CN114695875A - High-capacity single crystal ternary cathode material and preparation method thereof - Google Patents
High-capacity single crystal ternary cathode material and preparation method thereof Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 59
- 239000013078 crystal Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 73
- 239000002245 particle Substances 0.000 claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 64
- 239000000463 material Substances 0.000 claims description 52
- 229910052759 nickel Inorganic materials 0.000 claims description 45
- 239000000654 additive Substances 0.000 claims description 38
- 230000000996 additive effect Effects 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 150000004679 hydroxides Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 229910052712 strontium Inorganic materials 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 150000003891 oxalate salts Chemical class 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000001351 cycling effect Effects 0.000 abstract description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 36
- 239000000203 mixture Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 22
- 238000000498 ball milling Methods 0.000 description 18
- 239000010405 anode material Substances 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 8
- 150000001242 acetic acid derivatives Chemical class 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 description 4
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-capacity single crystal ternary cathode material and a preparation method thereof. The ternary cathode material has smaller particle size and uniform particle size, and the invention adopts a twice sintering and doping mode to improve the structural stability of the cathode material, further improve the electrochemical performance of the cathode material, and particularly greatly improve the specific discharge capacity and the cycling stability.
Description
Technical Field
The invention belongs to the field of new energy lithium ion battery materials, and particularly relates to a high-nickel single crystal ternary cathode material prepared by doping multiple elements and performing a high-temperature sintering process.
Background
Lithium ion batteries have been widely used in 3C products such as mobile devices, notebooks, and electric vehicle products due to their advantages such as high specific energy, excellent cycle performance, and environmental protection.
With the improvement of government requirements on energy density and endurance mileage of power batteries of electric vehicles, the requirements of the power batteries on anode materials are also continuously improved, and the key points of the domestic power battery market are gradually closed to high-nickel materials such as 811. At present, the domestic nickelic material is mainly pushed by secondary spherical particles of fine crystal grain agglomerated layers.
However, the conventional secondary spherical particles still have problems affecting the performance of the electrical properties: 1) the surface of the secondary ball particles can be completely coated, but the secondary ball is not easy to coat, so that the side reaction between the electrolyte and the material is difficult to inhibit during high-voltage charge and discharge; 2) gaps exist among primary particles of the secondary spheres, so that the overall electron and ion transmission of the secondary sphere particles is poor; 3) the traditional secondary spherical particles have poor internal firmness, and are easy to generate spherical crushing in the rolling process of a pole piece, so that the side reaction between a material and electrolyte is increased, and the cycling stability of a battery is poor; 4) secondary ball materials, particularly high nickel materials, have a lot of surface side reactions, which easily cause battery flatulence, thus causing negative effects on the safety of the battery. The NCM523 and NCM622 ternary materials with single crystal morphology in the current market show excellent performance in the aspect of safety, and have the advantages of long cycle life, high voltage resistance, high compaction density and the like.
Disclosure of Invention
Based on the above technical background, the present inventors have made a keen search and, as a result, have found that: the high-capacity single crystal ternary positive electrode material prepared by sintering a high-nickel precursor, a lithium source and an additive containing an M element for the first time, mixing the high-nickel precursor, the lithium source and the additive containing an A element and then sintering the mixture for the second time has smaller particle size, uniform particle size, good electrochemical performance, particularly higher specific discharge capacity and better cycling stability.
The invention provides a high-capacity single crystal ternary cathode material, which is prepared by sintering a high-nickel precursor, a lithium source and an additive containing an M element for the first time, mixing the high-nickel precursor, the lithium source and the additive containing an A element, and sintering the mixture for the second time.
A second aspect of the present invention provides a method for preparing a high capacity single crystal ternary positive electrode material according to the first aspect of the present invention, the method comprising the steps of:
step 1, mixing a high-nickel precursor, a lithium source and an additive containing an M element, and sintering;
step 2, carrying out wet processing on the sintering product obtained in the step 1;
and 3, carrying out secondary sintering on the material subjected to wet treatment in the step 2 and the additive containing the element A.
