CN114477312A - Method for preparing ternary cathode material precursor by layered doping - Google Patents
Method for preparing ternary cathode material precursor by layered doping Download PDFInfo
- Publication number
- CN114477312A CN114477312A CN202111658802.8A CN202111658802A CN114477312A CN 114477312 A CN114477312 A CN 114477312A CN 202111658802 A CN202111658802 A CN 202111658802A CN 114477312 A CN114477312 A CN 114477312A
- Authority
- CN
- China
- Prior art keywords
- solution
- precursor
- cathode material
- ternary cathode
- salt solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 53
- 239000010406 cathode material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 239000012266 salt solution Substances 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 34
- 238000000975 co-precipitation Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 19
- 150000003297 rubidium Chemical class 0.000 claims abstract description 18
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- 239000012716 precipitator Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910001419 rubidium ion Inorganic materials 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 3
- 239000011258 core-shell material Substances 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 238000012216 screening Methods 0.000 claims abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- -1 molybdenum ion Chemical class 0.000 claims description 3
- 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
- 229910003618 NixCoyMn1-x-y(OH)2 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 239000008367 deionised water Substances 0.000 abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 abstract description 4
- 230000006911 nucleation Effects 0.000 abstract description 4
- 238000010899 nucleation Methods 0.000 abstract description 4
- 239000002585 base Substances 0.000 description 14
- 239000003513 alkali Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- SDEPJGRDJDRALP-UHFFFAOYSA-N [Mo].[Rb] Chemical compound [Mo].[Rb] SDEPJGRDJDRALP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 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
- C01P2006/40—Electric properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing a ternary cathode material precursor by layered doping, which comprises the steps of adding a metal salt solution, a precipitator solution, a complexing agent solution and a rubidium salt solution into a bottom solution of a reaction kettle, carrying out coprecipitation reaction, suspending feeding when the particle size of particles in the reaction kettle grows to be smaller than a target particle size by 0.5-3 mu m, adding deionized water, and concentrating and displacing a feed liquid containing rubidium ions in the reaction kettle; then continuing the coprecipitation reaction, simultaneously adding a molybdenum salt solution to carry out the coprecipitation reaction until the average particle size of the particles grows to the target particle size, and stopping feeding to obtain a solution containing a precursor material; and stirring the obtained solution containing the precursor material, aging, washing, drying, screening and removing iron to obtain the precursor of the core-shell structure ternary cathode material. The invention can prevent the generation of cracks in the nucleation process of the precursor of the ternary cathode material, improve the high-temperature cycle performance and the rate capability of the ternary cathode material, and simultaneously improve the conductivity and the capacity retention rate of the lithium ion battery.
Description
Technical Field
The invention relates to a precursor of a ternary cathode material, in particular to a method for preparing the precursor of the ternary cathode material by layered doping.
