion batteries.
However, as the content of nickel increases, the discharge capacity of the positive electrode material increases, but the thermal stability, processability and capacity retention rate decrease. The high nickel ternary cathode material has some problems in the practical production and application process. First, the cycle performance is poor, for reasons including Ni in the lithium layer2+The presence tendency of (A) is high, leading to serious cation-mixing and deterioration of cycle performance. Secondly, unstable Ni formed during charging and discharging4+The quantity is increased, strong side reaction occurs with electrolyte, more byproducts are released, and polarization of the battery is increased and the capacity is rapidly reduced. There are varying degrees of stress and distortion in the secondary particles during co-precipitation. As lithium ions are deintercalated, the material expands and contracts in volume enough to cause propagation cracks near the grain boundaries inside the particles. New cracks continuously appearing in the material particles expose fresh surfaces, and the new cracks and the electrolyte generate side reactions to cause pulverization of electrode materials and failure of batteries. Poor processability and safety are caused by the residual Li on the surface of NCM8112O and LiOH, which are sensitive to the humidity of the air, react with CO in the air2And H2Reaction of O to Li2CO3And other lithium salts, obstructing Li+Diffuse and decompose at high potential in the charged stateProduction of CO2And the soft package battery bulges and other safety problems are caused.
In order to solve the problems, researchers can improve the electrochemical performance of the nickel-cobalt-manganese ternary cathode material to different degrees by optimizing a calcination system, synthesizing a gradient material, changing the shape of the material, coating the surface of the material, doping ions and the like. Some documents and patents report LiAlO on nickel-cobalt-manganese ternary cathode materials2And (4) coating modification. Tang et al (Journal of Power Sources 412(2019) 246-254) by hydrolyzing AlCl3Forming hydroxide on the surface of the precursor, and adding a lithium source for calcining to complete LiAlO2Coated LiNi0.8Co0.1Mn0.1O2And the cycling stability and the thermal stability of the material are improved. Chinese patent publication No. CN 109560266 by controlling Li2CO3、NH4H2PO4、Mn(OH)2、FeC2O4The lithium manganese iron phosphate precursor is obtained, and then an aluminum source is added for mixing and calcining to obtain LiAlO2The coated lithium ferric manganese phosphate cathode material has good rate performance and cycle performance. However, the above processes require additional lithium source, which results in increased cost and failure to remove lithium residues on the surface of the cathode material.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a lithium metaaluminate coated nickel-cobalt-manganese ternary cathode material. The preparation method comprises the steps of mixing a nickel-cobalt-manganese ternary precursor with a lithium source, sintering at a high temperature to prepare a nickel-cobalt-manganese ternary positive electrode material, and preparing LiAlO from aluminum isopropoxide by a hydro-thermal hydrolysis method2A coated positive electrode material. According to the method, a lithium source is not required to be additionally added, but lithium residues on the surface of the positive electrode material are used as raw materials, so that the lithium residues on the surface of the positive electrode material can be removed, and a layer of LiAlO is coated on the surface of the positive electrode material2The material is protected, so that the rate capability and the cycling stability of the anode material are improved.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a lithium metaaluminate coated nickel-cobalt-manganese ternary positive electrode material is characterized by comprising the following steps:
(1) placing the nickel-cobalt-manganese ternary precursor and the lithium source powder in an agate mortar for full grinding, then placing the mixed powder in a box type calcining furnace, carrying out secondary high-temperature calcination, taking out, grinding and sieving to obtain a nickel-cobalt-manganese ternary cathode material;
(2) dissolving aluminum isopropoxide in absolute ethyl alcohol, adding a mixed solution of the absolute ethyl alcohol and deionized water, heating and stirring, slowly adding the nickel-cobalt-manganese ternary positive electrode material obtained in the step (1), and fully stirring;
(3) transferring the mixed solution obtained in the step (2) to a high-temperature reaction kettle, putting the high-temperature reaction kettle into a drying oven for hydrothermal reaction, filtering and drying after the reaction is finished, and grinding the mixture into powder;
(4) and (4) placing the powder obtained in the step (3) in a box-type calcining furnace, and calcining at high temperature to obtain the lithium metaaluminate coated nickel-cobalt-manganese ternary positive electrode material.