The high-capacity single crystal ternary cathode material and the preparation method thereof provided by the invention have the following advantages:
(1) the high-capacity single crystal ternary cathode material has small and uniform particle size;
(2) the preparation method of the high-capacity single crystal ternary cathode material is simple, has good processing performance, and is beneficial to realizing industrialized production;
(3) the high-capacity single crystal ternary cathode material has good electrochemical performance and high specific discharge capacity.
Drawings
FIG. 1 shows SEM photographs of a high nickel ternary cathode material prepared in example 1 of the present invention;
fig. 2 shows an SEM magnified photograph of a high nickel ternary cathode material prepared in example 2 of the present invention;
FIG. 3 shows a cycle retention rate curve of a high-nickel ternary cathode material prepared in example 3 of the present invention;
fig. 4 shows a charge-discharge curve diagram of the high-nickel ternary cathode material prepared in example 4 of the present invention.
Detailed Description
The present invention will be described in detail below, and features and advantages of the present invention will become more apparent and apparent as the description proceeds.
The invention provides a high-capacity single crystal ternary cathode material, which is prepared by sintering a high-nickel precursor, a lithium source and an additive containing an M element for the first time, mixing the high-nickel precursor, the lithium source and the additive containing an A element, and sintering the mixture for the second time.
The high-nickel precursor is selected from one or more of oxides, hydroxides, oxalates, sulfates, nitrates and carbonates containing nickel, cobalt and manganese, preferably from one or more of oxides, hydroxides and carbonates containing nickel, cobalt and manganese, and more preferably from hydroxides containing nickel, cobalt and manganese.
The lithium source is selected from one or more of lithium carbonate, lithium phosphate, lithium hydroxide, lithium nitrate, lithium oxalate, lithium fluoride, lithium bromide, lithium chloride, lithium oxide and lithium dihydrogen phosphate, preferably selected from one or more of lithium carbonate, lithium phosphate, lithium hydroxide, lithium oxalate and lithium dihydrogen phosphate, and more preferably selected from one or two of lithium hydroxide and lithium carbonate.
The additive containing the M element is selected from one or more of oxide, hydroxide, oxalate, sulfate, nitrate, carbonate, acetate and ammonium salt of the M element, preferably, the additive containing the M element is selected from one or more of oxide, hydroxide, oxalate, sulfate and acetate of the M element, and more preferably, the additive containing the M element is selected from one or more of oxide, hydroxide and acetate of the M element.
In the invention, M element is selected from one or more of B, Na, Mg, Al, P, Ca, Ti, Cr, Sr, Y, Zr, Nb, Mo and W, preferably from one or more of B, Na, Mg, Al, P, Cr, Sr, Zr, Nb and Mo, and more preferably from one or more of B, Mg, Al, Cr, Sr and Zr.
The molar ratio of the metal element in the high-nickel precursor, the lithium element in the lithium source and the M element in the additive containing the M element is (0.1-1): 1: (0.0001 to 0.50), preferably (0.2 to 0.8): 1: (0.0005 to 0.20), more preferably (0.4 to 0.6): 1: (0.001-0.15).
The additive containing the A element is selected from one or more of oxides, hydroxides and inorganic salts of the A element, preferably from one or more of oxides, oxalates, carbonates, acetates and hydroxides of the A element, and more preferably from one or more of oxides, carbonates and acetates of the A element.
The element A is selected from one or more of B, Na, Mg, Al, P, Ca, Ti, Cr, Sr, Y, Zr, Nb, Mo and W, preferably selected from one or more of B, Na, Al, P, Ca, Sr, Y and Zr, and more preferably selected from one or more of Al, Sr, Y and Zr.
The high-capacity single crystal ternary cathode material is uniform in particle size, the median particle size is 1-8 mu m, and the specific surface area is 0.3-2.0 m2A specific surface area of 0.5 to 1.5 m/g2A specific surface area of 0.6 to 1.2 m/g2/g。
The lithium-ion battery has good electrochemical performance, the first discharge capacity is 180-220 mAh/g under the conditions of 25 ℃, 3.0-4.3V and 0.1C, and the cycle retention rate is 95-99% after 50 cycles of circulation at 25 ℃, 3.0-4.5V and 1C.
