CN114988490B - Lithium ion battery anode material precursor and preparation method and application thereof - Google Patents
Lithium ion battery anode material precursor and preparation method and application thereof Download PDFInfo
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- CN114988490B CN114988490B CN202110225441.1A CN202110225441A CN114988490B CN 114988490 B CN114988490 B CN 114988490B CN 202110225441 A CN202110225441 A CN 202110225441A CN 114988490 B CN114988490 B CN 114988490B
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- 239000002243 precursor Substances 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 239000010405 anode material Substances 0.000 title abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 88
- 239000002184 metal Substances 0.000 claims abstract description 87
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000011572 manganese Substances 0.000 claims abstract description 42
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 34
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 34
- 239000010941 cobalt Substances 0.000 claims abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 32
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 10
- 239000010955 niobium Substances 0.000 claims abstract description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 309
- 239000000243 solution Substances 0.000 claims description 113
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 84
- 239000002245 particle Substances 0.000 claims description 73
- 239000012266 salt solution Substances 0.000 claims description 70
- 239000007791 liquid phase Substances 0.000 claims description 65
- 239000003513 alkali Substances 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 239000002002 slurry Substances 0.000 claims description 50
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 49
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 49
- 239000013078 crystal Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 44
- 239000002585 base Substances 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 33
- 238000002441 X-ray diffraction Methods 0.000 claims description 21
- 238000000975 co-precipitation Methods 0.000 claims description 13
- 239000013067 intermediate product Substances 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 238000001228 spectrum Methods 0.000 claims description 5
- 239000010406 cathode material Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 abstract description 15
- 239000011163 secondary particle Substances 0.000 abstract description 12
- 239000011164 primary particle Substances 0.000 abstract description 11
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 62
- 238000010517 secondary reaction Methods 0.000 description 44
- 238000005406 washing Methods 0.000 description 36
- 238000003756 stirring Methods 0.000 description 32
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- 238000011049 filling Methods 0.000 description 28
- 238000004519 manufacturing process Methods 0.000 description 27
- 238000001035 drying Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 5
- 241000080590 Niso Species 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- 150000002696 manganese Chemical class 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005169 Debye-Scherrer Methods 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
- 229910017698 Ni 1-x-y Co Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- 229910015150 Ni1/3Co1/3Mn1/3(OH)2 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 102220200885 rs141929755 Human genes 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- -1 tap density Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- 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
- C01P2006/11—Powder tap density
-
- 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
-
- 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 relates to a lithium ion battery anode material precursor, a preparation method and application thereof. Wherein the precursor has a schematic chemical composition represented by the formula "first metal hydroxide-second metal hydroxide" or the formula "first metal hydroxide-second metal hydroxide-water"; the first metal is nickel, cobalt and manganese, wherein the content of nickel is 30-94%, the content of cobalt is 3-35% and the content of manganese is 3-35% based on the total mole amount of the first metal being 100%; the second metal is one or more of magnesium, aluminum, titanium, niobium, tungsten, zirconium and yttrium, and the total content of the second metal is 0 to 3 percent based on the total mole amount of the first metal being 100 percent. The precursor product of the invention has narrow secondary particle size distribution and high arrangement order of primary particles. The preparation method is simple and effective, and is easy for large-scale industrial production.
Description
Technical Field
The invention relates to a lithium ion battery anode material precursor, a preparation method and application thereof.
Background
The NCM ternary material (nickel cobalt lithium manganate containing or not containing doped metal) has the advantages of high energy density and long cycle life, and has been widely applied to the fields of consumer electronics, electric bicycles, electric automobiles and the like.
The production process of the NCM ternary material generally comprises two parts, namely a wet coprecipitation reaction for synthesizing an NCM precursor (nickel cobalt manganese hydroxide containing or not containing doped metal) and a pyrogenic high-temperature solid phase reaction for synthesizing the NCM ternary material. The physical and chemical properties of the NCM ternary material, such as particle morphology, the size and distribution of secondary particles, the size and distribution of primary particles, tap density, chemical composition and the like, are closely related to the properties of the NCM precursor. The more uniform the particle size of the NCM precursor secondary particles and primary particles, the higher the arrangement order degree of the primary particles (i.e. the smaller FWHM (101)) is, the higher the chemical composition and crystal structure consistency among the secondary particles is during high-temperature solid phase synthesis, and the higher the crystal structure consistency of single secondary particles from inside to outside is, so that the better the electrochemical performance of the NCM ternary material is. In the manufacturing method of NCM precursor, the batch method has low production efficiency, and is especially not suitable for manufacturing products with large particle size; therefore, a single-kettle continuous method for controlling crystallization coprecipitation is mainly adopted in industry, and the continuous method has high production efficiency, but the product has more fine particles, loose particles on the surface and particles with poor development degree, the particle size distribution is wider, the diameter distance (K90= (D90-D10)/D50) is generally larger than 1.3, and the urgent requirement of the field for prolonging the service life of the power battery for the electric automobile cannot be met.
There are a large number of documents disclosing the manufacturing techniques of NCM precursors, but none of these techniques solves the contradiction between production efficiency and product quality well, nor does it disclose products having both narrow secondary particle size distribution and ordered primary particle arrangement. For example, CN 111252815A discloses a preparation method and a preparation system of a precursor of a positive electrode material of a lithium ion battery, which are physically classified by a cyclone classifier to produce a precursor with narrow particle size distribution, but the physical method is difficult to completely remove small particle products, and is more incapable of a product with a medium particle size D50 of less than 5 microns, and the document does not consider the arrangement order of primary particles. As another example, CN 108598441A discloses a ternary precursor with different particle size distributions and a preparation method thereof, in order to achieve the purposes of narrow particle size distribution and high tap density of secondary particles, in the implementation process, as the reaction stage number increases, the ammonia concentration of the system increases, the pH value decreases, the feeding speed increases in multiples, and the solid content of a single kettle also gradually increases; however, this document does not disclose data on the particle size distribution of the secondary particles, nor does it consider the order of arrangement of the primary particles.
In view of the great market potential and commercial value of NCM ternary materials, there is an urgent need in the art for efficient manufacturing techniques that provide better performing precursors.
The information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and may include information that is not already known to those of ordinary skill in the art.
Disclosure of Invention
The first object of the present invention is to provide a method for preparing a precursor of a positive electrode material of a lithium ion battery, which can more effectively control the quality of the product. A second object of the present invention is to overcome the contradiction between production efficiency and product quality on the basis of achieving the first object. A third object of the present invention is to provide a precursor for a positive electrode material of a lithium ion battery having better quality, in addition to achieving the aforementioned object.
In order to achieve the above object, the present invention provides the following technical solutions.
1. A method for preparing a precursor of a positive electrode material of a lithium ion battery, wherein the precursor has a schematic chemical composition represented by a formula of 'first metal hydroxide and second metal hydroxide' or a formula of 'first metal hydroxide and second metal hydroxide and water'; the first metal is nickel, cobalt and manganese, wherein the content of nickel is 30-94%, the content of cobalt is 3-35% and the content of manganese is 3-35% based on the total mole amount of the first metal being 100%; the second metal is one or more of magnesium, aluminum, titanium, niobium, tungsten, zirconium and yttrium, and the total content of the second metal is 0-3% based on 100% of the total mole of the first metal;
The method comprises the following steps:
(1) Providing a reaction base solution containing seed crystals, wherein the medium granularity of the seed crystals is 2-3 mu m;
(2) Adding a salt solution, an alkali solution and ammonia water into the reaction base solution, wherein the liquid phase volume is increased by 2-5 times as one stage; adding a salt solution at a constant speed in each stage, wherein the adding time is 10-20 hours; in this step, the pH value of the liquid phase and the NH of the liquid phase are maintained 3 The concentration is stable; no overflow operation is included in this step.
2. The process according to 1, wherein the pH of the liquid phase is from 11.2 to 11.85, preferably from 11.2 to 11.8.
3. The process according to any of the preceding claims, characterized in that the reaction temperature is 50 ℃ to 70 ℃.
4. A method according to any one of the preceding claims, characterized in that the liquid phase NH 3 The concentration is 2g/L to 8g/L.
5. The method according to any one of the preceding claims, characterized in that the solid content of the liquid phase is 80g/L to 140g/L.
6. The method according to any one of the above, characterized in that the alkali solution is an aqueous sodium hydroxide solution, and the molar concentration thereof is preferably 5mol/L to 10mol/L.
7. The method according to any one of the above, characterized in that the mass fraction of the aqueous ammonia is 15% to 25%.
8. The method according to any of the foregoing, characterized in that the salt solution is an aqueous solution of a nickel salt, a cobalt salt, a manganese salt and optionally a second metal salt, the total molar concentration of metal ions of the salt solution preferably being 1.5mol/L to 2.5mol/L.
9. A method according to any one of the preceding claims, characterized in that the seed crystal is prepared by the following method: providing a reaction base solution, and adding a salt solution, an alkali solution and ammonia water into the reaction base solution until the volume of a liquid phase is 3-5 times of the volume of the reaction base solution; in the step, adding a salt solution at a constant speed for 10-20 hours; in this step, NH 3 The concentration is 2 g/L-8 g/L, the pH value is 11.7-11.9, and the reaction temperature is 50-70 ℃.
10. A method according to any of the preceding claims, characterized in that step (2) is one, two, three, four or five stages.
