CN115215383A - Positive electrode material precursor, preparation method thereof, positive electrode material and lithium battery - Google Patents
Positive electrode material precursor, preparation method thereof, positive electrode material and lithium battery Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 101
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 71
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 135
- 239000011164 primary particle Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 44
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 39
- 239000002585 base Substances 0.000 claims description 39
- 239000008139 complexing agent Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 31
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- 150000001768 cations Chemical class 0.000 claims description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 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 2
- 239000004471 Glycine Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 77
- 239000007864 aqueous solution Substances 0.000 description 37
- 239000010406 cathode material Substances 0.000 description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 238000001354 calcination Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- -1 NaOH Chemical class 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000003780 insertion Methods 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229940053662 nickel sulfate Drugs 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
-
- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of lithium battery materials, in particular to a positive electrode material precursor and a preparation method thereof, a positive electrode material and a lithium battery. The anode material precursor comprises a plurality of primary particles with rod-shaped structures, and the primary particles are radially arranged outside the anode material precursor core. According to the invention, the lithium ion battery anode material precursor with the outer part formed by the long radial structure is finally obtained by adjusting the coprecipitation reaction conditions, and the ternary anode material is further prepared by heating treatment.
Description
Technical Field
The invention relates to the field of lithium battery materials, in particular to a positive electrode material precursor and a preparation method thereof, a positive electrode material and a lithium battery.
Background
As the technical development and demand of mobile devices continue to increase, the demand of secondary batteries as an energy source has significantly increased. Lithium secondary batteries having high energy density, high voltage, long cycle life and low self-discharge rate performance have been commercialized and widely used. In a lithium battery, a material capable of reversibly intercalating and deintercalating lithium ions is used for a positive electrode and a negative electrode, respectively. At present, the lithium cobaltate positive electrode material is more and more widely applied to the positive electrode material of the lithium battery. However, the lithium cobaltate has the disadvantages of high cost, poor rate capability, unsafe performance and the like, so that the application of the lithium cobaltate in the field of batteries is limited.
Transition metal oxides such as lithium nickel cobalt manganese oxide (LiNi) 1-x-y Co x Mn y O 2 ) Has the advantages of high capacity, good cyclicity, low cost and the like, and is one of the most widely applied cathode materials at present. However, in the use process, particularly for high nickel materials, as the content of nickel increases, the energy density of the battery further increases, but the safety and the cycle stability are deteriorated.
Therefore, it is necessary to provide a positive electrode material having high energy density and good safety and cycle stability.
Disclosure of Invention
The first purpose of the invention is to provide a positive electrode material precursor, and the positive electrode material prepared by adopting the positive electrode material precursor has the advantages of high energy density, and good safety and cycling stability.
The second purpose of the invention is to provide a preparation method of the precursor of the cathode material, which is simple, easy to control, low in cost and suitable for large-scale production.
The third purpose of the invention is to provide a positive electrode material, which comprises a positive electrode material precursor and has the advantages of high energy density, safety and good cycle stability.
A fourth object of the present invention is to provide a lithium battery including a positive electrode material, which has advantages of high energy density, safety and cycle stability.
In order to achieve the above object, the present invention provides a precursor of a positive electrode material, which includes a plurality of primary particles having a rod-like structure, and the primary particles are radially arranged outside a core of the precursor of the positive electrode material.
The particle size range of the precursor of the positive electrode material is 5-18 um, and further 6-15 um; the length range of the primary particles with the rod-shaped structures is 2-5 um; the volume of the primary particles accounts for more than or equal to 30 percent of the volume of the precursor of the cathode material, further accounts for 30-95 percent of the volume of the precursor of the cathode material, and further accounts for 50-90 percent of the volume of the precursor of the cathode material.