In the invention, the high-capacity single crystal ternary cathode material is prepared by the method comprising the following steps:
step 1, mixing a high-nickel precursor, a lithium source and an additive containing an M element, and sintering;
step 2, carrying out wet processing on the sintering product obtained in the step 1;
and 3, carrying out secondary sintering on the material subjected to the wet treatment in the step 2 and the additive containing the element A.
The second aspect of the present invention provides a method for preparing the high-capacity single crystal ternary cathode material according to the first aspect of the present invention, the method comprising the steps of:
step 1, mixing a high-nickel precursor, a lithium source and an additive containing an M element, and sintering;
step 2, carrying out wet processing on the sintering product obtained in the step 1;
and 3, carrying out secondary sintering on the material subjected to the wet treatment in the step 2 and the additive containing the element A.
This step is specifically described and illustrated below.
Step 1, mixing a high nickel precursor, a lithium source and an additive containing M element, and sintering.
The high-nickel precursor is selected from one or more of oxides, hydroxides, oxalates, sulfates, nitrates and carbonates containing nickel, cobalt and manganese, preferably from one or more of oxides, hydroxides and carbonates containing nickel, cobalt and manganese, and more preferably from hydroxides containing nickel, cobalt and manganese.
The preferred median particle size of the high-nickel precursor is less than 5 mu m, and the more preferred median particle size is 3-5 mu m.
The lithium source is selected from one or more of lithium carbonate, lithium phosphate, lithium hydroxide, lithium nitrate, lithium oxalate, lithium fluoride, lithium bromide, lithium chloride, lithium oxide and lithium dihydrogen phosphate, preferably selected from one or more of lithium carbonate, lithium phosphate, lithium hydroxide, lithium oxalate and lithium dihydrogen phosphate, and more preferably selected from one or two of lithium hydroxide and lithium carbonate.
The M element-containing additive is selected from one or more of M element-containing oxides, hydroxides, oxalates, sulfates, nitrates, carbonates, acetates and ammonium salts, preferably, the M element-containing additive is selected from one or more of M element-containing oxides, hydroxides, oxalates, sulfates and acetates, and more preferably, the M element-containing additive is selected from one or more of M element-containing oxides, hydroxides and acetates.
According to the invention, M element is selected from one or more of B, Na, Mg, Al, P, Ca, Ti, Cr, Sr, Y, Zr, Nb, Mo and W, preferably from one or more of B, Na, Mg, Al, P, Cr, Sr, Zr, Nb and Mo, and more preferably from one or more of B, Mg, Al, Cr, Sr and Zr.
The molar ratio of the metal element in the high-nickel precursor, the lithium element in the lithium source and the M element in the additive containing the M element is (0.1-1): 1: (0.0001 to 0.50), preferably (0.2 to 0.8): 1: (0.0005 to 0.20), more preferably (0.4 to 0.6): 1: (0.001-0.15).
The weighed high nickel precursor, lithium source and additive containing M element are mixed, preferably mechanically mixed, more preferably ball-milled. The ball milling mixing speed is 50-500 r/min, preferably 100-300 r/min, and more preferably 200 r/min.
The mixing time is 0.5-5 h, preferably 1-3 h, and more preferably 2 h. Experiments show that the ternary cathode material prepared by ball milling, mixing and sintering has better electrochemical performance.
And sintering the mixed substances, wherein the sintering temperature is 650-1100 ℃, preferably 700-1000 ℃, and more preferably 800-950 ℃.
