CN113860395A - High-specific-surface-area hollow cathode material precursor and preparation method thereof - Google Patents
High-specific-surface-area hollow cathode material precursor and preparation method thereof Download PDFInfo
- Publication number
- CN113860395A CN113860395A CN202111332295.9A CN202111332295A CN113860395A CN 113860395 A CN113860395 A CN 113860395A CN 202111332295 A CN202111332295 A CN 202111332295A CN 113860395 A CN113860395 A CN 113860395A
- Authority
- CN
- China
- Prior art keywords
- reaction
- precursor
- stage
- equal
- 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.)
- Pending
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 57
- 239000010406 cathode material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 11
- 238000000975 co-precipitation Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 27
- 239000011164 primary particle Substances 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000011163 secondary particle Substances 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- -1 ammonium ions Chemical class 0.000 claims description 4
- 230000007423 decrease Effects 0.000 claims description 4
- 239000012066 reaction slurry Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910003684 NixCoyMnz 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
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 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
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000001000 micrograph Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Images
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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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 belongs to the technical field of lithium ion battery materials, and particularly relates to a precursor of a hollow cathode material with a high specific surface area and a preparation method thereof. The invention adopts a coprecipitation method to prepare the precursor of the hollow cathode material, air is continuously introduced in the whole process of the coprecipitation reaction under the condition of lower ammonium ion concentration, and the precursor with the inner part being sparse and the outer part being dense and high specific surface area is prepared by adjusting the air flow and the pH value. The whole process of the invention adopts air atmosphere, and nitrogen protection is not needed; the method has the advantages that the ammonium ion concentration is lower, the using amount of ammonia water is obviously reduced, the cost of precursor synthesis can be reduced, and the method is more environment-friendly.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a hollow cathode material precursor with a high specific surface area and a preparation method thereof.
Background
In recent years, lithium ion battery Hybrid Electric Vehicles (HEVs) have been rapidly developed, which have two power systems, an electric motor and an internal combustion engine. Compared with a pure electric vehicle (BEV), the hybrid electric vehicle can effectively relieve the mileage anxiety of a consumer, has higher safety, and provides good technical transition for the development of vehicle enterprises to pure electric vehicles; compared with the traditional fuel vehicle, the hybrid vehicle has better power performance and conforms to the national policy guidance. Lithium ion batteries are one of the key components of electric drive systems of hybrid vehicles, and compared with BEV power batteries, HEV power batteries are characterized by shallow charge and discharge, which do not have an excessively high requirement on energy density, but impose a high requirement on output performance of the batteries. The positive electrode material of the power battery must have proper particle size and high specific surface area, and can keep the structure of the material stable under high-rate discharge.
The hollow positive electrode material can well meet the requirement. The electrolyte can contact with the outside of the hollow positive electrode material particles and can also be soaked into the particles, so that the contact area of the positive electrode material and the electrolyte is effectively increased. In addition, the space inside the particles can effectively buffer the volume change of the material in the charging and discharging process, thereby keeping the stability of the structure. Precursor particles corresponding to the hollow cathode material need to form a double-layer structure with inner sparse and outer dense, fine primary particles are loosely stacked inside the precursor particles, larger primary particles are arranged outside the precursor particles relatively tightly, and the inner primary particles shrink towards the outer wall after the precursor particles are sintered at high temperature so as to form holes inside the particles.
The patent application publication No. CN105185979A discloses the following technical solutions: the precursor with a loose core and a compact shell is prepared by controlling the temperature and pH value conditions in the coprecipitation process in a segmented manner, and as can be seen from an electron microscope image, the particle diameter of the material is about 10-15 mu m, so that the precursor with a high specific surface area is difficult to prepare.
The patent application publication No. CN104136376A discloses the following technical solutions: the preparation process of the precursor is divided into a nucleus generation process and a particle growth process, wherein the nucleus generation process is carried out in an oxidizing atmosphere with the oxygen content of more than 1% (volume ratio), the particle growth process is carried out in a mixed atmosphere environment with the oxygen content of less than 1%, and the ammonium ion concentration is kept at 3-25 g/L. The precursor prepared by the process is sintered to obtain the cathode material with insufficient specific surface area (in the embodiment, the specific surface area of the cathode material is less than or equal to 1.4 m)2/g), the material requirements for higher output performance cannot be met.