As further description of the technical scheme of the invention, in the step (1), the nickel-cobalt-manganese ternary precursor comprises an NCM type precursor Ni1/3Co1/3Mn1/3(OH)2NCM523 type precursor Ni0.5Co0.2Mn0.3(OH)2NCM622 type precursor Ni0.6Co0.2Mn0.2(OH)2Or NCM811 type precursor Ni0.8Co0.1Mn0.1(OH)2Lithium hydroxide is preferred.
As a further description of the technical solution of the present invention, in the step (1), the lithium source includes lithium carbonate and lithium hydroxide, and the lithium-blending excess ratio is 1% to 9%, preferably 5%.
As a further description of the technical scheme of the invention, in the step (1), in the secondary high-temperature calcination, the calcination temperature of the first high-temperature calcination is 450-500 ℃, the calcination time is 4-6 h, and the temperature rise rate is 5-10 ℃/min;
preferably, the first calcination temperature is 480 ℃, the calcination time is 5h, and the temperature rise rate is 5 ℃/min.
The calcination temperature of the second high-temperature calcination is 700-800 ℃, the calcination time is 14-18 h, and the temperature rise rate is 5-10 ℃/min;
preferably, the second calcination temperature is 750 ℃, the calcination time is 16h, and the temperature rise rate is 5 ℃/min.
As a further description of the technical scheme of the invention, in the step (1), the sieving is carried out by using a sieve with 300-500 meshes, preferably a sieve with 400 meshes.
As a further description of the technical solution of the present invention, in the step (2), the mass ratio of the nickel-cobalt-manganese ternary positive electrode material to the aluminum isopropoxide is 200: 1, 100: 1, 50: 1 or 25: 1; the volume of absolute ethyl alcohol for dissolving aluminum isopropoxide is 30-50 mL; adding a mixed solution of absolute ethyl alcohol and deionized water, wherein the volume of the mixed solution is 50-100 mL, and stirring for 1-3 h at 60 ℃; preferably, the volume of the mixed solution of absolute ethyl alcohol and deionized water is 60mL, and the mixture is stirred at 60 ℃ for 2 h.
As a further description of the technical solution of the present invention, in the mixed solution of absolute ethyl alcohol and deionized water, the volume ratio of absolute ethyl alcohol and deionized water is 4: 1.
as further description of the technical scheme of the invention, in the step (3), the temperature of the hydrothermal reaction is 150 ℃, and the reaction time is 10-20 h, preferably 15 h.
As a further description of the technical scheme of the invention, in the step (4), the high-temperature calcination temperature is 450-550 ℃, and the calcination time is 2-6 h; preferably, the high-temperature calcination temperature is 500 ℃ and the calcination time is 4 hours.
Based on the technical scheme, compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the preparation method of the lithium metaaluminate coated nickel-cobalt-manganese ternary cathode material, provided by the invention, a lithium source is not required to be additionally added, but lithium residues on the surface of the cathode material are used as raw materials, so that the lithium residues on the surface of the cathode material can be removed, and a layer of LiAlO is coated on the surface of the cathode material2The material is protected, so that the rate capability and the cycling stability of the anode material are improved.
(2) Book (I)In the nickel-cobalt-manganese ternary cathode material prepared by the preparation method, a coating material LiAlO2Uniformly coated on positive electrode materials, e.g. LiNi0.8Co0.1Mn0.1O2The surface of the particles and does not negatively affect the structure of the positive electrode material.
(3) In the nickel-cobalt-manganese ternary positive electrode material prepared by the preparation method, the capacity retention rate of the material with the coating amount of 1% is increased to 80.6% from the original 68.1% and is integrally increased by 12.5% compared with the uncoated material after the material is circularly charged and discharged for 200 circles under 1C, which indicates that LiAlO2The coating layer plays a role in protecting the material, slows down the progress of the destruction of the internal structure of the material, and remarkably improves the cycle performance of the anode material.