Tests show that when the sintering temperature is 650-1100 ℃, the prepared anode material has good cycling stability and specific discharge capacity, which may be caused by that when the sintering temperature is lower than 650 ℃, the crystal structure of the material is not completely grown, and impurities exist in the material, so that the cycling stability of the prepared anode material in the charging and discharging process is poor, the electrochemical performance is reduced, and if the sintering temperature is higher than 1100 ℃, an oxygen-deficient compound is easily generated, secondary crystallization is promoted, and the improvement of the electrochemical performance of the anode material is also not facilitated.
The temperature rise rate is 0.1 to 6 ℃/min, preferably 1 to 6 ℃/min, more preferably 4 to 6 ℃/min, for example 5 ℃/min.
The sintering is preferably carried out in a sintering furnace, the sintering atmosphere is a mixed gas of oxygen and air, wherein the volume fraction of the oxygen is 50-100%, the volume fraction of the oxygen is preferably 60-95%, and the volume fraction of the oxygen is more preferably 70-95%.
The sintering atmosphere can influence the electrochemical performance of the finally prepared anode material, and the inventor finds that when the volume fraction of oxygen in the sintering atmosphere is 50-100%, the anode material is uniform in particle size, complete in crystal structure growth, good in structural stability, and capable of better exerting capacity and circulation advantages.
The sintering time is 4-20 h, preferably 5-15h, and more preferably 10-15 h. The sintering time also affects the electrochemical performance of the final cathode material, if the sintering time is too short, the crystal structure of the cathode material does not grow completely, and the amount of impurity phases in the prepared cathode material is large, so that the structural stability of the cathode material is poor, the improvement of the electrochemical performance is not facilitated, and if the sintering time is too long, the preparation efficiency is reduced.
And naturally cooling the sintered product, and then crushing, wherein the crushing is preferably carried out in a crusher, and the material is crushed until the median particle size is less than or equal to 8.0 mu m.
And 2, carrying out wet treatment on the sintered product obtained in the step 1.
And (3) carrying out wet processing on the sintered product crushed in the step (1), wherein the wet processing in the step (2) comprises washing, filtering and drying. The water washing of the invention is preferably stirring water washing, and the water used for water washing is preferably deionized water or ultrapure water.
The wet treatment can reduce the residual lithium amount on the surface of the matrix, thereby improving the electrochemical performance of the anode material.
The mass ratio of the water to the sintered product obtained in the step 1 is (0.4-2.5): 1, preferably (1-2.5): 1, more preferably (1.5 to 2.5): 1. the inventor finds that when the mass ratio of the water to the sintered product obtained in the step 1 is (0.4-2.5): 1, the washing effect was the best, and the amount of residual lithium on the surface of the substrate after washing was low.
The stirring speed of the water washing is 50-2000 r/min, preferably 100-1000 r/min.
The stirring time is 1-30 min, preferably 5-20 min.
And filtering the stirred mixture, wherein the filtering is filter pressing or suction filtration, preferably suction filtration. The purpose of the filtration is to remove the washed waste water.
And drying the filtered material, wherein the drying is preferably carried out in a dryer, and more preferably vacuum drying.
The drying temperature is 70-200 ℃, and the drying time is 4-20 h; preferably, the drying temperature is 80-150 ℃, and the drying time is 5-15 h.
And 3, carrying out secondary sintering on the material subjected to the wet treatment in the step 2 and the additive containing the element A.
The additive containing the A element is selected from one or more of oxides, hydroxides and inorganic salts of the A element, preferably from one or more of oxides, oxalates, carbonates, acetates and hydroxides of the A element, and more preferably from one or more of oxides, carbonates and acetates of the A element.
In the invention, the element A is selected from one or more of B, Na, Mg, Al, P, Ca, Ti, Cr, Sr, Y, Zr, Nb, Mo and W, preferably from one or more of B, Na, Al, P, Ca, Sr, Y and Zr, and more preferably from one or more of Al, Sr, Y and Zr.
According to the invention, the mass ratio of the additive containing the element A to the product obtained in the step 2 is 0.1-10%, preferably 0.2-5%, and more preferably 0.2-1%. The inventor finds that the additive containing the element A influences the electrochemical performance of the finally prepared product, if the additive is too small, the cycling stability of the prepared cathode material is deteriorated, and if the additive is too large, the cycling stability and the specific discharge capacity of the cathode material are also not improved.
