CN114538535A - Positive electrode material, precursor, preparation method of precursor and lithium ion battery - Google Patents
Positive electrode material, precursor, preparation method of precursor and lithium ion battery Download PDFInfo
- Publication number
- CN114538535A CN114538535A CN202210108102.XA CN202210108102A CN114538535A CN 114538535 A CN114538535 A CN 114538535A CN 202210108102 A CN202210108102 A CN 202210108102A CN 114538535 A CN114538535 A CN 114538535A
- Authority
- CN
- China
- Prior art keywords
- precursor
- positive electrode
- electrode material
- reactor
- source
- 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 111
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 36
- 238000005406 washing Methods 0.000 claims abstract description 28
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 23
- 239000008139 complexing agent Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 15
- 230000005389 magnetism Effects 0.000 claims abstract description 15
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 15
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 239000006104 solid solution Substances 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 31
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 31
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims description 26
- 239000012065 filter cake Substances 0.000 claims description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000003570 air Substances 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 230000003750 conditioning effect Effects 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 14
- 230000001276 controlling effect Effects 0.000 description 31
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 27
- 239000010406 cathode material Substances 0.000 description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 26
- 239000000843 powder Substances 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- 238000003756 stirring Methods 0.000 description 24
- 238000001556 precipitation Methods 0.000 description 22
- 238000002156 mixing Methods 0.000 description 17
- 239000011572 manganese Substances 0.000 description 16
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 229910021529 ammonia Inorganic materials 0.000 description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 239000010413 mother solution Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode material, a precursor, a preparation method of the positive electrode material and a lithium ion battery, and relates to the technical field of lithium ion materials. The preparation method of the precursor comprises the following steps: adding water into the reactor, and heating to a certain temperature; adding an adjusting reagent into the reactor to achieve a predetermined electrochemical oxidation reaction condition, wherein the predetermined electrochemical oxidation reaction condition is that the oxidation-reduction potential is less than or equal to-500 mv and the conductivity is more than or equal to 300 us/cm; adding a metal source, water, an oxidant and a complexing agent into a reactor at a certain speed, and carrying out an electrochemical oxidation reaction to generate a precipitate; and finishing feeding, performing aging treatment, and then separating, washing and drying to obtain a precursor of the positive electrode material, wherein the precursor of the positive electrode material is a solid solution of metal hydroxide and metal oxide and has magnetism. The electrochemical performance of the anode material prepared by the precursor is more excellent, and the first charge-discharge efficiency is improved to more than 94%.
Description
Technical Field
The invention relates to the field of battery materials, and particularly relates to a positive electrode material, a precursor, a preparation method of the positive electrode material and a lithium ion battery.
Background
The positive electrode material is used as a core material of the battery, and the comprehensive performance of the battery is severely limited by the material performance of the positive electrode material. The high-quality, low-cost and environment-friendly green lithium battery material is the main direction of future development of battery materials, particularly in the fields of vehicle-mounted automobiles and high-rate and high-voltage application. However, as the demand of electric vehicles is continuously increased, the capacity of battery materials is continuously increased, the pressure of the production of battery materials on the environment is also increased, and especially the control standard of the discharge amount of waste water is severe. The reduction of the discharge amount of wastewater in the production process becomes a development trend of battery material production.
The wastewater generated in the preparation process of the battery material mainly comes from the preparation process of a precursor, the precursor is prepared by a coprecipitation crystallization method, ternary material liquid (nickel-cobalt-manganese salt solution), a precipitator and a complexing agent solution (such as ammonia solution) are used as raw materials, and the precursor of the anode material is prepared by controlling precipitation conditions. In the process, a large amount of waste gas and waste water are easily generated, and the treatment cost is high.
At present, part of the technologies adopt a chemical corrosion crystallization mode to reduce waste gas and waste water in the production process of the precursor of the cathode material. However, the precursor obtained in this way does not have magnetism, and the positive electrode material prepared from the precursor has low first charge-discharge efficiency and charge-discharge gram capacity, and particularly for the positive electrode material with low Ni content, the electrochemical performance needs to be improved.
Disclosure of Invention
In order to overcome the defects, the invention provides a positive electrode material, a precursor, a preparation method of the positive electrode material and a lithium ion battery.
The first aspect of the present invention provides a method for preparing a precursor of a positive electrode material, comprising the steps of:
s1, adding water into the reactor, and heating to a certain temperature;
s2, adding an adjusting reagent into the reactor to reach a preset electrochemical oxidation reaction condition, wherein the preset electrochemical oxidation reaction condition is that the oxidation-reduction potential is less than or equal to-500 mv and the electric conductivity is more than or equal to 300 us/cm;
s3, adding a metal source, water, an oxidant and a complexing agent into the reactor at a certain speed, and carrying out an electrochemical oxidation reaction to generate a precipitate;
and S4, finishing feeding, performing aging treatment, and then separating, washing and drying to obtain the precursor of the positive electrode material, wherein the precursor of the positive electrode material is a solid solution of metal hydroxide and metal oxide and has magnetism.
Further, in one disclosed embodiment, the positive electrode material precursor can be completely magnetized under the magnetic condition of 10000 GS.
Further, in one embodiment of the disclosure, the metal source is selected from one or more of a Ni source, a Co source, and a Mn source.
Further, in a disclosed embodiment, in step S1, after the temperature of the reactor is raised to a certain temperature, ammonia water is introduced into the reactor in advance.
