CN114678524A - High-nickel positive electrode material and preparation method thereof - Google Patents
High-nickel positive electrode material and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 211
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 163
- 239000007774 positive electrode material Substances 0.000 title claims description 57
- 238000002360 preparation method Methods 0.000 title abstract description 31
- 239000010405 anode material Substances 0.000 claims abstract description 41
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000011591 potassium Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 10
- 229910003684 NixCoyMnz Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 56
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 42
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- 238000001816 cooling Methods 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 42
- 239000002243 precursor Substances 0.000 claims description 39
- 239000010406 cathode material Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 28
- 229910001414 potassium ion Inorganic materials 0.000 claims description 28
- 229910001415 sodium ion Inorganic materials 0.000 claims description 28
- 238000012216 screening Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 14
- 238000003825 pressing Methods 0.000 claims description 14
- 235000002639 sodium chloride Nutrition 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 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
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- 239000011734 sodium Substances 0.000 abstract description 13
- 239000011229 interlayer Substances 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000002427 irreversible effect Effects 0.000 abstract description 4
- 229910052700 potassium Inorganic materials 0.000 abstract description 4
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- 230000007704 transition Effects 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000008213 purified water Substances 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 9
- 238000007614 solvation Methods 0.000 description 4
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 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
-
- 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
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-nickel anode material and a preparation method thereof, wherein the chemical formula of the high-nickel anode material is LiaNabKcNixCoyMnzAl（1‑x‑y‑z）TdO2Adding potassium salt or sodium salt in the preparation process to realize K+、Na+Doping lithium; k migrating faster in the first charge-discharge process+、Na+Specific to Li+Earlier reaching the counter electrode, and preferentially forming SEI film and CEI film, thereby reducing Li+Irreversible consumption is realized, and the utilization rate of lithium ions is improved; li+Can occupy potassium and sodium vacancies, thereby obviously improving the first capacity and the first coulombic efficiency of the battery; k+、Na+Specific to Li+The diameter is larger, and the interlayer structure can be supported; then, the product is processedThe lithium-position doping and transition metal-position doping of other metal elements are combined, the interlayer spacing is widened while the layered structure of the high-nickel anode material is stabilized, ions are more rapidly removed/embedded in the charging and discharging processes, and therefore the rate capability of the battery is effectively improved. The invention has the characteristics of simple preparation process, low cost, small pollution, good electrochemical performance, contribution to industrial production and the like.
Description
Technical Field
The invention relates to the technical field of battery materials and batteries, in particular to a high-nickel positive electrode material and a preparation method thereof.
Background
With the rapid development of new energy markets, the market demands of secondary batteries, particularly power batteries, are exponentially increased; the high-nickel positive electrode material is one of the most used positive electrode materials on the EV battery in the current market based on high capacity, long cycle life and high working voltage; the lithium compound is used as one of necessary raw materials for preparing the anode material of the lithium ion battery, and the price of the lithium compound is greatly increased due to the market phenomenon of short supply in recent years, so that the production cost of the anode material is increased; in order to ensure sufficient lithium ion intercalation when preparing the cathode material at present, excessive lithium salt is added in the preparation process, and the low lithium ion utilization rate (the first charge-discharge efficiency is only about 90 percent under the room temperature 0.2C test condition) in the charge-discharge process of the current high-nickel cathode material further causes the waste of lithium resources.
Therefore, the method reasonably utilizes the lithium resource, improves the utilization rate of lithium ions in the battery to the maximum extent, and becomes an effective way for reducing cost and improving efficiency in the EV battery.
Disclosure of Invention
Aiming at the defect of low lithium utilization rate in the prior art, the invention aims to provide a high-nickel positive electrode material and a preparation method thereof, wherein Li in the first charge-discharge process of the high-nickel positive electrode material is reduced by doping potassium/sodium ions at lithium sites+The specific capacity of the first discharge and the first coulombic efficiency are improved; meanwhile, the cycle performance of the high-nickel anode material is effectively improved by combining lithium-site doping of other metal elements, transition metal-site doping and particle surface coating, and the preparation method has the characteristics of simple preparation process, low cost, small pollution, good electrochemical performance, contribution to industrial production and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-nickel positive electrode material with chemical formula of LiaNabKcNixCoyMnzAl(1-x-y-z)TdO2，
Wherein a is more than or equal to 0.8 and less than 1, b is more than or equal to 0 and less than or equal to 0.2, c is more than or equal to 0 and less than or equal to 0.2, d is more than 0 and less than or equal to 0.02, x is more than or equal to 0.8 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.2, z is more than or equal to 0 and less than or equal to 0.2, a + b + c is equal to 1, and x + y + z is less than or equal to 1;
t is one or two of Mg, Al, Ti, Zr, W, Sb, Y, Nb, Sr, Sc, Mo, Ta and Cr.
