CN114195204B - High sphericity manganese-rich carbonate precursor and preparation method and application thereof - Google Patents
High sphericity manganese-rich carbonate precursor and preparation method and application thereof Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 75
- 239000011572 manganese Substances 0.000 title claims abstract description 65
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 62
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims description 111
- 239000007864 aqueous solution Substances 0.000 claims description 42
- 239000013078 crystal Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000003513 alkali Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- 230000001105 regulatory effect Effects 0.000 claims description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 239000010413 mother solution Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 16
- 230000001276 controlling effect Effects 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 239000012295 chemical reaction liquid Substances 0.000 description 12
- 238000010899 nucleation Methods 0.000 description 10
- 230000006911 nucleation Effects 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 238000000975 co-precipitation Methods 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 6
- 239000012716 precipitator Substances 0.000 description 6
- 239000011343 solid material Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 229940044175 cobalt sulfate Drugs 0.000 description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229940053662 nickel sulfate Drugs 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910001170 xLi2MnO3-(1−x)LiMO2 Inorganic materials 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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
-
- 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
- C01P2006/12—Surface area
-
- 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
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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 belongs to the technical field of lithium ion battery materials, and particularly relates to a high sphericity manganese-rich carbonate precursor, and a preparation method and application thereof. The high-sphericity manganese-rich carbonate precursor has the advantages of uniform element distribution, high sphericity, uniform particle size distribution, good physical and chemical indexes of products, centralized and controllable particle size, higher sphericity and tap density, and is an ideal precursor material for preparing high-performance manganese-rich materials.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a high sphericity manganese-rich carbonate precursor, and a preparation method and application thereof.
Background
The lithium ion battery is a green secondary battery with high energy density, has the advantages of long service life, no memory effect, environmental friendliness and the like, and has been widely applied to the fields of 3C digital electronic products, electric tools, electric vehicles, energy storage and the like since commercialization of the lithium ion battery. The performance of the positive electrode material is one of the key and core in the lithium ion battery technology, and not only directly affects the performance of battery capacity, circulation, safety and the like, but also occupies about 40% of the total cost of the battery, so the performance and cost of the positive electrode material become key factors for limiting the performance and cost of the lithium ion battery.
Currently, the positive electrode material of the lithium ion battery mainly comprises ternary materials of lithium cobaltate, lithium manganate, lithium iron phosphate and nickel cobalt manganese. However, the capacity of the traditional positive electrode materials is generally not more than 200mAh/g, and the performance requirement of the future high specific energy lithium ion battery on the positive electrode materials cannot be met. Moreover, due to the high price and lack of resources of cobalt, the cost of the anode material is greatly influenced by serious national dependence on import. Accordingly, intensive research is being conducted to develop a novel positive electrode material having a higher specific capacity, lower cost, higher safety and longer life.
Lithium-rich manganese-based positive electrode material xLi 2 MnO 3 （1-x）LiMO 2 (m=co, ni, mn) is of great interest worldwide because of its high specific discharge capacity up to 250mAh/g or more, its high specific capacity, abundant inexpensive mineral resources, and lower manufacturing costs, and the U.S. department of energy even considers this material to be the first choice for the next generation of lithium ion power battery anode materials. However, although the lithium-rich manganese-based positive electrode material has incomparable advantages to other positive electrode materials in improving the energy density of the lithium ion battery, the lithium-rich manganese-based positive electrode material has the problems of large first irreversible capacity loss, poor rate performance, obvious voltage drop in the circulation process, poor circulation performance, poor safety performance and the like, and severely restricts the wide commercial application of the material. In addition, the lithium-rich material has a plurality of problems in preparation process and engineering preparation, has low cost and is environment-friendly, and is suitable for a process technical route of large-scale industrial production, thereby playing a vital role in the wide application of the material.
