CN114538535B - 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
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 120
- 239000002243 precursor Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 59
- 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 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008139 complexing agent Substances 0.000 claims abstract description 21
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 21
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- 230000005389 magnetism Effects 0.000 claims abstract description 16
- 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
- 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 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000006104 solid solution Substances 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- 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 34
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 34
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 21
- 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 12
- 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
- 239000012452 mother liquor Substances 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
- 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
- 239000002351 wastewater Substances 0.000 claims description 9
- 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
- 239000003513 alkali Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 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
- 239000000463 material Substances 0.000 abstract description 9
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 239000000843 powder Substances 0.000 description 26
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- 230000001276 controlling effect Effects 0.000 description 23
- 238000001556 precipitation Methods 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 239000000126 substance Substances 0.000 description 20
- 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
- 238000002156 mixing Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 239000011572 manganese Substances 0.000 description 14
- 239000010405 anode material Substances 0.000 description 13
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 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
- 239000002131 composite material Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 4
- 238000001000 micrograph Methods 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
- 239000010406 cathode material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 2
- 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
- 238000005245 sintering Methods 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
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910018209 Ni—Co—Mn Inorganic materials 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
- 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
- 239000010413 mother solution 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
- 239000011164 primary particle Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000008213 purified water Substances 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
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- 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
Abstract
The invention provides a positive electrode material, a precursor, a preparation method of the precursor 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 a regulating reagent into the reactor to reach preset electrochemical oxidation reaction conditions, wherein the preset electrochemical oxidation reaction conditions are oxidation-reduction potential less than or equal to-500 mv and electric conductivity more than or equal to 300us/cm; adding a metal source, water, an oxidant and a complexing agent into a reactor according to a certain speed to perform electrochemical oxidation reaction to generate a precipitate; and (3) finishing feeding, aging, separating, washing and drying to obtain a positive electrode material precursor, wherein the positive electrode material precursor is a solid solution of metal hydroxide and metal oxide and has magnetism. The electrochemical performance of the positive electrode material prepared by the precursor is more excellent, and the first charge and discharge efficiency is improved to more than 94%.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a positive electrode material, a precursor, a preparation method of the precursor and a lithium ion battery.
Background
The cathode material is used as a core material of the battery, and the comprehensive performance of the battery is severely restricted by the material performance of the cathode material. The high-quality, low-cost and environment-friendly green lithium battery material is a main direction of future development of battery materials, and is especially applied to the fields of vehicle-mounted automobiles and high-rate and high-voltage applications. However, as the requirements of electric automobiles are continuously increased, the productivity of battery materials is continuously increased, and the pressure caused by the production of the battery materials on the environment is also increased, especially the control standard for the discharge amount of wastewater is more serious. The reduction of the amount of wastewater discharge in the production process becomes a development trend of battery material production.
The waste water generated in the preparation process of the battery material mainly comes from the preparation process of the precursor, the preparation of the precursor generally adopts a coprecipitation crystallization method, and ternary feed liquid (nickel cobalt manganese salt solution), a precipitant and a complexing agent solution (such as ammonia water solution) are used as raw materials to prepare the precursor of the positive electrode material by controlling the precipitation condition. In this process, a large amount of waste gas and waste water are easily generated, and the treatment cost is high.
At present, some technologies adopt a chemical corrosion crystallization mode to reduce waste gas and waste water in the production process of the precursor of the positive electrode material. However, the precursor obtained in this way has no magnetism, and the positive electrode material prepared from the precursor has low initial charge-discharge efficiency and charge-discharge gram capacity, and particularly has low Ni content, and electrochemical performance is 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 precursor and a lithium ion battery.