11. The method according to any one of the above, characterized in that in the step (2), the particle size in the crystals at the end of the first stage is 4 μm to 6 μm, the particle size in the crystals at the end of the second stage is 6 μm to 9 μm, the particle size in the crystals at the end of the third stage is 9 μm to 11 μm, the particle size in the crystals at the end of the fourth stage is 13 μm to 16 μm, and the particle size in the crystals at the end of the fifth stage is 16 μm to 19 μm.
12. A method according to any of the preceding claims, characterized in that the range of variation of the half-width of the diffraction peak of the 101 crystal plane in XRD analysis of the product and intermediate product is less than 0.05 °, preferably less than 0.03 °.
13. A method according to any of the preceding claims, characterized in that the fluctuation range of the ratio I (101)/I (001) in XRD analysis of the product and its intermediate product is less than 0.1, preferably less than 0.05.
14. A method according to any of the preceding claims, characterized by the presence or absence of an ageing operation.
15. A method for preparing a precursor of a positive electrode material of a lithium ion battery, wherein the precursor has a schematic chemical composition represented by a formula of 'first metal hydroxide and second metal hydroxide' or a formula of 'first metal hydroxide and second metal hydroxide and water'; the first metal is nickel, cobalt and manganese, wherein the content of nickel is 30-94%, the content of cobalt is 3-35% and the content of manganese is 3-35% based on the total mole amount of the first metal being 100%; the second metal is one or more of magnesium, aluminum, titanium, niobium, tungsten, zirconium and yttrium, and the total content of the second metal is 0 to 3 percent based on 100 percent of the total mole of the first metal;
the method is a secondary, tertiary, quaternary, penta-or hexa-stage reaction comprising:
(1) Adding water accounting for 20-30% of the volume of the primary reaction kettle as base solution, and adding ammonia water and sodium hydroxide to make NH of the base solution 3 The concentration is adjusted to 2 g/L-8 g/L, and the pH value is adjusted to 11.7-11.9; adding a salt solution into a primary reaction kettle at a constant speed under an inert atmosphere, wherein the time for increasing the volume of a liquid phase to more than 80% of the volume of the primary reaction kettle is 10-20 h; the reaction temperature is 50-70 ℃; maintaining the pH value of the liquid phase and the NH of the liquid phase 3 The concentration is stable; obtaining seed crystal with the medium granularity D50 of 2-3 mu m;
(2) Uniformly dividing the slurry obtained from the previous-stage reaction kettle into reaction base solution of the next-stage reaction kettle, wherein the volume of the slurry of the previous-stage reaction kettle is 20% -30% of that of the next-stage reaction kettle; liquid phase NH 3 The concentration of (2) to (8) g/L, and the pH value of the liquid phase is 11.2 to 11.85 (preferably 11.2 to 11.8); adding the salt solution into the next-stage reaction kettle at a constant speed, wherein the time for increasing the volume of the liquid phase to more than 80% of the volume of the reaction kettle is 10-20 h; the reaction temperature is 50-70 ℃; maintaining the pH value of the liquid phase and the NH of the liquid phase 3 Concentration ofStabilizing; no overflow operation is included in this step.
16. The method according to 15, wherein the number of the reaction kettles at the next stage is 3 to 5 times the number of the reaction kettles at the previous stage.
17. A lithium ion battery cathode material precursor, characterized by being prepared by any one of the methods.
18. A lithium ion battery cathode material precursor, characterized in that the precursor has a schematic chemical composition represented by the formula "first metal hydroxide-second metal hydroxide" or the formula "first metal hydroxide-second metal hydroxide-water"; the first metal is nickel, cobalt and manganese, wherein the content of nickel is 30-94%, the content of cobalt is 3-35% and the content of manganese is 3-35% based on the total mole amount of the first metal being 100%; the second metal is one or more of magnesium, aluminum, titanium, niobium, tungsten, zirconium and yttrium, and the total content of the second metal is 0 to 3 percent based on 100 percent of the total mole of the first metal; the particle diameter distance of the precursor is less than 0.8; in the X-ray diffraction spectrum of the precursor, the half-peak width of the diffraction peak of the 101 crystal face is 0.45-0.75 degrees.
19. The precursor according to any one of the preceding claims, characterized in that the nickel content is 40 to 90%, the cobalt content is 5 to 30%, and the manganese content is 5 to 30% based on 100% of the total molar amount of the first metal.
20. Precursor according to any of the preceding claims, characterized in that the total content of the second metal is 0 to 1% based on 100% of the total molar amount of the first metal.
21. The precursor according to any of the foregoing, characterized in that the precursor has a median particle size of 4 μm to 6 μm, 6 μm to 9 μm, 9 μm to 11 μm, 13 μm to 16 μm or 16 μm to 19 μm.
22. Precursor according to any of the preceding claims, characterized in that the half-width fluctuation range of the diffraction peak of the 101 crystal plane in XRD analysis of the precursor and its intermediate product is less than 0.05 °, preferably less than 0.03 °.
23. Precursor according to any of the preceding claims, characterized in that the fluctuation range of the ratio I (101)/I (001) in XRD analysis of the precursor and its intermediate product is less than 0.1, preferably less than 0.05.
24. Precursor according to any of the preceding claims, characterized in that the second metal is magnesium and/or aluminum.
25. The precursor according to any one of the preceding claims, wherein the precursor has a tap density of 1.2g/cm 3 ～2.5g/cm 3 。
26. A lithium ion battery positive electrode material, characterized in that it is prepared from any one of the aforementioned precursors.
27. A lithium ion battery, wherein the positive electrode material of 26 is used.
28. The production device for manufacturing the lithium ion battery anode material precursor is characterized by being provided with more than two stages of reaction kettles, wherein a material outlet of a previous stage reaction kettle is connected with a material inlet of a next stage reaction kettle, and the effective volume of the next stage reaction kettle is 3-5 times of that of the previous stage reaction kettle.
29. The production device according to any one of the preceding claims, characterized in that the device is provided with a secondary, tertiary, quaternary, penta-or hexa-stage reaction vessel.
30. The production device according to any one of the above, wherein the effective volumes of the three or more reaction kettles are the same, and the stirring is the same, and the effective volumes are preferably 5m 3 ～20m 3 。
The NCM precursor has a plurality of control variables in the production process, the interweaving influence of each factor is very complex, and the synergy of all key factors and each variable is difficult to grasp; thus, although there are a number of literature disclosures describing the manufacture of NCM precursors, they employ varying control methods and parameters, so far no literature exists that can efficiently produce better performing products. The inventor has found the aforementioned technical solution through diligent research, thereby satisfying the urgent need set forth in the prior art.
Compared with the prior art, the invention can realize the following beneficial technical effects.
1. The invention conveniently realizes better control of the product quality by adjusting the adding rate of the salt solution in proper time and in proper quantity.
2. According to the invention, the slurry of the upper-stage reaction kettle is evenly distributed to more lower-stage reaction kettles to serve as base solution, so that the product quality is stably controlled, and the production efficiency is greatly improved.
3. The invention can be flexibly adjusted to produce products with various granularity standards.
4. The control method is simple and more effective, is not easy to generate waste, and is easier for large-scale industrial production.
5. In the product of the invention, the uniformity of the secondary particle size distribution is good, and the secondary particle size distribution is shown by small diameter distance K90; and simultaneously, the structural uniformity from the core to the surface of the secondary particles is higher, and the FWHM (101) and the ratio of I (101)/I (001) are more consistent in the XRD pattern.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a scanning electron microscope image of an NCM811-OH precursor prepared by the first order reaction in example 1;
FIG. 2 is a scanning electron microscope image of the NCM811-OH precursor prepared by the second-stage reaction in example 1;
FIG. 3 is a scanning electron microscope image of the NCM811-OH precursor prepared by the five-stage reaction of example 1;
FIG. 4 is a scanning electron microscope image of the NCM811-OH precursor prepared by the four-stage reaction of example 2;
FIG. 5 is a scanning electron microscope image of the NCM811-OH precursor prepared by the second stage reaction of example 4;
FIG. 6 is an X-ray crystallography chart of the NCM811-OH precursor obtained in examples 1-4.
Detailed Description
The invention is described in detail below in connection with the embodiments, but it should be noted that the scope of the invention is not limited by these embodiments and the principle explanation, but is defined by the claims.
In the present invention, any matters or matters not mentioned are directly applicable to those known in the art without modification except for those explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all considered as part of the original disclosure or description of the present invention, and should not be considered as new matters not disclosed or contemplated herein unless such combination would obviously be unreasonable to one skilled in the art.
All of the features disclosed in this invention may be combined in any combination which is known or described in the present invention and should be interpreted as specifically disclosed and described in the present invention unless the combination is obviously unreasonable by those skilled in the art. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the embodiments but also the end points of each numerical range in the specification, and any combination of these numerical points should be considered as a disclosed or described range of the present invention.
Technical and scientific terms used in the present invention are defined to have their meanings, and are not defined to have their ordinary meanings in the art.
Unless otherwise indicated, numerical ranges defined in the present invention include the endpoints of the numerical ranges.
The "inert gas" in the present invention refers to a gas that does not have any appreciable effect on the properties of the precursor product in the preparation process of the present invention.
In the present invention, increasing n-fold means n-fold more than before, i.e., the result becomes n+1-fold before.
In the present invention, the solid content refers to the mass of the solid remaining after the precursor slurry having a volume of 1L is dried.