(4) In the nickel-cobalt-manganese ternary positive modified material prepared by the preparation method, multiplying power performance tests of 0.2C, 0.5C, 1C, 2C, 5C and 0.2C are carried out, and LiAlO2Compared with the anode material which is not coated, the anode material with the coating amount of 1% has certain rate performance improvement.
(5) In the nickel-cobalt-manganese ternary positive electrode modified material prepared by the preparation method, LiAlO2The existence of the coating layer reduces the LiNi which is a positive electrode material0.8Co0.1Mn0.1O2Resistance of, LiAlO2The potential difference (DV ═ 0.138V) of the oxidation reduction peak of the cathode material with the coating amount of 1% is obviously smaller than that of the uncoated cathode material (DV ═ 0.191V), which fully shows that the coating modification of the material inhibits the phase change polarization of the cathode material to a certain extent, thereby improving the electrochemical performance of the cathode material.
Drawings
FIG. 1 shows uncoated LiNi0.8Co0.1Mn0.1O2SEM image of (d).
FIG. 2 shows LiNi prepared at different coating amounts0.8Co0.1Mn0.1O2Cycle performance map of (c).
FIG. 3 shows LiNi which was not coated and which was coated in an amount of 1%0.8Co0.1Mn0.1O2The rate performance graph of (1).
FIG. 4 shows uncoated LiNi0.8Co0.1Mn0.1O2Cyclic voltammogram of (a).
FIG. 5 shows LiNi prepared with a coating amount of 0.5%0.8Co0.1Mn0.1O2SEM image of (d).
FIG. 6 shows LiNi prepared with a coating amount of 1%0.8Co0.1Mn0.1O2SEM image of (d).
FIG. 7 shows LiNi prepared with a coating amount of 1%0.8Co0.1Mn0.1O2Cyclic voltammogram of (a).
FIG. 8 shows LiNi prepared with a coating amount of 2%0.8Co0.1Mn0.1O2SEM image of (d).
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. The invention provides a preferred embodiment. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1 (comparative example, no coating)
Separately weighing 46.611gNi0.8Co0.1Mn0.1(OH)2And 22.051 gLiOH. H2Placing the O in an agate mortar for fully grinding, then placing the mixed powder in a porcelain boat and placing the porcelain boat in a box type calcining furnace, and placing the mixture in a calcining furnace2Calcining in the atmosphere at the temperature rise rate of 5 ℃/min at 480 ℃ for 5h, heating to 750 ℃ for 16h, cooling to room temperature, taking out, grinding, and sieving with a 400-mesh sieve to obtain the cathode material LiNi0.8Co0.1Mn0.1O2(abbreviated as NCM 811);
this example was used as a control group to prepare a positive electrode material LiNi0.8Co0.1Mn0.1O2Is shown in fig. 1. It can be seen that since the surface of NCM811 is not coated, the particles of the positive electrode material are spherical and have a smooth surface with almost no fine particles attached.
0.32g of LiNi as a positive electrode material was weighed0.8Co0.1Mn0.1O20.04g of P VDF and 0.04g of acetylene black are added with 0.7g of NMP, mixed for 6min by a homogenizer, taken out and then added with 0.3g of NMP dropwise for mixing for 2min for pulping, slurry is coated on aluminum foil to prepare a pole piece, and the pole piece is placed in a vacuum drying oven for drying overnight at 120 ℃. And adopting metal lithium as a counter electrode, assembling the metal lithium into a CR2016 type button cell in a glove box, and carrying out electrochemical performance test.
The constant-current charge and discharge test is carried out under the conditions of 2.7-4.3V and 1C, the cycle performance graph of 200 cycles is shown in figure 2, the initial discharge specific capacity of NCM811 is 183.2mAh/g, the final discharge specific capacity is 124.7mAh/g, and the capacity retention rate of 200 cycles is 68.1%. Meanwhile, the results of the rate performance tests at 0.2C, 0.5C, 1C, 2C, 5C, 0.2C are shown in fig. 3. The first three rounds of cyclic voltammetry tests were carried out in a sweep voltage range of 2.7-4.3V at a sweep rate of 0.1mV/s, and the results are shown in fig. 4, where the potential difference DV between the redox peaks of the NCM811 cathode material was 0.191V.