Background
The nickel-cobalt-manganese ternary positive electrode material precursor is the most important raw material for preparing the positive electrode material of the lithium ion battery, the main preparation method of the ternary precursor is to add a nickel-cobalt-manganese metal salt solution, liquid caustic soda and ammonia water into a reaction kettle simultaneously for coprecipitation reaction, and microcracks are usually generated in the process of coprecipitation reaction nucleation due to the limitation of equipment and process conditions. In order to better exert the excellent performance of the ternary cathode material, the preparation of the precursor is crucial to the production of the ternary cathode material, because the quality (morphology, particle size distribution, specific surface area, impurity content, tap density and the like) of the precursor directly determines the physicochemical index of the final sintered product, the sintered ternary cathode material has general electrical property and poor cycle performance and specific capacity, in order to solve the defects, a method of doping other metal elements or coating the surface of the ternary precursor is mostly adopted in the preparation process of the ternary precursor at present, and although the doping or coating can improve the high-temperature cycle performance and the rate capability of the ternary cathode material, the conductivity and the capacity retention of the prepared lithium ion battery are poor, and the requirement cannot be met.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing a precursor of a ternary cathode material by layered doping, so that cracks are prevented from being generated in the nucleation process of the precursor of the ternary cathode material, the high-temperature cycle performance and the rate capability of the ternary cathode material are improved, and the conductivity and the capacity retention rate of a lithium ion battery are improved.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for preparing a precursor of a ternary cathode material by layered doping comprises the following steps:
(1) preparing a metal salt solution, a precipitator solution, a complexing agent solution, a rubidium salt solution and a molybdenum salt solution;
(2) adding water, a complexing agent solution and a precipitator solution into a reaction kettle, stirring and keeping constant temperature to prepare a reaction kettle bottom solution;
(3) adding a metal salt solution, a precipitator solution, a complexing agent solution and a rubidium salt solution into a bottom solution of the reaction kettle, carrying out coprecipitation reaction, stopping feeding when the particle size of particles in the reaction kettle grows to be 0.5-3 mu m smaller than a target particle size, and concentrating and displacing a feed liquid containing rubidium ions in the reaction kettle;
(4) then, continuously adding a metal salt solution, a precipitator solution and a complexing agent solution into the reaction kettle, simultaneously adding a molybdenum salt solution for coprecipitation reaction until the average particle size of the particles grows to a target particle size, and stopping feeding to obtain a solution containing a precursor material;
(5) and (4) stirring the solution containing the precursor material obtained in the step (4), aging, washing, drying, screening and removing iron to obtain the precursor of the core-shell structure ternary cathode material.
Further, the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt, the molar ratio of the nickel salt to the cobalt salt to the manganese salt is 60-90: 5-20: 10-30, the total concentration of metal ions in the metal salt solution is 1-2 mol/L, and the nickel salt, the cobalt salt and the manganese salt are at least one of sulfate, nitrate and halogen salt.
Further, the precipitator solution is a sodium hydroxide solution with the concentration of 5-12 mol/L, the complexing agent solution is an ammonia water solution with the mass concentration of 12% -24%, the rubidium ion concentration in the rubidium salt solution is 0.1-1 mol/L, and the molybdenum ion concentration in the molybdenum salt solution is 0.1-1 mol/L.
Further, in the step (3) and the step (4), the reaction temperature is controlled to be 40-70 ℃, the pH value is 11.5-13, the ammonia concentration is 2-16 g/L, and the stirring speed is 300-600 rpm.
Further, the feeding amount of the metal salt solution is 20-500L/h, the feeding amount ratio of the rubidium salt solution to the metal salt solution is 1: 200-10000, and the feeding amount ratio of the molybdenum salt solution to the metal salt solution is 1: 200-10000.
Further, the average particle size of the particles in the step (3) is a particle size distribution D50 value, and the target particle size is 3-13 μm.
Further, the molecular formula of the precursor of the prepared ternary cathode material is as follows: nixCoyMn1-x-y(OH)2[Rb]m[Mo]nAnd m and n are doping amount, wherein x is more than or equal to 0.50 and less than or equal to 0.90, y is more than or equal to 0.05 and less than or equal to 0.30, 0.05 and less than or equal to 1-x-y is less than or equal to 0.30, m is more than or equal to 0.0001 and less than or equal to 0.005, and n is more than or equal to 0.0001 and less than or equal to 0.005.
Further, in the step (3), the feed liquid containing rubidium ions in the reaction kettle is replaced by concentration.
The ternary cathode material is prepared by the method for preparing the precursor of the ternary cathode material by layered doping.
A lithium ion battery comprises the ternary cathode material.