It is reported that sphericity is a key dimension for evaluating a precursor, and high sphericity can improve tap density, rate performance, cycle performance, and the like of a positive electrode material. Therefore, how to increase the sphericity of the precursor is an important index and technique for improving the performance thereof. Currently, the manganese-rich precursor is generally synthesized by adopting a spray drying method, a hydroxide coprecipitation method, a carbonate coprecipitation method and the like. The precursor prepared by the spray drying method has good sphericity, but larger pores and lower compaction density of the material; the hydroxide coprecipitation method is adopted to prepare the manganese-rich ternary precursor, so that the problems of poor sphericity, large component fluctuation, low tap density and the like exist, the divalent manganese is easy to oxidize in a high-pH aqueous solution due to high manganese content, a large amount of inert gas is required to be introduced for protection, the processing cost is increased, a large amount of ammonia water with high volatility is also required to be used, and the cost is greatly increased due to the treatment and recovery of ammonia. The report of preparing carbonate precursor by carbonate coprecipitation technology is mature, as disclosed in Chinese patent CN202110215400.4Preparation method of surface area olive type carbonate ternary precursor, wherein the prepared precursor secondary particles are olive-shaped, loose and porous in surface, primary grains are powder, the diameter is 10-100 nm, and the specific surface area is 130-200m 2 /g; as another example, chinese patent CN 111498908A discloses a preparation method of a spheroidal manganese-rich ternary precursor, which adopts a method of adding a crystal nucleation control agent into a salt solution to prepare a spheroidal manganese-rich ternary precursor of carbonate, and the method can obtain a spheroidal precursor with higher tap density, but the sphericity of the precursor obtained by the method is not good enough, and a certain amount of crystal nucleation control agent is added, so that the process cost is increased.
Therefore, the development of the synthesis method of the high sphericity manganese-rich precursor, which has simple process, low production cost and suitability for large-scale industrial production, has positive significance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide the high-sphericity manganese-rich carbonate precursor, which effectively solves the problems of poor particle appearance, loose surface, difficult particle size control, non-uniformity and low tap density of the traditional manganese-rich precursor;
the second technical problem to be solved by the invention is to provide the preparation method of the high-sphericity manganese-rich carbonate precursor, which has strong controllability, can stably control the grain size of each production batch, and has simple process operation, low production cost and high efficiency.
In order to solve the technical problems, the high-sphericity manganese-rich carbonate precursor has a general formula Mn as shown in the specification x Ni z Co y CO 3 The structure shown, wherein x+y+z=1, and 0.5.ltoreq.x.ltoreq.0.95, 0.ltoreq.y.ltoreq.0.4, 0.ltoreq.z.ltoreq.0.4;
the grain diameter d10 of the high sphericity manganese-rich carbonate precursor is more than or equal to 3 mu m, d50=8-12 mu m, d90 is less than or equal to 20 mu m, and tap density is more than or equal to 1.8g/cm 3 Specific surface area of 5-30m 2 And/g, the shape is spherical or spheroid.
The invention also provides a method for preparing the high sphericity manganese-rich carbonate precursor, which comprises the following steps:
(1) Preparing a nickel-cobalt-manganese soluble salt mixed aqueous solution and a carbonate and ammonia-containing alkali mixed aqueous solution according to a selected stoichiometric ratio for later use;
(2) Adding pure water into the sealed reaction kettle, and adding ammonia-containing alkali liquor to adjust the pH value of the mother liquor to 8.0-9.0, wherein the mother liquor is used as bottom water;
(3) Regulating the rotating speed of the reaction kettle to 500-1500r/min at 40-65 ℃, respectively feeding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle, controlling the pH value of the reaction system to be slightly alkaline, stopping feeding when detecting that the D50 of the materials in the reaction kettle reaches 2.0-5.0 mu m (preferably 3.0-4.0 mu m), and continuing stirring and ageing to obtain crystal nucleus;
(4) Guiding out the reaction solution containing the crystal nucleus, concentrating to obtain concentrated solution, diluting, adding ammonia water, and adjusting pH value to alkalescence to obtain mother solution;
(5) Regulating the rotating speed and the temperature of the reaction kettle to be lower than the rotating speed and the temperature controlled in the step (3), continuously feeding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle, controlling the pH value of a reaction system to be lower than the pH value controlled in the step (3), gradually growing small crystal nucleus along with the continuous feeding, ensuring that the sphericity tends to be perfect, stopping feeding when the D50 of the materials in the reaction kettle reaches a target value, and continuously stirring and ageing treatment;
(6) And collecting a reaction product, washing, drying and sieving to obtain the required high sphericity manganese-rich carbonate precursor.