Further, in one disclosed embodiment, in step S2, the conditioning agent includes an oxidizing agent, a complexing agent, and a salt; the oxidant is selected from one or more of air, oxygen, hydrogen peroxide, peroxyacetic acid and nitric acid; the complexing agent is selected from one or more of ammonia water, ammonium sulfate, ammonium chloride and ammonium nitrate; the salt is selected from one or more of sodium sulfate, sodium chloride and sodium nitrate.
Further, in one embodiment of the disclosure, in step S4, the separating, washing and drying steps include: and carrying out solid-liquid separation on the product obtained after the aging treatment to obtain a filter cake and a mother solution, carrying out alkali washing on the filter cake, and drying to obtain the precursor of the positive electrode material, wherein the mother solution and the wastewater generated in the alkali washing process are reused for the electrochemical oxidation reaction.
Further, in one disclosed embodiment, in step S3, the oxidant is selected from one or more of air, oxygen, hydrogen peroxide, peracetic acid, and nitric acid; the complexing agent is selected from one or more of ammonia water, ammonium sulfate, ammonium chloride and ammonium nitrate.
A second aspect of the present invention provides a precursor of a positive electrode material, which is a solid solution of a metal hydroxide and a metal oxide and has magnetic properties, and which is produced by the production method according to any one of the above aspects.
Further, in one disclosed embodiment, in the positive electrode material precursor, the mole percentage of the metal hydroxide is M1, and the mole percentage of the metal oxide is M2, wherein, M1 is more than or equal to 40% and less than 100%; m2 is more than 0% and less than or equal to 60%.
Further, in one disclosed embodiment, the precursor of the positive electrode material is a body-centered cubic lattice, a unit cell parameter a is 3.02 to 3.14, a unit cell parameter b is 3.01 to 3.12, a unit cell parameter c is 4.29 to 4.88, and a unit cell volume is 32.52 to 41.89.
A third aspect of the present invention provides a positive electrode material obtained by mixing and sintering the positive electrode material precursor as defined in any one of the above and a lithium source.
A fourth aspect of the invention provides a lithium ion battery comprising the positive electrode material as described above.
The positive electrode material, the precursor, the preparation method of the positive electrode material and the lithium ion battery have the beneficial effects that:
under the predetermined electrochemical reaction conditions (the oxidation-reduction potential is less than or equal to-500 mv, and the conductivity is more than or equal to 300us/cm), the metal source, the oxidant and the complexing agent are subjected to electrochemical oxidation reaction to generate the precursor of the anode material. The crystal structure of the precursor is changed through electrochemical oxidation reaction, primary particles are refined, and the precursor of the positive electrode material is a solid solution of metal oxide and hydroxide and shows weak magnetism. The anode material obtained by sintering the anode material precursor and a lithium source has more excellent electrochemical performance, the first charge-discharge efficiency is improved to more than 94%, and particularly the first charge-discharge gram capacity of the anode material with low Ni content can be effectively improved. The preparation method has the advantages of easily controlled process, easily adjusted parameters, no wastewater generated in the preparation process, and environmental protection.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a flowchart of a method for preparing a precursor of a positive electrode material according to an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of the precursor of the positive electrode material obtained in example 1 of the present invention;
fig. 3 is a scanning electron micrograph of the positive electrode material obtained in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following provides a detailed description of the positive electrode material, the precursor, the preparation method thereof, and the lithium ion battery according to the embodiment of the present invention.
The preparation method of the precursor of the cathode material provided by the disclosure comprises the following steps:
s1, adding water into the reactor, and heating to a certain temperature;
s2, adding an adjusting reagent into the reactor to reach a preset electrochemical oxidation reaction condition, wherein the preset electrochemical oxidation reaction condition is that the oxidation-reduction potential is less than or equal to-500 mv and the electric conductivity is more than or equal to 300 us/cm;
s3, adding a metal source, water, an oxidant and a complexing agent into the reactor at a certain speed, and carrying out an electrochemical oxidation reaction to generate a precipitate;
and S4, finishing feeding, performing aging treatment, and then separating, washing and drying to obtain the precursor of the positive electrode material, wherein the precursor of the positive electrode material is a solid solution of metal hydroxide and metal oxide and has magnetism.
The respective steps of the method for producing the precursor of the positive electrode material will be specifically described below.
And step S1, adding water into the reactor, and heating to a certain temperature. Specifically, in one embodiment of the present disclosure, water is added to the reactor to raise the temperature to 50-60 ℃, and the stirring is started. The water in the reactor is preferably pure water to avoid introducing impurities.
Further, heating the reactor to 50-60 ℃, starting stirring, and then introducing ammonia water into the reactor in advance. By introducing ammonia for a period of time, the nucleation granularity of the precursor can be controlled, and the precipitation period of the electrochemical oxidation reaction can be controlled, so that the refinement degree of the particles is improved, and the electrochemical performance of the product is improved.
Further, the stirring input power of the reactor is 0.5-2 kw.h/m3For example 0.8 kw.h/m3、1.0kw·h/m3、1.5kw·h/m3And the like.
Step S2, adding an adjusting reagent into the reactor to reach a preset electrochemical oxidation reaction condition, wherein the preset electrochemical oxidation reaction condition is that the oxidation-reduction potential is less than or equal to-500 mv and the electric conductivity is more than or equal to 300 us/cm. More preferably, the oxidation-reduction potential is from-500 mv to-1500 mv, for example, from-500 mv to-600 mv to-700 mv to-800 mv to-900 mv to-1000 mv to-1100 mv to-1200 mv to-1300 mv to-1400 mv to-1500 mv. The conductivity is, for example, 300us/cm, 400us/cm, 500us/cm, 600us/cm or the like. The reaction degree of the electrochemical oxidation reaction is controlled by controlling the oxidation-reduction potential and the conductivity, so that the crystal structure of the precursor is changed, and the solid solution of the metal oxide and the metal hydroxide is generated.
