CN116177622A - Microwave-guided in-situ gallium metal oxide coated ternary cathode material and preparation method thereof - Google Patents
Microwave-guided in-situ gallium metal oxide coated ternary cathode material and preparation method thereof Download PDFInfo
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- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 44
- -1 gallium metal oxide Chemical class 0.000 title claims abstract description 33
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 32
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010406 cathode material Substances 0.000 title claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000007774 positive electrode material Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 230000002195 synergetic effect Effects 0.000 claims description 10
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical group [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010410 layer Substances 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000002356 single layer Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 230000010355 oscillation Effects 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- 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
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Abstract
The invention provides a preparation method of a microwave-guided in-situ gallium metal oxide coated ternary positive electrode material, which comprises the following steps: s1, uniformly mixing a ternary positive electrode material precursor, a lithium source, deionized water, ethanol and ethyl acetoacetate to obtain a mixed solution; s2, adding a gallium source into the mixed solution, and carrying out microwave hydrothermal reaction under the microwave condition; and S3, filtering the mixed solution after the microwave hydrothermal reaction to obtain a product, washing, drying and sintering the product to obtain the ternary positive electrode material coated with the inorganic gallium metal oxide. According to the invention, the surface of the ternary positive electrode material is coated with the inorganic gallium metal oxide layer by a single layer, so that side reactions between the ternary positive electrode material and the electrolyte can be effectively avoided, the stability of the material is enhanced, meanwhile, the transmission of Li+ can be well promoted by coating the inorganic gallium metal oxide layer, and the cycle performance and the multiplying power performance of the lithium ion battery are improved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anodes, in particular to a microwave-guided in-situ gallium metal oxide coated ternary anode material and a preparation method thereof.
Background
In recent years, with the demand for high energy density batteries, batteries have become thinner and lighter. Ternary layered transition metal oxides (LiNi) rich in nickel (Ni) x Co y M 1-x-y O 2 M=mn or Al) is a hot spot of current research due to its superior energy density and lower cost. However, the use of Ni-rich ternary layered transition metal oxides faces mainly the following three problems: (1) Due to the transition metal occupying Li + Vacancies, which distort the crystal lattice, resulting in a material with poor structural stability; (2) Erosion of the electrolyte results in dissolution of a portion of the transition metal in the material; (3) After the electrolyte at the positive electrode is decomposed, an SEI film is formed, resulting in an increase in internal resistance. Because of these drawbacks, commercial use of Ni-rich ternary layered transition metal oxides is limited.
Currently, the most predominant electrolyte lithium salt of an electrolyte in lithium ion batteries is lithium hexafluorophosphate (LiPF) 6 )，LiPF 6 The thermal stability of the lithium ion battery is poor, hydrogen Fluoride (HF) is easily generated by hydrolysis reaction with water, the HF can corrode the positive electrode material, transition metal ions in the material are dissolved, the phase of crystals is changed, and the battery performance is deteriorated. By coating a layer of inorganic non-gallium metal oxide on the surface of the ternary layered transition metal oxide material, side reactions between the electrolyte and the ternary positive electrode material can be effectively reduced, and thus the stability of the lithium ion battery in circulation is improved. Inorganic nonmetallic oxides, fluorides, phosphates, and the like are mainly used at present, including: silicon dioxide, cobalt oxide, molybdenum oxide, zirconium oxide, zinc oxide, aluminum fluoride, manganese phosphate and the like as coating materials for ternary layered transition metal oxides, although the cathode materials can be well protected from corrosion by the electrolyte, they are mostly non-conductive, which hinders Li to some extent + Transport over the surface of the positive electrode material, therebyAffecting the performance of the lithium battery.
Disclosure of Invention
Coating materials based on ternary layered transition metal oxides present in the background art hinder Li + The invention provides a microwave-guided in-situ gallium metal oxide coated ternary positive electrode material and a preparation method thereof, which are used for solving the technical problem that the performance of a lithium battery is affected due to the transmission of the surface of the positive electrode material.