Specifically, the preparation method of the high sphericity manganese-rich carbonate precursor comprises the following steps:
in the nickel-cobalt-manganese soluble salt mixed aqueous solution, the total concentration of metal ions is 0.5-4mol/L;
in the alkali mixed aqueous solution, the concentration of carbonate is 0.5-4mol/L, and the concentration of ammonia is 0.1-0.5mol/L.
Specifically, in the step (1), the soluble nickel-cobalt-manganese salt includes sulfate, chloride or nitrate of nickel, cobalt or manganese.
Specifically, in the step (1), the alkali mixed aqueous solution includes a mixed solution of sodium carbonate and ammonia water, or sodium carbonate and (NH) 4 ) 2 CO 3 /(NH 4 )HCO 3 Is a mixed solution of (a) and (b).
Specifically, in the step (2), a reaction kettle is adopted, wherein the reaction kettle is provided with a temperature control water bath jacket, a stirring paddle and an online pH meter; the amount of the bottom water is such that the bottom water just falls over all stirring paddles of the reaction kettle.
Preferably, in the step (2), the pH of the mother liquor is adjusted to 8.0-9.0.
In the whole crystal nucleus growth process of the reaction, the control of the rotating speed and the pH value is a key parameter affecting the sphericity; it is emphasized that the control of the rotational speed, temperature and pH in step (3) requires higher parameters than in step (5), but the specific range values may be adjusted appropriately. The rotating speed is affected by different sizes and shapes of stirring paddles, and the rotating speed does not have an accurate range, but the conventional range is generally within 500-1500r/min, the temperature is generally about 50-55 ℃, the range can be widened to 40-65 ℃, the pH value is relatively fixed, the reaction of the system needs to be controlled to be slightly alkaline, namely, the range of 7.5-9.0, and the maximum range cannot exceed 7.0-9.5. The aging time in the step (3) is not limited, and is generally 1 to several hours, and the aging time in the step (3) can be shorter than the standard.
Specifically, in the step (3), the rotating speed of the reaction kettle is regulated to be 800-1000r/min, the temperature is 55-65 ℃, and the pH value of the reaction system is controlled to be 8.0-9.0. In the step (3), the reaction temperature is controlled to be 55-65 ℃, which is favorable for forming crystal nuclei and accelerating the collision between the crystal nuclei, so that the crystal nuclei are more compact, the tap density is high, and the sphericity is improved. Too low a temperature is unfavorable for the rapid formation of crystal nuclei, and too high a temperature has no obvious improvement effect and increases the energy consumption.
In the step (3), the particle size is continuously sampled and tested in the reaction process, and the particle size of the primary material is detected by a laser particle size tester every 2 hours.
Specifically, in the step (4), the concentration step is to remove part of supernatant liquid from the reaction solution containing the crystal nucleus by standing and sedimentation, so as to obtain a concentrated solution with the solid content of 40 wt%.
Specifically, in the step (4), pure water is added into the concentrated solution for dilution until the solid content is 10-20wt%, a crystal nucleus-containing solution with the solid content of 10-20wt% is adopted as a mother solution, and the higher solid content is beneficial to increasing the collision and friction between crystal nuclei, so that the crystal nuclei grow compactly, the sphericity is improved, and the tap density is improved.
Preferably, in the step (4), the pH value of the feed liquid is adjusted to 7.5-8.5.
In the step (5), the adopted pH value is lower than the parameter control of the step (3), the higher pH value is adopted in the nucleation stage, the supersaturation degree of the reaction solution is improved, more crystal nuclei are formed, the pH value is reduced subsequently, and the growth of the crystal nuclei is facilitated.
In the step (5), the controlled rotation speed is lower than that in the step (3), and the higher rotation speed is adopted in the nucleation stage, so that the formation of crystal nuclei and the acceleration of collision between the crystal nuclei are facilitated, the crystal nuclei are more compact, the rotation speed is reduced subsequently, particles are deposited to form large crystal nuclei, the tap density is high, and the sphericity is improved.
Specifically, in the step (5), the rotating speed of the reaction kettle is regulated to be 500-800r/min, the temperature is 45-55 ℃, and the pH value of the reaction system is controlled to be 7.5-8.5.
In the step (5), the granularity is continuously sampled and tested in the reaction process, and the particle size of the primary material is detected by a laser granularity tester every 4 hours.