The prepared precursor of the hollow cathode material with high specific surface area and higher output performance is an important assistance for promoting the development of hybrid vehicles.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a precursor of a hollow cathode material with high specific surface area and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions.
Firstly, the invention provides a precursor of a hollow cathode material with high specific surface area, wherein the chemical general formula of the precursor is NixCoyMnzMt(OH)2+aWherein x is more than or equal to 0.3 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.4, and y is more than or equal to 0.1 and less than or equal to 0.7z is less than or equal to 0.5, t is less than or equal to 0.01 and a is less than or equal to 0.1, x + y + z + t =1 is satisfied, and M is one or more selected from Al, Mg, La, Ca, Ti, V, Zr and W. The precursor is a spheroid formed by agglomeration of a plurality of primary particles, and is provided with an inner core and an outer wall, wherein the inner core is in a loose and porous honeycomb structure, and the outer wall is relatively compact. The primary particles constituting the inner core are relatively fine, and the primary particles constituting the outer wall are relatively coarse. The average particle size of the precursor is 2-6 mu m, and the specific surface area is more than or equal to 35 m2A specific surface area of more than 40 m/g is preferred2/g。
Further, the average particle diameter of the primary particles constituting the inner core is less than 0.2 μm, and the average particle diameter of the primary particles constituting the outer wall is 0.2 to 2 μm.
Further, the thickness of the outer wall accounts for 5% -20% of the diameter of the secondary particles of the precursor. Preferably, the thickness of the outer wall accounts for 5% -13% of the diameter of the secondary particles of the precursor.
The ratio of the thickness of the outer wall to the diameter of the secondary particles of the precursor is determined in the following manner: firstly, cutting precursor powder by adopting an ion beam, shooting a SEM (scanning Electron microscope) image of the cross section of the cut powder, and then measuring the outer wall thickness and the diameter of secondary particles by adopting length measurement software. In order to accurately measure the wall thickness and the diameter, when the wall thickness and the diameter of a single particle are measured, the wall thickness and the diameter of the single particle need to be measured for more than 10 times respectively from different axial directions of the particle section, and then the average value is obtained, so that the ratio of the wall thickness to the diameter of the single particle is obtained. Then, the same measuring mode is adopted, more than 10 different particles are measured in total, and the final average value of the wall thickness/diameter is calculated.
The invention also provides a preparation method of the precursor of the hollow cathode material with high specific surface area, which comprises the following steps:
(1) preparing a nickel-cobalt-manganese metal salt solution with the total metal ion concentration of 0.5-2.5 mol/L; preparing an alkali solution with the concentration of 1-10 mol/L; preparing 2-6mol/L ammonia water solution; preparing salt solution of doping elements according to requirements.
(2) Adding pure water into a reaction kettle, controlling the reaction temperature to be 45-70 ℃, adjusting the pH value to be 11.5-12.5, adjusting the ammonium ion concentration to be 0.4-4g/L, and introducing air into the reaction kettle.
(3) And introducing a nickel-cobalt-manganese metal salt solution, an alkali solution, an ammonia water solution and an element-doped salt solution into the reaction kettle to perform coprecipitation reaction. The reaction process is divided into three stages: the reaction starts and enters a first stage, the pH value of a reaction system is kept at 11.5-12.5 in the first stage, the alkali solution is closed after a period of time, the pH value starts to decrease, the reaction enters a second stage, and the second stage is finished after the pH value decreases to 9.5-11.5; starting the alkali solution, maintaining the pH value at 9.5-11.5, and entering the third stage of the reaction. After 1-10% of the reaction time in the third stage, the air flow is reduced, and the reaction is continued until the particle size of the reaction slurry reaches the target value. The ammonium ion concentration of the reaction system is kept between 0.4 and 4g/L during the reaction process.
(4) And after the reaction is finished, filtering the reaction slurry, aging, washing, drying and filtering to obtain a solid phase, and obtaining a precursor of the hollow cathode material with high specific surface area.