The preparation method of the high-nickel cathode material comprises the following steps:
1) fully mixing the high-nickel precursor material with lithium salt, potassium salt, sodium salt and other doped metal salts to obtain a mixture A;
2) roasting, cooling, crushing and screening the mixture A to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) washing, centrifuging/filter pressing, drying and cooling the high-nickel positive electrode material B to obtain a high-nickel positive electrode material C;
4) and fully mixing the high-nickel positive electrode material C with the particle surface coating salt, and then carrying out secondary roasting, cooling, crushing and screening to obtain the high-nickel positive electrode material.
Further, the high nickel precursor material in the step 1) is NixCoyMnzAl(1-x-y-z)(OH)2(ii) a The lithium salt is selected from any one or more of lithium hydroxide, lithium carbonate, lithium fluoride or lithium chloride; the potassium salt is selected from any one or more of potassium hydroxide, potassium carbonate, potassium acetate, potassium oxalate or potassium sulfate; the sodium salt is selected from any one or more of sodium carbonate, sodium acetate, sodium chloride, sodium acetate, sodium oxalate, sodium sulfate or sodium bicarbonate; the other doped metal salt contains one or two of Mg, Al, Ti, Zr, W, Sb, Y, Nb, Sr, Sc, Mo, Ta and Cr.
Further, the roasting process in the step 2) is roasting at the temperature of 450-550 ℃ for 1-5 hours, and then roasting at the temperature of 600-850 ℃ for 4-20 hours.
Further, the solid content in the step 3) is 40-70% (mass ratio) during water washing, and the water washing time is 1-20 min.
Further, the drying temperature in the step 3) is 110-200 ℃, and the drying time is 1-8 h.
Further, the element contained in the particle surface coating salt in the step 4) is selected from any one or more of Co, F, B, W and Al.
Further, in the step 4), the roasting temperature is 250-350 ℃, and the roasting time is 4-12 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) adding potassium salt or sodium salt in the preparation process of the high-nickel anode material, and realizing lithium-site doping of potassium ions and sodium ions by high-temperature calcination; according to the principle of ion solvation, potassium and sodium ions which migrate faster in the first charge-discharge process reach the counter electrode earlier than lithium ions, and an SEI film and a CEI film are preferentially formed, so that Li is reduced+Irreversible consumption is realized, and the utilization rate of lithium ions is improved;
(2) li during first discharge lithium insertion+Can occupy potassium and sodium vacancies, thereby obviously improving the first capacity and the first coulombic efficiency of the battery;
(3) the sodium ions and the potassium ions have larger diameters than the lithium ions, can play a role in supporting an interlayer structure, and prevent the structure from collapsing in the lithium ion removing/embedding process, thereby stabilizing the layered structure of the high-nickel cathode material; the interlayer spacing is widened while the layered structure of the high-nickel anode material is stabilized by combining lithium-site doping and transition metal-site doping of other metal elements, so that ions are more rapidly removed/embedded in the charging and discharging processes, and the rate capability of the battery is effectively improved; finally, the surface of the combined particles is coated to effectively improve the cycle performance of the nickel anode material;
(4) the earth storage capacity of sodium salt and potassium salt is higher than that of lithium salt, the sources are wide, the market price is low, and the production cost of the anode material can be reduced;
(5) the preparation process is simple, no new process is required to be added, the preparation process is green and pollution-free, the cost is low, the preparation method is suitable for large-scale industrial production, the electrochemical performance of the high-nickel anode material is greatly improved, and the requirement of current social market development is well met.
Drawings
Fig. 1 is an SEM photograph at 5000 x of the high nickel cathode material prepared in example 1 of the present invention;
fig. 2 is an SEM photograph at 1000 x of the high nickel cathode material prepared in example 1 of the present invention;
fig. 3 is an XRD pattern of the high nickel cathode material prepared in example 1 of the present invention;
fig. 4 is a graph of electrochemical cycle performance at 0.3C for the high nickel cathode materials prepared in example 1 of the present invention and comparative examples 1 and 2, respectively.