It will be appreciated that the conductivity and the oxidation-reduction potential can be measured by respective conductivity and ORP meters, respectively.
In one embodiment of the present disclosure, in step S2, the conditioning reagent includes an oxidizing agent, a complexing agent, and a salt; the oxidant is selected from one or more of air, oxygen, hydrogen peroxide, peroxyacetic acid and nitric acid; the complexing agent is selected from one or more of ammonia water, ammonium sulfate, ammonium chloride and ammonium nitrate; the salt is selected from one or more of sodium sulfate, sodium chloride and sodium nitrate. The reaction environment of the reactor is adjusted by the adjusting reagent so as to meet the requirement of electrochemical oxidation reaction. For example, in one embodiment of the present disclosure, the feeding ratio of the oxidant, the complexing agent and the salt is 1-3: 1-3: for example, the feed ratio of the oxidizing agent, the complexing agent and the salt can be 2: 2: 1.1: 1: 1.1: 2: 1, etc.
After the predetermined electrochemical oxidation condition is reached by adjusting the reagent control, the process proceeds to step S3: adding a metal source, water, an oxidant and a complexing agent into a reactor at a certain speed, and carrying out electrochemical oxidation reaction to generate a precipitate.
In one embodiment of the present disclosure, in step S3, the metal source includes a Ni source, a Co source, and a Mn source, for example, in one embodiment, the molar ratio of the Ni source, the Co source, and the Mn source is 50 to 80: 5-30: 5 to 40. A nickel-cobalt-manganese ternary positive electrode material precursor is formed by a Ni source, a Co source and a Mn source, and ternary positive electrode materials with different contents, such as Ni5 ternary positive electrode materials and the like, are generated by regulating and controlling the molar ratio of different metals. The Ni source, Co source and Mn source may be, for example, metal powders of Ni, Co and Mn.
It is understood that in other embodiments of the present disclosure, the metal source is a single metal such as a Ni source, a Co source, or a Mn source, and the unitary positive electrode material is prepared; or the metal source is two of Ni source, Co source, Mn source and other metals, and the binary anode material is prepared. Or the metal source contains metals except Ni, Co and Mn to prepare the multi-element positive electrode material.
In one embodiment of the present disclosure, in step S3, the oxidant is selected from one or more of air, oxygen, hydrogen peroxide, peracetic acid, and nitric acid; the complexing agent is selected from one or more of ammonia water, ammonium sulfate, ammonium chloride and ammonium nitrate. Further preferably, the oxidizing agent is nitric acid, and the complexing agent is ammonia water.
It is to be understood that the method for preparing the positive electrode material precursor of the present disclosure may be a batch reaction or a continuous reaction.
In the electrochemical oxidation reaction process of the step S3, the oxidation-reduction potential and the conductivity in the reaction environment are maintained at the preset electrochemical oxidation reaction conditions by regulating and controlling the feeding speed of the oxidant and the complexing agent, namely the oxidation-reduction potential is maintained to be less than or equal to-500 mv, and the conductivity is maintained to be more than or equal to 300 us/cm. Specifically, in one embodiment of the present disclosure, in step S3, the pH is controlled to be 7 to 9, and the concentration of ammonia or ammonium ions is controlled to be 0.5 to 1.2 mol/L. Under the pH value and the ammonia concentration, the oxidation-reduction potential and the conductivity can be kept unchanged, the electrochemical oxidation degree is ensured, and the metal hydroxide can be converted into the metal oxide to generate the solid solution of the metal oxide and the metal hydroxide.
And after the electrochemical oxidation reaction is finished, the step S4 is carried out, the feeding is finished, the aging treatment is carried out, and then the precursor of the cathode material is obtained through separation, washing and drying. The aging treatment is used for enabling the metal powder to be fully reacted and avoiding the residue of the metal powder. Specifically, the aging process is a standing reaction for 1-5 hours.
In one embodiment of the present disclosure, after the aging process is completed, the separating, washing and drying steps include: and (3) carrying out solid-liquid separation on the product obtained after the aging treatment to obtain a filter cake and a mother solution, washing the filter cake with alkali, and drying to obtain the precursor of the positive electrode material. Specifically, the alkali washing is performed by, for example, washing with a sodium hydroxide solution of a certain concentration. And the generation of impurities is reduced through an alkali washing process.
In one embodiment of the present disclosure, the mother liquor and the wastewater generated in the alkaline washing process are recycled to the electrochemical oxidation reaction process in step S3, and water or reagents such as oxidant and complexing agent consumed in the electrochemical oxidation reaction are supplemented.
Through the preparation steps, the precursor of the positive electrode material is obtained, and the precursor of the positive electrode material is a solid solution of metal hydroxide and metal oxide and has magnetism. Specifically, the precursor was adsorbed by 10000GS magnetic rod and all of the precursor was converted into a magnetic substance. Under the magnetic condition of 10000GS, the magnetic material can be completely magnetized.
In one embodiment of the disclosure, in the precursor of the positive electrode material, the mole percentage of the metal hydroxide is M1, and the mole percentage of the metal oxide is M2, wherein, M1 is more than or equal to 40% and less than 100%; m2 is more than 0% and less than or equal to 60%. The content of the metal oxide in the precursor of the anode material is adjusted by regulating and controlling the reaction conditions and the reaction time of the electrochemical oxidation reaction. More preferably, the molar percentage of the metal hydroxide is 60 to 80%, and the molar percentage of the metal oxide is 20 to 40%. Under the proportion, the cathode material prepared from the cathode material precursor can obtain more excellent electrochemical performance.