Specifically, in the step (6), the washing step includes a step of soaking with deionized water and a step of washing with deionized water for a plurality of times (4-5 times).
Specifically, in the step (6), the drying step is that the drying is carried out at 80-110 ℃ until the moisture content is less than or equal to 1.0wt%.
The invention also discloses application of the high-sphericity manganese-rich carbonate precursor or the high-sphericity manganese-rich carbonate precursor prepared by the method in preparation of lithium ion battery anode materials, lithium ion battery anodes and lithium ion batteries.
The invention also discloses a lithium ion battery anode material, a lithium ion battery anode or a lithium ion battery prepared based on the high-sphericity manganese-rich carbonate precursor or the high-sphericity manganese-rich carbonate precursor prepared by the method.
The high-sphericity manganese-rich carbonate precursor has the advantages of uniform element distribution, high sphericity, uniform particle size distribution, good physical and chemical indexes of products, centralized and controllable particle size, higher sphericity and tap density, and effectively solves the problems of poor particle appearance, loose surface, difficult particle size control, uneven surface, low tap density and the like of the traditional manganese-rich precursor. The precursor can be used as a raw material to prepare a lithium-rich positive electrode material with good sphericity, uniform particle size distribution and high compaction density, and is an ideal precursor material for preparing a high-performance manganese-rich material. The metal element used by the manganese-rich carbonate precursor is mainly Mn element which is rich in resources and low in price, and the low-cost advantage of raw materials is obvious.
The preparation method of the high sphericity manganese-rich carbonate precursor adopts a special crystal nucleus method coprecipitation process, reaction conditions favorable for crystal nucleus formation are controlled firstly, a large number of fine crystal nuclei with good dispersibility are generated in a nucleation stage, then the crystal nuclei are simultaneously developed and grown by controlling a crystallization coprecipitation method, and in the growth process, the small crystal nuclei are slowly grown by controlling parameters such as stirring rotation speed, reaction temperature, reaction pH, flow and the like, so that the high sphericity product can be prepared. The preparation method of the high-sphericity manganese-rich carbonate precursor has strong controllability, can stably control the grain size of each production batch, does not need to pass through protective atmosphere and use a surfactant, has the advantages of simple process operation, low production cost, high production efficiency and less pollution, and is beneficial to further reduction of the total cost of the lithium-rich material and large-scale industrial production.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
FIG. 1 is a schematic diagram of the precursor obtained in example 1 under 2500X-ray electron microscope;
FIG. 2 is a schematic diagram of the precursor obtained in example 1 under 10000 times electron microscope;
FIG. 3 is a schematic diagram of a sintered product of the precursor obtained in example 1 under a 5000-fold electron microscope;
FIG. 4 is a schematic diagram of the precursor obtained in example 2 under 2500X-ray electron microscope;
FIG. 5 is a schematic diagram of the precursor obtained in example 2 under 10000 times electron microscope;
FIG. 6 is a schematic diagram of the precursor obtained in comparative example 1 under 2500X-ray electron microscope;
FIG. 7 is a schematic diagram of the precursor obtained in comparative example 1 under 10000 times of electron microscope;
FIG. 8 is a schematic diagram of a sintered product of the precursor obtained in comparative example 1 under a 5000-fold electron microscope;
FIG. 9 is a schematic diagram of the precursor obtained in comparative example 2 under 2500X-ray electron microscope.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments. These examples are only for aiding in the understanding of the invention, and the scope of the invention is to be determined by the claims and not limited by these examples.