Detailed description of the preferred embodiments
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a high-nickel cathode material, the chemical formula of which is LiaNabKcNixCoyMnzAl(1-x-y-z)TdO2，
Wherein a is more than or equal to 0.8 and less than 1, b is more than or equal to 0 and less than or equal to 0.2, c is more than or equal to 0 and less than or equal to 0.2, d is more than 0 and less than or equal to 0.02, x is more than or equal to 0.8 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.2, z is more than or equal to 0 and less than or equal to 0.2, a + b + c is equal to 1, and x + y + z is less than or equal to 1;
t is one or two of Mg, Al, Ti, Zr, W, Sb, Y, Nb, Sr, Sc, Mo, Ta and Cr.
The invention also provides a preparation method of the high-nickel cathode material, which comprises the following steps:
1) fully mixing the high-nickel precursor material with lithium salt, potassium salt, sodium salt and other doped metal salts to obtain a mixture A;
2) roasting, cooling, crushing and screening the mixture A to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) washing, centrifuging/filter pressing, drying and cooling the high-nickel positive electrode material B to obtain a high-nickel positive electrode material C;
4) and fully mixing the high-nickel positive electrode material C with the particle surface coating salt, and then carrying out secondary roasting, cooling, crushing and screening to obtain the high-nickel positive electrode material.
Adding potassium salt or sodium salt in the preparation process of the high-nickel anode material, and realizing lithium-site doping of potassium ions and sodium ions by high-temperature calcination; according to the principle of ion solvation, potassium and sodium ions which migrate faster in the first charge-discharge process reach the counter electrode earlier than lithium ions, and an SEI film and a CEI film are preferentially formed, so that Li is reduced+Irreversible consumption is realized, and the utilization rate of lithium ions is improved; li during first discharge lithium insertion+Can occupy potassium and sodium vacancies, thereby obviously improving the first capacity and the first coulombic efficiency of the battery; the lithium-site doping of potassium and sodium ions is combined with the lithium-site doping of other metal elements and the transition metal-site doping, so that the interlayer spacing is widened while the layered structure of the high-nickel anode material is stabilized, ions are more rapidly removed/inserted in the charging and discharging processes, and the rate capability of the battery is effectively improved; and finally, the surface of the combined particles is coated to effectively improve the cycle performance of the nickel anode material. The invention has the characteristics of simple preparation process, low cost, small pollution, good electrochemical performance, contribution to industrial production and the like.
The principle of ion solvation means that potassium and sodium ions are generally considered to have larger volume and atomic mass than lithium ions and have kinetic properties inferior to those of lithium ions, but ions always exist in a solvated form for ion diffusion in a solvent, and potassium and sodium ions have smaller solvated ions than lithium solvated ions due to weak lewis acidity, have high mobility of an electrolyte, large transport number and low desolvation energy, and therefore the diffusion kinetics of potassium and sodium ions are faster than those of lithium ions.
Preferably, the high nickel precursor material in the step 1) is NixCoyMnzAl(1-x-y-z)(OH)2(ii) a The lithium salt is selected from any one or more of lithium hydroxide, lithium carbonate, lithium fluoride or lithium chloride; the potassium salt is selected from one or more of potassium hydroxide, potassium carbonate, potassium acetate, potassium oxalate or potassium sulfate; the sodium salt is selected from any one or more of sodium carbonate, sodium acetate, sodium chloride, sodium acetate, sodium oxalate, sodium sulfate or sodium bicarbonate; the other doped metal salt contains Mg, Al, Ti, Zr, W, Sb, Y, Nb, Sr, Sc, Mo, Ta and CrOne or two.
Preferably, the roasting process in the step 2) is roasting at the temperature of 450-550 ℃ for 1-5 hours, and then roasting at the temperature of 600-850 ℃ for 4-20 hours.
Preferably, the solid content in the step 3) is 40-70% (mass ratio), and the washing time is 1-20 min.
Preferably, the drying temperature in the step 3) is 110-200 ℃, and the drying time is 1-8 h.
Preferably, the surface of the particles in step 4) is coated with one or more elements selected from Co, F, B, W and Al.
Preferably, the roasting temperature in the step 4) is 250-350 ℃, and the roasting time is 4-12 h.