The invention has the beneficial effects that: the method for preparing the precursor of the ternary cathode material by layered doping prevents cracks from being generated in the nucleation process of the precursor of the ternary cathode material, improves the high-temperature cycle performance and the rate capability of the ternary cathode material, and simultaneously improves the conductivity and the capacity retention rate of the lithium ion battery, wherein the maximum capacity of the lithium ion battery is 192.5mah/g after 100 cycles of 1C rate cycle, and the maximum conductivity is 9.7 multiplied by 10-3The capacity retention rate is 92.68% at most after 100 cycles.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
adding pure water into a reaction kettle, heating to 60 ℃, adjusting the pH value of the prepared liquid alkali solution to 12.0, adding an ammonia water solution to prepare a base solution to be 4.5g/L, and operating stirring blades in the reaction kettle at a rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then, 1.98mol/L of nickel cobalt manganese solution (nickel cobalt manganese molar ratio: 67: 13: 20) was added at a rate of 300L/h, 32% of aqueous alkali solution was added at a rate of 185L/h, 21% of aqueous ammonia solution was added at a rate of 30L/h, 0.5mol/L of rubidium salt solution was added at a rate of 100ml/min using a peristaltic pump, and during the reaction, the pH was decreased at a rate of 0.05/h to 11.60 and then maintained, and after 7 hours before the reaction, 99.99% pure nitrogen was introduced at a rate of 3000L/h, and after 8 hours, compressed air was introduced at a rate of 500L/h. After 30 hours of coprecipitation reaction in a reaction kettle, the granularity D50 grows to 3 mu m, feeding is suspended, deionized water is added, residual rubidium ions are replaced by concentrated clear liquid, feeding is continued after 2 hours, a rubidium salt solution is changed into a molybdenum salt solution, the flow is unchanged, feeding is stopped when the particle D50 value grows to 4 mu m, and the total reaction time is 75 hours. And washing impurities, filtering, dehydrating and drying the ternary cathode material precursor liquid to obtain the layered doped ternary cathode material precursor.
Example 2:
adding pure water into a reaction kettle, heating to 60 ℃, adjusting the pH value of the prepared liquid alkali solution to 11.95, adding an ammonia water solution to prepare the base solution to be 5g/L, and operating stirring blades in the reaction kettle at the rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then, 1.98mol/L nickel-cobalt-manganese solution was added at a flow rate of 300L/h, 32% aqueous alkali solution was added at a flow rate of 185L/h, and 21% aqueous ammonia solution was added at a flow rate of 30L/h, 0.5mol/L rubidium salt solution was added at a flow rate of 200mL/min using a peristaltic pump, and when the reaction was carried out, the pH was maintained after the rate was decreased to 11.60 at a rate of 0.05/h, nitrogen gas having a purity of 99.99% was introduced at a flow rate of 3000L/h for 6 hours before the reaction, and compressed air was introduced at a flow rate of 500L/h after 7 hours. After the coprecipitation reaction for 27 hours in the reaction kettle, the granularity D50 grows to 3 mu m, feeding is suspended, deionized water is added, residual rubidium ions are replaced by concentrated clear liquid, feeding is continued after 2 hours, feeding is continued after 3 hours, a rubidium salt solution is changed into a molybdenum salt solution, the flow is unchanged, the machine is stopped when the granularity continues to grow to 3.6-3.7 mu m, and the total reaction time is 68 hours. And washing impurities, filtering, dehydrating and drying the ternary precursor slurry to obtain the layered doped ternary precursor.
Example 3:
adding pure water into a reaction kettle, heating to 60 ℃, adjusting the pH value of the prepared liquid alkali solution to 11.55, then adding an ammonia water solution to prepare the base solution to be 6.5g/L, and operating stirring blades in the reaction kettle at the rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then, 1.98mol/L (ratio: 83: 7: 10) of nickel-cobalt-manganese solution is added at a flow rate of 360L/h, 32% of aqueous alkali solution is added at a flow rate of 135L/h, 21% of aqueous ammonia solution is added at a flow rate of 25L/h, 0.5mol/L of rubidium salt solution is added at a flow rate of 150ml/min by using a peristaltic pump, when the reaction is carried out for 2h, the ph is maintained after being reduced to 11.40 at a rate of 0.05/h, and 3000L/h of nitrogen with a purity of 99.99% is introduced into the whole reaction period for protection. After 60 hours of coprecipitation reaction in a reaction kettle, when the D50 value of particles grows to 8 mu m, stopping feeding, adding deionized water, replacing residual rubidium ions by concentrating and discharging the clear solution, continuing feeding after waiting for 2 hours, changing the rubidium salt solution into 0.5mol/L molybdenum salt solution, keeping the flow unchanged, stopping feeding when the D50 value of particles in the reaction kettle grows to 10 mu m, and keeping the total reaction time at 80 hours. And washing impurities, filtering, dehydrating and drying the ternary precursor slurry to obtain the layered doped ternary precursor.