Unless otherwise indicated, the reference to the volume of the reactor in this invention refers to the effective volume of the reactor.
In the invention, FWHM (101) refers to the half-width of a diffraction peak of a 101 crystal face in an X-ray diffraction pattern, and the half-width of the diffraction peak is obtained by fitting calculation of an XRD pattern by using MDI Jade 6 software.
In the present invention, the diameter k90= (D90-D10)/D50, where D10 means a particle size corresponding to a cumulative particle size distribution percentage of 10%, D50 means a particle size corresponding to a cumulative particle size distribution percentage of 50%, also called medium particle size, and D90 means a particle size corresponding to a cumulative particle size distribution percentage of 90%.
In the present invention, the fluctuation range of a parameter or index means the difference between the maximum value and the minimum value of the parameter or index.
In the present invention, the ratio of I (101)/I (001) refers to the ratio of the peak area of the characteristic peak of the 101 crystal plane to the peak area of the characteristic peak of the 001 crystal plane in XRD analysis.
The invention provides a preparation method of a lithium ion battery anode material precursor, which has a schematic chemical composition represented by a formula of first metal hydroxide and second metal hydroxide or a formula of first metal hydroxide and second metal hydroxide and water; the first metal is nickel, cobalt and manganese, wherein the content of nickel is 30-94%, the content of cobalt is 3-35% and the content of manganese is 3-35% based on the total mole amount of the first metal being 100%; the second metal is one or more of magnesium, aluminum, titanium, niobium, tungsten, zirconium and yttrium, and the total content of the second metal is 0 to 3 percent based on 100 percent of the total mole of the first metal;
The method comprises the following steps:
(1) Providing a reaction base solution containing seed crystals, wherein the medium granularity of the seed crystals is 2-3 mu m;
(2) Adding a salt solution, an alkali solution and ammonia water into the reaction base solution, wherein the liquid phase volume is increased by 2-5 times as one stage; adding a salt solution at a constant speed in each stage, wherein the adding time is 10-20 hours; in this step, the pH value of the liquid phase and the NH of the liquid phase are maintained 3 Concentration; no overflow operation is included in this step.
It will be appreciated that the precursor is an NCM precursor, the chemical composition of which is schematically expressed by the formula "first metal hydroxide-second metal hydroxide" or by the formula "first metal hydroxide-second metal hydroxide-water".
According to the preparation method of the invention, the first metal in the precursor is nickel, cobalt and manganese, and the molar total amount of the first metal is 100 percent,30-94% of nickel, 3-35% of cobalt and 3-35% of manganese; the second metal is one or more of magnesium, aluminum, titanium, niobium, tungsten, zirconium and yttrium, and the total content of the second metal is 0-3 percent based on the total mole of the first metal as 100 percent. Preferably, the nickel content is 30% -90%, the cobalt content is 5% -30% and the manganese content is 5% -30% based on 100% of the total mole amount of the first metal; the total content of the second metal is 0 to 1% based on 100% of the total molar amount of the first metal. When the total content of the second metal is 0, the anhydrous chemical composition of the precursor can be used as "Ni 1-x- y Co x Mn y (OH) 2 "representative.
It is known in the art that sometimes (especially immediately after synthesis) the precursor contains some amount of moisture, and may have a schematic chemical composition represented by "first metal hydroxide, second metal hydroxide, water"; after removal of the moisture by drying, a schematic chemical composition represented by the formula "first metal hydroxide-second metal hydroxide" can be obtained. Since the presence of this moisture does not substantially affect the performance and characterization of the precursor, the present invention recognizes that it is not necessary to limit the amount of this moisture.
According to the preparation method of the present invention, a person skilled in the art can select appropriate raw materials and proportions thereof according to the chemical composition of the precursor, and use any known method to manufacture the seed crystal of step (1).
The present invention provides a preferred mode of manufacturing the seed crystal of step (1), comprising: providing a reaction base solution, and adding a salt solution, an alkali solution and ammonia water into the reaction base solution until the volume of a liquid phase is 3-5 times of the volume of the reaction base solution; in the step, adding a salt solution at a constant speed for 10-20 hours; in this step, NH 3 The concentration is 2 g/L-8 g/L, the pH value is 11.7-11.9, and the reaction temperature is 50-70 ℃.
According to the preparation method of the present invention, the salt solution in the step (2) is an aqueous solution of nickel salt, cobalt salt and manganese salt, and optionally a second metal salt. The person skilled in the art can select a suitable ratio between metal ions according to the chemical composition of the precursor, and the total molar concentration of metal ions in the salt solution can be 1.5mol/L to 2.5mol/L. The nickel salt is preferably nickel sulfate or nickel chloride, the cobalt salt is preferably cobalt sulfate or cobalt chloride, and the manganese salt is preferably manganese sulfate or manganese chloride.
According to the preparation method of the invention, soluble nickel salt, cobalt salt and manganese salt, and optional soluble second metal salt are dissolved in deionized water to prepare salt solution. The proportion of each metal salt can be selected by one skilled in the art according to the chemical composition of the precursor.
According to the preparation method of the invention, any alkali metal hydroxide can be dissolved in deionized water to prepare an alkali solution. The alkali solution in the step (2) is preferably an aqueous sodium hydroxide solution, and the molar concentration thereof may be 5mol/L to 10mol/L.
According to the preparation method of the invention, in the ammonia water in the step (2), the mass fraction of ammonia can be 15% -25%.
According to the preparation method of the present invention, the reaction temperature in the step (2) may be 50 to 70 ℃. The coprecipitation reaction has small thermal effect and can easily keep the reaction temperature stable. Of course, the present invention can employ any temperature control means including conventional means to reduce fluctuations in reaction temperature, if desired.
According to the preparation method of the invention, in the step (2), the pH value of the liquid phase can be 11.2-11.7 or 11.7-11.85; preferably 11.2 to 11.7 or 11.7 to 11.8. In the reaction process of the invention, the stable pH value of the liquid phase can be ensured generally as long as the adding rate of each material is kept unchanged. Of course, any pH control means, including conventional means, may be employed in the present invention to reduce fluctuations in the pH of the liquid phase, if desired. For example, the liquid phase pH value can be automatically controlled, and the alkali solution flow pump can automatically adjust the flow of the alkali solution according to the set pH value and the feedback value actually measured by the pH meter, so as to keep the stability of the liquid phase pH value of the reaction system.
According to the preparation method of the present invention, in step (2), NH in liquid phase 3 The concentration can be 2g/L to 8g/L. In the reaction process of the invention, the addition rate of each material is kept unchanged, so that the reaction can be ensuredLiquid phase NH 3 The concentration is stable. Of course, any NH may be employed in the present invention, including conventional means, if desired 3 Concentration control means to reduce liquid phase NH 3 Fluctuation of the concentration.
According to the production method of the present invention, in the step (2), the solid content of the liquid phase is 80g/L to 300g/L, preferably 80g/L to 200g/L, more preferably 80g/L to 140g/L. In the reaction process of the invention, only a salt solution is added at a constant speed and the pH value and NH of the liquid phase are maintained 3 The concentration is stable, and the overflow operation is not performed, so that the solid content of the liquid phase is basically unchanged. If the solid content of the liquid phase is more than 200g/L, the uniformity of particle size of the precursor is lowered, and the loss of the reaction equipment is increased; if the solid content of the liquid phase is less than 50g/L, the sphericity and tap density of the precursor are obviously reduced, and the production efficiency is greatly affected.
Preferably, the same salt solution, alkali solution and ammonia water are used in each of the steps of producing seed crystal and step (2); and liquid phase NH 3 The concentration, the salt solution adding time and the reaction temperature are the same; in each stage of the step (2), the pH value of the liquid phase and the solid content of the liquid phase are the same.
According to the preparation method of the present invention, the step (2) may be one, two, three, four or five stages. In the invention, precursor products with different particle sizes can be obtained from different stages. The grain size in the crystals at the end of the first stage is generally from 4 μm to 6. Mu.m. The size of the crystals at the end of the second stage is generally 6 μm to 9. Mu.m. The grain size in the crystals at the end of the third stage is generally 9 μm to 11. Mu.m. The grain size in the crystals at the end of the fourth stage is generally from 13 μm to 16. Mu.m. The grain size in the crystals at the end of the fifth stage is generally 16 μm to 19. Mu.m.
According to the preparation method of the invention, the half-width fluctuation range of the diffraction peak of the 101 crystal face is less than 0.05 DEG, preferably less than 0.03 DEG in XRD analysis of the manufactured product and the intermediate product.
According to the preparation method of the invention, the fluctuation range of the ratio of I (101)/I (001) in XRD analysis of the manufactured product and the intermediate product is less than 0.1, preferably less than 0.05.
According to the preparation method of the invention, there may be or may not be an ageing operation.