Example 1
A preparation method of a high-nickel cathode material comprises the following steps:
1) high-nickel precursor material, lithium hydroxide, potassium hydroxide and sodium hydroxide are mixed according to a molar ratio of 1: 1.01: 0.015: 0.005 mixing, and taking Ni as high-nickel precursor material0.90Co0.05Mn0.04Al0.01(OH)2And 3000ppm of ZrO were added2And 3000ppm Sb2O3Fully mixing (based on the mass of the high-nickel precursor material) to obtain a mixture A;
2) roasting the mixture A at the low temperature of 500 ℃ for 4h in the oxygen atmosphere, then roasting at the high temperature of 810 ℃ for 12h, cooling, crushing and screening to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) mixing the high-nickel positive electrode material B with purified water with the same mass (the solid content is 50%), washing with water for 3min, centrifuging/filter pressing, drying for 2h at 160 ℃ in a vacuum environment, and cooling to obtain a high-nickel positive electrode material C;
4) mixing high nickel-based anode materials C and H3BO3According to a molar ratio of 1: 0.01, fully mixing, roasting for the second time at 300 ℃ for 8 hours, cooling, crushing and screening to obtain the high-nickel anode material with the chemical formula of Li0.98Na0.005K0.015Ni0.90Co0.05Mn0.037Al0.007Zr0.003Sb0.003O2。
Example 2
A preparation method of a high-nickel cathode material comprises the following steps:
1) high-nickel precursor material, lithium hydroxide, potassium hydroxide and sodium hydroxide are mixed according to a molar ratio of 1: 1.01: 0.015: 0.005 is mixed, and the high nickel precursor material is Ni0.90Co0.05Mn0.04Al0.01(OH)2Then 3000ppm of TiO was added2And 3000ppm Sb2O3Fully mixing (based on the mass of the high-nickel precursor material) to obtain a mixture A;
2) roasting the mixture A at the low temperature of 500 ℃ for 4h in the oxygen atmosphere, then roasting at the high temperature of 810 ℃ for 12h, cooling, crushing and screening to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) mixing the high-nickel positive electrode material B with purified water with the same mass (the solid content is 50%), washing with water for 3min, centrifuging/filter pressing, drying for 2h at 160 ℃ in a vacuum environment, and cooling to obtain a high-nickel positive electrode material C;
4) mixing high nickel-based anode materials C and H3BO3According to a molar ratio of 1: 0.01, fully mixing, roasting for the second time at 300 ℃ for 8 hours, cooling, crushing and screening to obtain the high-nickel anode material with the chemical formula of Li0.98Na0.005K0.015Ni0.90Co0.05Mn0.037Al0.007Ti0.003Sb0.003O2。
Example 3
A preparation method of a high-nickel cathode material comprises the following steps:
1) high-nickel precursor material, lithium hydroxide, potassium hydroxide and sodium hydroxide are mixed according to a molar ratio of 1: 1.01: 0.005: 0.015 percent of Ni as a high-nickel precursor material0.90Co0.05Mn0.04Al0.01(OH)2And 3000ppm of ZrO were added2And 3000ppm Sb2O3Fully mixing (based on the mass of the high-nickel precursor material) to obtain a mixture A;
2) roasting the mixture A at the low temperature of 450 ℃ for 5h in the oxygen atmosphere, then roasting at the high temperature of 690 ℃ for 12h, cooling, crushing and screening to obtain a potassium/sodium ion lithium-site doped nickelic anode material B;
3) mixing the high-nickel positive electrode material B with purified water (the solid content is 40%), washing with water for 1min, centrifuging/filter pressing, drying for 2h at 200 ℃ in a vacuum environment, and cooling to obtain a high-nickel positive electrode material C;
4) mixing high nickel-based anode materials C and H3BO3According to a molar ratio of 1: 0.01, fully mixing, then carrying out secondary roasting at the roasting temperature of 300 ℃ for 12 hours, then cooling, crushing and screening to obtain the high-nickel anode material with the chemical formula of Li0.98Na0.015K0.005Ni0.90Co0.05Mn0.037Al0.007Zr0.003Sb0.003O2。
Example 4
1) High-nickel precursor material, lithium hydroxide, potassium hydroxide and sodium hydroxide are mixed according to a molar ratio of 1: 1.01: 0.02: 0.02 is mixed, and the high nickel precursor material is Ni0.90Co0.05Mn0.04Al0.01(OH)2And 3000ppm of ZrO were added2And 3000ppm Sb2O3Fully mixing (based on the mass of the high-nickel precursor material) to obtain a mixture A;
2) roasting the mixture A at the low temperature of 550 ℃ for 1h in the oxygen atmosphere, then roasting at the high temperature of 650 ℃ for 12h, cooling, crushing and screening to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) mixing the high-nickel positive electrode material B with purified water (solid content is 70%), washing with water for 20min, centrifuging/filter pressing, drying for 2h at 200 ℃ in a vacuum environment, and cooling to obtain a high-nickel positive electrode material C;