Comparative example 1: (undoped rubidium molybdenum, otherwise same as example 1)
Adding pure water into a reaction kettle, heating to 60 ℃, then adjusting the pH of the prepared liquid alkali solution to 12.0, then adding an ammonia water solution to adjust the base solution to 4.5g/L, and operating stirring blades in the reaction kettle at a rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then 1.98mol/L nickel-cobalt-manganese solution is added at the flow rate of 300L/h, 32% liquid caustic soda solution is added at the flow rate of 185L/h, 21% ammonia solution is added at the flow rate of 30L/h, when the reaction is carried out, the pH is reduced to 11.60 at the speed of 0.05/h and then is kept, nitrogen with the purity of 99.99% is introduced at the flow rate of 3000L/h in 7 hours before the reaction, and compressed air is introduced at the flow rate of 500L/h after 8 hours. After 98 hours of coprecipitation reaction in the reaction kettle, the machine is stopped when the granularity grows to 3.6 um. And washing impurities, filtering, dehydrating and drying the ternary precursor slurry to obtain the ternary precursor.
Comparative example 2: (otherwise, same example 1 was repeated except that concentration and replacement were not performed)
Adding pure water into a reaction kettle, heating to 60 ℃, adjusting the pH value of the prepared liquid alkali solution to 12.0, adding an ammonia water solution to prepare a base solution to be 4.5g/L, and operating stirring blades in the reaction kettle at a rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then, 1.98mol/L nickel-cobalt-manganese solution was added at a rate of 300L/h, 32% aqueous alkali solution was added at a rate of 185L/h, and 21% aqueous ammonia solution was added at a rate of 30L/h, and 0.5mol/L rubidium salt solution was added at a rate of 100ml/min using a peristaltic pump, and when the reaction was carried out, the ph was maintained after the rate was decreased to 11.60 at a rate of 0.05/h, nitrogen gas having a purity of 99.99% was introduced at a rate of 3000L/h for 7 hours before the reaction, and compressed air was introduced at a rate of 500L/h after 8 hours. After 30 hours of coprecipitation reaction in the reactor, the particle size D50 was grown to 3 μm, feeding of rubidium salt solution was suspended, feeding of molybdenum salt solution was stopped at the same flow rate, and feeding was stopped when the particle D50 value was grown to 4 μm, and the total reaction time was 75 hours. And washing impurities, filtering, dehydrating and drying the ternary cathode material precursor liquid to obtain the layered doped ternary cathode material precursor.
Comparative example 3: (otherwise same as example 1, rubidium doped and molybdenum not doped)
Adding pure water into a reaction kettle, heating to 60 ℃, adjusting the pH value of the prepared liquid alkali solution to 12.0, adding an ammonia water solution to prepare a base solution to be 4.5g/L, and operating stirring blades in the reaction kettle at a rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then, 1.98mol/L of nickel-cobalt-manganese solution was added at a rate of 300L/h, 32% of aqueous alkali solution was added at a rate of 185L/h, 21% of aqueous ammonia solution was added at a rate of 30L/h, 0.5mol/L of rubidium salt solution was added at a rate of 100ml/min by means of a peristaltic pump, and when the reaction was carried out, ph was lowered to 11.60 at a rate of 0.05/h and then maintained, nitrogen gas having a purity of 99.99% was fed at a rate of 3000L/h for 7 hours before the reaction, and compressed air was fed at a rate of 500L/h after 8 hours. The feed was stopped when the particle D50 value grew to 4 μm and the total reaction time was 75 h. And washing impurities, filtering, dehydrating and drying the ternary cathode material precursor liquid to obtain the layered doped ternary cathode material precursor.