Example 1
The preparation method of the high sphericity manganese-rich precursor comprises the following steps:
(1) Nickel sulfate, cobalt sulfate and manganese sulfate are used as raw materials, and the molar ratio of nickel to cobalt to manganese is 0.167:0.167:0.666 preparing a solution with the total concentration of 2mol/L for later use; preparing a solution with the concentration of 2mol/L by using sodium carbonate as a precipitator, and adding ammonia water into an alkali liquor as a complexing agent to ensure that the concentration of ammonia in the alkali liquor is 0.2mol/L for later use;
(2) Adding pure water which is not used for stirring all the reaction kettle into a 20L reaction kettle, and then adding concentrated ammonia water to adjust the pH of the mother solution to 8.0, wherein the mother solution is used as bottom water;
(3) Nucleation: regulating the rotating speed of a stirring paddle of the reaction kettle to 1000r/min, controlling the reaction temperature to 55 ℃, and simultaneously adding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle in parallel by using an accurate metering pump, and keeping the pH value of the reaction solution to 8.0; continuously sampling the test granularity in the reaction process, stopping feeding when the D50 of the material in the reaction kettle reaches 4.0 mu m, and continuously stirring and ageing for 2 hours;
(4) The reaction liquid containing the crystal nucleus is led out, and is settled by standing, redundant supernatant liquid is removed, and the reaction liquid containing the crystal nucleus with the solid content of 40 weight percent is reserved; adding the obtained crystal nucleus reaction liquid into a reaction kettle, and adding pure water to dilute until the solid content is 10wt%;
(5) Regulating the stirring rotation speed of the reaction kettle to 800r/min, regulating the reaction temperature to 50 ℃, adding concentrated ammonia water to regulate the pH of the mother solution to 7.5, continuously adding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle in parallel by using a precise metering pump, regulating the flow of the alkali mixed aqueous solution, and controlling the pH of the reaction solution to 7.5; sampling every 4 hours to detect granularity, stopping feeding when the D50 of the materials in the reaction kettle reaches 10 mu m, and continuing stirring and ageing for 4 hours;
(6) Collecting the aged reaction product, washing the solid material with pure water for multiple times, drying and sieving to obtain the required high sphericity manganese-rich carbonate precursor.
Example 2
The preparation method of the high sphericity manganese-rich precursor specifically comprises the following steps:
(1) Nickel sulfate, cobalt sulfate and manganese sulfate are used as raw materials, and the molar ratio of nickel to cobalt to manganese is 0.30:0.06:0.54, preparing a solution with the total concentration of 2.5mol/L for later use; preparing 2.5mol/L solution by using sodium carbonate as a precipitator, and adding ammonia water into alkali liquor as a complexing agent to ensure that the concentration of ammonia in the alkali liquor is 0.4mol/L for later use;
(2) Adding pure water which is not used for stirring all the reaction kettle into a 20L reaction kettle, and then adding concentrated ammonia water to adjust the pH of the mother solution to 9.0, wherein the mother solution is used as bottom water;
(3) Nucleation: regulating the rotating speed of a stirring paddle of the reaction kettle to 800r/min, controlling the reaction temperature to 60 ℃, simultaneously adding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle by using an accurate metering pump in parallel flow, keeping the reaction pH at 9.0, continuously sampling the test granularity in the reaction process, stopping feeding when the D50 of the materials in the reaction kettle reaches 4.0 mu m, and continuing stirring and ageing for 2 hours;
(4) Leading out the reaction liquid containing the crystal nucleus, standing and settling, removing redundant supernatant, and retaining the reaction liquid containing the crystal nucleus with the solid content of 40 wt%; adding the obtained crystal nucleus reaction liquid into a reaction kettle, and adding pure water to dilute until the solid content is 15wt%;
(5) Regulating the stirring rotation speed of the reaction kettle to 600r/min, regulating the reaction temperature to 50 ℃, adding concentrated ammonia water to regulate the pH of the mother solution to 8.0, continuously adding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle in parallel by using a precise metering pump, regulating the flow of the alkali mixed aqueous solution, and controlling the pH of the reaction solution to 8.0; sampling every 4 hours to detect granularity, stopping feeding when the D50 of the materials in the reaction kettle reaches 8 mu m, and continuing stirring and ageing for 6 hours;
(6) Collecting the aged reaction product, washing the solid material with pure water for multiple times, and then drying and sieving to obtain the required high sphericity manganese-rich carbonate precursor.
