CN112250091A - High-nickel ternary precursor, positive electrode material and preparation method - Google Patents
High-nickel ternary precursor, positive electrode material and preparation method Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 41
- 239000002243 precursor Substances 0.000 title claims abstract description 34
- 239000007774 positive electrode material Substances 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000013078 crystal Substances 0.000 claims abstract description 40
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 24
- 239000010406 cathode material Substances 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000011258 core-shell material Substances 0.000 claims abstract description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000000975 co-precipitation Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 3
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000011164 primary particle Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 238000000227 grinding Methods 0.000 abstract description 6
- 238000007873 sieving Methods 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000009830 intercalation Methods 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 239000011241 protective layer Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000009826 distribution Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000002411 adverse Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 241000080590 Niso Species 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Chemical class 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910003678 NixCoyMnz(OH)2 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/06—Carbonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of new energy materials, and particularly relates to a hollow porous high-nickel ternary cathode material, a precursor thereof and a preparation method thereof. Nano-scale Li2CO3As a primary seed crystal, soluble Ni salt is added into Li2CO3Surface formation of NiCO3Protective layer to obtain Li2CO3/NiCO3Secondary seed crystals; soluble Ni, Co, Mn salts in Li2CO3/NiCO3Two timesThe surface of the seed crystal is subjected to coprecipitation reaction to generate Li2CO3/NiCO3A ternary precursor of a NCM multilayer core-shell structure; and mixing and sintering the precursor and a lithium source in a proper atmosphere, and crushing, grinding and sieving to obtain the hollow porous high-nickel ternary cathode material. Li prepared by the invention2CO3/NiCO3The NCM multilayer core-shell ternary cathode precursor has the characteristics of uniform particle size distribution and short production period, and the reserved space and pores in the center and the interior of the high-nickel NCM ternary cathode material with the hollow porous structure obtained after sintering can reduce Li+Volume strain during de-intercalation to form specific Li+And the migration channel improves the cycle stability and rate capability of the lithium battery. The lithium and nickel in the core can reduce the volatilization loss of lithium during sintering and increase the specific capacity.
Description
Technical Field
The invention belongs to the field of new energy materials, mainly relates to a lithium ion battery material, and particularly relates to a hollow porous single-crystal high-nickel ternary cathode material, a precursor and a preparation method thereof.
Background
With the accelerated development of new energy automobiles, nickel-cobalt-manganese/lithium aluminate ternary positive electrode materials, particularly high nickel (nickel content is more than 70%), become popular due to the fact that the comprehensive indexes of performance and cost of the nickel-cobalt-manganese/lithium aluminate ternary positive electrode materials are superior to those of traditional lithium cobaltate and lithium iron phosphate. Among them, the high nickel ternary material has the advantages of low cost, high energy density, environmental friendliness, etc., and is one of the research hotspots of the current lithium ion battery anode material.
At present, in the preparation process of the ternary cathode material, a ternary precursor is mostly prepared firstly, and then mixed and sintered with a lithium source to obtain the ternary cathode material. The increase of the Ni content in the ternary cathode material can further increase the capacity to meet the energy density requirement, but also brings a series of new problems, mainly classified into surface problems and bulk problems, such as: (1) the high nickel ternary material can expand and contract in volume in the process of lithium intercalation and deintercalation, so that the spherical structure is broken, and the cycling stability of the material is influenced. (2) The long-time sintering of the cathode material in a high-temperature oxygen-rich atmosphere inevitably leads to the volatilization loss of lithium, thereby causing the adverse effect of lattice defects in the material on the performance of the material. (3) In order to prevent such problems from occurring, an excessive proportion of lithium must be added to compensate for the amount of lithium that volatilizes when it is calcined at high temperatures. But due to Ni2+Its surface excess proportion of lithium is liable to form such as LiOH and Li2CO3Such as alkalinitySubstances (residual alkali) and residual alkali have adverse effects on the process and performance of the ternary material, such as capacity attenuation, inhibition of lithium ion diffusion and the like.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a high-nickel ternary cathode material with a hollow porous structure, a precursor material thereof and a preparation method thereof. The high-nickel ternary cathode material provided by the invention has the advantages of high capacity, good cycle performance, good rate performance and the like.
