CN112978813B - Nickel-containing hydroxide precursor, preparation method thereof and positive electrode material - Google Patents
Nickel-containing hydroxide precursor, preparation method thereof and positive electrode material Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002243 precursor Substances 0.000 title claims abstract description 63
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 title abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 20
- 230000006911 nucleation Effects 0.000 claims abstract description 19
- 238000010899 nucleation Methods 0.000 claims abstract description 19
- 239000011164 primary particle Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 21
- 230000032683 aging Effects 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 17
- 239000011163 secondary particle Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000012716 precipitator Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910003678 NixCoyMnz(OH)2 Inorganic materials 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 241000446313 Lamella Species 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012066 reaction slurry Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- 238000001354 calcination Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 description 16
- 239000011572 manganese Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001878 scanning electron micrograph Methods 0.000 description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 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
- 238000000227 grinding Methods 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
- 238000005096 rolling process Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 3
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000010923 batch production Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
- C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明属于锂离子电池材料技术领域，具体公开了一种含镍氢氧化物前驱体及其制备方法、以及一种正极材料。本发明在制备含镍氢氧化物前驱体过程中，先氮气保护，有效控制反应初期的成核数量，之后通入空气（氧气）氧化，制备得到的产物的一次颗粒形貌为规则板条状，且为疏松竖立排布特征，满足单晶正极材料的烧结要求。前驱体与锂源等混合焙烧后得到的正极材料，无需水洗即可控制正极材料的可溶锂总量≤1500ppm，在降低生产成本的同时，还避免了水洗材料带来的除杂成本、环境污染成本等负面影响。
The invention belongs to the technical field of lithium ion battery materials, and specifically discloses a nickel-containing hydroxide precursor, a preparation method thereof, and a positive electrode material. In the process of preparing the nickel-containing hydroxide precursor, the method firstly protects the nucleation with nitrogen to effectively control the number of nucleation in the initial stage of the reaction, and then introduces air (oxygen) for oxidation, and the primary particle morphology of the prepared product is a regular lath shape , and is characterized by loose vertical arrangement, which meets the sintering requirements of single crystal positive electrode materials. The cathode material obtained by mixing and calcining the precursor and the lithium source can control the total amount of soluble lithium of the cathode material to be less than or equal to 1500ppm without water washing. While reducing the production cost, it also avoids the cost of removing impurities and the environment caused by washing the material. Negative impacts such as pollution costs.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a high-nickel hydroxide precursor, a preparation method thereof and a positive electrode material.
Background
Lithium ion secondary batteries have become more and more important in people's lives, have been widely used as a source of portable electric power by people, and have the advantages of high voltage, high specific energy, long charging and discharging life, no memory effect, no pollution, rapid charging, low self-discharging rate, wide working temperature range, safety, reliability and the like. With the national emphasis on environmental protection, the industry is more and more urgently upgraded, and the new energy industry is well developed. In the technical aspect of new energy vehicles, batteries are the most concerned core components of new energy vehicles, and around the components, how to improve the energy density of matched batteries, how to improve the driving range and reduce the cost are the most concerned focuses of vehicle enterprises. The high nickel single crystal anode material matched with the lithium ion battery of the power automobile is researched and developed, and the high nickel single crystal anode material has wide application prospect.
At present, high-nickel polycrystalline positive electrode materials in the market are difficult to avoid rupture of secondary particles in a pressing process due to inherent structural instability of the secondary particles, and in the secondary particles, repeated volume change of primary crystal grains in a charge-discharge cycle process further aggravates rupture of the secondary particles, so that performance is reduced too fast, and particularly, the rupture of the materials is more serious when the voltage is more than 4.15V. In contrast, single crystal positive electrode materials with good structural integrity can exhibit high initial capacity, stable cycling performance and excellent rate performance in batteries even without surface modification. The coated single crystal cathode material shows the most excellent initial discharge specific capacity and capacity retention rate. In the conventional intermittent production process of the precursor of the high-nickel single crystal cathode material, the nucleation quantity is unstable due to the high nickel content, the physicochemical indexes of the product after coprecipitation are large in difference, great difficulty is brought to the realization of standard batch production, and meanwhile, the difference of the physicochemical indexes of the precursor has great negative influence on subsequent sintering.