Further, in the above-mentioned case,
the metal salt solution is one or more of sulfate, nitrate and chloride.
The alkali solution is any one of a sodium hydroxide solution and a mixed solution of sodium hydroxide and ammonia water.
Further, the oxygen content in the gas at the upper part of the reaction kettle is 1-21%, preferably 2-21% in the first 1-10% of the first stage, the second stage and the third stage. After 1-10% of the time of the third stage, the oxygen content in the gas at the upper part of the reaction kettle is 0.8-3%, preferably 1-2%.
Furthermore, the total time of the reaction process is not more than 50h, and preferably the total time of the reaction process is less than or equal to 30 h. The first stage accounts for 1% -5% of the total time; the reaction time of the second stage is determined by the pH value at the end of the first stage, the target pH value of the third stage and the flow rate of the metal salt; the third stage accounts for 80% -98% of the total time.
Furthermore, clear liquid is discharged in a physical sedimentation or filtration mode while the coprecipitation reaction is carried out, and the liquid level of the reaction kettle is controlled.
The invention adopts a coprecipitation method to prepare the precursor of the hollow cathode material, air is continuously introduced in the whole process of the coprecipitation reaction under the condition of lower ammonium ion concentration, and the precursor with the inner part being sparse and the outer part being dense and high specific surface area is prepared by adjusting the air flow and the pH value. Meanwhile, a small amount of doping elements can be doped in the synthesis stage of the precursor, so that the performance of the material is further improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) the precursor of the hollow cathode material with high specific surface area is prepared by the method, and doping elements can be selectively added in the coprecipitation process, so that the material performance is further improved.
(2) The whole process of the invention adopts air atmosphere, and nitrogen protection is not needed; the method has the advantages that the ammonium ion concentration is lower, the using amount of ammonia water is obviously reduced, the cost of precursor synthesis can be reduced, and the method is more environment-friendly.
(3) The method has simple process control and is very convenient for industrial application.
Drawings
FIG. 1 is a sectional electron microscope image of a precursor prepared in example 1 of the present invention, wherein a is a sectional electron microscope image at 20000 magnifications, and b is a sectional electron microscope image at 5000 magnifications.
FIG. 2 is a sectional electron microscope image of the precursor prepared in example 2 of the present invention, wherein a is a sectional electron microscope image at 20000 magnifications, and b is a sectional electron microscope image at 5000 magnifications.
FIG. 3 is a sectional electron microscope image of a precursor prepared according to a comparative example of the present invention, wherein a is a sectional electron microscope image at 20000 magnifications, and b is a sectional electron microscope image at 5000 magnifications.
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.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
Example 1
Preparing nickel sulfate, cobalt sulfate and manganese sulfate into a metal salt solution with the total metal ion concentration of 2mol/L, wherein the molar ratio of nickel to cobalt to manganese is 5:2: 3; preparing 2mol/L sodium hydroxide solution; 6mol/L ammonia water solution is prepared to be used as a complexing agent. Adding pure water into the reaction kettle, controlling the temperature at 60 ℃, adjusting the pH value to 12.0 by using sodium hydroxide, adjusting the ammonium ion concentration to 1.5g/L by using ammonia water, and continuously introducing air into the reaction kettle.
And (2) introducing a metal salt solution, a sodium hydroxide solution and an ammonia water solution into the reaction kettle, keeping the pH value at 12.0 +/-0.1 in the first stage, closing the sodium hydroxide solution after reacting for 30 minutes, entering the second stage, reducing the pH value to 11.3 +/-0.1 after about 30 minutes, starting the sodium hydroxide solution, entering the third stage, keeping the pH value at 11.3 +/-0.1, keeping the air flow unchanged, and gradually reducing the oxygen content in the gas at the upper part of the reaction kettle from the initial 21% to 2% due to continuous consumption of metal ions. After the reaction is carried out for 1 hour in the third stage, the air flow is adjusted downwards, the oxygen content in the gas at the upper part of the reaction kettle is reduced to 1.2%, the reaction is stopped after the reaction is continued for 28 hours, and the total reaction time is 30 hours. The concentration of ammonium ions in the reaction system is kept at 1.5g/L during the reaction.