4) mixing high nickel-based anode materials C and H3BO3According to the molar ratio of 1: 0.01 is fullMixing, roasting for the second time at 250 deg.C for 12h, cooling, crushing, and sieving to obtain high-nickel cathode material with chemical formula of Li0.96Na0.02K0.02Ni0.90Co0.05Mn0.037Al0.007Zr0.003Sb0.003O2。
Example 5
A preparation method of a high-nickel cathode material comprises the following steps:
1) high-nickel precursor material, lithium hydroxide, potassium hydroxide and sodium hydroxide are mixed according to a molar ratio of 1: 1.01: 0.01: 0.01, and the high nickel precursor material is Ni0.90Co0.05Mn0.04Al0.01(OH)2Adding 3000ppm ZrO2And 3000ppm Sb2O3Fully mixing (by mass of the high-nickel precursor material) to obtain a mixture A;
2) roasting the mixture A at the low temperature of 500 ℃ for 4h in the oxygen atmosphere, then roasting at the high temperature of 850 ℃ for 4h, cooling, crushing and screening to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) mixing the high-nickel positive electrode material B with purified water with the same mass (the solid content is 50%), washing with water for 3min, centrifuging/filter pressing, drying for 8h at 110 ℃ in a vacuum environment, and cooling to obtain a high-nickel positive electrode material C;
4) mixing high nickel-based anode materials C and H3BO3According to a molar ratio of 1: 0.01, fully mixing, roasting for the second time at 300 ℃ for 8 hours, cooling, crushing and screening to obtain the high-nickel anode material with the chemical formula of Li0.98Na0.01K0.01Ni0.90Co0.05Mn0.037Al0.007Zr0.003Sb0.003O2。
Example 6
A preparation method of a high-nickel cathode material comprises the following steps:
1) high-nickel precursor material, lithium hydroxide, potassium hydroxide and hydrogen and oxygenSodium chloride, and mixing the following raw materials in a molar ratio of 1: 1.01: 0.005: 0.005 mixing, and taking Ni as high-nickel precursor material0.90Co0.05Mn0.04Al0.01(OH)2And 3000ppm of ZrO were added2And 3000ppm Sb2O3Fully mixing (based on the mass of the high-nickel precursor material) to obtain a mixture A;
2) roasting the mixture A at the low temperature of 500 ℃ for 4h in the oxygen atmosphere, then roasting at the high temperature of 600 ℃ for 20h, cooling, crushing and screening to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) mixing the high-nickel positive electrode material B with purified water with the same mass (the solid content is 50%), washing with water for 3min, centrifuging/filter pressing, drying for 1h at 200 ℃ in a vacuum environment, and cooling to obtain a high-nickel positive electrode material C;
4) mixing high nickel-based anode materials C and H3BO3According to a molar ratio of 1: 0.01, fully mixing, roasting for the second time at 350 ℃ for 4 hours, cooling, crushing and screening to obtain the high-nickel anode material with the chemical formula of Li0.99Na0.005K0.005Ni0.90Co0.05Mn0.037Al0.007Zr0.003Sb0.003O2。
Example 7
A preparation method of a high-nickel cathode material comprises the following steps:
1) high-nickel precursor material, lithium hydroxide and sodium hydroxide are mixed according to a molar ratio of 1: 1.01: 0.2, mixing, and taking Ni as a high-nickel precursor material0.90Co0.05Mn0.04Al0.01(OH)2And 3000ppm of ZrO were added2And 3000ppm Sb2O3Fully mixing (based on the mass of the high-nickel precursor material) to obtain a mixture A;
2) roasting the mixture A at the low temperature of 500 ℃ for 4h in the oxygen atmosphere, then roasting at the high temperature of 810 ℃ for 12h, cooling, crushing and screening to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) mixing the high-nickel positive electrode material B with purified water with the same mass (the solid content is 50%), washing with water for 3min, centrifuging/filter pressing, drying for 2h at 160 ℃ in a vacuum environment, and cooling to obtain a high-nickel positive electrode material C;
4) mixing high nickel-based anode materials C and H3BO3According to a molar ratio of 1: 0.01, fully mixing, then carrying out secondary roasting at the roasting temperature of 300 ℃ for 8 hours, and then cooling, crushing and screening to obtain the high-nickel anode material with the chemical formula of Li0.80Na0.20Ni0.90Co0.05Mn0.037Al0.007Zr0.003Sb0.003O2。
Example 8
A preparation method of a high-nickel cathode material comprises the following steps:
1) mixing a high-nickel precursor material, lithium hydroxide and potassium hydroxide according to a molar ratio of 1: 1.01: 0.2, mixing, and taking Ni as a high-nickel precursor material0.90Co0.05Mn0.04Al0.01(OH)2And 3000ppm of ZrO were added2And 3000ppm Sb2O3Fully mixing (based on the mass of the high-nickel precursor material) to obtain a mixture A;