In the prior art, chinese patent application with publication number CN111333126A discloses a precursor of lithium nickel cobalt manganese oxide material and a preparation method thereof, wherein an oxidative additive is added in a coprecipitation process to modify and adjust the morphology and crystallinity index of primary particles of the precursor, so as to obtain a precursor with a radial primary particle section and spherical secondary particles. But the precursor is mainly used for polycrystalline materials.
The Chinese patent application with publication number CN112226820A discloses a single-crystal lithium nickel cobalt manganese oxide precursor and a preparation method thereof, wherein mixed gas with a volume ratio of oxygen to non-oxygen being a certain proportion is added in the whole coprecipitation process, the morphology and physical and chemical indexes of primary particles of the precursor are modified, and the single-crystal lithium nickel cobalt manganese oxide precursor with the primary particle lamella thickness of 100-200nm, the particle size D50 of 3.0-4.0 mu m and the particle size distribution (D90-D10)/D50 of less than or equal to 0.8 is obtained. However, in the scheme, the specific surface area of particles is increased due to oxidation in the initial nucleation stage of the reaction, so that the agglomeration is increased, and the nucleation amount is difficult to control.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the background technology and provide a high-nickel single crystal precursor with special morphology, a preparation method thereof and a high-nickel single crystal cathode material. The high-nickel single crystal positive electrode material has excellent cycle performance while keeping high specific capacity.
In order to solve the technical problems, the invention provides the following technical scheme:
firstly, the invention provides a nickel-containing hydroxide precursor with a chemical molecular formula of NixCoyMnz(OH)2Wherein x + y + z =1, x is more than or equal to 0.7 and less than 1.0, y is more than or equal to 0 and less than or equal to 0.2, and z is more than or equal to 0 and less than or equal to 0.2; the primary particles are regular laths and are vertically and loosely arranged, are vertically and vertically inserted towards the center of the secondary particles, and are rectangular blocks in a two-dimensional plane view; primary particle sheet layerThe length of the film is 300-1100nm, and the thickness of the film is 50-300 nm; the secondary particles are distributed narrowly, and the diameter distance is less than or equal to 0.75; carrying out chromatography on the precursor with a median particle size of 3.0-6.0 μm and a tap density of 1.5-2.2g/cm on a sieve having a specific surface area of 6-14 m/g.
The precursor provided by the invention has uniform primary particle size and proper arrangement porosity among particles, is convenient for effectively reducing the residual lithium after sintering, and improves the cycle efficiency.
As a general inventive concept, the present invention further provides the foregoing method for preparing a nickel-containing hydroxide precursor, comprising the steps of:
(1) according to the formula NixCoyMnz(OH)2Preparing a metal salt solution; wherein x + y + z =1, x is more than or equal to 0.7 and less than 1.0, y is more than or equal to 0 and less than or equal to 0.2, and z is more than or equal to 0 and less than or equal to 0.2;
(2) the reactions of nucleation and crystal growth are carried out in stages: respectively introducing a metal salt solution, a precipitator and a complexing agent into a reaction kettle with a base solution in a nitrogen protection atmosphere, and starting and finishing a nucleation process; respectively introducing a metal salt solution, a precipitator and a complexing agent into a reaction kettle in an oxygen atmosphere to start and finish a crystal growth process;
(3) and (3) carrying out solid-liquid separation on the reaction slurry obtained in the step (2), and carrying out aging, washing, dehydration, drying and screening treatment on the solid phase to obtain the precursor.
In the preparation method, the kettle body is sealed before the reaction starts, nitrogen is continuously introduced into the reaction kettle for at least 3 hours, and the reaction system in the nucleation stage is continuously introduced with nitrogen to prevent the nitrogen from being oxidized; after the nucleation stage is completed, the reactants are oxidized by switching nitrogen to air (oxygen). One of the key nodes of the technology is that nitrogen protection is adopted in the nucleation stage, the nucleation quantity is effectively controlled, the crystal growth is carried out in an oxygen-containing environment by switching the growth stage into air, the primary particle morphology of the product is in a required regular lath shape, the flow rate of the switched air is set to be 25-200L/h according to the characteristic index of the product and the volume of the reaction kettle, and the air flow introduced into the reaction kettle per cubic meter is set to be 25-200L/h.