Example 2 (LiAlO)2The coating amount is 0.5%)
The preparation method of the nickel-cobalt-manganese ternary cathode material coated by lithium metaaluminate comprises the following steps:
(1) positive electrode material LiNi0.8Co0.1Mn0.1O2Was prepared in the same manner as in example 1;
(2) dissolving 0.025g of aluminum isopropoxide in 40mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min, then adding 30mL of a mixed solution of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 4: 1), heating and stirring at 60 ℃ for 2h, and then slowly adding 5g of the LiNi obtained in the step (1) to obtain the cathode material0.8Co0.1Mn0.1O2Continuously stirring for 5 min;
(3) quickly transferring the mixed solution obtained in the step (2) to a high-temperature reaction kettle, putting the high-temperature reaction kettle into an oven, carrying out hydrothermal reaction for 15 hours at the temperature of 150 ℃, carrying out vacuum filtration on the mixed solution after the reaction is finished, putting the precipitate obtained by the filtration into the oven, heating for 2 hours at the temperature of 80 ℃, drying, and grinding into powder;
(4) placing the powder obtained in the step (3) in a box type calcining furnace in an atmosphere of O2Calcining at a heating rate of 5 ℃/min in the atmosphere, calcining at a high temperature of 500 ℃ for 4h, cooling to room temperature, taking out, grinding, and sieving with a 400-mesh sieve to obtain LiAlO2Positive electrode material LiNi with coating amount of 0.5%0.8Co0.1Mn0.1O2(abbreviated as LAO-0.5).
Prepared LiAlO2Positive electrode material LiNi with coating amount of 0.5%0.8Co0.1Mn0.1O2As shown in FIG. 5, it can be seen that the particles of LAO-0.5 are still spherical, the surface is slightly rough, and a small amount of small particles are attached.
The same procedure as in example 1 was used to prepare the pole pieces and assembled cells. The assembled battery is subjected to a cycle performance test, a constant-current charge and discharge test is carried out under the conditions of 2.7-4.3V and 1C, a cycle chart of 200 cycles is shown in fig. 2, the initial discharge specific capacity of LAO-0.5 is 184.6mAh/g, the final discharge specific capacity is 142.1mAh/g, the capacity retention rate of 200 cycles is 77.0%, the initial specific capacity is similar to that of the battery in the embodiment 1, but the capacity retention rate is greatly improved.
Example 3 (LiAlO)2The coating amount is 1.0%)
(1) Positive electrode material LiNi0.8Co0.1Mn0.1O2Was prepared in the same manner as in example 1;
(2) dissolving 0.05g of aluminum isopropoxide in 40mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min, then adding 30mL of a mixed solution of absolute ethyl alcohol and deionized water (volume ratio is 4: 1), heating and stirring at 60 ℃ for 2h, and then slowly adding 5g of LiNi obtained in the step (1) to obtain a positive electrode material0.8Co0.1Mn0.1O2Continuously stirring for 5 min;
(3) quickly transferring the mixed solution obtained in the step (2) to a high-temperature reaction kettle, putting the high-temperature reaction kettle into an oven, carrying out hydrothermal reaction for 15 hours at the temperature of 150 ℃, carrying out vacuum filtration on the mixed solution after the reaction is finished, putting the precipitate obtained by the filtration into the oven, heating for 2 hours at the temperature of 80 ℃, drying, and grinding into powder;
(4) placing the powder obtained in the step (3) in a box type calcining furnace in an atmosphere of O2Calcining at a heating rate of 5 ℃/min in the atmosphere, calcining at a high temperature of 500 ℃ for 4h, cooling to room temperature, taking out, grinding, and sieving with a 400-mesh sieve to obtain LiAlO2Positive electrode material LiNi with coating amount of 1%0.8Co0.1Mn0.1O2(abbreviated as LAO-1.0).