The present invention provides a preferred embodiment in the form of a two-, three-, four-, five-, or six-stage reaction comprising:
(1) Adding water accounting for 20-30% of the volume of the primary reaction kettle as base solution, and adding ammonia water and sodium hydroxide to make NH of the base solution 3 The concentration is adjusted to 2 g/L-8 g/L, and the pH value is adjusted to 11.7-11.9; adding a salt solution into a primary reaction kettle at a constant speed under an inert atmosphere, wherein the time for increasing the volume of a liquid phase to more than 80% of the volume of the primary reaction kettle is 10-20 h; the reaction temperature is 50-70 ℃; maintaining the pH value of the liquid phase and the NH of the liquid phase 3 The concentration is stable; obtaining seed crystal with the medium granularity D50 of 2-3 mu m;
(2) Uniformly dividing the slurry obtained from the previous-stage reaction kettle into reaction base solution of the next-stage reaction kettle, wherein the volume of the slurry of the previous-stage reaction kettle is 20% -30% of that of the next-stage reaction kettle; liquid phase NH 3 The concentration of the solution is 2 g/L-8 g/L, and the pH value of the liquid phase is 11.2-11.8; adding the salt solution into the next-stage reaction kettle at a constant speed, wherein the time for increasing the volume of the liquid phase to more than 80% of the volume of the reaction kettle is 10-20 h; the reaction temperature is 50-70 ℃; maintaining the pH value of the liquid phase and the NH of the liquid phase 3 The concentration is stable.
According to a preferred embodiment of the present invention, the number of the next stage reaction tanks is 3 to 5 times the number of the previous stage reaction tanks.
In a preferred embodiment of the present invention, the first-stage reaction corresponds to the aforementioned step of manufacturing seed crystals, and the "second-, third-, fourth-, fifth-and sixth-stage reactions" corresponds to the aforementioned "first, second, third, fourth and fifth stages"; the operating conditions and other features of each stage of reaction may be the same as the corresponding features in the foregoing, and the disclosure will not be repeated.
Preferably, the same salt solution, alkali solution and ammonia water are used in the first-stage to sixth-stage coprecipitation reaction process; and liquid phase NH 3 The concentration, the salt solution adding time and the reaction temperature are the same; second-stage to sixth-stage coprecipitation reactionIn the process, the pH value of the liquid phase and the solid content of the liquid phase are the same.
According to the preparation method provided by the invention, the reaction kettles at each stage can be arranged in a mode of increasing the volume step by step, a mode of increasing the number step by step or a mode of combining the two modes. For example, the reaction tanks of each stage may be provided in the following manner: the volume of the first-stage reaction kettle is 0.5m 3 ～1m 3 The volume of the secondary reaction kettle is 2m 3 ～5m 3 The volume of the three-level to six-level reaction kettle is 5m 3 ～20m 3 . Preferably, the reaction kettles used in the three-level to six-level coprecipitation reaction are the same, and the stirring rotation speeds are the same. The reaction kettles used in the first-stage to sixth-stage coprecipitation reaction can be the same, and the stirring rotation speed is the same.
It is well known in the art that sufficient mixing is required to uniformly disperse the materials in a co-precipitation reaction to produce NCM precursors. The mixing method of the coprecipitation reaction is not particularly limited, and any known mixing method such as mechanical stirring can be used.
The preparation method according to the invention further comprises a separation step of separating the precursor from the liquid phase after the reaction is completed, and a subsequent washing step and drying step. The operation of these steps is well known in the art and may be performed in any manner known in the art. For example, according to the requirement of the granularity of the product, after the reaction in any stage (any one of the two stages to the six stages) is finished, the precursor is separated from the liquid phase of the reaction system by adopting a filtering mode. The solid-liquid separation can be carried out by adopting a filter press, then the washing is carried out by using 1 to 2 mass percent of sodium hydroxide aqueous solution, and then the washing is carried out by using deionized water until the pH value of the washing effluent is less than 9; the drying temperature is generally 100-150 ℃, and the drying time is generally 5-10 h.
According to the preparation method of the present invention, the water may be any water known in the art to be suitable for the manufacture of NCM precursors, preferably deionized water.
According to the preparation method of the present invention, the inert gas may be any gas known in the art to be suitable for the manufacture of NCM precursors, preferably nitrogen.
The invention also provides a precursor prepared by any of the methods described above.
The invention provides a lithium ion battery positive electrode material precursor, which has a schematic chemical composition represented by a formula of first metal hydroxide and second metal hydroxide or a formula of first metal hydroxide and second metal hydroxide and water; the first metal is nickel, cobalt and manganese, wherein the content of nickel is 30-94%, the content of cobalt is 3-35% and the content of manganese is 3-35% based on the total mole amount of the first metal being 100%; the second metal is one or more of magnesium, aluminum, titanium, niobium, tungsten, zirconium and yttrium, and the total content of the second metal is 0 to 3 percent based on 100 percent of the total mole of the first metal; the particle diameter distance of the precursor is less than 0.8; in the X-ray diffraction spectrum of the precursor, the half-peak width of the diffraction peak of the 101 crystal face is 0.45-0.75 degrees.
It will be appreciated that the precursor is an NCM precursor, the chemical composition of which is schematically expressed by the formula "first metal hydroxide-second metal hydroxide" or by the formula "first metal hydroxide-second metal hydroxide-water".
According to the precursor of the invention, the first metal is nickel, cobalt and manganese, and the nickel content is 30-94%, the cobalt content is 3-35% and the manganese content is 3-35% based on the total mole amount of the first metal being 100%; the second metal is one or more of magnesium, aluminum, titanium, niobium, tungsten, zirconium and yttrium, and the total content of the second metal is 0-3 percent based on the total mole of the first metal as 100 percent. Preferably, the nickel content is 30% -90%, the cobalt content is 5% -30% and the manganese content is 5% -30% based on 100% of the total mole amount of the first metal; the total content of the second metal is 0 to 1% based on 100% of the total molar amount of the first metal. When the total content of the second metal is 0, the anhydrous chemical composition of the precursor can be used as "Ni 1-x-y Co x Mn y (OH) 2 "representative.
It is known in the art that sometimes (especially immediately after synthesis) the precursor contains some amount of moisture, and may have a schematic chemical composition represented by "first metal hydroxide, second metal hydroxide, water"; after removal of the moisture by drying, a schematic chemical composition represented by the formula "first metal hydroxide-second metal hydroxide" can be obtained. Since the presence of this moisture does not substantially affect the performance and characterization of the precursor, the present invention recognizes that it is not necessary to limit the amount of this moisture.
According to the precursor of the present invention, the intermediate particle size of the precursor is 4 μm to 6 μm, 6 μm to 9 μm, 9 μm to 11 μm, 13 μm to 16 μm or 16 μm to 19 μm.
According to the precursor of the present invention, the half-width fluctuation range of the diffraction peak of the 101 crystal plane is less than 0.05 DEG, preferably less than 0.03 DEG in XRD analysis of the precursor and an intermediate product thereof.
According to the precursor of the present invention, the fluctuation range of the ratio of I (101)/I (001) in XRD analysis of the precursor and its intermediate product is less than 0.1, preferably less than 0.05.
According to the precursor of the present invention, the second metal is preferably magnesium and/or aluminum.
According to the precursor of the present invention, the tap density of the precursor is 1.2g/cm 3 ～2.5g/cm 3 。
The invention also provides a lithium ion battery anode material which is prepared from any precursor.
The invention also provides a lithium ion battery, which uses the positive electrode material.
The invention also provides a production device for manufacturing the lithium ion battery anode material precursor, which is provided with more than two stages of reaction kettles, wherein the material outlet of the upper stage of reaction kettles is connected with the material inlet of the lower stage of reaction kettles, and the effective volume of the lower stage of reaction kettles is 3-5 times of that of the upper stage of reaction kettles.
The production device according to the invention is preferably provided with a secondary, tertiary, quaternary, penta-or hexa-reactor.
According to the production device of the invention, can adoptThe reaction kettles at each stage are arranged in a mode of increasing the volume step by step, a mode of increasing the number step by step or a mode of combining the two modes. For example, the reaction tanks of each stage may be provided in the following manner: the volume of the first-stage reaction kettle is 0.5m 3 ～1m 3 The volume of the secondary reaction kettle is 2m 3 ～5m 3 The volume of the three-level to six-level reaction kettle is 5m 3 ～20m 3 . Preferably, the three-level to six-level reaction kettles are identical and stirring is identical. The first-level reaction kettle and the sixth-level reaction kettle can be identical and are stirred identically, and when the method is adopted, through pipeline switching, each-level reaction kettle can be flexibly selected from all reaction kettles.
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way.
Reagents, instruments and tests
The starting materials used in the examples were all obtained by commercial routes.
In the examples, the pH of the liquid phase and the NH of the liquid phase 3 The concentration is basically unchanged, the test device is provided with a liquid phase pH value automatic control device, and the liquid phase NH is 3 The concentration was measured once per hour; the liquid phase solids content is very stable.
In the examples, the product loss rate at sieving is small and negligible.
Instrument, method and conditions for analysis of metal element content: an ICP-7500 inductively coupled plasma atomic emission spectrometer of Shimadzu was used.
Apparatus, method and conditions for particle size analysis: mastersizer 2000 laser particle size tester, malvern, uk.
Apparatus, method and conditions for tap density analysis: a BT-300 tap density tester of Dandong Baite instruments Co., ltd; weighing 100g of powder material, loading the powder material into a 100mL three-scale measuring cylinder, and fixing the measuring cylinder on a tap density tester for testing; the test parameters are as follows: the vibration frequency is 300 times/min, the amplitude is 3mm, and the vibration time is 5min.