In the above preparation method, preferably, in the step (2), the total concentration of the metal ions in the metal salt solution is 1.5 to 2.5mol/L, the concentration of the precipitant is 3.0 to 10.0mol/L, and the concentration of the complexing agent is 4.0 to 13.5 mol/L. The concentration of the metal ions in the metal salt solution and the concentrations of the precipitator and the complexing agent are selected and determined by comprehensively considering the growth rate of the particles, the dispersion condition of the particles and the morphological characteristics among the particles in the production process.
In the above preparation method, preferably, the precipitant is one or more of potassium hydroxide, sodium hydroxide and ammonium carbonate; preferably, the complexing agent is one or more of ethylenediamine tetraacetate, ammonia water and tartaric acid; the base solution is a mixed solution of sodium hydroxide and ammonia water, and preferably, the temperature of the base solution is 55-70 ℃; preferably, the concentration of ammonia water in the base solution is 5-15g/L, and the pH value is 10.00-11.80.
In the preparation method, preferably, in the crystal growth stage in the step (2), the stirring rotation speed is 120-300r/min, the pH value of the reaction system is 9.80-11.80, and the concentration of ammonia water is 5-15 g/L; the solid content in the reaction system is 200-600g/L, and the reaction time is 35-65 h.
In the preparation method, preferably, during aging, 5-20wt% of alkali liquor is adopted to carry out aging reaction on the solid phase (coprecipitation product), wherein the aging temperature is 50-80 ℃, and the aging reaction time is 30-60 min; during washing, deionized water is adopted for washing, and the pH value of the washing end point is 8.0-8.5; controlling the water content of the material to be below 20% after dehydration; during drying, the drying temperature is 120-180 ℃, and the water content of the dried material is 0.20-1.00%.
In addition, the invention also provides a high-nickel single crystal cathode material, which is obtained by mixing and roasting the nickel-containing hydroxide precursor, a lithium source and/or other substances, and the total amount of soluble lithium of the cathode material is less than or equal to 1500ppm without washing.
Compared with the prior art, the invention has the following beneficial effects:
1. the nickel-containing hydroxide precursor is mixed with a lithium source and the like and roasted to obtain the cathode material, washing is not needed, the total amount of soluble lithium of the cathode material is less than or equal to 1500ppm, and the negative effects of impurity removal cost, environmental pollution cost and the like caused by washing the material are avoided while the production cost is reduced.
2. In the process of preparing the nickel-containing hydroxide precursor, nitrogen is firstly used for protection, the nucleation number at the initial stage of the reaction is effectively controlled, then air (oxygen) is introduced for oxidation, and the pH value balance position of the reaction system is reduced, so that the pH value of the crystal growth environment is reduced on the premise that no new nucleus is generated, the primary particle morphology of the product is in a required regular strip shape, the product is in a loose vertical arrangement characteristic, and the sintering requirement of the single crystal anode material is met.
3. The preparation method disclosed by the invention is simple in process flow, high in automation degree, stable in product quality, capable of realizing batch production and wide in application prospect.
Drawings
Fig. 1 is a scanning electron micrograph of the precursor material prepared in example 1.
Fig. 2 is a scanning electron micrograph of the precursor material prepared in example 2.
Fig. 3 is a scanning electron micrograph of the precursor material prepared in comparative example 1.
Fig. 4 is a scanning electron micrograph of the precursor material prepared in comparative example 2.
Fig. 5 is a scanning electron micrograph of the positive electrode material prepared in example 1.
Fig. 6 is a scanning electron micrograph of the positive electrode material prepared in example 2.
Fig. 7 is a scanning electron micrograph of the positive electrode material prepared in comparative example 1.
Detailed Description
The present invention will now be described in detail with reference to the drawings, which are given by way of illustration and explanation only and should not be construed to limit the scope of the present invention in any way. Furthermore, those skilled in the art can combine features from the embodiments of this document and from different embodiments accordingly based on the description of this document.