The solution of the invention is realized by the following steps:
a high-nickel ternary precursor which is Li2CO3/NiCO3the/NCM multilayer core-shell structure has an innermost layer of Li with the radius of about 400-600 nm2CO3A core, a second layer of NiCO with a thickness of about 400-600 nm3A third layer of Ni with a thickness of about 2.5 to 3.5 μmxCoyMnz(OH)2Layer (x + y + z =1, x ≧ 0.7), primary particles in the form of elongated needles or flakes.
The preparation method of the high-nickel ternary precursor comprises the following steps:
(1) mixing nano-grade Li2CO3Adding the crystal seed as a primary crystal seed into a crystal seed reactor, adding soluble Ni salt, reacting for a period of time, and filtering by using a microporous filter to obtain Li2CO3/NiCO3Secondary seed crystals;
(2) mixing and dissolving soluble Ni salt, Co salt and Mn salt according to a certain molar ratio to obtain a mixed salt solution;
(3) adding hot water into a reaction kettle at a certain temperature and a certain rotating speed, continuously adding a complexing agent and a precipitating agent with a certain concentration, and maintaining the ammonia concentration and the pH value of the solution in the reaction kettle;
(4) mixing Li2CO3/NiCO3Simultaneously adding the secondary seed crystal and the mixed salt solution into a reaction kettle for coprecipitation reaction;
(5) after the reaction is stopped, filtering, washing and drying the product to obtain the high-nickel ternary precursor Li with the multilayer core-shell structure2CO3/NiCO3/NCM。
Preferably, the nano Li in the step (1)2CO3The particle size of the particles is 500-600 nm, and the dosage is 50-80 g/L.
Preferably, the Ni salt used in step (1) is NiSO4∙6H2O、Ni(NO3)2∙6H2O、NiCl2∙6H2O、Ni(CH3COO)2∙4H2At least one of O.
Preferably, in step (1), the soluble Ni salt is added in an amount calculated as Ni, Ni and Li2CO3The molar ratio of (A) to (B) is 0.8 to 1.2.
Preferably, Li produced in step (1)2CO3/NiCO3The grain size of the secondary seed crystal is 1-2 μm.
Preferably, the total amount of the mixed salt in the step (2) is 120. + -.5 g/L.
Preferably, the complexing agent in the step (3) is at least one of ammonia water and ammonium bicarbonate, the concentration of the complexing agent is 7.5-10 mol/L, and the concentration of ammonia in the reaction kettle is 8.0-8.5 g/L.
Preferably, in the step (3), the precipitator is one of sodium hydroxide and sodium carbonate, the concentration of the precipitator is 8-12 mol/L, and the pH of the solution in the reaction kettle is 11.50-11.80.
Preferably, the flow rate of the mixed salt solution in the step (4) is 20-40L/h, and the flow rate of the added secondary seed crystal is 6.5-10 mL/min.
Preferably, the ternary precursor prepared in the step (5) has an average particle diameter D50 of 3.7-4.3 μm.
Based on the same inventive concept, the invention provides a hollow and porous high-nickel ternary cathode material, which has the following structure: the innermost layer is a hollow layer; a little bit of outer layer is LiNiO2A layer having a plurality of irregular voids therein; the outermost layer is LiNixCoyMnzO2From the above-mentioned high-nickel ternary precursor Li2CO3/NiCO3the/NCM is mixed with a certain amount of lithium source, sintered, ground and sieved to obtain the lithium ion battery.
Further, the sintering is carried out in two steps, wherein the first sintering temperature is 750-850 ℃ in pure oxygen atmosphere, and the time is 4-8 h. The second sintering temperature is 750-950 ℃, and the time is 6-10 h.