Further, in one disclosed embodiment, the precursor of the positive electrode material is a body-centered cubic lattice, the unit cell parameter a is 3.02 to 3.14, the unit cell parameter b is 3.01 to 3.12, the unit cell parameter c is 4.29 to 4.88, and the unit cell volume is 32.52 to 41.89. The lattice structure of the precursor of the cathode material proves that the product prepared by the method is a solid solution. For example, the unit cell parameters of the precursor can be determined by means of a diffractometer or the like, and the oxide content of the precursor can be reflected by the unit cell parameters.
In one disclosed embodiment, the prepared precursor of the cathode material is spherical-like particles, wherein the median particle diameter D50 is 3-18 um.
The present disclosure also provides a positive electrode material, which is obtained by mixing the positive electrode material precursor as described above with a lithium source and sintering. Specifically, in one disclosed embodiment, a positive electrode material precursor and a lithium source are uniformly mixed and calcined at 600-1100 ℃ for 5-30 h to obtain the positive electrode material. The ratio of the amount of lithium in the lithium source to the amount of metal in the metal source is 1 to 1.1: 1.
In one disclosed embodiment, the lithium source may be, for example, one or more of lithium hydroxide, lithium carbonate, lithium nitrate, and lithium acetate.
The present disclosure also provides a lithium ion battery comprising the positive electrode material described above. Specifically, a lithium ion battery includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte. The positive electrode includes the positive electrode material described above.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The positive electrode material precursor provided by the embodiment is obtained by the following steps:
(1) preparing metal powder from nickel powder, cobalt powder and manganese powder, wherein the ratio of Ni: co: the molar ratio of Mn is 80: 11.5: 8.5.
(2) 2/3 kettle volumes of high purity water were added to the kettle and the temperature was raised to 50 ℃. Starting stirring, wherein the stirring input power is 1 kw.h/m3And ammonia is pre-introduced.
(3) Mixing nitric acid, ammonia water and sodium sulfate according to a mass ratio of 1: 1:1, adding the mixture into a reaction kettle at the same time, uniformly stirring, and controlling the oxidation-reduction potential orp value to be-500 mv and the electric conductivity to be 300 us/cm.
(4) And (2) adding the metal powder obtained in the step (1), nitric acid and ammonia water which are uniformly mixed at a certain speed to generate a precipitate, wherein in the precipitation process, the pH value is controlled to be 7-9 by controlling the feeding speed of the nitric acid, the ammonia concentration is controlled to be 0.5-1.2 mol/L by controlling the feeding speed of the ammonia water, and the oxidation-reduction potential and the conductivity in the electrochemical oxidation process are maintained to generate the precipitate.
(5) And controlling the precipitation time to be 50-60 h, after the precipitation is finished, aging until the reaction is complete, performing solid-liquid separation on the obtained slurry to obtain mother liquor and a filter cake, drying and sieving the filter cake through alkali washing to obtain a precursor of the nickel-cobalt-manganese anode material with weak magnetism, and feeding the filtrate and washing water generated in the process back to the reaction kettle for continuous reaction.
The obtained nickel-cobalt-manganese positive material precursor is adsorbed by a 10000GS magnetic rod and can be completely converted into a magnetic substance. The scanning electron microscope image of the nickel-cobalt-manganese cathode material precursor is shown in fig. 2, and as can be seen from fig. 2, the particles of the nickel-cobalt-manganese cathode material precursor are uniformly distributed, the shape of the nickel-cobalt-manganese cathode material precursor is spheroidal, and the particle size D50 is 3-18 um.
And uniformly mixing the obtained nickel-cobalt-manganese positive electrode material precursor and lithium carbonate, wherein Li/Me is 1.1:05, and Li represents the quantity of Li in the lithium carbonate, and Me represents the total quantity of the positive electrode material precursor. And then calcining the mixture at 800 ℃ for 12 hours to finally obtain composite oxide powder with Li/Me being 1.05, namely the cathode material. The scanning electron microscope image of the cathode material is shown in fig. 3, and as can be seen from fig. 3, the sintered cathode material has uniform particles and is a single crystal product.
Example 2
The positive electrode material precursor provided by the embodiment is obtained by the following steps:
(1) preparing metal powder from nickel powder, cobalt powder and manganese powder, wherein the ratio of Ni: co: the molar ratio of Mn is 72: 8: 20.
(2) 2/3 kettle volumes of high purity water were added to the kettle and the temperature was raised to 50 ℃. Starting stirring, wherein the stirring input power is 1 kw.h/m3And introducing ammonia water in advance.
(3) Mixing nitric acid, ammonia water and sodium sulfate according to a mass ratio of 1: 2: 1, adding the mixture into a reaction kettle at the same time, uniformly stirring, and controlling the oxidation-reduction potential orp value to be-600 mv and the electric conductivity to be 400 us/cm.
(4) And (3) adding the metal powder obtained in the step (1), nitric acid and ammonia water which are uniformly mixed at a certain speed to generate a precipitate. In the precipitation process, the pH is controlled to be 7-9 by controlling the feeding speed of nitric acid, the ammonia concentration is controlled to be 0.5-1.2 mol/L by controlling the feeding speed of ammonia water, and the oxidation-reduction potential and the conductivity in the electrochemical oxidation process are maintained.