Example 1
Preparing a nickel-containing hydroxide precursor comprising the steps of:
(1) according to the molecular formula Ni0.88Co0.09Mn0.03(OH)2Preparing materials, namely preparing nickel sulfate, cobalt sulfate and manganese sulfate into a mixed salt solution with the total metal ion concentration of 2mol/L according to the molar ratio of nickel to cobalt to manganese of 0.88:0.09: 0.03.
(2) Adding deionized water into a reaction kettle with the volume of 1m for carrying out dry distillation, controlling the stirring speed at 280r/min, heating to 67.5 ℃, and adding ammonia water and a sodium hydroxide solution into the reaction kettle to form a bottom solution of the reaction kettle; the ammonia water concentration in the bottom liquid of the reaction kettle is 12g/L, the pH value is adjusted to 11.80, and nitrogen is continuously introduced for 3 hours before feeding.
(3) And (2) under the protection of nitrogen, enabling the mixed salt solution in the step (1), a precipitator with the concentration of 6mol/L and complexing agent ammonia water with the concentration of 8mol/L to flow into the reaction kettle in a concurrent flow manner, maintaining the pH value of the reaction system at 11.80 for 1h, and reducing the pH value within 2h until no new nucleus is generated.
(4) And (3) closing the nitrogen, starting air, keeping the air flow at 100L/h, continuously feeding for coprecipitation reaction, gradually reducing the stirring speed of the coprecipitation reaction to 250r/min from 280r/min along with the prolonging of the reaction time in the feeding process, keeping the concentration of ammonia water at 12g/L, controlling the reaction temperature at 67.5 ℃ and the pH value at 11.70-11.80, detecting the particle size of a sample in the process, reacting for 60h, keeping the median particle size at 3.80 mu m, and stopping feeding.
(5) Carrying out aging reaction on the reaction material by using alkali liquor with the mass fraction of 5wt% at 65 ℃, wherein the aging reaction time is 30min, washing the material subjected to the aging reaction by using deionized water at normal temperature, the pH value at the washing end point is 8.2, dehydrating, drying at 120 ℃ and screening the washed reaction material to obtain a precursor of nickel, cobalt and manganese coprecipitation for the high-nickel single crystal positive electrode material, wherein the tap density of the precursor is 1.81g/cm, and the specific surface area is 9.68m2/g。
FIG. 1 is a scanning electron micrograph of the precursor material prepared in example 1; as can be seen from fig. 1, the primary particles of the precursor are uniform, slender laths, are vertically and loosely arranged, are vertically and straightly inserted towards the center of the secondary particles, and are rectangular blocks in a two-dimensional plane view; the secondary particles are narrow in distribution, round and smooth and good in dispersibility.
100kg of Ni precursor material prepared in this example0.88Co0.09Mn0.03(OH)2Mixing with 45kg of lithium hydroxide for 30min, calcining at 800 ℃ in an oxygen atmosphere for 10h, discharging, grinding and rolling, performing cyclone separation, sieving, and performing heat treatment to obtain the secondary agglomerated spherical high-nickel single crystal cathode material with the D50 of 5.05 um.
Fig. 5 is a scanning electron micrograph of the cathode material prepared in example 1, and it can be seen from fig. 5 that the cathode material has a single crystal form, uniform particle size, and excellent uniformity.
Example 2
Preparing a nickel-containing hydroxide precursor comprising the steps of:
(1) according to the molecular formula Ni0.70Co0.05Mn0.25(OH)2Preparing materials, namely preparing nickel sulfate, cobalt sulfate and manganese sulfate into mixed salt solution with the total ion concentration of 2.2mol/L according to the molar ratio of nickel, cobalt and manganese of 0.70:0.05: 0.25.
(2) Adding deionized water into a reaction kettle with the volume of 100L, controlling the stirring speed at 300r/min, heating to 60 ℃, and adding ammonia water and a sodium hydroxide solution into the reaction kettle to form a bottom solution of the reaction kettle; the concentration of ammonia water in the bottom liquid of the reaction kettle is 10g/L, the pH value is adjusted to 11.50, and nitrogen is continuously introduced for 3 hours before feeding.