Example 3
The preparation method of the high sphericity manganese-rich precursor comprises the following steps:
(1) Nickel nitrate, cobalt nitrate and manganese nitrate are used as raw materials, and the molar ratio of nickel to cobalt to manganese is 0.40:0.10:0.50, preparing a solution with the total concentration of 0.5mol/L for later use; preparing 0.5mol/L solution by using sodium carbonate as a precipitator, and adding ammonia water into alkali liquor as a complexing agent to ensure that the concentration of ammonia in the alkali liquor is 0.1mol/L for later use;
(2) Adding pure water which is not used for stirring all the reaction kettle into a 20L reaction kettle, and then adding concentrated ammonia water to adjust the pH of the mother solution to 8.5, wherein the mother solution is used as bottom water;
(3) Nucleation: regulating the rotating speed of a stirring paddle of the reaction kettle to 900r/min, controlling the reaction temperature to 65 ℃, and simultaneously adding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle in parallel by using an accurate metering pump, and keeping the pH value of the reaction solution to 8.5; continuously sampling the test granularity in the reaction process, stopping feeding when the D50 of the material in the reaction kettle reaches 4.0 mu m, and continuously stirring and ageing for 1 hour;
(4) The reaction liquid containing the crystal nucleus is led out, and is settled by standing, redundant supernatant liquid is removed, and the reaction liquid containing the crystal nucleus with the solid content of 40 weight percent is reserved; adding the obtained crystal nucleus reaction liquid into a reaction kettle, and adding pure water to dilute until the solid content is 10wt%;
(5) Regulating the stirring rotation speed of the reaction kettle to 500r/min, regulating the reaction temperature to 55 ℃, adding concentrated ammonia water to regulate the pH of the mother solution to 8.0, continuously adding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle in parallel by using a precise metering pump, regulating the flow of the alkali mixed aqueous solution, and controlling the pH of the reaction solution to 8.0; sampling every 4 hours to detect granularity, stopping feeding when the D50 of the materials in the reaction kettle reaches 12 mu m, and continuing stirring and ageing for 8 hours;
(6) Collecting the aged reaction product, washing the solid material with pure water for multiple times, drying and sieving to obtain the required high sphericity manganese-rich carbonate precursor.
Example 4
The preparation method of the high sphericity manganese-rich precursor comprises the following steps:
(1) Nickel chloride, cobalt chloride and manganese chloride are adopted as raw materials, and the molar ratio of nickel to cobalt to manganese is 0.05:0:0.95 preparing a solution with the total concentration of 4mol/L for standby; adopting ammonium bicarbonate as a precipitator and a complexing agent simultaneously to prepare a solution with the concentration of 4mol/L for later use;
(2) Adding pure water which is not used for stirring all the reaction kettle into a 20L reaction kettle, and then adding concentrated ammonia water to adjust the pH of the mother solution to 8.0, wherein the mother solution is used as bottom water;
(3) Nucleation: regulating the rotating speed of a stirring paddle of the reaction kettle to 800r/min, controlling the reaction temperature to 55 ℃, and simultaneously adding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle in parallel by using an accurate metering pump, and keeping the pH value of the reaction solution to 8.0; continuously sampling the test granularity in the reaction process, stopping feeding when the D50 of the material in the reaction kettle reaches 3.0 mu m, and continuously stirring and ageing for 2 hours;
(4) The reaction liquid containing the crystal nucleus is led out, and is settled by standing, redundant supernatant liquid is removed, and the reaction liquid containing the crystal nucleus with the solid content of 40 weight percent is reserved; adding the obtained crystal nucleus reaction liquid into a reaction kettle, and adding pure water to dilute until the solid content is 20wt%;
(5) Regulating the stirring rotation speed of the reaction kettle to 700r/min, regulating the reaction temperature to 45 ℃, adding concentrated ammonia water to regulate the pH of the mother solution to 7.5, continuously adding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle in parallel by using a precise metering pump, regulating the flow of the alkali mixed aqueous solution, and controlling the pH of the reaction solution to 7.5; sampling every 4 hours to detect granularity, stopping feeding when the D50 of the materials in the reaction kettle reaches 8 mu m, and continuing stirring and ageing for 4 hours;
(6) Collecting the aged reaction product, washing the solid material with pure water for multiple times, drying and sieving to obtain the required high sphericity manganese-rich carbonate precursor.