(5) And controlling the precipitation time to be 80-90 h, after the precipitation is finished, aging until the reaction is complete, performing solid-liquid separation on the obtained slurry to obtain mother liquor and a filter cake, drying and sieving the filter cake through alkali washing to obtain a precursor of the nickel-cobalt-manganese anode material with weak magnetism, and feeding the filtrate and washing water generated in the process back to the reaction kettle for continuous reaction.
The obtained nickel-cobalt-manganese positive material precursor is adsorbed by a 10000GS magnetic rod and can be completely converted into a magnetic substance. The nickel-cobalt-manganese anode material precursor is uniform in particle distribution, spherical in shape and 3-18 um in particle size D50.
And uniformly mixing the obtained nickel-cobalt-manganese positive electrode material precursor and lithium carbonate, wherein Li/Me is 1.1:1, Li represents the amount of Li in the lithium carbonate, and Me represents the total amount of the positive electrode material precursor. And then calcining the mixture at 800 ℃ for 12 hours to finally obtain composite oxide powder with Li/Me being 1.1, namely the cathode material. The positive electrode material has uniform particles and is a single crystal product.
Example 3
The positive electrode material precursor provided by the embodiment is obtained by the following steps:
(1) preparing metal powder from nickel powder, cobalt powder and manganese powder, wherein the ratio of Ni: co: the molar ratio of Mn is 66: 7: 27.
(2) 2/3 kettle volumes of high purity water were added to the kettle and the temperature was raised to 55 ℃. Starting stirring, wherein the stirring input power is 1.2 kw.h/m3And ammonia is pre-introduced.
(3) Mixing nitric acid, ammonia water and sodium sulfate according to a mass ratio of 1: 2: 1, adding the mixture into a reaction kettle at the same time, uniformly stirring, and controlling the oxidation-reduction potential orp value to be-700 mv and the electric conductivity to be 500 us/cm.
(4) And (3) adding the metal powder obtained in the step (1), nitric acid and ammonia water which are uniformly mixed at a certain speed to generate a precipitate. In the precipitation process, the pH is controlled to be 7-9 by controlling the feeding speed of nitric acid, the ammonia concentration is controlled to be 0.5-1.2 mol/L by controlling the feeding speed of ammonia water, and the oxidation-reduction potential and the conductivity in the electrochemical oxidation process are maintained.
(5) And controlling the precipitation time to be 110-130 h, after the precipitation is finished, aging until the reaction is complete, performing solid-liquid separation on the obtained slurry to obtain mother liquor and a filter cake, drying and sieving the filter cake through alkali washing to obtain a precursor of the nickel-cobalt-manganese anode material with weak magnetism, and feeding the filtrate and washing water generated in the process back to the reaction kettle for continuous reaction.
The obtained nickel-cobalt-manganese positive material precursor is adsorbed by a 10000GS magnetic rod and can be completely converted into a magnetic substance. The nickel-cobalt-manganese anode material precursor is uniform in particle distribution, spherical in shape and 3-18 um in particle size D50.
And uniformly mixing the obtained nickel-cobalt-manganese positive electrode material precursor and lithium carbonate, wherein Li/Me is 1.1:1, Li represents the amount of Li in the lithium carbonate, and Me represents the total amount of the positive electrode material precursor. And then calcining the mixture at 800 ℃ for 12 hours to finally obtain composite oxide powder with Li/Me being 1.1, namely the cathode material. The positive electrode material has uniform particles and is a single crystal product.
Example 4
The positive electrode material precursor provided by the embodiment is obtained by the following steps:
(1) preparing metal powder from nickel powder, cobalt powder and manganese powder, wherein the ratio of Ni: co: the molar ratio of Mn is 58: 6.5: 35.5.
(2) 2/3 kettle volumes of high purity water were added to the kettle and the temperature was raised to 60 ℃. Starting stirring, wherein the stirring input power is 0.8 kw.h/m3And ammonia is pre-introduced.
(3) Mixing nitric acid, ammonia water and sodium sulfate according to a mass ratio of 2: 2: 1, adding the mixture into a reaction kettle at the same time, uniformly stirring, and controlling the oxidation-reduction potential orp value to be-600 mv and the electric conductivity to be 500 us/cm.
(4) And (3) adding the metal powder obtained in the step (1), nitric acid and ammonia water which are uniformly mixed at a certain speed to generate a precipitate. In the precipitation process, the pH is controlled to be 7-9 by controlling the feeding speed of nitric acid, the ammonia concentration is controlled to be 0.5-1.2 mol/L by controlling the feeding speed of ammonia water, and the oxidation-reduction potential and the conductivity in the electrochemical oxidation process are maintained.
(5) And controlling the precipitation time to be 70-80 h, after the precipitation is finished, aging until the reaction is complete, performing solid-liquid separation on the obtained slurry to obtain mother liquor and a filter cake, performing alkaline washing, drying and sieving on the filter cake to obtain a precursor of the nickel-cobalt-manganese anode material with weak magnetism, and feeding the filtrate and washing water generated in the process back to the reaction kettle for continuous reaction.
The obtained nickel-cobalt-manganese positive material precursor is adsorbed by a 10000GS magnetic rod and can be completely converted into a magnetic substance. The nickel-cobalt-manganese anode material precursor is uniform in particle distribution, spherical in shape and 3-18 um in particle size D50.