The invention provides a microwave-guided in-situ gallium metal oxide coated ternary cathode material and a preparation method thereof, and the preparation method comprises the following steps:
s1, uniformly mixing a ternary positive electrode material precursor, a lithium source, deionized water, ethanol and ethyl acetoacetate to obtain a mixed solution;
s2, adding a gallium source into the mixed solution, and carrying out microwave hydrothermal reaction under the microwave condition;
and S3, filtering the mixed solution after the microwave hydrothermal reaction to obtain a product, washing, drying and sintering the product to obtain the ternary positive electrode material coated with the inorganic gallium metal oxide.
In a preferred embodiment of the present invention, in step S1, the ternary cathode material precursor, the lithium source, the deionized water, the ethanol and the ethyl acetoacetate are uniformly mixed in an ultrasonic microwave synergistic chemical reactor, wherein the temperature of the ultrasonic microwave synergistic chemical reactor is 150-180 ℃, and the mixing time is 5-10 hours.
In a preferred embodiment of the present invention, in step S1, the ternary positive electrode material precursor has the chemical formula Ni x Co y Mn z (OH) 2 Wherein: 0.4<x<1，0<y<0.4，0<z<1, x+y+z=1; preferably 0.6.ltoreq.x<1，0.05≤y<0.2，0.05≤z<0.2，x+y+z＝1。
In a preferred embodiment of the present invention, in step S1, the lithium source is lithium acetate, and the molar ratio of the sum of Ni, co, mn elements in the ternary cathode material precursor to Li in the lithium source is 1:1.01 to 1.10; preferably, the molar ratio of the sum of Ni, co and Mn elements in the ternary cathode material precursor to Li in the lithium source is 1:1.02-1.06.
In a preferred embodiment of the present invention, in step S1, the volume ratio of deionized water, ethanol, and ethyl acetoacetate is 1:1:1 to 3; preferably, the volume ratio of deionized water, ethanol and ethyl acetoacetate is 1:1:2.
in a preferred embodiment of the present invention, in step S2, the gallium source is gallium isopropoxide, and the coating amount is 500-2000ppm; preferably, the coating amount is 1000-1500ppm.
In a preferred embodiment of the present invention, in step S2, the temperature of the microwave hydrothermal reaction is 100-200 ℃ and the reaction time is 5-20 hours; preferably, the temperature of the microwave hydrothermal reaction is 150-180 ℃ and the reaction time is 5-10h.
In a preferred embodiment of the present invention, in step S3, the washing is performed several times with ethanol, the drying temperature is 50-100 ℃, and the drying time is 2-6 hours; preferably, the drying temperature is 60-80 ℃ and the drying time is 3-5h.
In a preferred embodiment of the present invention, in step S3, the sintering is performed in an air atmosphere or an oxygen atmosphere, the sintering temperature is 400-1000 ℃, and the sintering time is 5-20 hours; preferably, the sintering temperature is 500-700 ℃ and the sintering time is 10-10 h.
The invention also provides a microwave-guided in-situ gallium metal oxide coated ternary anode material, which is prepared by the preparation method.
According to the preparation method of the microwave-guided in-situ gallium metal oxide coated ternary positive electrode material, disclosed by the invention, the surface of the ternary positive electrode material is coated with a layer of inorganic gallium metal oxide in a single layer, so that side reaction between the ternary positive electrode material and electrolyte can be effectively avoided, the stability of the material is enhanced, and the cycle performance of a battery is improved; the microwave hydrothermal synthesis method can directly supply energy to molecules, has no obvious temperature gradient system uniformity and uniform particle size distribution, can efficiently improve the structural uniformity and stability of the ternary positive electrode material, and simultaneously can well promote Li through inorganic gallium metal oxide coating + And improves the cycle performance and the rate capability of the lithium ion battery.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1:
a microwave-guided in-situ gallium metal oxide coated ternary positive electrode material and a preparation method thereof comprise the following steps:
s1, adding a mixed solvent of deionized water, ethanol and ethyl acetoacetate into an ultrasonic microwave synergistic chemical reactor, wherein the volume ratio of the deionized water to the ethanol to the ethyl acetoacetate is 500mL:500mL:1000mL, 300g of NCM60-05-35 precursor (molar ratio of Ni, co, mn of 60%, 5%, 35%) and 221g of CH 3 Uniformly dispersing COOLi into the solvent, and uniformly mixing by utilizing the rapid selective heating of microwaves and the ultrasonic oscillation principle to obtain a mixed solution;
s2, adding 1.06g of gallium isopropoxide into the mixed solution, uniformly stirring, then loading the solution into a microwave hydrothermal synthesis reaction kettle, setting the temperature to 180 ℃, and preserving the temperature for 15 hours;
s3, collecting the sample after heat preservation in a beaker, cleaning the sample by using ethanol, and then drying the sample in an oven, wherein the temperature of the oven is set to 80 ℃ and the drying time is 5 hours; placing the dried sample into a sagger, then placing the sagger into a muffle furnace, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 15h, and continuously introducing compressed air in the whole reaction process, wherein the air flow is 0.6m 3 /h; and crushing the sintered sample, and sieving to obtain the ternary positive electrode material coated with lithium metagallate.