And filtering, aging, washing, drying and screening the synthesized slurry to obtain the precursor.
Example 2
Preparing nickel sulfate, cobalt sulfate and manganese sulfate into a metal salt solution with the total metal ion concentration of 2mol/L, wherein the molar ratio of nickel to cobalt to manganese is 5:2: 3; preparing 2mol/L sodium hydroxide solution; preparing 6mol/L ammonia water solution as a complexing agent; preparing 0.01mol/L sodium tungstate solution. Adding pure water into the reaction kettle, controlling the temperature at 60 ℃, adjusting the pH value to 12.0 by using sodium hydroxide, adjusting the ammonium ion concentration to 3.0g/L by using ammonia water, and continuously introducing air into the reaction kettle.
And (2) introducing a metal salt solution, a sodium hydroxide solution, an ammonia water solution and a sodium tungstate solution into the reaction kettle, maintaining the pH value at 12.3 +/-0.1 in the first stage, closing the sodium hydroxide solution after reacting for 50 minutes, entering the second stage, reducing the pH value to 11.2 +/-0.1 after about 60 minutes, opening the sodium hydroxide solution, entering the third stage, maintaining the pH value at 11.2 +/-0.1, maintaining the air flow at a fixed flow rate, and gradually reducing the oxygen content in the gas at the upper part of the reaction kettle from the initial 21% to 2.5% due to continuous consumption of metal ions. After the reaction time of the third stage is 100 minutes, the air flow is adjusted downwards, the oxygen content in the gas at the upper part of the reaction kettle is reduced to 1.5%, the reaction is continued for 26.5 hours, and the reaction is stopped for 30 hours in total. The concentration of ammonium ions in the reaction system is kept at 3.0g/L during the reaction.
And filtering, aging, washing, drying and screening the synthesized slurry to obtain the precursor.
Comparative example 1
Preparing nickel sulfate, cobalt sulfate and manganese sulfate into a metal salt solution with the total metal ion concentration of 2mol/L, wherein the molar ratio of nickel to cobalt to manganese is 5:2: 3; preparing 2mol/L sodium hydroxide solution; 6mol/L ammonia water solution is prepared to be used as a complexing agent. Adding pure water into a reaction kettle, controlling the temperature at 60 ℃, adjusting the pH value to 12.3 by using sodium hydroxide, adjusting the ammonium ion concentration to 5g/L by using ammonia water, and continuously introducing mixed gas of air and nitrogen into the reaction kettle.
And (2) introducing a metal salt solution, a sodium hydroxide solution and an ammonia water solution into the reaction kettle, keeping the pH value at 12.3 +/-0.1 in the first stage, closing the sodium hydroxide solution after 50 minutes of reaction, entering the second stage, reducing the pH value to 11.2 +/-0.1 after about 60 minutes, continuously adjusting the flow of air and nitrogen, and keeping the oxygen content in the gas at the upper part of the reaction kettle at about 5%. After the sodium hydroxide solution is started, the third stage is carried out, and the pH is maintained at 11.2 +/-0.1. After the third stage, the reaction was stopped by switching to nitrogen immediately to an oxygen content of about 0.7% and continuing the reaction for 28.2 hours for a total of 30 hours. The concentration of ammonium ions in the reaction system is kept at 5g/L during the reaction process.
And filtering, aging, washing, drying and screening the synthesized slurry to obtain the precursor.
Fig. 1 is a scanning electron microscope image of a cross section of the precursor prepared in example 1, from which it can be seen that the precursor has a loose inner core and a relatively dense outer wall, primary particles of the inner core are very fine, primary particles of the outer wall are relatively coarse, gaps between the primary particles of the outer wall are obvious, and the proportion of the thickness of the outer wall in the particle diameter is low. Fig. 2 is a scanning electron microscope image of a cross section of the precursor prepared in example 2, from which it can be seen that the precursor has a loose inner core and a relatively dense outer wall, primary particles of the inner core are very fine, the outer wall is also composed of primary particles with larger sizes in a loose arrangement, and the proportion of the thickness of the outer wall in the diameter of the particles is low.