Comparative example 1
The preparation method of the manganese-rich precursor in the comparative example comprises the following steps:
(1) Nickel sulfate, cobalt sulfate and manganese sulfate are used as raw materials, and the molar ratio of nickel to cobalt to manganese is 0.167:0.167:0.666 preparing a solution with the total concentration of 2mol/L for later use; preparing a solution with the concentration of 2mol/L by using sodium carbonate as a precipitator, and adding ammonia water into an alkali liquor as a complexing agent to ensure that the concentration of ammonia in the alkali liquor is 0.2mol/L for later use;
(2) Adding pure water which is not passed through all stirring paddles of a reaction kettle into a 20L reaction kettle, and then adding a concentrated ammonia water solution to adjust the pH of the mother solution to 7.5, wherein the mother solution is used as bottom water;
(3) Rotating a stirring paddle to 800r/min, controlling the reaction temperature at 55 ℃, simultaneously adding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into a reaction kettle by using an accurate metering pump in parallel flow, keeping the reaction pH at 7.5, continuously sampling the test granularity in the reaction process, stopping feeding when the D50 of the materials in the reaction kettle reaches about 10 mu m, and continuing stirring and ageing for 2 hours;
(4) And collecting the aged reaction product, washing the solid material with pure water for multiple times, and then drying and sieving to obtain the required manganese-rich carbonate precursor.
Comparative example 2
The preparation method of the manganese-rich precursor in the comparative example comprises the following steps:
(1) Nickel sulfate, cobalt sulfate and manganese sulfate are used as raw materials, and the molar ratio of nickel to cobalt to manganese is 0.167:0.167:0.666 preparing a solution with the total concentration of 2mol/L for later use; preparing a solution with the concentration of 2mol/L by using sodium carbonate as a precipitator, and adding ammonia water into an alkali liquor as a complexing agent to ensure that the concentration of ammonia in the alkali liquor is 0.2mol/L for later use;
(2) Adding pure water which is not used for stirring all the reaction kettle into a 20L reaction kettle, and then adding concentrated ammonia water to adjust the pH of the mother solution to 8.0, wherein the mother solution is used as bottom water;
(3) Nucleation: regulating the rotating speed of a stirring paddle of the reaction kettle to 1000r/min, controlling the reaction temperature to 55 ℃, and simultaneously adding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle in parallel by using an accurate metering pump, and keeping the pH value of the reaction solution to 8.0; continuously sampling the test granularity in the reaction process, stopping feeding when the D50 of the material in the reaction kettle reaches 4.0 mu m, and continuously stirring and ageing for 2 hours;
(4) Collecting the aged reaction product, washing the solid material with pure water for multiple times, drying and sieving to obtain the required manganese-rich carbonate precursor.
Experimental example
The precursors obtained in comparative example 1 and example 1 were used in the following ratios: the metal is mixed with lithium carbonate in a molar ratio of 1.5:1, and the mixture is subjected to air atmosphere at 500 ℃ for 5 hours to 850 ℃Sintering for 12 hours to obtain a finished product, wherein the morphology of the finished product is basically continuous with the spherical morphology of the precursor. The tap densities of the finished products obtained in comparative example 1 and example 1 were 1.91g/cm, respectively 3 And 2.35g/cm 3 . The finished product obtained was mixed with PVDF and Super P according to a ratio of 95:2.5: pulping and coating according to a mass ratio of 2.5, drying the pole piece, rolling under 30Mpa pressure, and measuring the quality and thickness of the pole piece. The pole piece compactions of comparative example 1 and example 1 were measured to be 2.83g/cm, respectively 3 And 3.22g/cm 3 It can be seen that the finished material fired from the precursor of the examples has significant advantages in tap density and compacted density.
Table 1 below gives the particle size and tap density test data for the manganese carbonate-rich precursors prepared in examples 1-2 and comparative example 1, and fig. 1-9 give SEM images of the manganese carbonate-rich precursors prepared in examples 1-2 and comparative examples 1-2, respectively.