Apparatus, method and computer program product for XRD analysisConditions are as follows: an X-ray powder diffractometer of us Thermo Fisher Thermo ESCALAB; the sample preparation method comprises the following steps: taking a certain amount of powder sample, placing the powder sample in a groove of a ground glass sheet, and flattening the powder sample by a flat plate; test parameters: by Cu target K α Light source, wavelength λ=0.154 nm, sweep speed 5 °/min, step size 0.04 °, device test power 200kW. The half-width of the 101 diffraction peak and the peak intensity ratio of I (101)/I (001) are obtained by fitting XRD spectra by using MDI Jade 6 software.
Apparatus, methods and conditions for Scanning Electron Microscope (SEM) analysis: and performing morphology observation on the NCM precursor sample by adopting a FEI Quanta 200FEG scanning electron microscope.
Example 1
This example is for the purpose of illustrating Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Synthesis of (NCM 811-OH) precursor.
(1) Preparation of salt solution A and alkali solution B
NiSO is carried out 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O is added into deionized water according to the mole ratio of Ni to Co to Mn=8:1:1 to prepare a salt solution A with the total metal ion concentration of nickel, cobalt and manganese being 2.0 mol/L; dissolving NaOH in deionized water to prepare alkali solution B with the molar concentration of 7.5 mol/L;
(2) Preparation of small particle size NCM811-OH by first order reaction
At an effective volume of 0.5m 3 Adding 100L deionized water as base solution into a first-stage reaction kettle, and adding 18 mass percent of concentrated ammonia water to make NH of the base solution 3 The concentration was adjusted to 4g/L, and the pH of the base solution was adjusted to 11.7 by adding an alkali solution B. At N 2 And under the atmosphere, adding the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18% into a primary reaction kettle in parallel flow at a constant speed. The total time for filling the reaction kettle with the materials is 20 hours by controlling the adding speed of the solution A and the solution B and the ammonia water. Other reaction parameters were: the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 400rpm, and the NH in the liquid phase in the system 3 The concentration of (C) was 4g/L and the pH was 11.7, and the medium particle size D50 of the prepared NCM811-OH was 2.74. Mu.m.
(3) Secondary reaction
Transferring all the slurry containing NCM811-OH in step (2) to an effective volume of 2m 3 The volume of the transferred slurry in the secondary reaction kettle accounts for about 25 percent of the effective volume of the secondary reaction kettle. At N 2 Under the atmosphere, adding a salt solution A, an alkali solution B and ammonia water with mass fraction of 18% into a secondary reaction kettle in parallel flow at a constant speed, wherein the total time for filling the secondary reaction kettle with materials is 20h, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 300rpm, and NH in a system 3 The concentration of (2) was 4g/L, the pH was 11.5, the system solids content was 117g/L, and the medium particle size D50 of the prepared NCM811-OH precursor was 5.24. Mu.m.
(4) Three-stage reaction
Transferring all the slurry containing NCM811-OH in step (3) to an effective volume of 10m 3 The volume of the transferred slurry in the three-stage reaction kettle is about 20 percent of the effective volume of the three-stage reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18% are added into a three-stage reaction kettle in parallel, the total time for filling the reaction kettle with materials is 20h, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 100rpm, and NH in the system 3 The concentration of (C) is 4g/L, the pH value is 11.5, the solid content of the system is 117g/L, and the medium particle size D50 of the prepared NCM811-OH precursor is 8.61 mu m.
(5) Four-stage reaction
Transferring the NCM811-OH containing slurry of step (4) to 4 volumes of 10m on average 3 The volume of the slurry transferred in the four-stage reaction kettle accounts for about 25 percent of the effective volume of the four-stage reaction kettle. The reaction conditions of the 4 four-stage reaction kettles are the same and are N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18% are added into a four-stage reaction kettle in parallel, the total time for filling the reaction kettle with materials is 20 hours, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 100rpm, and NH in the system 3 The concentration of (C) is 4g/L, the pH value is 11.5, the solid content of the system is 117g/L, and the medium particle size D50 of the prepared NCM811-OH precursor is 10.05 mu m.
(6) Five-stage reaction
One of the steps (5) is 10m 3 The slurry containing NCM811-OH in the reaction kettle was transferred to 2 effective bodies on averageProduct is 20m 3 The volume of the transferred slurry in the five-stage reaction kettle accounts for about 25 percent of the effective volume of the five-stage reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18% are added into a reaction kettle in parallel, the total time for filling the reaction kettle with materials is 20 hours, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 80rpm, and NH in the system 3 The concentration of (2) was 4g/L, the pH was 11.5, the system solids content was 117g/L, and the medium particle size D50 of the prepared NCM811-OH precursor was 15.792. Mu.m.
(7) Filtering the materials in the five-stage reaction kettle to remove mother liquor, washing with sodium hydroxide aqueous solution with the mass fraction of 2%, washing with pure water until the pH of the washing water is less than 9, putting the materials into a drying oven after washing is finished, drying at 120 ℃ for 10 hours, and sieving to obtain NCM811-OH precursor with the medium granularity D50 of 15.717 mu m.
Example 2
Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 (NCM 811-OH) Synthesis of precursor:
(1) Preparation of salt solution A and alkali solution B
NiSO is carried out 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O is added into deionized water according to the mole ratio of Ni to Co to Mn=8:1:1 to prepare a salt solution A with the total metal ion concentration of nickel, cobalt and manganese being 2.5 mol/L; dissolving NaOH in deionized water to prepare alkali solution B with the molar concentration of 10 mol/L;
(2) Preparation of small particle size NCM811-OH by first order reaction
At an effective volume of 1.0m 3 Adding 300L deionized water as base solution into a first-stage reaction kettle, and adding 25 mass percent of concentrated ammonia water and sodium hydroxide solution to obtain NH (NH) of the base solution 3 The concentration was adjusted to 6g/L and the pH to 11.9. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 25% are added into a first-stage reaction kettle in parallel, the total time for filling the reaction kettle with materials is 20h, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 300rpm, and NH in the system 3 The concentration of (C) was 6g/L and the pH was 11.9, and the medium particle size D50 of the prepared NCM811-OH was 2.11. Mu.m.
(3) Secondary reaction
Transferring all the slurry containing NCM811-OH in step (2) to an effective volume of 5m 3 The volume of the transferred slurry in the secondary reaction kettle is about 20 percent of the effective volume of the secondary reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 25% are added into a secondary reaction kettle in parallel, the total time for filling the secondary reaction kettle with materials is 20h, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 400rpm, and NH in the system 3 The concentration of (2) was 6g/L, the pH was 11.6, the system solids content was 140g/L, and the medium particle size D50 of the prepared NCM811-OH precursor was 5.35. Mu.m.
(4) Three-stage reaction
Transferring the NCM811-OH containing slurry of step (3) to 2 volumes 10m on average 3 The volume of the transferred slurry in the three-stage reaction kettle is about 25 percent of the effective volume of the three-stage reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 25% are added into a three-stage reaction kettle in parallel, the total time for filling the reaction kettle with materials is 20h, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 200rpm, and NH in the system 3 The concentration of (2) was 6g/L, the pH was 11.6, the system solids content was 140g/L, and the medium particle size D50 of the prepared NCM811-OH precursor was 8.0. Mu.m.
(5) Four-stage reaction
Transferring the NCM811-OH containing slurry of step (4) to 4 volumes of 10m on average 3 The volume of the slurry transferred in the four-stage reaction kettle accounts for about 25 percent of the effective volume of the four-stage reaction kettle. The reaction conditions of the 4 four-stage reaction kettles are the same and are N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 25% are added into a four-stage reaction kettle in parallel, the total time for filling the reaction kettle with materials is 20h, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 200rpm, and NH in the system 3 The concentration of (C) is 6g/L, the pH value is 11.6, the solid content of the system is 140g/L, and the medium particle size D50 of the prepared NCM811-OH precursor is 10.75 mu m.
(6) Removing mother liquor from materials in a four-stage reaction kettle, washing with 1% sodium hydroxide aqueous solution by mass percent, washing with pure water until the pH of washing water is less than 9, drying the materials in a drying oven at 150 ℃ for 5 hours after washing is finished, and sieving to obtain NCM811-OH precursor with the medium granularity D50 of 10.68 mu m.
Example 3
Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 (NCM 811-OH) Synthesis of precursor:
(1) Preparation of salt solution A and alkali solution B
NiSO is carried out 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O is added into deionized water according to the mole ratio of Ni to Co to Mn=8:1:1 to prepare a salt solution A with the total metal ion concentration of nickel, cobalt and manganese being 1.5 mol/L; dissolving NaOH in deionized water to prepare an alkali solution B with the molar concentration of 5 mol/L;
(2) Preparation of small particle size NCM811-OH by first order reaction
At an effective volume of 1.0m 3 250L deionized water is added into a primary reaction kettle as base solution, and then ammonia water and sodium hydroxide solution with mass percent of 20% are added into the base solution to carry out NH (NH) treatment 3 The concentration was adjusted to 4g/L and the pH to 11.80. At N 2 Under the atmosphere, adding the salt solution A, the alkali solution B and ammonia water with the mass fraction of 20% into a first-stage reaction kettle in parallel, wherein the total time for filling the reaction kettle with materials is 10 hours, the reaction temperature is 50 ℃, the stirring speed of the reaction kettle is 400rpm, and NH in the system 3 The concentration of (C) was 4g/L and the pH was 11.80, and the medium particle size D50 of the prepared NCM811-OH was 2.86. Mu.m.