2) roasting the mixture A at the low temperature of 500 ℃ for 4h in the oxygen atmosphere, then roasting at the high temperature of 810 ℃ for 12h, cooling, crushing and screening to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) mixing the high-nickel positive electrode material B with purified water with the same mass (the solid content is 50%), washing with water for 3min, centrifuging/filter pressing, drying for 2h at 160 ℃ in a vacuum environment, and cooling to obtain a high-nickel positive electrode material C;
4) mixing high nickel-based anode materials C and H3BO3According to a molar ratio of 1: 0.01, fully mixing, roasting for the second time at 300 ℃ for 8 hours, cooling, crushing and screening to obtain the high-nickel anode material with the chemical formula of Li0.80K0.20Ni0.90Co0.05Mn0.037Al0.007Zr0.003Sb0.003O2。
Example 9
A preparation method of a high-nickel cathode material comprises the following steps:
1) mixing a high-nickel precursor material, lithium hydroxide, potassium hydroxide and sodium hydroxide according to a molar ratio of 1: 1.01: 0.01: 0.01, and the high nickel precursor material is Ni0.90Co0.06Mn0.04(OH)2And 3000ppm of ZrO were added2And 3000ppm Sb2O3Fully mixing (based on the mass of the high-nickel precursor material) to obtain a mixture A;
2) roasting the mixture A at the low temperature of 500 ℃ for 4h in the oxygen atmosphere, then roasting at the high temperature of 850 ℃ for 4h, cooling, crushing and screening to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) mixing the high-nickel positive electrode material B with purified water with the same mass (the solid content is 50%), washing with water for 3min, centrifuging/filter pressing, drying for 8h at 110 ℃ in a vacuum environment, and cooling to obtain a high-nickel positive electrode material C;
4) mixing high nickel-based anode materials C and H3BO3According to a molar ratio of 1: 0.01, fully mixing, roasting for the second time at 300 ℃ for 8 hours, cooling, crushing and screening to obtain the high-nickel anode material with the chemical formula of Li0.98Na0.01K0.01Ni0.90Co0.06Mn0.034Zr0.003Sb0.003O2。
Example 10
A preparation method of a high-nickel cathode material comprises the following steps:
1) high-nickel precursor material, lithium hydroxide and sodium hydroxide are mixed according to a molar ratio of 1: 1.01: 0.02 is mixed, and the high nickel precursor material is Ni0.90Co0.06Mn0.04(OH)2And 3000ppm of ZrO were added2And 3000ppm Sb2O3Fully mixing (based on the mass of the high-nickel precursor material) to obtain a mixture A;
2) roasting the mixture A at the low temperature of 500 ℃ for 4h in the oxygen atmosphere, then roasting at the high temperature of 810 ℃ for 12h, cooling, crushing and screening to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) mixing the high-nickel positive electrode material B with purified water with the same mass (the solid content is 50%), washing with water for 3min, centrifuging/filter pressing, drying for 2h at 160 ℃ in a vacuum environment, and cooling to obtain a high-nickel positive electrode material C;
4) mixing high nickel-based anode materials C and H3BO3According to a molar ratio of 1: 0.01, fully mixing, roasting for the second time at 300 ℃ for 8 hours, cooling, crushing and screening to obtain the high-nickel anode material with the chemical formula of Li0.98Na0.02Ni0.90Co0.06Mn0.034Zr0.003Sb0.003O2。
Example 11
A preparation method of a high-nickel cathode material comprises the following steps:
1) high-nickel precursor material, lithium hydroxide and potassium hydroxide are mixed according to a molar ratio of 1: 1.01: 0.02 is mixed, and the high nickel precursor material is Ni0.90Co0.06Mn0.04(OH)2Adding 3000ppm ZrO2And 3000ppm Sb2O3Fully mixing (based on the mass of the high-nickel precursor material) to obtain a mixture A;
2) roasting the mixture A at the low temperature of 500 ℃ for 4h in the oxygen atmosphere, then roasting at the high temperature of 810 ℃ for 12h, cooling, crushing and screening to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) mixing the high-nickel positive electrode material B with purified water with the same mass (the solid content is 50%), washing with water for 3min, centrifuging/filter pressing, drying for 2h at 160 ℃ in a vacuum environment, and cooling to obtain a high-nickel positive electrode material C;
4) mixing high nickel-based anode materials C and H3BO3According to a molar ratio of 1: 0.01, fully mixing, then carrying out secondary roasting at the roasting temperature of 300 ℃ for 8 hours, and then cooling, crushing and screening to obtain the high nickelA positive electrode material of the formula Li0.98K0.02Ni0.90Co0.06Mn0.034Zr0.003Sb0.003O2。
Comparative example 1
Compared with the embodiment 1, the preparation method of the high-nickel cathode material is different from the embodiment 1 in that sodium hydroxide and potassium hydroxide are not added in the step 1), and other parameters and steps are completely the same as those in the embodiment 1.