(3) Under the protection of nitrogen, enabling the mixed salt solution in the step (1), a precipitator with the concentration of 5mol/L and complexing agent ammonia water with the concentration of 5mol/L to flow into a reaction kettle, and completing nucleation and quantity confirmation;
(4) and (3) closing nitrogen, starting air, keeping the air flow at 4L/h, continuously feeding for coprecipitation reaction, gradually reducing the stirring speed of the coprecipitation reaction to 280r/min from 300r/min along with the prolonging of the reaction time in the feeding process, keeping the concentration of ammonia water at 10g/L, controlling the reaction temperature at 60 ℃, controlling the pH value to be 11.50-11.20, detecting the particle size of a sample in the process, reacting for 72 hours, and stopping feeding, wherein the median particle size is 4.0 mu m.
(5) Carrying out aging reaction on the reaction material by using alkali liquor with the mass fraction of 8wt% at the temperature of 60 ℃, wherein the aging reaction time is 40min, washing the material subjected to the aging reaction by using deionized water at normal temperature, the pH value at the washing end point is 8.2, dehydrating, drying at the temperature of 125 ℃ and screening the washed reaction material to obtain a precursor of nickel, cobalt and manganese coprecipitation for the high-nickel single crystal positive electrode material, wherein the tap density of the precursor is 1.85g/cm, and the specific surface area of the precursor is 9.73m2/g。
FIG. 2 is a scanning electron micrograph of the precursor material prepared in example 2; as can be seen from FIG. 2, the primary particles of the precursor are uniform laths, are in vertical loose arrangement, and have the characteristics of narrow secondary particle distribution, round secondary particles, no agglomerated particles, and good dispersibility.
100kg of Ni precursor material prepared in this example0.70Co0.05Mn0.25(OH)2Mixing with 39kg of lithium hydroxide for 25min, calcining at 850 ℃ in an oxygen atmosphere for 12h, discharging, grinding and rolling, performing cyclone separation, sieving, and performing heat treatment to obtain the secondary agglomerated spherical high-nickel single crystal cathode material with the D50 of 5.19 um.
Fig. 6 is a scanning electron micrograph of the single crystal cathode material prepared in example 2, and it can be seen from fig. 6 that the cathode material has a single crystal form, uniform particle size, and excellent uniformity.
Comparative example 1
In comparison with example 1, the reaction atmosphere in the crystal growth stage of this comparative example was also nitrogen. Specifically, the preparation method of the precursor material comprises the following steps:
(1) according to the molecular formula Ni0.88Co0.09Mn0.03(OH)2Preparing materials, namely preparing nickel sulfate, cobalt sulfate and manganese sulfate into mixed salt solution with the total ion concentration of 2mol/L according to the molar ratio of nickel to cobalt to manganese of 0.88:0.09: 0.03.
(2) Adding deionized water into a reaction kettle with the volume of 1m for carrying out dry distillation, controlling the stirring speed at 280r/min, heating to 67.5 ℃, and adding ammonia water and a sodium hydroxide solution into the reaction kettle to form a bottom solution of the reaction kettle; the ammonia water concentration in the bottom liquid of the reaction kettle is 12g/L, the pH value is adjusted to 11.80, and nitrogen is continuously introduced for 3 hours before feeding.
(3) And (3) under the protection of nitrogen, enabling the mixed salt solution in the step (1), a precipitator with the concentration of 6mol/L and complexing agent ammonia water with the concentration of 8mol/L to flow into a reaction kettle, and completing nucleation and quantity confirmation.
(4) And continuously feeding the materials to carry out coprecipitation reaction under the nitrogen protection atmosphere, gradually reducing the stirring speed of the coprecipitation reaction in the feeding process from 280r/min to 250r/min along with the prolonging of the reaction time, keeping the concentration of ammonia water at 12g/L, controlling the reaction temperature at 67.5 ℃ and the pH value at 11.70-11.80, detecting the particle size of a sample in the process, reacting for 60 hours, and stopping feeding, wherein the median particle size is 3.65 mu m.