Comparative example 4: otherwise same as example 1, with molybdenum doping, without rubidium doping)
Adding pure water into a reaction kettle, heating to 60 ℃, adjusting the pH value of the prepared liquid alkali solution to 12.0, adding an ammonia water solution to prepare a base solution to be 4.5g/L, and operating stirring blades in the reaction kettle at a rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then 1.98mol/L nickel-cobalt-manganese solution is added at the flow rate of 300L/h, 32% liquid alkali solution is added at the flow rate of 185L/h, 21% ammonia solution is added at the flow rate of 30L/h, 0.5mol/L molybdenum salt solution is added at the flow rate of 100ml/min by using a peristaltic pump, when the reaction is carried out, the ph is kept after the speed is reduced to 11.60 at the rate of 0.05/h, nitrogen with the purity of 99.99% is introduced at the flow rate of 3000L/h in 7 hours before the reaction, and compressed air is introduced at the flow rate of 500L/h after 8 hours. The feed was stopped when the particle D50 value grew to 4 μm and the total reaction time was 75 h. And washing impurities, filtering, dehydrating and drying the ternary cathode material precursor liquid to obtain the layered doped ternary cathode material precursor.
The electrochemical performance detection method comprises the following steps:
1. the precursors prepared in examples and comparative examples and lithium hydroxide were uniformly mixed in a molar ratio of M (Ni + Co + Mn) to M (li) of 1:1.03, then calcined at 450 ℃ for 4 hours, then ground and calcined at 750 ℃ for 20 hours, and finally ground to obtain positive electrode materials, which are respectively designated as a1, a2, A3, D1, D2, D3 and D4;
2. and (3) mixing the obtained positive electrode material according to the following ratio: conductive carbon: polyvinylidene fluoride (PVDF) ═ 90: 5: 5 preparing slurry, preparing a positive pole piece (the compaction density of the pole piece is 3.3g/cm2), and assembling the button cell 2025 by using a metal lithium piece as a negative electrode material;
3. with 1M LiPF6 EC: DEC: DMC 1: 1:1 (V%) is electrolyte, after three cycles of activation under 0.2C multiplying power, the electrolyte is cycled for 100 times under 0.2C multiplying power, the discharge capacity at the 1 st cycle and the discharge capacity at the 100 th cycle are respectively measured, and the capacity retention rate at the 100 th cycle is calculated;
4. the method comprises the steps of fixing four leads on a glass slide in sequence by adopting conductive silver adhesive, uniformly coating a pasty lithium ion battery anode material on the glass slide, then carrying out vacuum drying, obtaining a film layer on the glass slide, measuring current I by adopting an ammeter, measuring voltage U by adopting a voltmeter, and then calculating the conductivity sigma of the lithium ion battery anode material according to a formula sigma IL/US.
TABLE 1 electrochemical Properties of positive electrode materials obtained in examples and comparative examples
Claims (10)
1. A method for preparing a precursor of a ternary cathode material by layered doping is characterized by comprising the following steps:
(1) preparing a metal salt solution, a precipitator solution, a complexing agent solution, a rubidium salt solution and a molybdenum salt solution;
(2) adding water, a complexing agent solution and a precipitator solution into a reaction kettle, stirring and keeping constant temperature to prepare a reaction kettle bottom solution;
(3) adding a metal salt solution, a precipitator solution, a complexing agent solution and a rubidium salt solution into a bottom solution of the reaction kettle, carrying out coprecipitation reaction, stopping feeding when the particle size of particles in the reaction kettle grows to be 0.5-3 mu m smaller than a target particle size, and concentrating and displacing a feed liquid containing rubidium ions in the reaction kettle;
(4) then, continuously adding a metal salt solution, a precipitator solution and a complexing agent solution into the reaction kettle, simultaneously adding a molybdenum salt solution for coprecipitation reaction until the average particle size of the particles grows to a target particle size, and stopping feeding to obtain a solution containing a precursor material;
(5) and (4) stirring the solution containing the precursor material obtained in the step (4), aging, washing, drying, screening and removing iron to obtain the precursor of the core-shell structure ternary cathode material.