(3) Secondary reaction
Transferring the NCM811-OH containing slurry of step (2) to 2 volumes 2m on average 3 The volume of the transferred slurry in the secondary reaction kettle accounts for about 25 percent of the effective volume of the secondary reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 20% are added into a secondary reaction kettle in parallel, the total time for filling the secondary reaction kettle with materials is 10 hours, the reaction temperature is 50 ℃, the stirring speed of the reaction kettle is 260rpm, and NH in the system 3 The concentration of (C) is 4g/L, the pH value is 11.6, the solid content of the system is 80g/L, and the preparation The medium particle size D50 of the NCM811-OH precursor was 5.35. Mu.m.
(4) Three-stage reaction
Transferring the NCM811-OH containing slurry of step (3) to 2 volumes 5m on average 3 The volume of the transferred slurry in the three-stage reaction kettle is about 20 percent of the effective volume of the three-stage reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 20% are added into a three-stage reaction kettle in parallel, the total time for filling the reaction kettle with materials is 10 hours, the reaction temperature is 50 ℃, the stirring speed of the reaction kettle is 80rpm, and NH in the system 3 The concentration of (C) is 4g/L, the pH value is 11.6, the solid content of the system is 80g/L, and the medium-particle size D50 of the prepared NCM811-OH precursor is 7.989 mu m.
(5) Removing mother liquor from materials in a three-stage reaction kettle, washing with a sodium hydroxide aqueous solution with the mass percent of 2%, washing with pure water until the pH of washing water is less than 9, putting the materials into a drying oven after washing is finished, drying at 100 ℃ for 10 hours, and sieving to obtain the NCM811-OH precursor with the medium granularity D50 of 7.946 mu m.
Example 4
Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 (NCM 811-OH) Synthesis of precursor:
(1) Preparation of salt solution A and alkali solution B
NiCl is added 2 ·6H 2 O、CoCl 2 ·6H 2 O、MnCl 2 ·4H 2 O is added into deionized water according to the mole ratio of Ni to Co to Mn=8:1:1 to prepare a salt solution A with the total metal ion concentration of nickel, cobalt and manganese being 2.5 mol/L; dissolving NaOH in deionized water to prepare alkali solution B with the molar concentration of 10 mol/L;
(2) Preparation of small particle size NCM811-OH by first order reaction
At an effective volume of 1.0m 3 300L deionized water is added into a first-stage reaction kettle as base solution, and then 18.5 percent of concentrated ammonia water and sodium hydroxide solution are added to make NH of the base solution 3 The concentration was adjusted to 2g/L and the pH to 11.90. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18.5 percent are added into the primary reaction in parallel flowIn the kettle, the total time of the material filling reaction kettle is 10 hours, the reaction temperature is 70 ℃, the stirring speed of the reaction kettle is 500rpm, and NH in the system 3 The concentration of (C) was 2g/L and the pH was 11.90, and the medium particle size D50 of the prepared NCM811-OH was 2.15. Mu.m.
(3) Secondary reaction
Transferring the NCM811-OH containing slurry of step (2) to 2 volumes 2m on average 3 The volume of the transferred slurry in the secondary reaction kettle accounts for about 25 percent of the effective volume of the secondary reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18.5% are added into a secondary reaction kettle in parallel, the total time for filling the secondary reaction kettle with materials is 20 hours, the reaction temperature is 70 ℃, the stirring speed of the reaction kettle is 400rpm, and NH in the system 3 The concentration of (2) g/L, the pH value of (11.4) and the system solid content of 140g/L, and the medium-particle size D50 of the prepared NCM811-OH precursor is 4.659 mu m.
(4) And (3) removing mother liquor from the materials in the secondary reaction kettle, washing with 1.0% by mass of sodium hydroxide aqueous solution, washing with pure water until the pH of the washing water is less than 9, drying the materials in a drying oven at 150 ℃ for 10 hours after washing, and sieving to obtain the NCM811-OH precursor with the medium granularity D50 of 4.848 mu m.
Example 5
Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Synthesis of (NCM 9055-OH) precursor:
(1) Preparation of salt solution A and alkali solution B
NiSO is carried out 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O is added into deionized water according to the mole ratio of Ni to Co to Mn=9 to 0.5 to prepare a salt solution A with the total metal ion concentration of nickel, cobalt and manganese being 2.0 mol/L; dissolving NaOH in deionized water to prepare alkali solution B with the molar concentration of 7.5 mol/L;
(2) Preparation of small-particle-size NCM9055-OH by first-order reaction
At an effective volume of 1.0m 3 200L deionized water is added into a first-stage reaction kettle as base solution, and then 18.5 percent of concentrated ammonia water and sodium hydroxide solution by mass percent are addedNH of base solution 3 The concentration was adjusted to 8g/L and the pH to 11.9. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18.5% are added into a first-stage reaction kettle in parallel, the total time for filling the reaction kettle with materials is 15h, the reaction temperature is 55 ℃, the stirring speed of the reaction kettle is 400rpm, and NH in the system 3 The concentration of (C) was 8g/L and the pH was 11.9, and the medium particle size D50 of the prepared NCM9055-OH was 2.63. Mu.m.
(3) Secondary reaction
Transferring all the slurry containing NCM9055-OH in the step (2) to an effective volume of 5m 3 The volume of the transferred slurry in the secondary reaction kettle is about 20 percent of the effective volume of the secondary reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18.5% are added into a secondary reaction kettle in parallel, the total time for filling the secondary reaction kettle with materials is 15 hours, the reaction temperature is 55 ℃, the stirring speed of the reaction kettle is 200rpm, and NH in the system 3 The concentration of (C) is 8g/L, the pH value is 11.8, the solid content of the system is 117g/L, and the medium particle size D50 of the prepared NCM9055-OH precursor is 5.48 mu m.
(4) Three-stage reaction
Transferring the NCM 9055-OH-containing slurry of step (3) to 2 volumes of 10m on average 3 The volume of the transferred slurry in the three-stage reaction kettle is about 25 percent of the effective volume of the three-stage reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with mass fraction of 18.5% are added into a three-stage reaction kettle in parallel, the total time for filling the reaction kettle with materials is 15h, the reaction temperature is 55 ℃, the stirring speed of the reaction kettle is 100rpm, and NH in the system 3 The concentration of (C) is 8g/L, the pH value is 11.8, the solid content of the system is 117g/L, and the medium particle size D50 of the prepared NCM9055-OH precursor is 7.85 mu m.
(5) Four-stage reaction
Transferring the NCM 9055-OH-containing slurry in step (4) to 4 volumes of 10m on average 3 The volume of the slurry transferred in the four-stage reaction kettle accounts for about 25 percent of the effective volume of the four-stage reaction kettle. The reaction conditions of the 4 four-stage reaction kettles are the same and are N 2 Under the atmosphere, salt solution A, alkali solution B and massAmmonia water with the fraction of 18.5% is added into a four-stage reaction kettle in parallel, the total time for filling the reaction kettle with materials is 15 hours, the reaction temperature is 55 ℃, the stirring speed of the reaction kettle is 100rpm, and NH in the system 3 The concentration of (C) is 8g/L, the pH value is 11.8, the solid content of the system is 117g/L, and the medium particle size D50 of the prepared NCM9055-OH precursor is 9.904 mu m.
(6) Removing mother liquor from materials in a four-stage reaction kettle, washing with 1.0% sodium hydroxide aqueous solution by mass percent, washing with pure water until the pH of washing effluent is less than 9, drying the materials in a drying oven at 100 ℃ for 10 hours after washing is finished, and sieving to obtain NCM9055-OH precursor with medium granularity D50 of 9.891 mu m.
Example 6
Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 (NCM 523-OH) Synthesis of precursor:
(1) Preparation of salt solution A and alkali solution B
NiCl is added 2 ·6H 2 O、CoCl 2 ·6H 2 O、MnCl 2 ·4H 2 O is added into deionized water according to the mole ratio of Ni to Co to Mn=5 to 2 to 3 to prepare a salt solution A with the total metal ion concentration of nickel, cobalt and manganese being 2.2 mol/L; dissolving NaOH in deionized water to prepare alkali solution B with the molar concentration of 10 mol/L;
(2) Preparation of small particle size NCM523-OH by Primary reaction
At an effective volume of 0.5m 3 150L deionized water is added into a first-stage reaction kettle as base solution, and then 18.5 mass percent of concentrated ammonia water and sodium hydroxide solution are added to carry out NH on the base solution 3 The concentration was adjusted to 3g/L and the pH to 11.9. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with mass fraction of 18.5% are added into a vigorously stirred primary reaction kettle in parallel, the total time for filling the reaction kettle with materials is 10 hours, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 400rpm, and NH in the system 3 The concentration of (C) was 3g/L and the pH was 11.9, and the medium particle size D50 of the prepared NCM523-OH was 2.05. Mu.m.
(3) Secondary reaction
Transferring all of the NCM 523-OH-containing slurry of step (2) to a slurry havingThe effective volume is 2m 3 The volume of the transferred slurry in the secondary reaction kettle accounts for about 25 percent of the effective volume of the secondary reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18.5% are added into a secondary reaction kettle in parallel, the total time for filling the secondary reaction kettle with materials is 15 hours, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 260rpm, and NH in the system 3 The concentration of (C) was 3g/L, the pH was 11.5, the solid content of the system was 134g/L, and the medium particle size D50 of the prepared NCM523-OH was 4.953. Mu.m.