(5) Carrying out aging reaction on the reaction material by using alkali liquor with the mass fraction of 5wt% at 65 ℃, wherein the aging reaction time is 30min, washing the material subjected to the aging reaction by using deionized water at normal temperature, the pH value at the washing end point is 8.2, dehydrating, drying at 120 ℃ and screening the washed reaction material to obtain a precursor of nickel, cobalt and manganese coprecipitation for the high-nickel single crystal positive electrode material, wherein the tap density of the precursor is 2.11g/cm, and the specific surface area is 4.79m2/g。
The precursor material obtained in the comparative example is 100kgNi0.88Co0.09Mn0.03(OH)2And mixing the precursor with 47kg of lithium hydroxide for 25 inches, calcining in oxygen at 800 ℃ for 12 hours, discharging, grinding and rolling, performing cyclone separation, sieving, and performing heat treatment to obtain the secondary agglomerated spherical high-nickel single crystal anode material D50 of 4.99 um.
FIG. 3 is a scanning electron micrograph of the precursor material prepared in comparative example 1; as can be seen from FIG. 3, the primary particles of the precursor are irregular stone-like and are arranged vertically and densely, the secondary particles are distributed narrowly, the secondary particles are round and smooth, and the dispersibility is good. Fig. 7 is a scanning electron micrograph of the positive electrode material prepared in comparative example 1; as can be seen from fig. 7, the positive electrode material had a single crystal form, but the particles varied in size and fine powder appeared.
Comparative example 2
In comparison with example 2, this comparative example also passed an oxygen atmosphere during the nucleation stage. Specifically, the preparation method of the precursor material comprises the following steps:
(1) according to the molecular formula Ni0.70Co0.05Mn0.25(OH)2Preparing materials, namely preparing nickel sulfate, cobalt sulfate and manganese sulfate into mixed salt solution with the total ion concentration of 2.2mol/L according to the molar ratio of nickel, cobalt and manganese of 0.70:0.05: 0.25.
(2) Adding deionized water into a reaction kettle with the volume of 100L, controlling the stirring speed at 300r/min, heating to 60 ℃, and adding ammonia water and a sodium hydroxide solution into the reaction kettle to form a bottom solution of the reaction kettle; the concentration of ammonia water in the bottom liquid of the reaction kettle is 10g/L, the pH value is adjusted to 11.50, and nitrogen is not introduced for protection;
(3) under the air atmosphere, the air flow is 4L/h, the mixed salt solution in the step (1), a precipitator with the concentration of 5mol/L and complexing agent ammonia water with the concentration of 5mol/L flow into a reaction kettle, and nucleation and quantity confirmation are completed;
(4) keeping the air flow at 4L/h, continuously feeding for coprecipitation reaction, gradually reducing the stirring speed of the coprecipitation reaction to 280r/min from 300r/min along with the prolonging of the reaction time in the feeding process, keeping the concentration of ammonia water at 10g/L, controlling the reaction temperature at 60 ℃, controlling the pH value to be 11.50-11.20, detecting the particle size of a sample in the process, and stopping feeding after the median particle size is 4.2 mu m after the reaction is carried out for 35 h.
(5) Carrying out aging reaction on the reaction material by using alkali liquor with the mass fraction of 8wt% at the temperature of 60 ℃, wherein the aging reaction time is 40min, washing the material subjected to the aging reaction by using deionized water at normal temperature, the pH value at the washing end point is 8.2, dehydrating, drying at the temperature of 125 ℃ and screening the washed reaction material to obtain a precursor of nickel, cobalt and manganese coprecipitation for the high-nickel single crystal positive electrode material, wherein the tap density of the precursor is 1.35g/cm, and the specific surface area of the precursor is 15.69m2/g。
The precursor material obtained in the comparative example is 50kgNi0.70Co0.05Mn0.25(OH)2The precursor was mixed with 22.5kg of lithium hydroxide for 25min, then at 750 deg.CCalcining in oxygen for 10h, discharging, grinding, rolling, cyclone separating, sieving, and heat treating to obtain the secondary agglomerated spherical high-nickel monocrystal anode material with D50 of 5.12 um.
FIG. 4 is a scanning electron micrograph of the precursor material prepared in comparative example 2; as can be seen from fig. 4, the primary particles of the precursor are in a thin sheet state, the gaps among the primary particles are large and large, the secondary particles are seriously agglomerated, and the twinning growth phenomenon of multiple spheres is presented.