Table 1 table of physical properties test data of precursor materials prepared in comparative example 1 and examples 1-2
| Average particle size D50 (μm) | Tap density (g/cm) 3 ） | |
| Comparative example 1 | 9.6 | 1.72 |
| Example 1 | 10.2 | 2.11 |
| Example 2 | 8.1 | 1.96 |
As can be seen from the above Table 1 and the accompanying FIGS. 1-9, the manganese-rich carbonate precursor prepared in examples 1-2 has uniform particle size, high sphericity, high tap density, smooth surface and no obvious pores on the surface; the manganese-rich carbonate precursor prepared in comparative examples 1-2 had the disadvantages of poor sphericity, low tap, non-smooth surface and some voids.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (5)
1. A high sphericity manganese-rich carbonate precursor is characterized by having a general formula Mn x Ni z Co y CO 3 The structure shown, wherein x+y+z=1, and 0.5.ltoreq.x.ltoreq.0.95, 0.ltoreq.y.ltoreq.0.4, 0.ltoreq.z.ltoreq.0.4;
the grain diameter d10 of the high sphericity manganese-rich carbonate precursor is more than or equal to 3 mu m, d50=8-12 mu m, d90 is less than or equal to 20 mu m, and tap density is more than or equal to 1.8g/cm 3 Specific surface area of 5-30m 2 G, the shape is spherical or spheroid;
the preparation method of the high sphericity manganese-rich carbonate precursor comprises the following steps:
(1) Preparing a nickel-cobalt-manganese soluble salt mixed aqueous solution and a carbonate and ammonia-containing alkali mixed aqueous solution according to a selected stoichiometric ratio for later use;
(2) Adding pure water into the sealed reaction kettle, adding ammonia-containing alkali liquor to adjust the pH value of the mother liquor to 8.0-9.0, and taking the mother liquor as bottom water;
(3) Regulating the rotating speed of the reaction kettle to 800-1000r/min at the temperature of 55-65 ℃, respectively feeding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle, controlling the pH value of a reaction system to 8.0-9.0, stopping feeding when detecting that the D50 of the materials in the reaction kettle reaches 2.0-5.0 mu m, and continuing stirring and ageing treatment to obtain crystal nuclei;
(4) The reaction solution containing the crystal nucleus is led out and concentrated to obtain concentrated solution, and the concentrated solution is diluted and added with ammonia water to adjust the pH value to 7.5-8.5, so as to be used as mother solution;
(5) Regulating the rotating speed and the temperature of the reaction kettle to be lower than the rotating speed and the temperature controlled in the step (3), continuously feeding the salt mixed aqueous solution and the alkali mixed aqueous solution prepared in the step (1) into the reaction kettle, controlling the pH value of a reaction system to be lower than the pH value controlled in the step (3), stopping feeding when the D50 of the materials in the reaction kettle is detected to reach a target value, and continuously stirring and ageing;
(6) Collecting a reaction product, washing, drying and sieving to obtain a required high sphericity manganese-rich carbonate precursor;
wherein, in the step (1): in the nickel-cobalt-manganese soluble salt mixed aqueous solution, the total concentration of metal ions is 0.5-4mol/L; in the alkali mixed aqueous solution, the concentration of carbonate is 0.5-4mol/L, and the concentration of ammonia is 0.1-0.5mol/L;
in the step (4): the concentration step is that the reaction solution containing crystal nucleus is settled by standing to remove part of supernatant fluid, and concentrated solution with the solid content of 40wt percent is obtained;
the dilution step is to add pure water into the concentrated solution to dilute until the solid content is 10-20wt%; in the step (5), the rotating speed of the reaction kettle is regulated to be 500-800r/min, the temperature is 45-55 ℃, and the pH value of the reaction system is controlled to be 7.5-8.5.
2. The high spherically enriched manganese carbonate precursor of claim 1, wherein in step (1) the nickel cobalt manganese soluble salt comprises a sulfate, chloride or nitrate of nickel, cobalt, manganese.
3. The high sphericity manganese carbonate precursor according to claim 1, wherein in step (6):
the washing step comprises a step of soaking in deionized water and a step of washing with deionized water for a plurality of times;
the drying step is that the water content is less than or equal to 1.0 weight percent after drying at 80-110 ℃.
4. Use of the high sphericity manganese-rich carbonate precursor according to any one of claims 1-3 for the preparation of a lithium ion battery positive electrode material, a lithium ion battery positive electrode, a lithium ion battery.
5. A lithium ion battery positive electrode material, a lithium ion battery positive electrode or a lithium ion battery prepared based on the high sphericity manganese-rich carbonate precursor of any one of claims 1-3.
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| US20190115595A1 (en) * | 2016-08-30 | 2019-04-18 | Shandong Yuhuang New Energy Technology Co., Ltd. | High-quality, lithium-rich and manganese-based positive electrode material for lithium ion battery, and method for synthesizing same |
| CN111498908A (en) * | 2020-04-27 | 2020-08-07 | 中信大锰矿业有限责任公司 | Preparation method of quasi-spherical manganese-rich ternary precursor |
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