Example 2:
a microwave-guided in-situ gallium metal oxide coated ternary positive electrode material and a preparation method thereof comprise the following steps:
s1, adding a mixed solvent of deionized water, ethanol and ethyl acetoacetate into an ultrasonic microwave synergistic chemical reactor, wherein the volume ratio of the deionized water to the ethanol to the ethyl acetoacetate is 500mL:500mL:1000mL, 300g of NCM60-05-35 precursor (Ni, co, mn three)The molar ratio of the elements is 60%, 5%, 35%) and 221g of CH 3 Uniformly dispersing COOLi into the solvent, and uniformly mixing by utilizing the rapid selective heating of microwaves and the ultrasonic oscillation principle to obtain a mixed solution;
s2, adding 2.12g of gallium isopropoxide into the mixed solution, uniformly stirring, then loading the solution into a microwave hydrothermal synthesis reaction kettle, setting the temperature to 180 ℃, and preserving the temperature for 15 hours;
s3, collecting the sample after heat preservation in a beaker, cleaning the sample by using ethanol, and then drying the sample in an oven, wherein the temperature of the oven is set to 80 ℃ and the drying time is 5 hours; placing the dried sample into a sagger, then placing the sagger into a muffle furnace, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 15h, and continuously introducing compressed air in the whole reaction process, wherein the air flow is 0.6m 3 /h; and crushing the sintered sample, and sieving to obtain the ternary positive electrode material coated with lithium metagallate.
Example 3:
a microwave-guided in-situ gallium metal oxide coated ternary positive electrode material and a preparation method thereof comprise the following steps:
s1, adding a mixed solvent of deionized water, ethanol and ethyl acetoacetate into an ultrasonic microwave synergistic chemical reactor, wherein the volume ratio of the deionized water to the ethanol to the ethyl acetoacetate is 500mL:500mL:1000mL, 300g of NCM60-05-35 precursor (molar ratio of Ni, co, mn of 60%, 5%, 35%) and 221g of CH 3 Uniformly dispersing COOLi into the solvent, and uniformly mixing by utilizing the rapid selective heating of microwaves and the ultrasonic oscillation principle to obtain a mixed solution;
s2, adding 1.59g of gallium isopropoxide into the mixed solution, uniformly stirring, then loading the solution into a microwave hydrothermal synthesis reaction kettle, setting the temperature to 180 ℃, and preserving the temperature for 15 hours;
s3, collecting the sample after heat preservation in a beaker, cleaning the sample by using ethanol, and then drying the sample in an oven, wherein the temperature of the oven is set to 80 ℃ and the drying time is 5 hours; placing the dried sample into a sagger, then placing into a muffle furnace, and heating to a temperature at a heating rate of 2 ℃/minKeeping the temperature at 850 ℃ for 15 hours, and continuously introducing compressed air in the whole reaction process, wherein the air flow is 0.6m 3 /h; and crushing the sintered sample, and sieving to obtain the ternary positive electrode material coated with lithium metagallate.