The first aspect of the present invention provides a method for preparing a positive electrode material precursor, comprising the steps of:
s1, adding water into a reactor, and heating to a certain temperature;
s2, adding an adjusting reagent into the reactor to reach preset electrochemical oxidation reaction conditions, wherein the preset electrochemical oxidation reaction conditions are oxidation-reduction potential less than or equal to-500 mv and electric conductivity more than or equal to 300us/cm;
s3, adding a metal source, water, an oxidant and a complexing agent into the reactor according to a certain speed, and performing electrochemical oxidation reaction to generate a precipitate;
s4, finishing feeding, aging, separating, washing and drying to obtain a positive electrode material precursor, wherein the positive electrode material precursor is a solid solution of metal hydroxide and metal oxide and has magnetism.
Further, in one disclosed embodiment, the positive electrode material precursor is capable of being fully magnetized under magnetic conditions 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 one disclosed embodiment, in step S1, ammonia is introduced into the reactor in advance after the reactor is warmed up to a certain temperature.
Further, in one embodiment of the disclosure, in step S2, the conditioning agent includes an oxidizing agent, a complexing agent, and a salt; the oxidant is one or more selected from 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; the salt is selected from one or more of sodium sulfate, sodium chloride and sodium nitrate.
Further, in one disclosed embodiment, in step S4, the separating, washing, 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 liquor, carrying out alkali washing on the filter cake, and drying to obtain the positive electrode material precursor, wherein the mother liquor and wastewater generated in the alkali washing process are recycled for electrochemical oxidation reaction.
Further, in one disclosed embodiment, in step S3, the oxidizing agent 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.
The second aspect of the present invention provides a positive electrode material precursor, which is a solid solution of a metal hydroxide and a metal oxide and has magnetism, and is prepared by the preparation method according to any one of the above.
Further, in one disclosed embodiment, in the positive electrode material precursor, the molar percentage of the metal hydroxide is M1, and the molar 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 positive electrode material precursor is a body-centered cubic lattice, the unit cell parameter a is 3.02-3.14, the unit cell parameter b is 3.01-3.12, the unit cell parameter c is 4.29-4.88, and the unit cell volume is 32.52-41.89.
A third aspect of the present invention provides a positive electrode material, wherein the positive electrode material precursor according to any one of the above is mixed with a lithium source, and sintered to obtain the positive electrode material.
A fourth aspect of the invention provides a lithium ion battery comprising a positive electrode material as described above.
The positive electrode material, the precursor, the preparation method thereof and the lithium ion battery have the beneficial effects that:
under the preset electrochemical reaction conditions (oxidation-reduction potential is less than or equal to-500 mv and conductivity is more than or equal to 300 us/cm), the metal source, the oxidant and the complexing agent perform electrochemical oxidation reaction to generate a positive electrode material precursor. The crystal structure of the precursor is changed through electrochemical oxidation reaction, primary particles are thinned, and the precursor of the positive electrode material is a solid solution of metal oxide and hydroxide and shows weak magnetism. The positive electrode material obtained by sintering the positive electrode material precursor and the lithium source has better electrochemical performance, improves the first charge and discharge efficiency to more than 94 percent, and particularly can effectively improve the first charge and discharge gram capacity of the positive electrode material with lower Ni content. The preparation method is easy to control, various parameters are easy to adjust, and no waste water is generated in the preparation process, so that the preparation method is environment-friendly.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart 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 positive electrode material precursor obtained in example 1 of the present invention;
fig. 3 is a scanning electron microscope image 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 more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The positive electrode material, the precursor, the preparation method thereof and the lithium ion battery according to the embodiment of the invention are specifically described below.
The preparation method of the positive electrode material precursor provided by the disclosure comprises the following steps:
s1, adding water into a reactor, and heating to a certain temperature;
s2, adding an adjusting reagent into the reactor to reach preset electrochemical oxidation reaction conditions, wherein the preset electrochemical oxidation reaction conditions are oxidation-reduction potential less than or equal to-500 mv and electric conductivity more than or equal to 300us/cm;
s3, adding a metal source, water, an oxidant and a complexing agent into the reactor according to a certain speed, and performing electrochemical oxidation reaction to generate a precipitate;
s4, finishing feeding, aging, separating, washing and drying to obtain a positive electrode material precursor, wherein the positive electrode material precursor is a solid solution of metal hydroxide and metal oxide and has magnetism.