Comparative example 2
Compared with the embodiment 1, the preparation method of the high-nickel cathode material is characterized in that ZrO is not added in the step 1)2And Sb2O3The remaining parameters and procedures were exactly the same as in example 1.
Comparative example 3
Compared with the embodiment 1, the preparation method of the high-nickel cathode material is characterized in that sodium hydroxide and potassium hydroxide are not added in the step 1), and ZrO is not added2And Sb2O3The remaining parameters and procedures were exactly the same as in example 1.
The high nickel cathode material obtained in example 1 is subjected to SEM characterization and XRD characterization, wherein fig. 1 and 2 are SEM photographs with magnification of 5000 times and 1000 times, respectively, and it can be seen that the material is a secondary particle sphere formed by aggregation of primary particles, and fig. 3 is an XRD chart, and the result shows a sharp diffraction peak, indicating that the material has high crystallinity and stable crystal structure.
Table 1 shows the first specific discharge capacity at different current densities, the first coulombic efficiency at 0.2C, and the capacity retention rate after 100 cycles of the button cell assembled from the high-nickel cathode materials prepared in examples 1 to 11 and comparative examples 1 to 3; wherein the test conditions of the button cell are LR2032, 2.5-4.25V, vs. Li+and/Li. The positive pole piece of the battery is as follows: conductive agent: PVDF 96: 1.5: 2.5 of the raw materials.
As can be seen from the data in table 1:
(1) examples 1-11 compared to comparative example 1, examples 1-11 had specific discharge capacities at different current densities, first coulombic efficiencies at 0.2C, and 100 cycles at 0.3CThe ring capacity retention rate is obviously superior to that of the comparative example 1, according to the ion solvation principle, potassium ions and sodium ions which migrate faster in the first charge-discharge process reach the counter electrode earlier than lithium ions, and an SEI film and a CEI film are preferentially formed, so that the Li is reduced+Irreversible consumption; li during first discharge lithium insertion+Can occupy potassium and sodium vacancies, thereby obviously improving the first capacity and the first coulombic efficiency of the battery;
(2) compared with the comparative example 2, the discharge specific capacity, the first coulombic efficiency at 0.2C and the 100-week cycle capacity retention rate at 0.3C of the examples 1 to 11 under different current densities are obviously superior to those of the comparative example 2, and it can be seen that the interlayer inactive site doping is crucial to the electrochemical performance of the high-nickel anode material, and the interlayer inactive sites existing in the doped elements not only can support the interlayer structure, widen the interlayer spacing and increase the lithium ion active sites, thereby improving the capacity, but also can maintain the stability of the layered structure in the lithium ion de-intercalation/intercalation process and improve the cycle stability of the high-nickel anode material;
(3) compared with the comparative example 3, the discharge specific capacity, the first coulombic efficiency at 0.2C and the 100-cycle capacity retention rate at 0.3C of the comparative example 2 under different current densities are obviously superior to those of the comparative example 3, which shows that the introduction of sodium ions and potassium ions can assist in maintaining the stability of a laminated structure to a certain extent;
(4) the electrochemical performances of the discharge specific capacity, the first coulombic efficiency at 0.2 ℃ and the 100-cycle capacity retention rate at 0.3 ℃ of the lithium ion battery in the embodiment 1 and the embodiment 2 under different current densities are similar, so that the interlayer doping elements with the equivalent functions of Zr and Ti can be freely replaced without affecting the functions of sodium ions and potassium ions. Therefore, the lithium site doping of sodium ions and potassium ions is attached to the doping basis of the interlayer inactive sites, so that the functions of the lithium site doping can be better played;
(5) compared with example 9, the capacity retention rate of 100 cycles of example 5 is better than that of example 9, and the discharge specific capacity of example 9 is higher than that of example 5 under different current densities; compared with example 10, the capacity retention ratio of 100 cycles of example 7 is better than that of example 10, and the discharge specific capacity of example 10 is higher than that of example 7 under different current densities; example 8 compared with example 11, the 100-cycle capacity retention ratio of example 8 is better than that of example 11, and the specific discharge capacity of example 11 is higher than that of example 8 under different current densities; therefore, the aluminum element occupies partial active lithium sites and inactive lithium sites, so that the capacity improvement of the high-nickel anode material is hindered, and the cycle retention rate of the layered anode material can be effectively improved; therefore, the method is suitable for the high-nickel cathode material.