With nanoscale Li2CO3For primary seeding, with the aid of soluble Ni salts in Li2CO3Protective layer formed on the surface to obtain Li2CO3/NiCO3And secondary seed crystal is used for preparing the precursor of the multilayer core-shell structure. Then with the core Li2CO3And adding a proper amount of lithium source as a part of lithium source, mixing, and sintering at a programmed temperature. In this process, Li2CO3And NiCO3Decomposition to Li at high temperature2O, NiO and CO2CO escaping from the core2Leaving pores in the outer shell structure and Li2O reacts with NiO to generate LiNiO2. Outer layer of lithium source and NixCoyMnz(OH)2Reaction to produce LiNixCoyMnzO2Thereby preparing the high-nickel ternary cathode material with a hollow porous structure.
Compared with the prior art, the invention has the following advantages:
(1) the prepared hollow porous ternary cathode material has the advantages that the reserved space and pores in the center of the material can reduce Li+The volume strain in the de-intercalation process improves the cycle stability of the lithium battery. In addition, CO escaping from the core2Specific Li is formed on the shell structure+And the migration channel is beneficial to improving the rate capability of the lithium battery.
(2) The invention uses Li2CO3The ternary cathode material is prepared by the primary seed crystal, so that the volatilization loss of lithium in the sintering process can be reduced, and Ni is inhibited2+The phenomenon of mixed arrangement in the lithium layer, on the other hand, the lithium core can reduce the dosage of an external lithium source, thereby reducing the adverse effect caused by excessive surface residual alkali.
Drawings
FIG. 1 is a sectional FESEM image of a ternary cathode material precursor with a multilayer core-shell structure prepared in example 1;
fig. 2 is a 1C cycle performance curve of the high nickel ternary positive electrode material prepared in example 1 of the present invention.
Detailed Description
The present invention will now be described in detail with reference to the drawings, which are given by way of illustration and explanation only and should not be construed to limit the scope of the present invention in any way. Furthermore, features from embodiments in this document and from different embodiments may be combined accordingly by a person skilled in the art from the description in this document.
Example 1
The embodiment comprises the following steps:
(1) mixing Li with the particle size of 500 nm2CO3Adding into a seed crystal reactor, wherein the solid content is 50 g/L, and then introducing NiSO with the concentration of 300 g/L4∙6H2O, using a microporous filter having a filter opening of 1 μm to obtain Li having a particle size of about 1 μm2CO3/NiCO3Secondary seed crystals;
(2) mixing NiSO4∙6H2O、CoSO4∙7H2O、MnSO4∙H2Mixing O according to a molar ratio of 7:2:1, dissolving in deionized water, and preparing a mixed salt solution with a total concentration of 120 g/L;
(3) introducing half-kettle hot water into the reaction kettle and introducing NH into the reaction kettle under the conditions that the temperature and the rotating speed are 60 ℃ and 500 rpm respectively3·H2O, keeping the concentration of ammonia in the reaction kettle at about 8 g/L, and adjusting the pH of the solution in the reaction kettle to 11.70 by using NaOH solution;
(4) introducing the mixed salt solution and the secondary seed crystal into a reaction kettle at the speed of 20L/h and 6.5 mL/min respectively at the same time, and carrying out coprecipitation reaction;
(5) when the material D50 in the reaction kettle reached 3.7 μm, the feeding was stopped. Washing and drying the product to obtain the single crystal type high nickel ternary precursor Li with the multilayer core-shell structure2CO3/NiCO3/NCM；
(6) Mixing the precursor with LiOH ∙ H2O is added into the mixture in a molar ratio of 1: 0.89 mixing, and sintering at 700 deg.C for 6 hr in oxygen atmosphere at programmed temperatureAnd (3) crushing, grinding and sieving at the temperature of 800 ℃ for 8 h to obtain the high-nickel ternary cathode material.