The physical and chemical indexes of the positive electrode materials prepared in examples 1 and 2 and comparative examples 1 and 2 were further examined and analyzed, and the results are shown in table 1.
Table 1 physical property indexes after sintering precursors of examples 1 and 2 and comparative examples 1 and 2 into single crystal positive electrode material
As can be seen from table 1, compared with the cathode material obtained by calcining the precursor prepared in the comparative example, in examples 1 and 2, the cathode material prepared by the technical scheme provided by the present application has a lower soluble lithium content, a higher first charge-discharge efficiency, and a higher 0.1C discharge capacity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (3)
1. A method for preparing a nickel-containing hydroxide precursor is characterized in that,
the chemical molecular formula of the precursor is NixCoyMnz(OH)2Wherein x + y + z =1, x is more than or equal to 0.7 and less than 1.0, y is more than or equal to 0 and less than or equal to 0.2, and z is more than or equal to 0 and less than or equal to 0.2; the primary particles of the precursor are regular laths and are vertically and loosely arranged, are vertically and vertically inserted towards the center of the secondary particles, and are rectangular blocks in a two-dimensional plane view; the length of the primary particle lamella is 300-1100nmThe thickness is 50-300 nm; the secondary particles are distributed narrowly, and the diameter distance is less than or equal to 0.75; carrying out chromatography on the precursor with a median particle size of 3.0-6.0 μm and a tap density of 1.5-2.2g/cm on a sieve having a specific surface area of 6-14 m/g;
the preparation method comprises the following steps:
(1) according to the formula NixCoyMnz(OH)2Preparing a metal salt solution; wherein x + y + z =1, x is more than or equal to 0.7 and less than 1.0, y is more than or equal to 0 and less than or equal to 0.2, and z is more than or equal to 0 and less than or equal to 0.2; the total concentration of metal ions in the metal salt solution is 1.5-2.5 mol/L;
(2) the reactions of nucleation and crystal growth are carried out in stages: respectively introducing a metal salt solution, a precipitator and a complexing agent into a reaction kettle with a base solution in a nitrogen protection atmosphere, and starting and finishing a nucleation process; respectively introducing a metal salt solution, a precipitator and a complexing agent into a reaction kettle in an oxygen atmosphere to start and finish a crystal growth process; after the nucleation reaction is finished, switching the nitrogen into air or oxygen, and setting the air flow rate of the air introduced into each cubic meter of the reaction kettle to be (25-200) L.h according to the volume of the reaction kettle-1；
The concentration of the precipitator is 3.0-10.0mol/L, and the concentration of the complexing agent is 4.0-13.5 mol/L; the base solution is a mixed solution of sodium hydroxide and ammonia water, the temperature is 55-70 ℃, the concentration of the ammonia water is 5-15g/L, and the pH value is 10.00-11.80;
in the stage of crystal growth, the stirring speed is 120-300r/min, the pH value of the reaction system is 9.80-11.80, the concentration of ammonia water is 5-15g/L, the content of solid matters in the reaction system is 200-600g/L, and the reaction time is 35-65 h;
(3) and (3) carrying out solid-liquid separation on the reaction slurry obtained in the step (2), and carrying out aging, washing, dehydration, drying and screening treatment on the solid phase to obtain the precursor.
2. The preparation method according to claim 1, wherein the precipitant is one or more of potassium hydroxide, sodium hydroxide, and ammonium carbonate; the complexing agent is one or more of ethylenediamine tetraacetate, ammonia water and tartaric acid.
3. The process according to claim 1, wherein in the step (3), the solid phase is aged with 5 to 20wt% of alkali solution at 50 to 80 ℃ for 30 to 60 min; during washing, deionized water is adopted for washing, and the pH value of the washing end point is 8.0-8.5; controlling the water content of the material to be below 20% after dehydration; during drying, the drying temperature is 120-180 ℃, and the water content of the dried material is 0.20-1.00%.
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| CN113582256B (en) * | 2021-09-28 | 2021-12-10 | 金驰能源材料有限公司 | A kind of high nickel single crystal positive electrode material and its precursor, and the preparation method of the precursor |
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