Example 4:
a microwave-guided in-situ gallium metal oxide coated ternary positive electrode material and a preparation method thereof comprise the following steps:
s1, adding a mixed solvent of deionized water, ethanol and ethyl acetoacetate into an ultrasonic microwave synergistic chemical reactor, wherein the volume ratio of the deionized water to the ethanol to the ethyl acetoacetate is 500mL:500mL:1000mL, 300g of NCM60-05-35 precursor (molar ratio of Ni, co, mn of 60%, 5%, 35%) and 221g of CH 3 Uniformly dispersing COOLi into the solvent, and uniformly mixing by utilizing the rapid selective heating of microwaves and the ultrasonic oscillation principle to obtain a mixed solution;
s2, adding 1.06g of gallium isopropoxide into the mixed solution, uniformly stirring, then loading the solution into a microwave hydrothermal synthesis reaction kettle, setting the temperature to 180 ℃, and preserving the temperature for 15 hours;
s3, collecting the sample after heat preservation in a beaker, cleaning the sample by using ethanol, and then drying the sample in an oven, wherein the temperature of the oven is set to 80 ℃ and the drying time is 5 hours; placing the dried sample into a sagger, then placing the sagger into a muffle furnace, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 15h, and continuously introducing compressed air in the whole reaction process, wherein the air flow is 0.6m 3 /h; and crushing the sintered sample, and sieving to obtain the ternary positive electrode material coated with lithium metagallate.
Example 5:
a microwave-guided in-situ gallium metal oxide coated ternary positive electrode material and a preparation method thereof comprise the following steps:
s1, adding a mixed solvent of deionized water, ethanol and ethyl acetoacetate into an ultrasonic microwave synergistic chemical reactor, wherein the volume ratio of the deionized water to the ethanol to the ethyl acetoacetate is 500mL:500mL:1000mL, 300g of NCM60-05-35 precursor (Ni, co, mn three)The molar ratio of the elements is 60%, 5%, 35%) and 221g of CH 3 Uniformly dispersing COOLi into the solvent, and uniformly mixing by utilizing the rapid selective heating of microwaves and the ultrasonic oscillation principle to obtain a mixed solution;
s2, adding 1.06g of gallium isopropoxide into the mixed solution, uniformly stirring, then loading the solution into a microwave hydrothermal synthesis reaction kettle, setting the temperature to 180 ℃, and preserving the temperature for 15 hours;
s3, collecting the sample after heat preservation in a beaker, cleaning the sample by using ethanol, and then drying the sample in an oven, wherein the temperature of the oven is set to 80 ℃ and the drying time is 5 hours; placing the dried sample into a sagger, then placing the sagger into a muffle furnace, heating to 750 ℃ at a heating rate of 2 ℃/min, preserving heat for 15h, and continuously introducing compressed air in the whole reaction process, wherein the air flow is 0.6m 3 /h; and crushing the sintered sample, and sieving to obtain the ternary positive electrode material coated with lithium metagallate.
Comparative example 1:
s1, adding a mixed solvent of deionized water, ethanol and ethyl acetoacetate into an ultrasonic microwave synergistic chemical reactor, wherein the volume ratio of the deionized water to the ethanol to the ethyl acetoacetate is 500mL:500mL:1000mL, then uniformly dispersing 300g of NCM60-05-35 precursor (the molar ratio of Ni, co and Mn is 60%, 5%, 35%) and 221g of CH3COOLi into the solvent, and uniformly mixing by utilizing the rapid selective heating of microwaves and the ultrasonic oscillation principle to obtain a mixed solution;
s2, filling the mixed solution into a microwave hydrothermal synthesis reaction kettle, setting the temperature to 180 ℃, and preserving the heat for 15 hours;
s3, collecting the sample after heat preservation in a beaker, cleaning the sample by using ethanol, and then drying the sample in an oven, wherein the temperature of the oven is set to 80 ℃ and the drying time is 5 hours; placing the dried sample into a sagger and a muffle furnace, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 15h, and continuously introducing compressed air in the whole reaction process, wherein the air flow is 0.6m 3 /(V-shaped); crushing the sintered sample, and sieving to obtain the ternary anode material.