FIG. 3 is a scanning electron micrograph of a cross section of the precursor prepared in comparative example 1, and it can be seen from the micrograph that the precursor has a core and outer wall structure, but the ratio of the outer wall thickness to the particle diameter is high.
The precursors prepared in example 1, example 2 and comparative example 1 were further tested and analyzed for physicochemical parameters and outer wall thickness, with the results shown in table 1.
TABLE 1 physical Properties and wall thickness data of precursors
The BET of the precursor prepared in example 1 and example 2 is more than 40m2The ratio of the outer wall thickness to the secondary particle diameter is less than 15%. The precursor prepared in comparative example 1 had a loose inner core, but had an outer wall thickness of up to 21% of the secondary particle diameter, and a low BET.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The precursor of the hollow cathode material with high specific surface area is characterized in that the chemical general formula of the precursor is NixCoyMnzMt(OH)2+aWherein x is more than or equal to 0.3 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.4, z is more than or equal to 0.1 and less than or equal to 0.5, t is more than or equal to 0 and less than or equal to 0.01, a is more than or equal to 0 and less than or equal to 0.1, x + y + z + t =1 is satisfied, and M is one selected from Al, Mg, La, Ca, Ti, V, Zr and WOr more than two; the precursor is a spheroid formed by agglomeration of a plurality of primary particles, and is provided with an inner core and an outer wall, wherein the inner core is in a loose and porous honeycomb structure, and the outer wall is relatively compact; the primary particles forming the inner core are relatively fine, and the primary particles forming the outer wall are relatively coarse; the average particle size of the precursor is 2-6 mu m, and the specific surface area is more than or equal to 35 m2/g。
2. The precursor of a hollow positive electrode material with a high specific surface area according to claim 1, wherein the average particle size of the primary particles constituting the inner core is less than 0.2 μm, and the average particle size of the primary particles constituting the outer wall is 0.2 to 2 μm.
3. The precursor of the hollow positive electrode material with high specific surface area according to claim 1, wherein the thickness of the outer wall accounts for 5-20% of the diameter of the secondary particles of the precursor.
4. A preparation method of a precursor of a hollow cathode material with high specific surface area is characterized by comprising the following steps:
(1) preparing a nickel-cobalt-manganese metal salt solution, an alkali solution and an ammonia water solution; preparing a salt solution of doping elements according to requirements;
(2) adding pure water into a reaction kettle, controlling the reaction temperature to be 45-70 ℃, adjusting the pH value to be 11.5-12.5, adjusting the ammonium ion concentration to be 0.4-4g/L, and introducing air into the reaction kettle;
(3) introducing a nickel-cobalt-manganese metal salt solution, an alkali solution, an ammonia water solution and an element-doped salt solution into a reaction kettle to perform coprecipitation reaction;
the reaction process is divided into three stages: the reaction starts and enters a first stage, the pH value of a reaction system is kept at 11.5-12.5 in the first stage, the alkali solution is closed after a period of time, the pH value starts to decrease, the reaction enters a second stage, and the second stage is finished after the pH value decreases to 9.5-11.5; starting an alkali solution, maintaining the pH value to be 9.5-11.5, and entering a third stage of reaction;
after 1-10% of the reaction time in the third stage, reducing the air flow, and continuing the reaction until the granularity of the reaction slurry reaches a target value;
keeping the concentration of ammonium ions in the reaction system to be 0.4-4g/L in the reaction process;
(4) and after the reaction is finished, filtering the reaction slurry, aging, washing, drying and filtering to obtain a solid phase, and obtaining a precursor of the hollow cathode material with high specific surface area.
5. The method according to claim 4, wherein the metal salt is one or more of a sulfate, a nitrate and a chloride.
6. The method of claim 4, wherein the concentration of total metal ions in the nickel cobalt manganese metal salt solution is from 0.5 to 2.5 mol/L; the concentration of the alkali solution is 1-10 mol/L; the concentration of the ammonia water solution is 2-6 mol/L.
7. The method according to claim 6, wherein the alkali solution is any one of a sodium hydroxide solution and a mixed solution of sodium hydroxide and aqueous ammonia.