FIG. 1 is a sectional FESEM image of the high nickel ternary precursor material prepared in example 1, wherein the precursor material is divided into 3 layers, and the innermost layer is arranged in a disordered and compact manner and has irregular pores; the outer layer is NiCO3Growing a layer on Li2CO3/NiCO3Obvious growth stacking gaps can be observed on the interface; the outermost layer is a dense and orderly-grown NCM layer.
Fig. 2 is a 1C cycle performance curve of the ternary cathode material prepared in example 1, and it can be seen from the graph that after 100 cycles and 200 cycles, the capacity retention rates of the samples are respectively above 95% and 70%, indicating that the ternary cathode material has good cycle performance.
Example 2
The embodiment comprises the following steps:
(1) mixing Li with the particle size of 500 nm2CO3Adding into a seed crystal reactor with solid content of 50 g/L, and introducing Ni (NO) with concentration of 400 g/L3)2∙6H2O, using a microporous filter having a filter opening of 1 μm to obtain Li having a particle size of about 1 μm2CO3/NiCO3Secondary seed crystals;
(2) mixing Ni (NO)3)2∙6H2O、Co(NO3)2∙6H2O、Mn(NO3)2∙4H2Mixing and dissolving O in deionized water according to the molar ratio of 7:1:2 to prepare a mixed salt solution with the total concentration of 120 g/L;
(3) introducing half-kettle hot water into the reaction kettle and introducing NH into the reaction kettle under the conditions that the temperature and the rotating speed are 60 ℃ and 600rpm respectively4HCO3The ammonia concentration in the reaction kettle is kept at about 8.5 g/L, and Na is used2CO3The solution adjusts the pH value of the solution in the reaction kettle to 11.50;
(4) introducing the mixed salt solution and the secondary seed crystal into a reaction kettle at the speed of 30L/h and 8.0 mL/min respectively at the same time, and carrying out coprecipitation reaction;
(5) when the material D50 in the reaction kettle is detected to reach 4.0 μm,the feed was stopped. Washing and drying the product to obtain the single crystal type high nickel ternary precursor Li with the multilayer core-shell structure2CO3/NiCO3/NCM；
(6) Mixing the precursor with LiOH ∙ H2O is added into the mixture in a molar ratio of 1: 0.87, performing temperature programmed sintering in an oxygen atmosphere, wherein the first-stage sintering temperature is 750 ℃, the time is 5 hours, the second-stage sintering temperature is 850 ℃, the time is 7 hours, and crushing, grinding and sieving are performed to obtain the high-nickel ternary cathode material.
Example 3
The embodiment comprises the following steps:
(1) mixing Li with the particle size of 500 nm2CO3Adding into a seed crystal reactor with solid content of 70 g/L, and introducing NiCl with concentration of 500 g/L2∙6H2O, using a microporous filter having a filter opening of 1 μm to obtain Li having a particle size of about 1 μm2CO3/NiCO3Secondary seed crystals;
(2) mixing NiCl2∙6H2O、CoCl2∙6H2O、MnCl2∙6H2Mixing and dissolving O in deionized water according to the molar ratio of 8:1:1 to prepare a mixed salt solution with the total concentration of 120 g/L;
(3) introducing half-kettle hot water into the reaction kettle at the temperature and the rotating speed of 60 ℃ and 650 rpm respectively, and introducing NH3·H2O to keep the ammonia concentration in the reaction kettle at about 8.5 g/L, and Na is used2CO3The solution adjusts the pH value of the solution in the reaction kettle to 11.60;
(4) introducing the mixed salt solution and the secondary seed crystal into a reaction kettle at the speed of 40L/h and 10 mL/min respectively at the same time, and carrying out coprecipitation reaction;
(5) when the material D50 in the reaction kettle reached 3.9 μm, the feeding was stopped. Washing and drying the product to obtain the single crystal type high nickel ternary precursor Li with the multilayer core-shell structure2CO3/NiCO3/NCM；
(6) Mixing the precursor with LiOH ∙ H2O is added into the mixture in a molar ratio of 1: 0.83 mixing, and sintering at 800 deg.C for a certain time in oxygen atmosphereAnd 4 h, the second-stage sintering temperature is 900 ℃, the time is 6 h, and the high-nickel ternary cathode material is obtained after crushing, grinding and sieving.