The steps of the method for preparing the positive electrode material precursor are specifically described below.
Step S1, adding water into a 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 stirring is turned on. The water in the reactor is preferably pure water, avoiding the introduction of impurities.
Further, after the temperature of the reactor is raised to 50-60 ℃, stirring is started, and then ammonia water is introduced into the reactor in advance. The nucleation granularity of the precursor can be controlled and the precipitation period of the electrochemical oxidation reaction can be controlled by pre-introducing ammonia for a period of time, so that the refinement degree of 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/m 3 For example 0.8 kw.h/m 3 、1.0kw·h/m 3 、1.5kw·h/m 3 Etc.
And S2, adding a regulating reagent into the reactor to reach preset electrochemical oxidation reaction conditions, wherein the preset electrochemical oxidation reaction conditions are oxidation-reduction potential less than or equal to-500 mv and electric conductivity more than or equal to 300us/cm. Further preferably, the redox potential is-500 to-1500 mv, for example, -500mv, -600mv, -700mv, -800mv, -900mv, -1000mv, -1100mv, -1200mv, -1300mv, -1400mv, -1500mv. The electrical conductivity is, for example, 300us/cm, 400us/cm, 500us/cm, 600us/cm, etc. The oxidation-reduction potential and the conductivity are controlled to control the reaction degree of the electrochemical oxidation reaction, 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 is understood that the conductivity and the redox potential can be measured by a corresponding conductivity meter and ORP meter, respectively.
In one embodiment of the present disclosure, in step S2, the conditioning agent comprises an oxidizing agent, a complexing agent, and a salt; the oxidant is one or more selected from 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; the salt is selected from one or more of sodium sulfate, sodium chloride and sodium nitrate. The reaction environment of the reactor is regulated by the regulating reagent so as to meet the requirements of electrochemical oxidation reaction. For example, in one embodiment of the present disclosure, the oxidant, complexing agent, and salt are fed in a ratio of 1 to 3:1 to 3:1, for example, the feed ratio of the oxidizing agent, complexing agent and salt may be 2:2: 1.1: 1: 1.1: 2:1, etc.
After the regulation and control of the reagent reach the preset electrochemical oxidation condition, the step S3 is carried out: adding a metal source, water, an oxidant and a complexing agent into a reactor according to a certain speed to perform 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 example, the molar ratio of the Ni source, the Co source, and the Mn source is 50 to 80: 5-30: 5 to 40. Ni source, co source and Mn source form Ni-Co-Mn ternary positive electrode material precursor, and ternary positive electrode materials with different contents, such as Ni5 ternary positive electrode materials, 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 Ni source, co source, mn source, or other metal, prepared to obtain a unitary positive electrode material; 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, and the multielement anode material is prepared.
In one embodiment of the present disclosure, in step S3, the oxidizing agent 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, nitric acid is used as the oxidant and ammonia water is used as the complexing agent.
It can be appreciated that the preparation method of 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 electric conductivity in the reaction environment are maintained at 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 electric conductivity is maintained to be more than or equal to 300us/cm. Specifically, in one embodiment of the present disclosure, in step S3, the pH is controlled to be between 7 and 9, and the concentration of ammonia or ammonium ions is controlled to be 0.5 to 1.2mol/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 a solid solution of the metal oxide and the metal hydroxide.
After the electrochemical oxidation reaction is finished, the step S4 is carried out, the feeding is finished, the ageing treatment is carried out, and then the positive electrode material precursor is obtained through separation, washing and drying. The aging treatment is used for enabling the metal powder to fully react and avoiding the residue of the metal powder. Specifically, the aging process is standing reaction for 1-5 h.