(4) Three-stage reaction
Transferring all the slurry containing NCM523-OH in step (3) to an effective volume of 10m 3 The volume of the transferred slurry in the three-stage reaction kettle is about 20 percent of the effective volume of the three-stage reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18.5% are added into a three-stage stirred reaction kettle in parallel, the total time for filling the reaction kettle with materials is 15h, the reaction temperature is 55 ℃, the stirring speed of the reaction kettle is 100rpm, and NH in the system 3 The concentration of (C) was 3g/L, the pH was 11.5, the system solids content was 134g/L, and the medium particle size D50 of the prepared NCM523-OH precursor was 7.85. Mu.m.
(5) Four-stage to six-stage reactions
The effective volume of the reaction kettles used for the four-level to six-level reactions is 10m 3 The volume of the transferred slurry accounts for about 20% of the effective volume of the next stage reaction kettle, and the coprecipitation reaction control parameters in the step (4) are repeatedly adopted. The medium particle size D50 of M523-OH synthesized by the six-stage reaction was 18.202. Mu.m.
(6) Removing mother liquor from materials in a six-stage reaction kettle, washing with a sodium hydroxide aqueous solution with the mass percent of 2%, washing with pure water until the pH value of washing water is less than 9, drying the materials in a drying oven at 100 ℃ for 10 hours after washing is finished, and sieving to obtain an NCM523-OH precursor with the medium granularity D50 of 18.162 mu m.
Example 7
Ni 1/3 Co 1/3 Mn 1/3 (OH) 2 Synthesis of (NCM 111-OH) precursor:
(1) Preparation of salt solution A and alkali solution B
NiCl is added 2 ·6H 2 O、CoCl 2 ·6H 2 O、MnCl 2 ·4H 2 O is added into deionized water according to the mole ratio of Ni to Co to Mn=1:1:1 to prepare a salt solution A with the total metal ion concentration of nickel, cobalt and manganese being 2.0 mol/L; dissolving NaOH in deionized water to prepare an alkali solution B with the molar concentration of 6 mol/L;
(2) Preparation of small particle size NCM111-OH by first order reaction
At an effective volume of 0.5m 3 150L deionized water is added into a first-stage reaction kettle as base solution, and then 18.5 mass percent of concentrated ammonia water and sodium hydroxide solution are added to carry out NH on the base solution 3 The concentration was adjusted to 2.5g/L and the pH to 11.7. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with mass fraction of 18.5% are added into a vigorously stirred primary reaction kettle in parallel, the total time for filling the reaction kettle with materials is 15 hours, the reaction temperature is 50 ℃, the stirring speed of the reaction kettle is 600rpm, and NH in the system 3 The concentration of (C) was 2.5g/L and the pH was 11.7, and the medium particle size D50 of the prepared NCM111-OH was 2.25. Mu.m.
(3) Secondary reaction
Transferring all the slurry containing NCM111-OH in the step (2) to an effective volume of 2m 3 The volume of the transferred slurry in the secondary reaction kettle accounts for about 25 percent of the effective volume of the secondary reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18.5% are added into a secondary reaction kettle in parallel, the total time for filling the secondary reaction kettle with materials is 20 hours, the reaction temperature is 50 ℃, the stirring speed of the reaction kettle is 200rpm, and NH in the system 3 The concentration of (C) was 2.5g/L, the pH was 11.20, the solid content of the system was 100g/L, and the medium particle size D50 of the prepared NCM111-OH was 5.004. Mu.m.
(4) And (3) removing mother liquor from the materials in the secondary reaction kettle, washing with a sodium hydroxide aqueous solution with the mass percent of 2%, washing with pure water until the pH value of the washing water is less than 9, and after washing, putting the materials into a drying box, and drying at 120 ℃ for 10 hours to obtain the NCM111-OH precursor with the medium granularity D50 of 5.102 mu m.
Comparative example 1
This comparative example is used for comparative illustration of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Synthesis of (NCM 811-OH) precursor.
(1) Preparation of salt solution A and alkali solution B
NiSO is carried out 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O is added into deionized water according to the mole ratio of Ni to Co to Mn=8:1:1 to prepare a salt solution A with the total metal ion concentration of nickel, cobalt and manganese being 2.0 mol/L; dissolving NaOH in deionized water to prepare alkali solution B with the molar concentration of 7.5 mol/L;
(2) Preparation of small particle size NCM811-OH by first order reaction
At an effective volume of 0.5m 3 Adding 100L deionized water as base solution into a first-stage reaction kettle, and adding 18 mass percent of concentrated ammonia water to make NH of the base solution 3 The concentration was adjusted to 4g/L, and the pH of the base solution was adjusted to 11.7 by adding an alkali solution B. At N 2 And under the atmosphere, adding the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18% into a primary reaction kettle in parallel flow at a constant speed. The total time for filling the reaction kettle with the materials is 20 hours by controlling the adding speed of the solution A and the solution B and the ammonia water. Other reaction parameters were: the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 400rpm, and NH in the system 3 The concentration of (C) was 4g/L and the pH was 11.7, and the medium particle size D50 of the prepared NCM811-OH was 2.68. Mu.m.
(3) Secondary reaction
Transferring the NCM811-OH containing slurry of step (2) to an effective volume of 2m 3 The volume of the transferred slurry in the secondary reaction kettle accounts for about 25 percent of the effective volume of the secondary reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18% are added into a secondary reaction kettle in parallel, the total time for filling the secondary reaction kettle with materials is 20 hours, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 300rpm, and NH in the system 3 The concentration of (2) was 8g/L, the pH was 11.2, the system solids content was 117g/L, and the medium particle size D50 of the prepared NCM811-OH precursor was 5.64. Mu.m.
(4) Three-stage reaction
The step (3) comprises The NCM811-OH slurry was transferred to an effective volume of 10m 3 The volume of the transferred slurry in the three-stage reaction kettle is about 20 percent of the effective volume of the three-stage reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18% are added into a three-stage reaction kettle in parallel, the total time for filling the reaction kettle with materials is 20h, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 100rpm, and NH in the system 3 The concentration of (2) was 8g/L, the pH was 11.2, the system solids content was 117g/L, and the medium particle size D50 of the prepared NCM811-OH precursor was 9.42. Mu.m.
(5) Four-stage reaction
Transferring the NCM811-OH containing slurry of step (4) to 4 volumes of 10m on average 3 The volume of the slurry transferred in the four-stage reaction kettle is about 20 percent of the effective volume of the four-stage reaction kettle. The reaction conditions of the 4 four-stage reaction kettles are the same and are N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18% are added into a four-stage reaction kettle in parallel, the total time for filling the reaction kettle with materials is 20 hours, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 100rpm, and NH in the system 3 The concentration of (C) is 8g/L, the pH value is 11.8, the solid content of the system is 117g/L, and the medium particle size D50 of the prepared NCM811-OH precursor is 10.85 mu m.
(6) Five-stage reaction
One of the steps (5) is 10m 3 The slurry containing NCM811-OH in the reaction vessel was transferred to 2 reaction vessels having an effective volume of 20m on average 3 The volume of the transferred slurry in the five-stage reaction kettle accounts for about 20 percent of the effective volume of the five-stage reaction kettle. At N 2 Under the atmosphere, the salt solution A, the alkali solution B and ammonia water with the mass fraction of 18% are added into a reaction kettle in parallel, the total time for filling the reaction kettle with materials is 20 hours, the reaction temperature is 60 ℃, the stirring speed of the reaction kettle is 80rpm, and NH in the system 3 The concentration of (C) is 8g/L, the pH value is 11.8, the solid content of the system is 117g/L, and the medium-particle size D50 of the prepared NCM811-OH precursor is 13.522 mu m.
(7) Filtering the materials in the five-stage reaction kettle to remove mother liquor, washing with sodium hydroxide aqueous solution with the mass percent of 2%, washing with pure water until the pH value of the washing water is less than 9, drying the materials in a drying oven at 120 ℃ for 10 hours after washing, and sieving to obtain NCM811-OH precursor with the medium granularity D50 of 13.42 mu m.
Test example 1
The nickel cobalt manganese hydroxide precursor samples synthesized in examples 1-7 were subjected to particle size distribution and crystal structure testing using a Mastersizer model 2000 laser particle size tester from malvern, england and an X-ray powder diffractometer model Thermo Fisher Thermo ESCALAB, respectively, and the test results are shown in table 1.
TABLE 1
| Examples | Precursor type | Reaction progression | D10/μm | D50/μm | D90/μm | Diameter distance | FWHM(101)/° |
| Example 1 | NCM811-OH | Five-stage | 9.806 | 15.717 | 21.677 | 0.76 | 0.655 |
| Example 2 | NCM811-OH | Four-stage | 7.520 | 10.682 | 15.117 | 0.71 | 0.681 |
| Example 3 | NCM811-OH | Three stages | 4.766 | 7.946 | 11.049 | 0.79 | 0.684 |
| Example 4 | NCM811-OH | Second-level | 3.350 | 4.848 | 6.976 | 0.75 | 0.502 |
| Example 5 | NCM9055-OH | Four-stage | 6.290 | 9.891 | 14.093 | 0.79 | 0.750 |
| Example 6 | NCM523-OH | Six-stage | 12.855 | 18.163 | 24.587 | 0.65 | 0.668 |
| Example 7 | NCM333-OH | Second-level | 3.434 | 5.102 | 7.516 | 0.80 | 0.452 |
As can be seen from table 1, the ternary precursor synthesized by the multistage coprecipitation reaction has very high uniformity of particle diameters of the secondary particles, and precursor materials of different particle sizes and different (101) peak half peak widths can be synthesized by adjusting the reaction control parameters.