8. The method of claim 4, wherein the oxygen content in the gas at the top of the reaction vessel is 1% to 21% during the first 1% to 10% of the first, second, and third stages, and the oxygen content in the gas at the top of the reaction vessel is 0.8% to 3% after the 1% to 10% of the third stage.
9. The process according to claim 4, wherein the total time of the reaction process is not more than 50 hours; the first stage accounts for 1% -5% of the total time; the third stage accounts for 80% -98% of the total time.
10. The method according to claim 4, wherein the coprecipitation reaction is carried out while discharging a clear solution by physical sedimentation or filtration to control the liquid level of the reaction vessel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111332295.9A CN113860395A (en) | 2021-11-11 | 2021-11-11 | High-specific-surface-area hollow cathode material precursor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111332295.9A CN113860395A (en) | 2021-11-11 | 2021-11-11 | High-specific-surface-area hollow cathode material precursor and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113860395A true CN113860395A (en) | 2021-12-31 |
Family
ID=78987805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111332295.9A Pending CN113860395A (en) | 2021-11-11 | 2021-11-11 | High-specific-surface-area hollow cathode material precursor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113860395A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043438A (en) * | 2022-05-24 | 2022-09-13 | 华友新能源科技（衢州）有限公司 | Ternary precursor and preparation method thereof |
| CN115172738A (en) * | 2022-08-08 | 2022-10-11 | 陕西红马科技有限公司 | High-power cathode material with hollow interior and preparation method thereof |
| CN115417463A (en) * | 2022-09-26 | 2022-12-02 | 广东佳纳能源科技有限公司 | Control method for increasing specific surface area of NCM6 precursor through oxidation |
| CN115477332A (en) * | 2022-09-21 | 2022-12-16 | 广东佳纳能源科技有限公司 | Nickel-manganese binary precursor and preparation method thereof, nickel-manganese positive electrode material and battery |
| CN116873989A (en) * | 2023-09-08 | 2023-10-13 | 浙江帕瓦新能源股份有限公司 | Nickel-cobalt-manganese ternary precursor, preparation method thereof, positive electrode material and lithium ion battery |
| CN118047423A (en) * | 2024-01-09 | 2024-05-17 | 中南大学 | Lithium-rich manganese-based precursor, preparation method thereof, lithium-rich manganese-based positive electrode material and lithium ion battery |
| WO2024174328A1 (en) * | 2023-02-21 | 2024-08-29 | 广东邦普循环科技有限公司 | High-nickel large-particle ternary precursor and preparation method therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019106238A (en) * | 2017-12-08 | 2019-06-27 | 住友金属鉱山株式会社 | Nickel manganese cobalt composite hydroxide, method for manufacturing the same, and lithium nickel manganese cobalt composite oxide |
| WO2021196324A1 (en) * | 2020-04-03 | 2021-10-07 | 宁波容百新能源科技股份有限公司 | Ternary positive electrode material precursor, and preparation method therefor |
-
2021
- 2021-11-11 CN CN202111332295.9A patent/CN113860395A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019106238A (en) * | 2017-12-08 | 2019-06-27 | 住友金属鉱山株式会社 | Nickel manganese cobalt composite hydroxide, method for manufacturing the same, and lithium nickel manganese cobalt composite oxide |
| WO2021196324A1 (en) * | 2020-04-03 | 2021-10-07 | 宁波容百新能源科技股份有限公司 | Ternary positive electrode material precursor, and preparation method therefor |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043438A (en) * | 2022-05-24 | 2022-09-13 | 华友新能源科技（衢州）有限公司 | Ternary precursor and preparation method thereof |
| CN115043438B (en) * | 2022-05-24 | 2023-09-26 | 华友新能源科技（衢州）有限公司 | Ternary precursor and preparation method thereof |
| CN115172738A (en) * | 2022-08-08 | 2022-10-11 | 陕西红马科技有限公司 | High-power cathode material with hollow interior and preparation method thereof |
| CN115477332A (en) * | 2022-09-21 | 2022-12-16 | 广东佳纳能源科技有限公司 | Nickel-manganese binary precursor and preparation method thereof, nickel-manganese positive electrode material and battery |
| CN115477332B (en) * | 2022-09-21 | 2024-04-30 | 广东佳纳能源科技有限公司 | Nickel-manganese binary precursor, preparation method thereof, nickel-manganese positive electrode material and battery |
| CN115417463A (en) * | 2022-09-26 | 2022-12-02 | 广东佳纳能源科技有限公司 | Control method for increasing specific surface area of NCM6 precursor through oxidation |