In one embodiment of the present disclosure, after the aging process is completed, the separating, washing, drying steps include: and (3) carrying out solid-liquid separation on the product obtained after the ageing treatment to obtain a filter cake and a mother solution, and drying the filter cake after alkali washing to obtain a positive electrode material precursor. Specifically, the alkaline washing is, for example, washing with a sodium hydroxide solution of a certain concentration. The generation of impurities is reduced through an alkaline 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, supplementing water or reagents such as oxidizing agents, complexing agents, etc. consumed in the electrochemical oxidation reaction.
Through the preparation steps, the positive electrode material precursor is obtained, is a solid solution of metal hydroxide and metal oxide, and has magnetism. Specifically, the precursor is adsorbed by 10000GS magnetic rod and can be completely converted into magnetic substance. Can be completely magnetized under the magnetic condition of 10000 GS.
In one embodiment of the present disclosure, in the positive electrode material precursor, the molar percentage of the metal hydroxide is M1, the molar 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 further adjusted by adjusting and controlling the reaction conditions and the reaction time of the electrochemical oxidation reaction. Further preferably, the molar percentage of the metal hydroxide is 60 to 80% and the molar percentage of the metal oxide is 20 to 40%. In this ratio, the positive electrode material prepared from the positive electrode material precursor can obtain more excellent electrochemical properties.
Further, in one embodiment disclosed, the positive electrode material precursor is a body centered cubic lattice, the unit cell parameter a is between 3.02 and 3.14, the unit cell parameter b is between 3.01 and 3.12, the unit cell parameter c is between 4.29 and 4.88, and the unit cell volume is between 32.52 and 41.89. The lattice structure of the precursor of the positive electrode material proves that the product prepared by the method is solid solution. The unit cell parameters of the precursor may be determined, for example, by means of a diffractometer or the like, by means of which the oxide content of the precursor is reflected.
In one embodiment disclosed, the positive electrode material precursor is prepared as spheroidal particles having a median particle diameter D50 of from 3 to 18um.
The disclosure also provides a positive electrode material, which is obtained by mixing the positive electrode material precursor and 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 hours to obtain a positive electrode material. The ratio of the amount of lithium species in the lithium source to the amount of metal species in the metal source is 1 to 1.1:1.
In one embodiment of the disclosure, 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 as 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 capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The positive electrode material precursor provided in this embodiment is obtained according to the following steps:
(1) Preparing metal powder by nickel powder, cobalt powder and manganese powder, wherein Ni: co: the molar ratio of Mn is 80:11.5:8.5.
(2) 2/3 of the volume of high purity water was added to the reactor, and the temperature was raised to 50 ℃. Turning on the stirrerStirring with input stirring power of 1 kw.h/m 3 And pre-introducing ammonia water.
(3) Nitric acid, ammonia water and sodium sulfate are mixed according to the mass ratio of 1:1:1 are added into a reaction kettle at the same time and stirred uniformly, the oxidation-reduction potential orp value is controlled at-500 mv, and the conductivity is 300us/cm.
(4) Adding the metal powder, nitric acid and ammonia water obtained in the step (1) uniformly mixed at a certain speed to generate precipitate, controlling the pH value between 7 and 9 by controlling the feeding speed of the nitric acid in the precipitation process, controlling the ammonia concentration between 0.5 and 1.2mol/L by controlling the feeding speed of the ammonia water, and maintaining the oxidation-reduction potential and the conductivity in the electrochemical oxidation process to generate precipitate.
(5) The precipitation time is controlled to be 50-60 hours, after the precipitation is finished, aging is carried out until the reaction is complete, solid-liquid separation is carried out on the obtained slurry to obtain mother liquor and filter cakes, the filter cakes are dried and sieved through alkaline washing, and then the nickel-cobalt-manganese anode material precursor with weak magnetism is obtained, and filtrate and washing water generated in the process are fed back to a reaction kettle for continuous reaction.