And uniformly mixing the obtained nickel-cobalt-manganese positive electrode material precursor and lithium carbonate, wherein Li/Me is 1.1:1, Li represents the amount of Li in the lithium carbonate, and Me represents the total amount of the positive electrode material precursor. And then calcining the mixture at 800 ℃ for 12 hours to finally obtain composite oxide powder with Li/Me being 1.1, namely the cathode material. The positive electrode material has uniform particles and is a single crystal product.
Comparative example 1
The precursor of the cathode material is obtained according to the following steps:
(1) preparing metal powder from nickel powder, cobalt powder and manganese powder, wherein the ratio of Ni: co: the molar ratio of Mn is 80: 11.5: 8.5.
(2) 2/3 kettle volumes of high purity water were added to the kettle and the temperature was raised to 50 ℃. Starting stirring, wherein the stirring input power is 1 kw.h/m3And ammonia is pre-introduced. Then, mixing nitric acid, ammonia water and sodium sulfate according to the mass ratio of 1: 1:1, adding the mixture into a reaction kettle at the same time, uniformly stirring, and controlling the oxidation-reduction potential orp value to be 0mv and the electric conductivity to be 200 us/cm.
(3) Adding the metal powder, the nitric acid and the ammonia water which are uniformly mixed at a certain speed, controlling the pH value to be 7-9 by the nitric acid in the precipitation process, and controlling the ammonia concentration to be 0.8-1.5 mol/L.
(4) And controlling the precipitation time to be 70-80 h, carrying out solid-liquid separation on the obtained slurry after the precipitation is finished to obtain mother liquor and a filter cake, washing the filter cake by pure water, drying and sieving to obtain the precursor of the cathode material. The nickel-cobalt-manganese positive electrode material is adsorbed by a 10000GS magnetic rod, cannot be adsorbed and has no magnetism.
And uniformly mixing the obtained nickel-cobalt-manganese positive electrode material precursor and lithium carbonate, wherein Li/Me is 1.05:1, Li represents the amount of Li in the lithium carbonate, and Me represents the total amount of the positive electrode material precursor. And then calcining the mixture at 800 ℃ for 12 hours to finally obtain composite oxide powder with Li/Me being 1.05, namely the cathode material.
Comparative example 2
The precursor of the cathode material is obtained according to the following steps:
(1) preparing metal powder from nickel powder, cobalt powder and manganese powder, wherein the ratio of Ni: co: the molar ratio of Mn is 58: 6.5: 35.5.
(2) 2/3 kettle volumes of high purity water were added to the kettle and the temperature was raised to 60 ℃. Starting stirring, wherein the stirring input power is 0.8 kw.h/m3And introducing ammonia water in advance. Then mixing nitric acid, ammonia water and sodium sulfate according to the mass ratio of 2: 2: 1, adding the mixture into a reaction kettle at the same time, uniformly stirring, and controlling the oxidation-reduction potential orp value to be 100mv and the electric conductivity to be 100 us/cm.
(3) Adding the metal powder, the nitric acid and the ammonia water which are uniformly mixed at a certain speed, controlling the pH value to be 7-9 by the nitric acid in the precipitation process, and controlling the ammonia concentration to be 0.8-1.5 mol/L.
(4) And controlling the precipitation time to be 70-80 h, carrying out solid-liquid separation on the obtained slurry after the precipitation is finished to obtain mother liquor and a filter cake, washing the filter cake by pure water, drying and sieving to obtain the precursor of the cathode material. The nickel-cobalt-manganese positive electrode material is adsorbed by a 10000GS magnetic rod, cannot be adsorbed and has no magnetism.
And uniformly mixing the obtained nickel-cobalt-manganese positive electrode material precursor and lithium carbonate, wherein Li/Me is 1.1:1, Li represents the amount of Li in the lithium carbonate, and Me represents the total amount of the positive electrode material precursor. And then calcining the mixture at 800 ℃ for 12 hours to finally obtain composite oxide powder with Li/Me being 1.1, namely the cathode material.
Comparative example 3
The precursor of the cathode material is obtained according to the following steps:
(1) preparing metal powder from nickel powder, cobalt powder and manganese powder, wherein the ratio of Ni: co: the molar ratio of Mn is 58: 6.5: 35.5.
(2) 2/3 kettle volumes of high purity water were added to the kettle and the temperature was raised to 60 ℃. Starting stirring, wherein the stirring input power is 1 kw.h/m3And then, mixing the metal powder, nitric acid and sodium sulfate according to the mass ratio of 10: 1:1, adding the mixture into a reaction kettle for reaction, adding 10g/L ammonia water, and controlling the oxidation-reduction potential orp value to be-1000 mv, the conductivity to be 200us/cm and the pH value to be 6-8 in the reaction process.
(4) And controlling the precipitation time to be 30-50 h, adsorbing the obtained slurry by using a magnetic bar of 100GS after the precipitation is finished, removing unreacted metal powder, then carrying out solid-liquid separation to obtain a mother solution and a filter cake, washing the filter cake by pure water, drying and sieving to obtain the nickel-cobalt-manganese anode material precursor. The nickel-cobalt-manganese positive electrode material is adsorbed by a 10000GS magnetic rod, cannot be adsorbed and has no magnetism.
And uniformly mixing the obtained nickel-cobalt-manganese positive electrode material precursor with lithium carbonate, wherein Li/Me (1.1: 1) represents the quantity of Li in the lithium carbonate, and Me represents the total quantity of the positive electrode material precursor. And then calcining the mixture at 800 ℃ for 12 hours to finally obtain composite oxide powder with Li/Me being 1.1, namely the cathode material.