2. The method for preparing the precursor of the ternary cathode material by layered doping according to claim 1, wherein: the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt, the molar ratio of the nickel salt to the cobalt salt to the manganese salt is 60-90: 5-20: 10-30, the total concentration of metal ions in the metal salt solution is 1-2 mol/L, and the nickel salt, the cobalt salt and the manganese salt are at least one of sulfate, nitrate and halide.
3. The method for preparing the precursor of the ternary cathode material by layered doping according to claim 1, wherein: the precipitator solution is a sodium hydroxide solution with the concentration of 5-12 mol/L, the complexing agent solution is an ammonia water solution with the mass concentration of 12% -24%, the rubidium ion concentration in the rubidium salt solution is 0.1-1 mol/L, and the molybdenum ion concentration in the molybdenum salt solution is 0.1-1 mol/L.
4. The method for preparing the precursor of the ternary cathode material by layered doping according to claim 1, wherein: in the step (3) and the step (4), the reaction temperature is controlled to be 40-70 ℃, the pH value is 11.5-13, the ammonia concentration is 2-16 g/L, and the stirring rotating speed is 300-600 rpm.
5. The method for preparing the precursor of the ternary cathode material by layered doping according to claim 1, wherein: the feeding amount of the metal salt solution is 20-500L/h, the feeding amount ratio of the rubidium salt solution to the metal salt solution is 1: 200-10000, and the feeding amount ratio of the molybdenum salt solution to the metal salt solution is 1: 200-10000.
6. The method for preparing the precursor of the ternary cathode material by layered doping according to claim 1, wherein: the average particle size of the particles in the step (3) is a particle size distribution D50 value, and the target particle size is 3-13 μm.
7. The method for preparing the precursor of the ternary cathode material by layered doping according to claim 1, wherein: the molecular formula of the precursor of the prepared ternary cathode material is as follows: nixCoyMn1-x-y(OH)2[Rb]m[Mo]nAnd m and n are doping amount, wherein x is more than or equal to 0.50 and less than or equal to 0.90, y is more than or equal to 0.05 and less than or equal to 0.30, 0.05 and less than or equal to 1-x-y is less than or equal to 0.30, m is more than or equal to 0.0001 and less than or equal to 0.005, and n is more than or equal to 0.0001 and less than or equal to 0.005.
8. The method for preparing the precursor of the ternary cathode material by layered doping according to claim 1, wherein: and (3) in the step (3), the feed liquid containing rubidium ions in the reaction kettle is replaced by concentration.
9. The ternary cathode material prepared by the method for preparing the ternary cathode material precursor through layered doping according to claims 1-8.
10. A lithium ion battery, characterized by: the lithium ion battery includes the ternary cathode material of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111658802.8A CN114477312B (en) | 2021-12-31 | 2021-12-31 | Method for preparing ternary positive electrode material precursor by layered doping |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111658802.8A CN114477312B (en) | 2021-12-31 | 2021-12-31 | Method for preparing ternary positive electrode material precursor by layered doping |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114477312A true CN114477312A (en) | 2022-05-13 |
| CN114477312B CN114477312B (en) | 2023-07-11 |
Family
ID=81497100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111658802.8A Active CN114477312B (en) | 2021-12-31 | 2021-12-31 | Method for preparing ternary positive electrode material precursor by layered doping |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114477312B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114988491A (en) * | 2022-05-27 | 2022-09-02 | 荆门市格林美新材料有限公司 | Bimetal alternately-doped nickel-manganese precursor and preparation method and application thereof |