The obtained nickel cobalt manganese positive electrode 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 positive electrode material precursor is shown in fig. 2, and as can be seen from fig. 2, the particles of the nickel cobalt manganese positive electrode material precursor are uniformly distributed, the morphology is similar to a sphere, 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 the mixture is uniformly mixed according to Li/Me=1.1:05, li represents the amount of Li substances in the lithium carbonate, and Me represents the total amount of substances in the positive electrode material precursor. And calcining at 800 ℃ for 12 hours to finally obtain the composite oxide powder with Li/Me=1.05, namely the positive electrode material. The scanning electron microscope image of the positive electrode material is shown in fig. 3, and as can be seen from fig. 3, the sintered positive electrode material has uniform particles and is a single crystal product.
Example 2
The positive electrode material precursor provided in this embodiment is obtained according to the following steps:
(1) Preparing metal powder by nickel powder, cobalt powder and manganese powder, wherein Ni: co: the molar ratio of Mn is 72:8:20.
(2) 2/3 of the volume of high purity water was added to the reactor, and the temperature was raised to 50 ℃. Stirring is started, and the input power of stirring is 1 kw.h/m 3 And (3) pre-introducing ammonia water.
(3) Nitric acid, ammonia water and sodium sulfate are mixed according to the mass ratio of 1:2:1 are added into a reaction kettle at the same time and stirred uniformly, the oxidation-reduction potential orp value is controlled at-600 mv, and the conductivity is 400us/cm.
(4) Adding the metal powder, nitric acid and ammonia water obtained in the step (1) uniformly mixed at a certain speed to generate a precipitate. The pH is controlled between 7 and 9 by controlling the feeding speed of nitric acid in the precipitation process, the ammonia concentration is controlled between 0.5 and 1.2mol/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) The precipitation time is controlled to be 80-90 h, after the precipitation is finished, aging is carried out until the reaction is complete, solid-liquid separation is carried out on the obtained slurry to obtain mother liquor and filter cakes, the filter cakes are dried and sieved through alkaline washing, and then the nickel-cobalt-manganese anode material precursor with weak magnetism is obtained, and filtrate and washing water generated in the process are fed back to a reaction kettle for continuous reaction.
The obtained nickel cobalt manganese positive electrode material precursor is adsorbed by a 10000GS magnetic rod, and can be completely converted into a magnetic substance. The nickel cobalt manganese positive electrode material precursor has uniform particle distribution, is spherical-like in shape and has a particle size D50 of 3-18 um.
And uniformly mixing the obtained nickel cobalt manganese positive electrode material precursor and lithium carbonate, wherein the uniform mixing is carried out according to Li/Me=1.1:1, li represents the amount of substances of Li in the lithium carbonate, and Me represents the total amount of substances of the positive electrode material precursor. And calcining at 800 ℃ for 12 hours to finally obtain the composite oxide powder with Li/Me=1.1, namely the positive electrode material. The anode material has uniform particles and is a monocrystalline product.
Example 3
The positive electrode material precursor provided in this embodiment is obtained according to the following steps:
(1) Preparing metal powder by nickel powder, cobalt powder and manganese powder, wherein Ni: co: the molar ratio of Mn is 66:7:27.
(2) Adding into a reaction kettle2/3 of the volume of the autoclave was purified water and the temperature was raised to 55 ℃. Stirring is started, and the input power of stirring is 1.2 kw.h/m 3 And pre-introducing ammonia water.
(3) Nitric acid, ammonia water and sodium sulfate are mixed according to the mass ratio of 1:2:1, simultaneously adding the mixture into a reaction kettle, uniformly stirring, and controlling the oxidation-reduction potential orp value at-700 mv and the conductivity at 500us/cm.