Test example 1
The positive electrode materials obtained in examples 1 to 4 and comparative examples 1 to 3 were made into electrode sheets and assembled into button cells. The specific process is as follows: firstly, fully grinding and mixing the positive electrode material, the acetylene black and the PVDF according to the mass ratio of 8:1:1, then adding NMP to dissolve the mixture, and continuously stirring for 6 hours; and then coated on a clean aluminum foil using a doctor blade. Vacuum drying at 120 deg.C for 12h, and punching to obtain 14mm diameter electrode sheet. It was assembled in a braun glove box into a button half cell model CR 2032. And carrying out electrochemical performance test on the CR2032 button half-cell, and testing the first charge-discharge efficiency, the first charge gram capacity and the first discharge gram capacity of the anode material. The test results are shown in table 1.
TABLE 1
As can be seen from Table 1, compared with comparative examples 1-2, the electrochemical oxidation is enhanced by adjusting the electrochemical reaction conditions in the examples, the first charge-discharge efficiency of the obtained cathode material reaches more than 94%, and the first charge-discharge efficiency is remarkably improved compared with comparative examples 1-2. And the gram capacity of charge reaches more than 217mAh/g, and the gram capacity of discharge reaches more than 196 mAh/g. In addition, compared with the comparative example 3, ammonia water is introduced in advance, and after the preset electrochemical oxidation reaction condition is achieved, metal powder is added for reaction, so that the charge and discharge gram capacity of the product can be further improved.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (12)
1. A preparation method of a precursor of a positive electrode material is characterized by comprising the following steps:
s1, adding water into the reactor, and heating to a certain temperature;
s2, adding an adjusting reagent into the reactor to reach a preset electrochemical oxidation reaction condition, wherein the preset electrochemical oxidation reaction condition is that the oxidation-reduction potential is less than or equal to-500 mv and the electric conductivity is more than or equal to 300 us/cm;
s3, adding a metal source, water, an oxidant and a complexing agent into the reactor at a certain speed, and carrying out an electrochemical oxidation reaction to generate a precipitate;
and S4, finishing feeding, performing aging treatment, and then separating, washing and drying to obtain the precursor of the positive electrode material, wherein the precursor of the positive electrode material is a solid solution of metal hydroxide and metal oxide and has magnetism.
2. The method for producing a positive electrode material precursor according to claim 1, wherein the positive electrode material precursor can be completely magnetized under magnetic conditions of 10000 GS.
3. The method for producing a precursor for a positive electrode material according to claim 1, wherein the metal source is one or more selected from a Ni source, a Co source, and a Mn source.
4. The method according to claim 1, wherein in step S1, ammonia water is introduced into the reactor in advance after the temperature of the reactor has been raised to a predetermined temperature.
5. The method for preparing a precursor of a positive electrode material according to claim 1, wherein in step S2, the conditioning agent includes an oxidizing agent, a complexing agent, and a salt; the oxidant is selected from one or more of air, oxygen, hydrogen peroxide, peroxyacetic acid and nitric acid; the complexing agent is selected from one or more of ammonia water, ammonium sulfate, ammonium chloride and ammonium nitrate; the salt is selected from one or more of sodium sulfate, sodium chloride and sodium nitrate.
6. The method for preparing a precursor of a positive electrode material according to claim 1, wherein the separating, washing, and drying step in step S4 includes: and carrying out solid-liquid separation on the product obtained after the aging treatment to obtain a filter cake and a mother liquor, washing the filter cake with alkali, and drying to obtain the precursor of the positive electrode material, wherein the mother liquor and the wastewater generated in the alkali washing process are reused for the electrochemical oxidation reaction.
7. The method for preparing the precursor of the positive electrode material according to claim 1, wherein in step S3, the oxidizing agent is one or more selected from the group consisting of air, oxygen, hydrogen peroxide, peracetic acid, and nitric acid; the complexing agent is selected from one or more of ammonia water, ammonium sulfate, ammonium chloride and ammonium nitrate.
8. A precursor of a positive electrode material, which is prepared by the preparation method according to any one of claims 1 to 7, is a solid solution of a metal hydroxide and a metal oxide, and has magnetism.
9. The precursor of the positive electrode material of claim 8, wherein the molar percentage of the metal hydroxide is M1, the molar percentage of the metal oxide is M2, and M1 is more than or equal to 40% and less than 100%; m2 is more than 0% and less than or equal to 60%.
10. The precursor of the positive electrode material according to claim 8, wherein the precursor of the positive electrode material is a body-centered cubic lattice, a unit cell parameter a is 3.02 to 3.14, a unit cell parameter b is 3.01 to 3.12, a unit cell parameter c is 4.29 to 4.88, and a unit cell volume is 32.52 to 41.89.
11. A positive electrode material, characterized in that the positive electrode material precursor according to any one of claims 8 to 10 is mixed with a lithium source and sintered to obtain a positive electrode material.