And (3) mixing the additive containing the element A with the material subjected to the wet treatment in the step (2), wherein the mixing is preferably mechanical mixing, and more preferably ball milling mixing. The mixing speed is preferably 100 to 500r/min, and the mixing time is preferably 0.5 to 3 hours.
And carrying out secondary sintering on the mixed materials, wherein the secondary sintering temperature is 150-1000 ℃, preferably 400-900 ℃, and more preferably 700-850 ℃.
The temperature rise rate of the secondary sintering is 0.1-6 ℃/min, preferably the temperature rise rate of the secondary sintering is 1-6 ℃/min, and more preferably the temperature rise rate of the secondary sintering is 3-6 ℃/min.
In the invention, the secondary sintering temperature is low, and tests show that when the secondary sintering temperature is in the range of 150-1000 ℃, particularly when the secondary sintering temperature is 700-850 ℃, the finally prepared cathode material has better cycle performance and higher specific discharge capacity.
The secondary sintering is preferably carried out in a sintering furnace, and the secondary sintering atmosphere is a mixed gas of oxygen and air, wherein the volume fraction of the oxygen is about 20-100%, preferably the volume fraction of the oxygen is 40-90%, and more preferably the volume fraction of the oxygen is 50-80%. The oxygen atmosphere causes less impurity gases in the sintering process to reduce possible side reactions on the surface of the material.
The secondary sintering time is 2-15 h, preferably 5-15h, and more preferably 8-15 h.
The high-capacity single crystal ternary cathode material finally prepared by the method has good product consistency, the median particle size is 1-8 mu m, and the specific surface area is 0.3-2.0 m2/g。
The high-capacity single crystal ternary cathode material has good electrochemical performance, the first discharge capacity of the high-capacity single crystal ternary cathode material is 180-220 mAh/g under the conditions of 25 ℃, 3.0-4.3V and 0.1C, and the cycle retention rate is 95-99% after 50 cycles of circulation at 25 ℃, 3.0-4.5V and 1C.
The invention has the following beneficial effects:
(1) the preparation method of the high-capacity single crystal ternary cathode material is simple, has good processing performance, and is easy to realize large-scale industrial production;
(2) the high-capacity single crystal ternary cathode material has the advantages of small particle size, uniform diameter, particle size range of 1-8 mu m and specific surface area of 0.3-2.0 m2/g；
(3) The high-capacity single crystal ternary cathode material has a stable structure in the charging and discharging processes, has excellent electrochemical performance, especially has high specific discharge capacity, has a first discharge capacity of 180-220 mAh/g under the conditions of 25 ℃, 3.0-4.3V and 0.1C, and has a good capacity retention rate, wherein the capacity retention rate is more than 96% after 50 cycles of circulation at 25 ℃, 3.0-4.5V and 1C.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1
16.00g of small particle (median diameter 4.2 μm) precursor Ni0.75Co0.10Mn0.15 (OH)2Adding 8.31g of lithium hydroxide into a ball milling tank, adding 3.116g of aluminum hydroxide, and carrying out ball milling mixing for 2h at the rotating speed of 200r/min to obtain a mixture.
And (3) placing the obtained mixture in a 70% oxygen atmosphere furnace, raising the temperature to 950 ℃ at the heating rate of 5 ℃/min, sintering at the constant temperature of 950 ℃ for 15 hours, and naturally cooling to obtain the ternary material with the single crystal morphology. Crushing by a crusher to obtain powdery material.
Washing the powdery material with deionized water according to the ratio of 1:2, and then filtering and drying at the drying temperature of 80 ℃ for 15h to obtain the dried material.
Ball-milling and mixing the dried material and 0.5% of nano alumina at the rotating speed of 200r/min for 1h, sintering the mixture for 15h at 850 ℃ in a 70% oxygen atmosphere furnace to obtain a high-nickel ternary cathode material, and testing the specific surface area of the high-nickel ternary cathode material to be 1.0m by a BET (surface area test)2The/g, morphology is shown in FIG. 1, and the enlarged morphology is shown in FIG. 2.