(4) Adding the metal powder, nitric acid and ammonia water obtained in the step (1) uniformly mixed at a certain speed to generate a precipitate. The pH is controlled between 7 and 9 by controlling the feeding speed of nitric acid in the precipitation process, the ammonia concentration is controlled between 0.5 and 1.2mol/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) The precipitation time is controlled to be 110-130 h, after the precipitation is finished, aging is carried out until the reaction is complete, solid-liquid separation is carried out on the obtained slurry to obtain mother liquor and filter cakes, the filter cakes are dried and sieved through alkaline washing, and then the nickel-cobalt-manganese anode material precursor with weak magnetism is obtained, and filtrate and washing water generated in the process are fed back to a reaction kettle for continuous reaction.
The obtained nickel cobalt manganese positive electrode material precursor is adsorbed by a 10000GS magnetic rod, and can be completely converted into a magnetic substance. The nickel cobalt manganese positive electrode material precursor has uniform particle distribution, is spherical-like in shape and has a particle size D50 of 3-18 um.
And uniformly mixing the obtained nickel cobalt manganese positive electrode material precursor and lithium carbonate, wherein the uniform mixing is carried out according to Li/Me=1.1:1, li represents the amount of substances of Li in the lithium carbonate, and Me represents the total amount of substances of the positive electrode material precursor. And calcining at 800 ℃ for 12 hours to finally obtain the composite oxide powder with Li/Me=1.1, namely the positive electrode material. The anode material has uniform particles and is a monocrystalline product.
Example 4
The positive electrode material precursor provided in this embodiment is obtained according to the following steps:
(1) Preparing metal powder by nickel powder, cobalt powder and manganese powder, wherein Ni: co: the molar ratio of Mn is 58:6.5:35.5.
(2) Adding 2/3 of the volume of high-purity water into the reaction kettle, and heating to 60 deg.CDEG C. Stirring is started, and the input power of stirring is 0.8 kw.h/m 3 And pre-introducing ammonia water.
(3) Nitric acid, ammonia water and sodium sulfate are mixed according to the mass ratio of 2:2:1 are added into a reaction kettle at the same time and stirred uniformly, the oxidation-reduction potential orp value is controlled at 600mv, and the conductivity is 500us/cm.
(4) Adding the metal powder, nitric acid and ammonia water obtained in the step (1) uniformly mixed at a certain speed to generate a precipitate. The pH is controlled between 7 and 9 by controlling the feeding speed of nitric acid in the precipitation process, the ammonia concentration is controlled between 0.5 and 1.2mol/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) The precipitation time is controlled to be 70-80 h, after the precipitation is finished, aging is carried out until the reaction is complete, solid-liquid separation is carried out on the obtained slurry to obtain mother liquor and filter cakes, the filter cakes are dried and sieved through alkaline washing, and then the nickel-cobalt-manganese anode material precursor with weak magnetism is obtained, and filtrate and washing water generated in the process are fed back to a reaction kettle for continuous reaction.
The obtained nickel cobalt manganese positive electrode material precursor is adsorbed by a 10000GS magnetic rod, and can be completely converted into a magnetic substance. The nickel cobalt manganese positive electrode material precursor has uniform particle distribution, is spherical-like in shape and has a particle size D50 of 3-18 um.
And uniformly mixing the obtained nickel cobalt manganese positive electrode material precursor and lithium carbonate, wherein the uniform mixing is carried out according to Li/Me=1.1:1, li represents the amount of substances of Li in the lithium carbonate, and Me represents the total amount of substances of the positive electrode material precursor. And calcining at 800 ℃ for 12 hours to finally obtain the composite oxide powder with Li/Me=1.1, namely the positive electrode material. The anode material has uniform particles and is a monocrystalline product.
Comparative example 1
The positive electrode material precursor provided in this comparative example is obtained according to the following steps:
(1) Preparing metal powder by nickel powder, cobalt powder and manganese powder, wherein Ni: co: the molar ratio of Mn is 80:11.5:8.5.