Example 4
The embodiment comprises the following steps:
(1) mixing Li with the particle size of 500 nm2CO3Adding into a seed crystal reactor with solid content of 80g/L, and introducing Ni (CH) with concentration of 600 g/L3COO)2∙4H2O, using a microporous filter having a filter opening of 1 μm to obtain Li having a particle size of about 1 μm2CO3/NiCO3Secondary seed crystals;
(2) mixing Ni (CH)3COO)2∙4H2O、Co(CH3COO)2∙4H2O、Mn(CH3COO)2∙4H2Mixing O according to a molar ratio of 7:2:1, dissolving in deionized water, and preparing a mixed salt solution with a total concentration of 120 g/L;
(3) introducing half-kettle hot water into the reaction kettle and introducing NH into the reaction kettle under the conditions that the temperature and the rotating speed are 60 ℃ and 600rpm respectively4HCO3The ammonia concentration in the reaction kettle is kept at about 8 g/L, and the pH value of the solution in the reaction kettle is adjusted to 11.80 by NaOH solution;
(4) introducing the mixed salt solution and the secondary seed crystal into a reaction kettle at the speed of 30L/h and 8 mL/min respectively at the same time, and carrying out coprecipitation reaction;
(5) when the material D50 in the reaction kettle reached 4.2 μm, the feeding was stopped. Washing and drying the product to obtain the single crystal type high nickel ternary precursor Li with the multilayer core-shell structure2CO3/NiCO3/NCM；
(6) Mixing the precursor with LiOH ∙ H2O is added into the mixture in a molar ratio of 1: 0.81, performing temperature programmed sintering in an oxygen atmosphere, wherein the first-stage sintering temperature is 750 ℃, the time is 6 hours, the second-stage sintering temperature is 900 ℃, the time is 8 hours, and crushing, grinding and sieving are performed to obtain the high-nickel ternary cathode material.
Example 5
The embodiment comprises the following steps:
(1) mixing Li with the particle size of 500 nm2CO3Adding into a seed crystal reactor, wherein the solid content is 50 g/L, and then introducing NiSO with the concentration of 300 g/L4∙6H2O, using a microporous filter having a filter opening of 1 μm to obtain Li having a particle size of about 1 μm2CO3/NiCO3Secondary seed crystals;
(2) mixing NiSO4∙6H2O、CoSO4∙7H2O、MnSO4∙H2Mixing and dissolving O in deionized water according to a molar ratio of 9:0.5:0.5, and preparing a mixed salt solution with the total concentration of 120 g/L;
(3) introducing half-kettle hot water into the reaction kettle at the temperature and the rotating speed of 60 ℃ and 650 rpm respectively, and introducing NH3·H2O, keeping the concentration of ammonia in the reaction kettle at about 8 g/L, and adjusting the pH of the solution in the reaction kettle to 11.70 by using NaOH solution;
(4) introducing the mixed salt solution and the secondary seed crystal into a reaction kettle at the speed of 35L/h and 9 mL/min respectively at the same time, and carrying out coprecipitation reaction;
(5) when the material D50 in the reaction kettle reached 4.1 μm, the feeding was stopped. Washing and drying the product to obtain the single crystal type high nickel ternary precursor Li with the multilayer core-shell structure2CO3/NiCO3/NCM；
(6) Mixing the precursor with LiOH ∙ H2O is added into the mixture in a molar ratio of 1: 0.85, performing temperature programmed sintering in an oxygen atmosphere, wherein the first-stage sintering temperature is 750 ℃, the time is 6 hours, the second-stage sintering temperature is 850 ℃, the time is 9 hours, and crushing, grinding and sieving are performed to obtain the high-nickel ternary cathode material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A high-nickel ternary precursor is characterized in that the high-nickel ternary precursor is Li2CO3/NiCO3the/NCM multilayer core-shell structure has an innermost layer of Li with the radius of about 400-600 nm2CO3A core, a second layer of NiCO with a thickness of about 400-600 nm3A third layer of Ni with a thickness of about 2.5 to 3.5 μmxCoyMnz(OH)2A layer, wherein x ≧ 0.7, x + y + z = 1; the primary particles are in the form of elongated needles or flakes.