The positive electrode materials obtained in example 1, example 2, example 3, example 4, example 5, and comparative example 1 were respectively conductive carbon black and PVDF according to 90:5:5, uniformly mixing the materials by using NMP as a solvent, uniformly coating the mixture on an aluminum foil, and manufacturing a button cell to test the electrochemical performance: the test was carried out at room temperature of 25℃for the first five weeks with 0.2C/0.2C, 0.33C/0.33C, 1C/1C, 2C/2C, 5C/5C respectively, followed by 1C/1C charge and discharge, and cycling for 50 cycles, with all test voltage ranges between 2.8-4.45V, and the buckling performance data are shown in Table 1:
TABLE 1
From the results in table 1, it can be seen that by coating a layer of inorganic gallium metal oxide on the surface of the ternary positive electrode material in a single layer, side reactions between the ternary positive electrode material and the electrolyte can be effectively avoided, so that the stability of the material is enhanced, and the cycle performance of the battery is improved.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the microwave-guided in-situ gallium metal oxide coated ternary positive electrode material is characterized by comprising the following steps of:
s1, uniformly mixing a ternary positive electrode material precursor, a lithium source, deionized water, ethanol and ethyl acetoacetate to obtain a mixed solution;
s2, adding a gallium source into the mixed solution, and carrying out microwave hydrothermal reaction under the microwave condition;
and S3, filtering the mixed solution after the microwave hydrothermal reaction to obtain a product, washing, drying and sintering the product to obtain the ternary positive electrode material coated with the inorganic gallium metal oxide.
2. The method for preparing the microwave-guided in-situ gallium metal oxide coated ternary cathode material according to claim 1, wherein in the step S1, ternary cathode material precursors, a lithium source, deionized water, ethanol and ethyl acetoacetate are uniformly mixed in an ultrasonic microwave synergistic chemical reactor, wherein the temperature of the ultrasonic microwave synergistic chemical reactor is 150-180 ℃, and the mixing time is 5-10h.
3. The method for preparing a microwave-guided in-situ gallium metal oxide coated ternary cathode material according to claim 1, wherein in step S1, the ternary cathode material precursor has a chemical formula of Ni x Co y Mn z (OH) 2 Wherein: 0.4<x<1，0<y<0.4，0<z<1, x+y+z=1; preferably 0.6.ltoreq.x<1，0.05≤y<0.2，0.05≤z<0.2，x+y+z＝1。
4. The method for preparing a microwave-guided in-situ gallium metal oxide coated ternary cathode material according to claim 1, wherein in the step S1, the lithium source is lithium acetate, and the molar ratio of the sum of Ni, co, mn elements in the ternary cathode material precursor to Li in the lithium source is 1:1.01 to 1.10; preferably, the molar ratio of the sum of Ni, co and Mn elements in the ternary cathode material precursor to Li in the lithium source is 1:1.02-1.06.
5. The method for preparing a microwave-guided in-situ gallium metal oxide coated ternary cathode material according to claim 1, wherein in step S1, the volume ratio of deionized water, ethanol and ethyl acetoacetate is 1:1:1 to 3; preferably, the volume ratio of deionized water, ethanol and ethyl acetoacetate is 1:1:2.
6. the method for preparing a microwave-guided in-situ gallium metal oxide coated ternary cathode material according to claim 1, wherein in step S2, the gallium source is gallium isopropoxide, and the coating amount is 500-2000ppm; preferably, the coating amount is 1000-1500ppm.
7. The method for preparing a microwave-guided in-situ gallium metal oxide coated ternary cathode material according to claim 1, wherein in the step S2, the temperature of the microwave hydrothermal reaction is 100-200 ℃ and the reaction time is 5-20 h; preferably, the temperature of the microwave hydrothermal reaction is 150-180 ℃ and the reaction time is 5-10h.
8. The method for preparing a microwave-guided in-situ gallium metal oxide coated ternary cathode material according to claim 1, wherein in the step S3, the washing is performed several times by using ethanol, the drying temperature is 50-100 ℃, and the drying time is 2-6h; preferably, the drying temperature is 60-80 ℃ and the drying time is 3-5h.
9. The method for preparing a microwave-guided in-situ gallium metal oxide coated ternary cathode material according to claim 1, wherein in the step S3, the sintering is performed in an air atmosphere or an oxygen atmosphere, the sintering temperature is 400-1000 ℃, and the sintering time is 5-20 h; preferably, the sintering temperature is 500-700 ℃ and the sintering time is 10-10 h.
10. A microwave-guided in-situ gallium metal oxide coated ternary cathode material produced by the method of any one of claims 1-9.
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| CN102244236A (en) * | 2011-06-10 | 2011-11-16 | 北京理工大学 | Method for preparing lithium-enriched cathodic material of lithium ion battery |
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