(2) 2/3 of the volume of high purity water was added to the reactor, and the temperature was raised to 50 ℃. Stirring is started, and the input power of stirring is 1 kw.h/m 3 And pre-introducing ammonia water. Then nitric acid, ammonia water and sodium sulfate are mixed according to the mass ratio of 1:1:1, simultaneously adding the mixture into a reaction kettle, uniformly stirring, and controlling the oxidation-reduction potential orp value at 0mv and the conductivity at 200us/cm.
(3) Adding metal powder, nitric acid and ammonia water at a certain speed, controlling pH between 7-9 by nitric acid during precipitation, and controlling ammonia concentration to be 0.8-1.5 mol/L.
(4) The precipitation time is controlled to be 70-80 h, after the precipitation is finished, the obtained slurry is subjected to solid-liquid separation to obtain mother liquor and filter cakes, and the filter cakes are washed by pure water, dried and sieved to obtain the precursor of the anode 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 the uniform mixing is carried out according to Li/Me=1.05:1, li represents the amount of substances of Li in the lithium carbonate, and Me represents the total amount of substances of the positive electrode material precursor. And calcining at 800 ℃ for 12 hours to finally obtain the composite oxide powder with Li/Me=1.05, namely the positive electrode material.
Comparative example 2
The positive electrode material precursor provided in this comparative example is obtained according to the following steps:
(1) Preparing metal powder by nickel powder, cobalt powder and manganese powder, wherein Ni: co: the molar ratio of Mn is 58:6.5:35.5.
(2) 2/3 of the volume of high purity water was added to the reactor, and the temperature was raised to 60 ℃. Stirring is started, and the input power of stirring is 0.8 kw.h/m 3 And (3) pre-introducing ammonia water. Then nitric acid, ammonia water and sodium sulfate are mixed according to the mass ratio of 2:2:1, simultaneously adding the mixture into a reaction kettle, uniformly stirring, and controlling the oxidation-reduction potential orp value at 100mv and the conductivity at 100us/cm.
(3) Adding metal powder, nitric acid and ammonia water at a certain speed, controlling pH between 7-9 by nitric acid during precipitation, and controlling ammonia concentration to be 0.8-1.5 mol/L.
(4) The precipitation time is controlled to be 70-80 h, after the precipitation is finished, the obtained slurry is subjected to solid-liquid separation to obtain mother liquor and filter cakes, and the filter cakes are washed by pure water, dried and sieved to obtain the precursor of the anode 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 the uniform mixing is carried out according to Li/Me=1.1:1, li represents the amount of substances of Li in the lithium carbonate, and Me represents the total amount of substances of the positive electrode material precursor. And calcining at 800 ℃ for 12 hours to finally obtain the composite oxide powder with Li/Me=1.1, namely the positive electrode material.
Comparative example 3
The positive electrode material precursor provided in this comparative example is obtained according to the following steps:
(1) Preparing metal powder by nickel powder, cobalt powder and manganese powder, wherein Ni: co: the molar ratio of Mn is 58:6.5:35.5.
(2) 2/3 of the volume of high purity water was added to the reactor, and the temperature was raised to 60 ℃. Stirring is started, and the input power of stirring is 1 kw.h/m 3 Then metal powder, nitric acid and sodium sulfate are mixed according to the mass ratio of 10:1:1, simultaneously adding the mixture into a reaction kettle to react, adding 10g/L ammonia water, controlling the oxidation-reduction potential orp value at-1000 mv and the conductivity at 200us/cm in the reaction process, and controlling the pH value between 6 and 8.
(4) The precipitation time is controlled to be 30-50 h, the obtained slurry is adsorbed by a magnetic rod of 100GS after the precipitation is finished, unreacted metal powder is removed, then solid-liquid separation is carried out to obtain mother liquor and filter cake, and the filter cake is washed by pure water, dried and sieved 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 and lithium carbonate, wherein the uniform mixing is carried out according to Li/Me=1.1:1, li represents the amount of substances of Li in the lithium carbonate, and Me represents the total amount of substances of the positive electrode material precursor. And calcining at 800 ℃ for 12 hours to finally obtain the composite oxide powder with Li/Me=1.1, namely the positive electrode material.