Prepared LiAlO2Positive electrode material LiNi with coating amount of 1%0.8Co0.1Mn0.1O2As shown in fig. 6, it can be seen that the particles are still spherical, the surface is slightly rough, and the amount of fine particles attached to the surface is increased.
The same procedure as in example 1 was used to prepare the pole pieces and assembled cells. Constant-current charge and discharge test is carried out under the conditions of 2.7-4.3V and 1C, the cycle chart of 200 cycles is shown in figure 2, the initial specific discharge capacity of LAO-1.0 is 186.6mAh/g, the final specific discharge capacity is 150.4mAh/g, and the capacity retention rate of 200 cycles is 80.6 percent
Although the initial discharge specific capacity is slightly reduced, the capacity retention rate is improved by 12.5% compared with the NCM811 in example 1, and the modification effect is obvious.
The rate capability test is performed at 0.2C, 0.5C, 1C, 2C, 5C, 0.2C, the result is shown in FIG. 3, the specific discharge capacity (fifth circle) of NCM811 at 0.2C, 0.5C, 1C, 2C, 5C, 0.2C rate is 197.3mAhg respectively-1、189.5mAhg-1、180.7mAhg-1、166.1mAhg-1、151.3mAhg-1And 186.5mAhg-1The retention ratio of the specific discharge capacity at 5C to the initial capacity was 75.8%, and the capacity retention ratio returned to 0.2C was 93.5%.
LAO-1.0 has a specific discharge capacity of 182.5mAhg at 1C-1And started to exceed NCM811, the specific discharge capacity at 5C was 162.8mAhg-1The capacity retention was 82.9%, both of which were much higher than NCM 811. This indicates that LAO-1.0 has a rate capability superior to NCM811 and a higher rate advantageObviously, the rate capability of the coated cathode material is improved to a certain extent.
The first three cycles of cyclic voltammetry tests were performed at a sweep rate of 0.1mV/s over a sweep voltage range of 2.7-4.3V, and the results are shown in FIG. 7, where LiAlO can be seen2The potential difference (DV ═ 0.138V) of the redox peak of the cathode material with the coating amount of 1% is obviously smaller than that of the uncoated cathode material (DV ═ 0.191V), which fully indicates that the coating modification of the material inhibits the phase transition polarization of the cathode material to a certain extent, thereby improving the electrochemical performance of the cathode material, and the cathode material prepared in the embodiment has the best electrochemical performance.
Example 4 (LiAlO)2The coating amount is 2.0%)
(1) Positive electrode material LiNi0.8Co0.1Mn0.1O2Was prepared in the same manner as in example 1;
(2) dissolving 0.1g of aluminum isopropoxide in 40mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min, then adding 30mL of a mixed solution of absolute ethyl alcohol and deionized water (volume ratio is 4: 1), heating and stirring at 60 ℃ for 2h, and then slowly adding 5g of LiNi obtained in the step (1) to obtain a positive electrode material0.8Co0.1Mn0.1O2Continuously stirring for 5 min;
(3) quickly transferring the mixed solution obtained in the step (2) to a high-temperature reaction kettle, putting the high-temperature reaction kettle into an oven, carrying out hydrothermal reaction for 15 hours at the temperature of 150 ℃, carrying out vacuum filtration on the mixed solution after the reaction is finished, putting the precipitate obtained by the filtration into the oven, heating for 2 hours at the temperature of 80 ℃, drying, and grinding into powder;
(4) placing the powder obtained in the step (3) in a box type calcining furnace in an atmosphere of O2Calcining at a heating rate of 5 ℃/min in the atmosphere, calcining at a high temperature of 500 ℃ for 4h, cooling to room temperature, taking out, grinding, and sieving with a 400-mesh sieve to obtain LiAlO2Positive electrode material LiNi with coating amount of 2%0.8Co0.1Mn0.1O2(LAO-2.0)。
Prepared LiAlO2Positive electrode material LiNi with coating amount of 2%0.8Co0.1Mn0.1O2As shown in fig. 8, it can be seen that the particles are still spherical, have a rough surface, and have small particles attached.