12. A lithium ion battery comprising the positive electrode material according to claim 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210108102.XA CN114538535B (en) | 2022-01-28 | 2022-01-28 | Positive electrode material, precursor, preparation method of precursor and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210108102.XA CN114538535B (en) | 2022-01-28 | 2022-01-28 | Positive electrode material, precursor, preparation method of precursor and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114538535A true CN114538535A (en) | 2022-05-27 |
| CN114538535B CN114538535B (en) | 2023-12-15 |
Family
ID=81674452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210108102.XA Active CN114538535B (en) | 2022-01-28 | 2022-01-28 | Positive electrode material, precursor, preparation method of precursor and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114538535B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070082902A (en) * | 2006-02-17 | 2007-08-22 | 주식회사 엘지화학 | Lithium-metal composite oxides and electrochemical device using the same |
| US20070292763A1 (en) * | 2006-06-19 | 2007-12-20 | University Of Chicago | Cathode material for lithium batteries |
| CN107845801A (en) * | 2017-09-04 | 2018-03-27 | 济南大学 | A kind of fluorophosphoric acid cobalt lithium anode material of modified synergic and preparation method thereof |
| WO2018096972A1 (en) * | 2016-11-22 | 2018-05-31 | 国立研究開発法人産業技術総合研究所 | Lithium-manganese complex oxide and method for producing same |
| CN111943281A (en) * | 2020-08-04 | 2020-11-17 | 厦门厦钨新能源材料股份有限公司 | Environment-friendly precursor and composite oxide powder as well as preparation method and application thereof |
| CN111977706A (en) * | 2020-08-24 | 2020-11-24 | 厦门厦钨新能源材料股份有限公司 | Lithium-intercalated metal oxide and preparation method and application thereof |
| CN112174227A (en) * | 2020-09-30 | 2021-01-05 | 厦门厦钨新能源材料股份有限公司 | Single crystal material precursor and composite oxide powder, and preparation method and application thereof |
| WO2021212729A1 (en) * | 2020-04-24 | 2021-10-28 | 四川万邦胜辉新能源科技有限公司 | Nickel-manganese-based positive electrode material precursor and synthesis method for positive electrode material thereof |
-
2022
- 2022-01-28 CN CN202210108102.XA patent/CN114538535B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070082902A (en) * | 2006-02-17 | 2007-08-22 | 주식회사 엘지화학 | Lithium-metal composite oxides and electrochemical device using the same |
| US20070292763A1 (en) * | 2006-06-19 | 2007-12-20 | University Of Chicago | Cathode material for lithium batteries |
| WO2018096972A1 (en) * | 2016-11-22 | 2018-05-31 | 国立研究開発法人産業技術総合研究所 | Lithium-manganese complex oxide and method for producing same |
| CN107845801A (en) * | 2017-09-04 | 2018-03-27 | 济南大学 | A kind of fluorophosphoric acid cobalt lithium anode material of modified synergic and preparation method thereof |
| WO2021212729A1 (en) * | 2020-04-24 | 2021-10-28 | 四川万邦胜辉新能源科技有限公司 | Nickel-manganese-based positive electrode material precursor and synthesis method for positive electrode material thereof |
| CN111943281A (en) * | 2020-08-04 | 2020-11-17 | 厦门厦钨新能源材料股份有限公司 | Environment-friendly precursor and composite oxide powder as well as preparation method and application thereof |
| CN111977706A (en) * | 2020-08-24 | 2020-11-24 | 厦门厦钨新能源材料股份有限公司 | Lithium-intercalated metal oxide and preparation method and application thereof |
| CN112174227A (en) * | 2020-09-30 | 2021-01-05 | 厦门厦钨新能源材料股份有限公司 | Single crystal material precursor and composite oxide powder, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114538535B (en) | 2023-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11440811B2 (en) | Ternary precursor particles and method for manufacturing the same | |
| US9553313B2 (en) | 3V class spinel complex oxides as cathode active materials for lithium secondary batteries, method for preparing the same by carbonate coprecipitation, and lithium secondary batteries using the same | |
| CN107123792B (en) | Ternary cathode material with double-layer composite structure and preparation method thereof | |
| CN108767216B (en) | Lithium ion battery anode material with variable slope and full concentration gradient and synthesis method thereof | |
| EP3487813A1 (en) | A method for upscalable precipitation synthesis of battery materials with tunable particle size distribution | |
| CN110921723A (en) | Preparation method of hollow lithium ion battery anode material precursor | |
| CN104766970A (en) | Synthetic method for lithium nickel manganese oxygen covered with lithium titanate | |
| CN110534737B (en) | High-rate doped nickel-cobalt-manganese ternary material and preparation method thereof | |
| WO2005104272A1 (en) | Alkaline battery and method for producing positive electrode material therefor | |
| AU2005291782B2 (en) | Process for producing lithium transition metal oxides | |
| CN115520846B (en) | Preparation method and application of lithium iron manganese phosphate | |
| CN115520900B (en) | Phosphorus doped nano-grade manganous-manganic oxide, preparation method thereof and battery | |
| CN114084914A (en) | Ternary precursor and preparation method and application thereof | |
| CN114835173A (en) | Positive electrode material precursor, preparation method thereof and positive electrode material | |
| CN113582254B (en) | Layered positive electrode material and preparation method and application thereof | |
| CN111434617A (en) | Aluminum-coated precursor and preparation method and application thereof | |
| CN112582597A (en) | Preparation method and modification method of ternary cobalt-free cathode material | |
| CN114538535B (en) | Positive electrode material, precursor, preparation method of precursor and lithium ion battery | |
| CN115490276A (en) | Surface-modified positive electrode material precursor and preparation method and application thereof | |
| US20220274847A1 (en) | Process to produce cathode materials for rechargeable li batteries | |
| CN114933292A (en) | Preparation method and application of lithium iron phosphate | |
| CN114655997A (en) | Method for preparing ternary precursor by micro-bubble pre-oxidation and application thereof | |
| CN111422917A (en) | High-nickel low-cobalt carbonate precursor with sandwich structure and preparation method and application thereof | |
| CN111186862A (en) | Preparation method of battery-grade high-purity trimanganese tetroxide | |
| CN114105208B (en) | Low-sulfur manganous-manganic oxide and preparation method 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 |