2. A method of preparing the high-nickel ternary precursor of claim 1, comprising the steps of:
(1) mixing nano-grade Li2CO3Adding the crystal seed as a primary crystal seed into a crystal seed reactor, adding soluble Ni salt, reacting for a period of time, and filtering by using a microporous filter to obtain Li2CO3/NiCO3Secondary seed crystals;
(2) mixing and dissolving soluble Ni salt, Co salt and Mn salt according to a certain molar ratio to obtain a mixed salt solution;
(3) adding hot water into a reaction kettle at a certain temperature and a certain rotating speed, continuously adding a complexing agent and a precipitating agent with a certain concentration, and maintaining the ammonia concentration and the pH value of the solution in the reaction kettle;
(4) mixing Li2CO3/NiCO3Simultaneously adding the secondary seed crystal and the mixed salt solution into a reaction kettle for coprecipitation reaction;
(5) after the reaction is stopped, filtering, washing and drying the product to obtain the high-nickel ternary precursor Li with the multilayer core-shell structure2CO3/NiCO3/NCM。
3. The method of claim 2, wherein the nano Li in step (1)2CO3The particle size of the particles is 500-600 nm, and the dosage is 50-80 g/L.
4. The method of claim 2, wherein the Ni salt used in step (1) is NiSO4∙6H2O、Ni(NO3)2∙6H2O、NiCl2∙6H2O、Ni(CH3COO)2∙4H2At least one of O.
5. The method according to claim 2 or 4, wherein in the step (1), the soluble Ni salt is added in an amount calculated as Ni and Li2CO3The molar ratio of (A) to (B) is 0.8 to 1.2.
6. The method of claim 2, wherein the Li produced in step (1)2CO3/NiCO3The grain size of the secondary seed crystal is 1-2 μm.
7. The method of claim 2, wherein the total amount of mixed salt in step (2) is 120 ± 5 g/L; the complexing agent in the step (3) is at least one of ammonia water and ammonium bicarbonate, the concentration of the complexing agent is 7.5-10 mol/L, and the concentration of ammonia in the reaction kettle is 8.0-8.5 g/L; in the step (3), the precipitator is one of sodium hydroxide and sodium carbonate, the concentration of the precipitator is 8-12 mol/L, and the pH value of the solution in the reaction kettle is 11.50-11.80; the flow rate of the mixed salt solution in the step (4) is 20-40L/h, and the flow rate of the added secondary seed crystal is 6.5-10 mL/min.
8. The method according to claim 2, wherein the ternary precursor obtained in step (5) has an average particle diameter D50 of 3.7 to 4.3 μm.
9. A hollow porous high-nickel ternary cathode material is characterized by having the following structure: the innermost layer is a hollow layer; a little bit of outer layer is LiNiO2A layer having a plurality of irregular voids therein; the outermost layer is LiNixCoyMnzO2(ii) a High nickel ternary precursor Li, prepared by the method of claim 1 or any of claims 2 to 82CO3/NiCO3the/NCM is mixed with a certain amount of lithium source, sintered, ground and sieved to obtain the lithium ion battery.
10. The hollow porous high-nickel ternary positive electrode material of claim 9, wherein the sintering is a two-stage sintering process: under the pure oxygen atmosphere, the first sintering temperature is 750-850 ℃, and the time is 4-8 h; the second sintering temperature is 750-950 ℃, and the time is 6-10 h.
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