Test example 1
The positive electrode materials obtained in examples 1 to 4 and comparative examples 1 to 3 were fabricated into electrode sheets and assembled into button cells. The specific process is as follows: firstly, fully grinding and mixing a positive electrode material, acetylene black and PVDF according to a 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 120deg.C for 12 hr, and punching to obtain electrode plate with diameter of 14 mm. This was assembled in a Braun glove box into button half-cells model CR 2032. The CR2032 button half battery is subjected to electrochemical performance test, and the first charge and discharge efficiency, the first charge gram capacity and the first discharge gram capacity of the positive electrode material are tested. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, compared with comparative examples 1 to 2, the electrochemical oxidation is enhanced by adjusting the electrochemical reaction conditions in the examples, and the first charge and discharge efficiencies of the obtained cathode materials are all up to 94% or more, which is significantly improved compared with comparative examples 1 to 2. And the charge gram capacity reaches more than 217mAh/g, and the discharge gram capacity reaches more than 196 mAh/g. In addition, compared with comparative example 3, the charge-discharge gram capacity of the product can be further improved by introducing ammonia water in advance, and adding metal powder for reaction after a predetermined electrochemical oxidation reaction condition is reached.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the 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 made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (10)
1. The preparation method of the positive electrode material precursor is characterized by comprising the following steps of:
s1, adding water into a reactor, and heating to 50-60 ℃;
s2, adding an adjusting reagent into the reactor to reach preset electrochemical oxidation reaction conditions, wherein the preset electrochemical oxidation reaction conditions are oxidation-reduction potential less than or equal to-500 mv and electric conductivity more than or equal to 300us/cm;
s3, adding a metal source, water, an oxidant and a complexing agent into the reactor to perform electrochemical oxidation reaction to generate a precipitate; wherein the metal source is selected from one or more of a Ni source, a Co source and a Mn source; the oxidant is one or more selected from 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;
s4, finishing feeding, aging, separating, washing and drying to obtain a positive electrode material precursor, wherein the positive electrode material precursor 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 a magnetic condition of 10000 GS.
3. The method for preparing a positive electrode material precursor according to claim 1, wherein in step S1, ammonia water is introduced into the reactor in advance after the temperature of the reactor is raised to 50 to 60 ℃.
4. The method for preparing a positive electrode material precursor according to claim 1, wherein in step S2, the adjusting agent includes an oxidizing agent, a complexing agent, and a salt; the oxidant is one or more selected from 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; the salt is selected from one or more of sodium sulfate, sodium chloride and sodium nitrate.
5. The method for preparing a positive electrode material precursor according to claim 1, wherein 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 liquor, carrying out alkali washing on the filter cake, and drying to obtain the positive electrode material precursor, wherein the mother liquor and wastewater generated in the alkali washing process are recycled for electrochemical oxidation reaction.
6. The positive electrode material precursor, which is a solid solution of a metal hydroxide and a metal oxide and has magnetism, is prepared by the preparation method according to any one of claims 1 to 5.
7. The positive electrode material precursor according to claim 6, wherein in the positive electrode material precursor, the molar percentage of the metal hydroxide is M1, the molar percentage of the metal oxide is M2, wherein M1 is 40% +.ltoreq.m1 < 100%; m2 is more than 0% and less than or equal to 60%.
8. The positive electrode material precursor according to claim 7, wherein the positive electrode material precursor is in a body-centered cubic lattice, the unit cell parameter a is 3.02-3.14, the unit cell parameter b is 3.01-3.12, the unit cell parameter c is 4.29-4.88, and the unit cell volume is 32.52-41.89.
9. A positive electrode material, characterized in that the positive electrode material precursor according to any one of claims 6 to 8 is mixed with a lithium source, and sintered to obtain the positive electrode material.
10. A lithium ion battery comprising the positive electrode material of claim 9.
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