| CN115924991A (en) * | 2022-12-15 | 2023-04-07 | 蜂巢能源科技股份有限公司 | High-nickel hydroxide precursor, preparation method thereof and ternary cathode material |
| CN117276534A (en) * | 2023-11-21 | 2023-12-22 | 宜宾光原锂电材料有限公司 | High-cycle positive electrode material precursor, preparation method thereof, positive electrode material and battery |
| CN117303465A (en) * | 2023-11-28 | 2023-12-29 | 宜宾光原锂电材料有限公司 | Ternary precursor, positive electrode material, preparation method of ternary precursor and positive electrode material, and lithium battery |
| CN117623405A (en) * | 2023-10-28 | 2024-03-01 | 荆门市格林美新材料有限公司 | Method for preparing ternary precursor small particles by oxidation method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102820464A (en) * | 2012-09-03 | 2012-12-12 | 济宁市无界科技有限公司 | Preparation method of manganese-based compound positive pole material for secondary lithium ion battery |
| US20150079471A1 (en) * | 2013-09-16 | 2015-03-19 | Ningde Amperex Technology Limited | Lithium-ion battery positive electrode material and preparation method thereof |
| CN110391416A (en) * | 2019-07-11 | 2019-10-29 | 光鼎铷业(广州)集团有限公司 | A kind of rubidium doping concentration gradient tertiary cathode material and preparation method thereof |
| CN112164790A (en) * | 2020-08-27 | 2021-01-01 | 荆门市格林美新材料有限公司 | Precursor for coated lithium battery, lithium battery positive electrode material and preparation method of lithium battery positive electrode material |
| CN112357973A (en) * | 2020-09-30 | 2021-02-12 | 宜宾光原锂电材料有限公司 | Preparation method of positive electrode material precursor and prepared positive electrode material precursor |
| CN112758991A (en) * | 2020-12-28 | 2021-05-07 | 宜宾光原锂电材料有限公司 | Preparation method of core-shell structure ternary cathode material precursor |
-
2021
- 2021-12-31 CN CN202111658802.8A patent/CN114477312B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102820464A (en) * | 2012-09-03 | 2012-12-12 | 济宁市无界科技有限公司 | Preparation method of manganese-based compound positive pole material for secondary lithium ion battery |
| US20150079471A1 (en) * | 2013-09-16 | 2015-03-19 | Ningde Amperex Technology Limited | Lithium-ion battery positive electrode material and preparation method thereof |
| CN110391416A (en) * | 2019-07-11 | 2019-10-29 | 光鼎铷业(广州)集团有限公司 | A kind of rubidium doping concentration gradient tertiary cathode material and preparation method thereof |
| CN112164790A (en) * | 2020-08-27 | 2021-01-01 | 荆门市格林美新材料有限公司 | Precursor for coated lithium battery, lithium battery positive electrode material and preparation method of lithium battery positive electrode material |
| CN112357973A (en) * | 2020-09-30 | 2021-02-12 | 宜宾光原锂电材料有限公司 | Preparation method of positive electrode material precursor and prepared positive electrode material precursor |
| CN112758991A (en) * | 2020-12-28 | 2021-05-07 | 宜宾光原锂电材料有限公司 | Preparation method of core-shell structure ternary cathode material precursor |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114988491A (en) * | 2022-05-27 | 2022-09-02 | 荆门市格林美新材料有限公司 | Bimetal alternately-doped nickel-manganese precursor and preparation method and application thereof |
| WO2023226220A1 (en) * | 2022-05-27 | 2023-11-30 | 荆门市格林美新材料有限公司 | Dual-metal alternately-doped nickel-manganese precursor, and preparation method therefor and use thereof |
| CN115924991A (en) * | 2022-12-15 | 2023-04-07 | 蜂巢能源科技股份有限公司 | High-nickel hydroxide precursor, preparation method thereof and ternary cathode material |
| CN117623405A (en) * | 2023-10-28 | 2024-03-01 | 荆门市格林美新材料有限公司 | Method for preparing ternary precursor small particles by oxidation method |
| CN117276534A (en) * | 2023-11-21 | 2023-12-22 | 宜宾光原锂电材料有限公司 | High-cycle positive electrode material precursor, preparation method thereof, positive electrode material and battery |
| CN117276534B (en) * | 2023-11-21 | 2024-02-13 | 宜宾光原锂电材料有限公司 | High-cycle positive electrode material precursor, preparation method thereof, positive electrode material and battery |
| CN117303465A (en) * | 2023-11-28 | 2023-12-29 | 宜宾光原锂电材料有限公司 | Ternary precursor, positive electrode material, preparation method of ternary precursor and positive electrode material, and lithium battery |