| WO2024174328A1 (en) * | 2023-02-21 | 2024-08-29 | 广东邦普循环科技有限公司 | High-nickel large-particle ternary precursor and preparation method therefor |
| CN116873989A (en) * | 2023-09-08 | 2023-10-13 | 浙江帕瓦新能源股份有限公司 | Nickel-cobalt-manganese ternary precursor, preparation method thereof, positive electrode material and lithium ion battery |
| CN116873989B (en) * | 2023-09-08 | 2023-12-08 | 浙江帕瓦新能源股份有限公司 | Nickel-cobalt-manganese ternary precursor, preparation method thereof, positive electrode material and lithium ion battery |
| CN118047423A (en) * | 2024-01-09 | 2024-05-17 | 中南大学 | Lithium-rich manganese-based precursor, preparation method thereof, lithium-rich manganese-based positive electrode material and lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113860395A (en) | High-specific-surface-area hollow cathode material precursor and preparation method thereof | |
| CN113247970B (en) | Hollow positive electrode material, precursor thereof and preparation method | |
| KR102025190B1 (en) | A positive electrode active material, a manufacturing method thereof, and a lithium secondary battery including the same | |
| CN110050366B (en) | Nickel active material precursor, method for producing same, nickel active material, and lithium secondary battery | |
| CN110073527B (en) | Nickel active material precursor, method for producing same, nickel active material, and lithium secondary battery | |
| CN107004852B (en) | Positive electrode active material for lithium battery having porous structure and method for producing same | |
| CN110226251B (en) | Nickel active material precursor, method for producing same, nickel active material, and lithium secondary battery | |
| KR100725399B1 (en) | Core-shell structured cathode active materials with high capacity and safety and their preparing method for lithium secondary batteries | |
| CN110921723B (en) | Preparation method of hollow lithium ion battery anode material precursor | |
| CN110931772A (en) | Preparation method of high-power type positive electrode material for lithium ion battery | |
| CN103928673B (en) | A kind of composite multi-component anode material for lithium-ion batteries and preparation method thereof | |
| CN111689528B (en) | Ternary material precursor and preparation method and application thereof | |
| JP2020513657A (en) | Nickel-based active material precursor for lithium secondary battery, method for producing the same, nickel-based active material for lithium secondary battery formed therefrom, and lithium secondary battery including positive electrode containing the same | |
| EP2023426A1 (en) | A positive electrode material for secondary battery and the preparation method of the same | |
| CN108155357B (en) | Nickel-based active material for lithium secondary battery, method for preparing same, and lithium secondary battery including positive electrode including same | |
| CN112830527B (en) | Precursor of hollow cathode material and preparation method thereof | |
| CN110518221B (en) | Method for preparing lithium silicate coated lithium nickel cobalt manganese oxide positive electrode material by anti-solvent method | |
| CN109786734A (en) | A kind of preparation method of the nickelic positive electrode of lithium secondary battery | |
| WO2022105696A1 (en) | Positive electrode active material precursor and preparation method therefor, positive electrode active material and preparation method therefor, positive electrode of lithium ion secondary battery, and lithium ion secondary battery | |
| EP3882217A1 (en) | Positive electrode active material and secondary battery including positive electrode active material | |
| EP4398341A1 (en) | Coated positive electrode material and preparation method therefor, secondary battery, positive electrode, and electric device | |
| KR102707663B1 (en) | Cathode material having a multi-cavity structure and its manufacturing method and lithium ion battery | |
| CN115974173A (en) | Cathode material, preparation method thereof and lithium ion battery | |
| EP3723173A1 (en) | Cathode active material for lithium secondary battery and lithium secondary battery comprising same | |
| CN113666430A (en) | Lithium-rich cathode material, preparation method thereof and lithium ion battery |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211231 |