TABLE 1
Although some embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and those skilled in the art can make equivalent modifications or substitutions without departing from the spirit of the present invention, and such equivalent modifications or substitutions are included in the scope of the present invention defined by the claims.
Claims (8)
1. A high-nickel anode material is characterized in that the chemical formula of the high-nickel anode material is LiaNabKcNixCoyMnzAl(1-x-y-z)TdO2，
Wherein a is more than or equal to 0.8 and less than 1, b is more than or equal to 0 and less than or equal to 0.2, c is more than or equal to 0 and less than or equal to 0.2, d is more than 0 and less than or equal to 0.02, x is more than or equal to 0.8 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.2, z is more than or equal to 0 and less than or equal to 0.2, a + b + c is equal to 1, and x + y + z is less than or equal to 1;
t is one or two of Mg, Al, Ti, Zr, W, Sb, Y, Nb, Sr, Sc, Mo, Ta and Cr.
2. A method for preparing the high nickel positive electrode material according to claim 1, comprising the steps of:
1) fully mixing the high-nickel precursor material with lithium salt, potassium salt, sodium salt and other doped metal salts to obtain a mixture A;
2) roasting, cooling, crushing and screening the mixture A to obtain a potassium/sodium ion lithium-site doped high-nickel positive electrode material B;
3) washing, centrifuging/filter pressing, drying and cooling the high-nickel positive electrode material B to obtain a high-nickel positive electrode material C;
4) and fully mixing the high-nickel positive electrode material C with the particle surface coating salt, and then carrying out secondary roasting, cooling, crushing and screening to obtain the high-nickel positive electrode material.
3. The method for preparing the high-nickel cathode material according to claim 2, wherein the high-nickel precursor material in the step 1) is NixCoyMnzAl(1-x-y-z)(OH)2(ii) a The lithium salt is selected from any one or more of lithium hydroxide, lithium carbonate, lithium fluoride or lithium chloride; the potassium salt is selected from any one or more of potassium hydroxide, potassium carbonate, potassium acetate, potassium oxalate or potassium sulfate; the sodium salt is selected from any one or more of sodium carbonate, sodium acetate, sodium chloride, sodium acetate, sodium oxalate, sodium sulfate or sodium bicarbonate; the other doped metal salt contains one or two of Mg, Al, Ti, Zr, W, Sb, Y, Nb, Sr, Sc, Mo, Ta and Cr.
4. The method for preparing the high-nickel cathode material according to claim 2, wherein the roasting in the step 2) is carried out at a temperature of 450-550 ℃ for 1-5 hours and at a temperature of 600-850 ℃ for 4-20 hours.
5. The method for preparing the high-nickel cathode material according to claim 2, wherein the solid content in the step 3) is 40 to 70 percent (mass ratio) and the washing time is 1 to 20 min.
6. The method for preparing the high-nickel cathode material according to claim 5, wherein the drying temperature in the step 3) is 110-200 ℃, and the drying time is 1-8 h.
7. The method for preparing a high-nickel cathode material according to claim 2, wherein the surface coating salt of the particles in the step 4) contains one or more elements selected from Co, F, B, W and Al.
8. The method for preparing the high-nickel cathode material according to claim 2, wherein the roasting temperature in the step 4) is 250-350 ℃, and the roasting time is 4-12 hours.
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| CN112768687A (en) * | 2021-01-21 | 2021-05-07 | 中国科学院长春应用化学研究所 | Lithium-site-doped modified high-nickel low-cobalt ternary cathode material for lithium ion battery and preparation method thereof |
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