The same procedure as in example 1 was used to prepare the pole pieces and assembled cells. And (3) carrying out cycle performance test on the assembled battery, carrying out constant-current charge and discharge test at 2.7-4.3V and 1C, wherein the cycle chart of 200 cycles is shown in figure 2, the initial discharge specific capacity is 183.6mAh/g, the final discharge specific capacity is 132.3mAh/g, the capacity retention rate of 200 cycles is 72.1%, the capacity retention rate is greatly improved, but the initial specific capacity is greatly reduced.
The foregoing is illustrative and explanatory only, and is described in greater detail and detail, but is not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications are possible without departing from the inventive concept, and such obvious alternatives fall within the scope of the invention.
Claims (10)
1. A preparation method of a lithium metaaluminate coated nickel-cobalt-manganese ternary positive electrode material is characterized by comprising the following steps:
(1) placing the nickel-cobalt-manganese ternary precursor and the lithium source powder in an agate mortar for full grinding, then placing the mixed powder in a box type calcining furnace, carrying out secondary high-temperature calcination, taking out, grinding and sieving to obtain a nickel-cobalt-manganese ternary cathode material;
(2) dissolving aluminum isopropoxide in absolute ethyl alcohol, adding a mixed solution of the absolute ethyl alcohol and deionized water, heating and stirring, slowly adding the nickel-cobalt-manganese ternary positive electrode material obtained in the step (1), and fully stirring;
(3) transferring the mixed solution obtained in the step (2) to a high-temperature reaction kettle, putting the high-temperature reaction kettle into a drying oven for hydrothermal reaction, filtering and drying after the reaction is finished, and grinding the mixture into powder;
(4) and (4) placing the powder obtained in the step (3) in a box-type calcining furnace, and calcining at high temperature to obtain the lithium metaaluminate coated nickel-cobalt-manganese ternary positive electrode material.
2. The method according to claim 1, wherein in step (1), the nickel-cobalt-manganese ternary precursor comprises a precursor of the NCM type, Ni1/3Co1/3Mn1/3(OH)2NCM523 type precursor Ni0.5Co0.2Mn0.3(OH)2NCM622 type precursor Ni0.6Co0.2Mn0.2(OH)2Or NCM811 type precursor Ni0.8Co0.1Mn0.1(OH)2。
3. The method according to claim 1, wherein in the step (1), the lithium source comprises lithium carbonate and lithium hydroxide, and the lithium compounding excess ratio is 1% to 9%.
4. The preparation method according to claim 1, wherein in the step (1), in the secondary high-temperature calcination, the calcination temperature of the first high-temperature calcination is 450 to 500 ℃, the calcination time is 4 to 6 hours, and the temperature rise rate is 5 to 10 ℃/min; the calcination temperature of the second high-temperature calcination is 700-800 ℃, the calcination time is 14-18 h, and the temperature rise rate is 5-10 ℃/min.
5. The method according to claim 1, wherein in the step (1), the sieving is performed by using a 300-500 mesh sieve.
6. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the nickel-cobalt-manganese ternary positive electrode material to the aluminum isopropoxide is 200: 1, 100: 1, 50: 1 or 25: 1; the volume of absolute ethyl alcohol for dissolving aluminum isopropoxide is 30-50 mL; adding 50-100 mL of mixed solution of absolute ethyl alcohol and deionized water, and stirring at 60 ℃ for 1-3 h.
7. The method according to claim 6, wherein the volume ratio of the absolute ethyl alcohol to the deionized water in the mixed solution of the absolute ethyl alcohol and the deionized water is 4: 1.
8. the preparation method according to claim 1, wherein in the step (3), the hydrothermal reaction temperature is 150 ℃ and the reaction time is 10-20 h.
9. The preparation method according to claim 1, wherein in the step (4), the high-temperature calcination temperature is 450-550 ℃ and the calcination time is 2-6 h.
10. A pole piece comprising the nickel-cobalt-manganese ternary positive electrode material of any one of claims 1 to 9.
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