| CN117303465B (en) * | 2023-11-28 | 2024-02-13 | 宜宾光原锂电材料有限公司 | Ternary precursor, positive electrode material, preparation method of ternary precursor and positive electrode material, and lithium battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114477312B (en) | 2023-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11345609B2 (en) | High voltage lithium nickel cobalt manganese oxide precursor, method for making the same, and high voltage lithium nickel cobalt manganese oxide cathode material | |
| CN110048118B (en) | High-nickel cobalt lithium manganate single crystal precursor, preparation method thereof and high-nickel cobalt lithium manganate single crystal positive electrode material | |
| CN114477312B (en) | Method for preparing ternary positive electrode material precursor by layered doping | |
| CN113363492B (en) | Composite coating modified high-nickel NCA positive electrode material and preparation method thereof | |
| CN108767216B (en) | Lithium ion battery anode material with variable slope and full concentration gradient and synthesis method thereof | |
| CN112531158B (en) | High-nickel ternary single crystal material and preparation method thereof | |
| CN111916727B (en) | Dual-ion wet-doped ternary high-nickel cathode material and preparation method thereof | |
| CN115196691A (en) | Nickel-iron-manganese ternary precursor for sodium ion battery and preparation method and application thereof | |
| CN114349068B (en) | Preparation method of large-particle-size nickel-cobalt-aluminum ternary positive electrode material precursor | |
| CN104733724A (en) | Positive electrode material for high-nickel lithium ionic secondary battery and preparation method thereof | |
| CN111682197B (en) | Single crystal type anion and cation co-doped nickel-magnesium binary cobalt-free precursor, positive electrode material and preparation method | |
| CN110890535A (en) | Cathode material, preparation method thereof and application of cathode material in lithium ion battery | |
| CN111180724B (en) | Preparation method of ternary monocrystal anode material | |
| CN114000195B (en) | Preparation method of monodisperse high-nickel ternary monocrystal positive electrode material | |
| CN111540898A (en) | Preparation method and application of precursor with good primary particle uniformity | |
| CN114620777B (en) | Ultrahigh nickel ternary precursor and preparation method thereof | |
| WO2024066892A1 (en) | Manganese-rich oxide precursor, preparation method therefor, and use thereof | |
| CN111029561A (en) | Ternary lithium battery positive electrode material precursor and preparation method thereof, ternary lithium battery positive electrode material and preparation method and application thereof | |
| CN110817976B (en) | Positive electrode material precursor and preparation method and application thereof | |
| WO2024178793A1 (en) | Modified sodium-ion battery positive electrode precursor, and preparation method therefor and use thereof | |
| CN115732674A (en) | Sodium anode precursor material and preparation method and application thereof | |
| CN113603153A (en) | Tungsten-doped high-nickel cobalt-free precursor and preparation method thereof | |
| CN113629229A (en) | Phosphate-coated wet-method-doped ternary cathode material and preparation method thereof | |
| CN114220959B (en) | Preparation method of component-controllable multielement doped high-nickel ternary positive electrode material | |
| CN116119739A (en) | Ion doped manganese-based sodium ion positive electrode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 644200 yangchunba Industrial Park, Jiang'an County, Yibin City, Sichuan Province Patentee after: YIBIN GUANGYUAN LITHIUM BATTERY CO.,LTD. Country or region after: China Patentee after: Yibin Lithium Treasure New Materials Co.,Ltd. Address before: 644200 yangchunba Industrial Park, Jiang'an County, Yibin City, Sichuan Province Patentee before: YIBIN GUANGYUAN LITHIUM BATTERY CO.,LTD. Country or region before: China Patentee before: Yibin Libao New Materials Co.,Ltd. |