The prepared cathode material is assembled into a CR2032 type button battery, and then the battery is tested at 25 ℃, 3.0-4.3V and 0.1C charge-discharge rate, and the first discharge capacity of the battery is tested to be 186.5 mAh/g.
Example 2
16.00g of small-particle (median diameter of 3.0 μm) precursor Ni0.75Co0.10Mn0.15 (OH)2Adding 8.31g of lithium hydroxide into a ball milling tank, adding 3.116g of aluminum hydroxide, and carrying out ball milling mixing for 2h at the rotating speed of 200r/min to obtain a mixture.
And placing the obtained mixture in a furnace with 70% oxygen atmosphere, raising the temperature to 950 ℃ at the heating rate of 5 ℃/min, sintering at 950 ℃ for 15 hours at constant temperature, and naturally cooling to obtain the ternary material with the single crystal morphology. Crushing with a crusher to obtain a powdery material.
Washing the powdery material with deionized water according to the ratio of 1:2, and then filtering and drying at the drying temperature of 80 ℃ for 15h to obtain the dried material.
Ball-milling and mixing the dried material and 0.5% of zirconium oxide at the rotating speed of 200r/min for 1h, sintering the mixture for 15h at 850 ℃ in a 70% oxygen atmosphere furnace to obtain a high-nickel ternary cathode material, and testing the specific surface area of the high-nickel ternary cathode material to be 1.1m by a BET (surface area test)2/g。
The prepared cathode material is assembled into a CR2032 type button battery, and then the battery is tested at 25 ℃, 3.0-4.3V and 0.1C charge-discharge rate, and the first discharge capacity of the battery is tested to be 180.5 mAh/g.
Example 3
32.00g of small-particle (median diameter 4.3 μm) precursor Ni0.80Co0.10Mn0.10 (OH)2And 17.231g of lithium hydroxide, 0.0794g of magnesium oxide and the mixture are added into a ball milling tank, and ball milling and mixing are carried out for 2 hours at the rotating speed of 200r/min, so as to obtain a mixture.
And (3) placing the obtained mixture in a furnace with 90% oxygen atmosphere, heating to 920 ℃ at the heating rate of 5 ℃/min, sintering at the constant temperature of 920 ℃ for 15 hours, and naturally cooling to obtain the ternary material with the single crystal morphology. Crushing with a crusher to obtain a powdery material.
Washing the powdery material with deionized water according to the ratio of 1:2, and then filtering and drying at the drying temperature of 80 ℃ for 15h to obtain the dried material.
Ball-milling and mixing the dried material and 0.5% of nano alumina for 1h at the rotating speed of 200r/min, sintering for 15h at 800 ℃ in a 50% oxygen atmosphere furnace to obtain the high-nickel ternary cathode material, and testing the specific surface area of the high-nickel ternary cathode material to be 0.9m by a BET (surface area test)2/g。
The prepared cathode material is assembled into a CR2032 type button battery, then the test is carried out at 25 ℃, 3.0-4.3V and 0.1C charge-discharge rate, the first discharge capacity of the battery is 199.0mAh/g, and the cycle performance chart is shown in figure 3.
Example 4
32.00g of small-particle (median diameter 4.5 μm) precursor Ni0.83Co0.10Mn0.07 (OH)2And 15.347g of lithium hydroxide are added into a ball milling tank, 0.0707g of magnesium oxide is additionally added, and the mixture is ball milled and mixed for 2 hours at the rotating speed of 200r/min to obtain a mixture.
And placing the obtained mixture in a furnace with 80% oxygen atmosphere, heating to 880 ℃ at the heating rate of 5 ℃/min, sintering at 880 ℃ for 13h at constant temperature, and naturally cooling to obtain the ternary material with the single crystal morphology. Crushing with a crusher to obtain a powdery material.