The crystal structure of the NCM811-OH precursor synthesized by the second-to fifth-order reactions in examples 1 to 7 and comparative example 1 was tested by using a Philips type X-ray powder diffractometer in the United states, and the XRD spectrum was simulated by using Jade 6 software to obtain diffraction peak half-width data of the 101 crystal plane and the I (101)/I (001) peak intensity ratio, and the calculation results are shown in tables 2 and 3, respectively.
TABLE 2
TABLE 3 Table 3
The materials synthesized by the precipitation reactions of each stage in example 1 and comparative example 1 were subjected to X-ray diffraction analysis, and the spectra were simulated by using the Jade 6 software, and the calculation results are shown in tables 2 and 3. As can be seen from Table 2, the (101) diffraction peak half-width of the sample obtained by each stage of the reaction of example 1 was 0.65 to 0.68 ° In the samples obtained by the three-level to five-level reaction, particularly, the half-peak width of the (101) diffraction peak is basically kept unchanged, and the correspondence between the half-peak width of the (101) peak and the thickness of the primary crystal grain is known from the Debye-Scherrer formula, so that the uniformity of the primary particle size and the stacking order of the synthesized samples are very high. The I (101)/I (001) peak Jiang Bi is an important index for the primary particle stacking order, as can be seen from Table 3, example 1 is due to the system NH 3 The content and the pH value are very stable to control, and the fluctuation of the peak intensity ratio of I (101)/I (001) is very small, which indicates that the stacking order of primary particles is high and the alignment consistency is high; in addition, the half-width and the I (101)/I (001) peak intensity ratio of each of the reaction synthesis samples in examples 2, 3, 5 and 6 were relatively stable. Comparative example 1, however, the sample obtained by each stage of reaction was NH due to the reaction process 3 The content and the pH value have larger changes, the half-peak width of the (101) diffraction peak and the peak intensity ratio of I (101)/I (001) have larger fluctuation, which shows that the primary particle size uniformity and stacking order degree of the crystals from inside to outside are very poor and the defects are more. From the above results, it can be seen that high quality precursors with high uniformity can be synthesized only by maintaining the stability of the control parameters during the multistage precipitation reaction.
The precursor synthesized in examples 1 to 7 and comparative example 1 was subjected to main element content analysis by inductively coupled plasma atomic emission spectrometer (ICP-7500) of Shimadzu, and the test results are shown in Table 4.
TABLE 4 Table 4
| Examples | Ni | Co | Mn | Chemical formula |
| Example 1 | 0.798 | 0.102 | 0.100 | Ni 0.798 Co 0.102 Mn 0.100 (OH) 2 |
| Example 2 | 0.801 | 0.098 | 0.101 | Ni 0.801 Co 0.098 Mn 0.101 (OH) 2 |
| Example 3 | 0.801 | 0.100 | 0.099 | Ni 0.801 Co 0.100 Mn 0.099 (OH) 2 |
| Example 4 | 0.799 | 0.102 | 0.099 | Ni 0.799 Co 0.102 Mn 0.099 (OH) 2 |
| Example 5 | 0.902 | 0.050 | 0.048 | Ni 0.902 Co 0.050 Mn 0.048 (OH) 2 |
| Example 6 | 0.502 | 0.203 | 0.295 | Ni 0.502 Co 0.203 Mn 0.295 (OH) 2 |
| Example 7 | 0.335 | 0.334 | 0.331 | Ni 0.335 Co 0.334 Mn 0.331 (OH) 2 |
| Comparative example 1 | 0.801 | 0.099 | 0.100 | Ni 0.801 Co 0.099 Mn 0.100 (OH) 2 |
As can be seen from the data in table 4, the molar ratios and the feed ratios of the main metal elements of the synthesized precursor materials are substantially identical.
Claims (10)
1. A preparation method of a lithium ion battery positive electrode material precursor, wherein the precursor has a schematic chemical composition represented by a formula of 'first metal hydroxide, second metal hydroxide' or a formula of 'first metal hydroxide, second metal hydroxide, water'; the first metal is nickel, cobalt and manganese, wherein the content of nickel is 30-94%, the content of cobalt is 3-35% and the content of manganese is 3-35% based on the total mole amount of the first metal being 100%; the second metal is one or more of magnesium, aluminum, titanium, niobium, tungsten, zirconium and yttrium, and the total content of the second metal is 0 to 3 percent based on 100 percent of the total mole of the first metal;
the method is a quaternary, penta or hexa stage reaction comprising:
(1) Adding water accounting for 20-30% of the volume of the primary reaction kettle as base solution, and adding ammonia water and sodium hydroxide to make NH of the base solution 3 The concentration is adjusted to 2 g/L-8 g/L, and the pH value is adjusted to 11.7-11.9; adding a salt solution into a primary reaction kettle at a constant speed under an inert atmosphere, wherein the time for increasing the volume of a liquid phase to more than 80% of the volume of the primary reaction kettle is 10-20 h; the reaction temperature is 50-70 ℃; maintaining the pH value of the liquid phase and the NH of the liquid phase 3 The concentration is stable; obtaining seed crystal with the medium granularity D50 of 2-3 mu m;
(2) Uniformly dividing the slurry obtained from the previous-stage reaction kettle into reaction base solution of the next-stage reaction kettle, wherein the volume of the slurry of the previous-stage reaction kettle is 20% -30% of that of the next-stage reaction kettle; liquid phase NH 3 The concentration of the solution is 2 g/L-8 g/L, and the pH value of the liquid phase is 11.2-11.85; adding the salt solution into the next-stage reaction kettle at a constant speed, wherein the time for increasing the volume of the liquid phase to more than 80% of the volume of the reaction kettle is 10-20 h h; the reaction temperature is 50-70 ℃; maintaining the pH value of the liquid phase and the NH of the liquid phase 3 The concentration is stable; the overflow operation is not included in the step;
in the first-stage to sixth-stage coprecipitation reaction process, the same salt solution, alkali solution and ammonia water are used; and liquid phase NH 3 The concentration and the reaction temperature are the same; in the process of the secondary-to-sixth-level coprecipitation reaction, the pH value of the liquid phase and the solid content of the liquid phase are the same, and the solid content of the liquid phase is 80g/L to ultra 200g/L；
The grain size in the crystals at the end of the second-stage reaction is 4-6 μm, the grain size in the crystals at the end of the third-stage reaction is 6-9 μm, the grain size in the crystals at the end of the fourth-stage reaction is 9-11 μm, the grain size in the crystals at the end of the fifth-stage reaction is 13-16 μm, and the grain size in the crystals at the end of the sixth-stage reaction is 16-19 μm.
2. The method according to claim 1, wherein the number of the reaction vessels of the next stage is 3 to 5 times the number of the reaction vessels of the previous stage.
3. A lithium ion battery cathode material precursor, characterized in that it is prepared by the method of any one of claims 1-2.
4. A precursor according to claim 3, wherein the precursor has a schematic chemical composition represented by the formula "first metal hydroxide, second metal hydroxide" or the formula "first metal hydroxide, second metal hydroxide, water"; the first metal is nickel, cobalt and manganese, wherein the content of nickel is 30-94%, the content of cobalt is 3-35% and the content of manganese is 3-35% based on the total mole amount of the first metal being 100%; the second metal is one or more of magnesium, aluminum, titanium, niobium, tungsten, zirconium and yttrium, and the total content of the second metal is 0 to 3 percent based on 100 percent of the total mole of the first metal; the particle diameter distance of the precursor is less than 0.8; in the X-ray diffraction spectrum of the precursor, the half-peak width of a diffraction peak of a 101 crystal face is 0.45-0.75 degrees; in XRD analysis of the precursor and an intermediate product thereof, the half-width fluctuation range of a diffraction peak of a 101 crystal face is smaller than 0.05 degrees; in XRD analysis of the precursor and an intermediate product thereof, the fluctuation range of the ratio of I (101)/I (001) is less than 0.1; the intermediate particle size of the precursor is 9-11 μm, 13-16 μm or 16-19 μm.
5. The precursor according to claim 4, wherein the nickel content is 40% to 90%, the cobalt content is 5% to 30%, and the manganese content is 5% to 30% based on 100% of the total molar amount of the first metal.
6. The precursor according to claim 4, wherein the total content of the second metal is 0 to 1% based on 100% of the total molar amount of the first metal.
7. The precursor according to claim 4, wherein the precursor and its intermediate product have a range of variation in the half-width of the diffraction peak of the 101 crystal plane of less than 0.03 ° in XRD analysis.
8. The precursor according to claim 4, wherein the precursor and its intermediate product have a fluctuation range of the ratio I (101)/I (001) of less than 0.05 in XRD analysis.
9. A lithium ion battery cathode material, characterized in that it is prepared from the precursor according to any one of claims 3 to 8.
10. A lithium ion battery, characterized in that the positive electrode material according to claim 9 is used.
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| CN108172892A (en) * | 2017-11-28 | 2018-06-15 | 清远佳致新材料研究院有限公司 | Multistage continuity method synthesis size distribution is concentrated, the preparation method of multiple types presoma |
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