Washing the powdery material with deionized water according to the ratio of 1:2, and then filtering and drying at the drying temperature of 80 ℃ for 15h to obtain the dried material.
Ball-milling and mixing the dried material and 0.5% of nano alumina at the rotating speed of 200r/min for 1h, sintering the mixture for 15h at the temperature of 750 ℃ in an 80% oxygen atmosphere furnace to obtain a high-nickel ternary cathode material, and testing the specific surface area of the high-nickel ternary cathode material to be 1.0m by a BET (surface area test)2/g。
The prepared cathode material is assembled into a CR2032 type button cell, then the test is carried out at 25 ℃, 3.0-4.5V and 0.1C charge-discharge rate, the first discharge capacity of the cell is tested to be 209.7mAh/g, and the charge-discharge curve is shown in figure 4.
Example 5
32.00g of small-particle (median diameter 4.6 μm) precursor Ni0.85Co0.08Mn0.07 (OH)2Adding 15.0002g lithium hydroxide into a ball milling pot, adding 0.0691g magnesium oxide and 0.0597g boron oxide, and ball milling and mixing at the rotating speed of 200r/min for 2h to obtain a mixture.
And placing the obtained mixture in a furnace with 90% oxygen atmosphere, raising the temperature to 890 ℃ at the heating rate of 5 ℃/min, sintering at the constant temperature of 890 ℃ for 13h, and naturally cooling to obtain the ternary material with the single crystal morphology. Crushing by a crusher to obtain powdery material.
Washing the powdery material with deionized water according to the ratio of 1:2, and then filtering and drying at the drying temperature of 80 ℃ for 15 hours to obtain the dried material.
Ball-milling and mixing the dried material and 0.5 percent of nano alumina for 1h at the rotating speed of 200r/min, putting the mixture in an oxygen atmosphere furnace of 80 percent,sintering for 15h at 720 ℃ to obtain the high-nickel ternary cathode material, and the BET test shows that the specific surface area of the high-nickel ternary cathode material is 0.8m2/g。
The prepared cathode material is assembled into a CR2032 type button battery, and then the battery is tested at 25 ℃, 3.0-4.3V and 0.1C charge-discharge rate, and the first discharge capacity of the battery is tested to be 211.5 mAh/g.
Example 6
32.00g of small-particle (median diameter 4.4 μm) precursor Ni0.90Co0.05Mn0.05 (OH)2The mixture was added to a ball mill pot with 14.328g of lithium hydroxide, and 0.2017g of zirconia and 0.0220g of magnesia were added thereto and ball milled and mixed at a rotation speed of 200r/min for 2 hours to obtain a mixture.
And (3) placing the obtained mixture in a furnace with 95% oxygen atmosphere, heating to 870 ℃ at the heating rate of 5 ℃/min, sintering at 870 ℃ for 13h at constant temperature, and naturally cooling to obtain the ternary material with the single crystal morphology. Crushing with a crusher to obtain a powdery material.
Washing the powdery material with deionized water according to the ratio of 1:2, and then filtering and drying at the drying temperature of 80 ℃ for 15h to obtain the dried material.
Ball-milling and mixing the dried material and 0.5% of nano-alumina at the rotating speed of 200r/min for 1h, sintering the mixture for 15h at 720 ℃ in a 50% oxygen atmosphere furnace to obtain a single crystal anode material, and testing the specific surface area of the single crystal anode material to be 0.6m by a BET (BET method)2/g。
The prepared cathode material is assembled into a CR2032 type button battery, and then the battery is tested at 25 ℃, 3.0-4.3V and 0.1C charge-discharge rate, and the first discharge capacity of the battery is tested to be 213.2 mAh/g.
Examples of the experiments
Experimental example 1SEM test
The positive electrode material obtained in example 1 was subjected to a scanning electron microscope test, and the test results are shown in fig. 1 and 2, and fig. 2 is an enlarged photograph of the positive electrode material.
As can be seen from the figures 1 and 2, the ternary cathode material prepared by the method has uniform and small particle size, and the particle size range is 1-8 mu m.
Experimental example 2 cycle performance test
The ternary cathode material prepared in the example 3 is assembled into a CR2032 type button battery, and a cycle performance test is carried out on the button battery, wherein the test conditions are as follows: 25 ℃, 3.0-4.5V and 1C charge-discharge rate. The test results are shown in fig. 3.
As can be seen from fig. 3, after 50 cycles, the cycle retention of the ternary cathode material prepared in example 3 is still maintained above 96%, which indicates that the ternary cathode material of the present invention has a higher cycle retention.
Experimental example 3 specific discharge capacity test
The ternary cathode material prepared in the example 4 is assembled into a CR2032 type button battery, and a cycle performance test is carried out on the button battery, wherein the test conditions are as follows: charge and discharge rate of 0.1C at 25 deg.C and 3.0-4.5V. The test results are shown in fig. 4.
As can be seen from FIG. 4, the ternary cathode material prepared in example 4 has a specific first discharge capacity of 210mAh/g at 25 ℃, 3.0-4.5V and 0.1C.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A high-capacity single crystal ternary cathode material is characterized in that a high-nickel precursor, a lithium source and an additive containing an M element are subjected to primary sintering, then mixed with the additive containing an A element and subjected to secondary sintering to obtain the high-capacity single crystal ternary cathode material.
2. The high capacity single crystal ternary positive electrode material according to claim 1,
the high nickel precursor is selected from one or more of oxides, hydroxides, oxalates, sulfates, nitrates and carbonates containing nickel, cobalt and manganese;
m element is selected from one or more of B, Na, Mg, Al, P, Ca, Ti, Cr, Sr, Y, Zr, Nb, Mo and W.
3. The high capacity single crystal ternary positive electrode material according to claim 1,
the high-capacity single crystal ternary positive electrode material has a median particle size of 1-8 mu m and a specific surface area of 0.3-2.0 m2And the first discharge capacity of the material at 25 ℃, 3.0-4.3V and 0.1C is 180-220 mAh/g.
4. Preparing the high capacity single crystal ternary positive electrode material of claim 1, prepared by a process comprising the steps of:
step 1, mixing a high-nickel precursor, a lithium source and an additive containing an M element, and sintering;
step 2, carrying out wet processing on the sintering product obtained in the step 1;
and 3, carrying out secondary sintering on the material subjected to the wet treatment in the step 2 and the additive containing the element A.
5. A preparation method of a high-capacity single crystal ternary cathode material is characterized by comprising the following steps:
step 1, mixing a high-nickel precursor, a lithium source and an additive containing an M element, and sintering;
step 2, carrying out wet processing on the sintering product obtained in the step 1;
and 3, carrying out secondary sintering on the material subjected to the wet treatment in the step 2 and the additive containing the element A.
6. The production method according to claim 5, wherein, in step 1,
the molar ratio of the metal element in the high-nickel precursor, the lithium element in the lithium source and the M element in the additive containing the M element is (0.1-1): 1 (0.0001-0.5).
7. The production method according to claim 5, wherein, in step 1,
the sintering temperature is 650-1100 ℃, the heating rate is 0.1-6 ℃/min, the sintering atmosphere is a mixed gas of oxygen and air, the volume fraction of the oxygen is 50-100%, and the sintering time is 4-20 h.
8. The method according to claim 5, wherein in step 2, the wet treatment comprises water washing, filtering and drying;
the mass ratio of the water to the sintered product obtained in the step 1 is (0.4-2.5): 1;
the drying temperature is 70-200 ℃.
9. The method according to claim 5, wherein the mass ratio of the additive containing the element A to the product obtained in step 2 in step 3 is 0.1-10%.
10. The production method according to claim 5, wherein, in step 3,
the secondary sintering temperature is 150-1000 ℃, the secondary sintering atmosphere is a mixed gas of oxygen and air, the volume fraction of the oxygen is 20-100%, and the secondary sintering time is 2-15 h.
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