The invention also provides a preparation method of the precursor of the cathode material, which comprises the following steps: providing a base solution, wherein the base solution comprises a first molar concentration C 0 The first complexing agent of (a), the first molar concentration C 0 Refers to the molarity of the first complexing agent in the base solution; providing a reaction solution, wherein the reaction solution comprises a metal salt, a precipitator and a second molar concentration C 1 A second complexing agent of (1), wherein, C 0 ＜C 1 The second molar concentration C 1 Means the molar concentration of the second complexing agent in the reaction solution; adding the reaction solution into the base solution to react to form a precursor solid-liquid mixture; and filtering the solid-liquid mixture of the precursor and drying to obtain the precursor of the anode material.
Preparing a base solution containing a first complexing agent by water, alkali and the first complexing agent with a first molar concentration, wherein the specific adding mode of the base solution is as follows: firstly, preparing an aqueous solution of alkali and an aqueous solution of a first complexing agent, and then adding the aqueous solution and water into a reaction kettle together to form a base solution. After the base solution is added, adding a reaction solution in an inert gas atmosphere for reaction, wherein the reaction solution comprises metal salt, a second complexing agent with a second molar concentration, a precipitating agent and water, and the specific adding mode of the reaction solution is as follows: firstly, preparing a metal salt aqueous solution, a second complexing agent aqueous solution with a second molar concentration and a precipitator aqueous solution, and then dropwise adding the reaction solution into a base solution for reaction.
In practical operation, the metal salt and the precipitant in the reaction solution need to be added to the base solution independently, but the metal salt and the complexing agent may be added to the base solution independently, or may be added to the base solution after being mixed, for example, the metal salt is configured into a metal salt solution and then added to the base solution through an independent pipeline, the precipitant is also added to the base solution through an independent pipeline, and the complexing agent may be added to the base solution through an independent pipeline, or may be added after being mixed with the metal salt.
The metal salt precipitate is formed by combining a metal cation with a precipitant anion, such as NaOH, na 2 CO 3 、NaHCO 3 、Na 2 C 2 O 4 、LiOH、Li 2 CO 3 、LiHCO 3 、Li 2 C 2 O 4 、KOH、K 2 CO 3 、KHCO 3 、K 2 C 2 O 4 The anion of any one or more of these can combine with the cation herein to form a metal salt precipitate.
The concentration of the second complexing agent in the reaction liquid is greater than that of the first complexing agent in the base liquid, so that the concentration of the total complexing agent in the reaction kettle is kept to be increased slowly. As an embodiment, the concentration of the complexing agent in the reaction kettle gradually increases as the reaction proceeds; in particular, it may increase in a parabolic manner up to a maximum value. As an embodiment, the second molar concentration C of the second complexing agent in the reaction solution 1 Greater than the first molarity C of the first complexing agent in the base solution 0 In this case, the reaction solution is introduced at a constant flow rate, and the concentration of the complexing agent in the reaction vessel can be gradually increased. The base solution also comprises alkali, the initial stage of the reaction in the reaction process is a particle nucleation process, preferably, the high pH value is kept at the initial stage, the pH value can be reduced to a proper pH value or kept unchanged after the reaction is stable, and the pH value of the base solution is between 12 and 12.8; the initial high pH value and the complexing agent concentration are matched together, which is more beneficial to the growth and radial arrangement of primary particles. The pH value can be adjusted and controlled through the pH controller, the pH controller can be connected with a pump filled with a pH regulator, and the pH regulator is adjusted in the pump through the pH controllerThereby controlling the pH of the reaction process.
The reaction temperature needs to be controlled stably in the reaction process, and is 25-90 ℃, and further 30-70 ℃; the reaction time is 40 to 100 hours; further 50-80 hours; the stirring speed is 100-1000r/min during the reaction.
The metal cation of the metal salt is selected from one of Mg, ca, ti, V, cr, mn, fe, co, ni, cu and Al or any combination of the metal cations; preferably, the metal cations comprise at least two of Ni, mn and Co. Wherein the molar ratio of metal cations in the nickel salt, the manganese salt and the cobalt salt is a: b:1-a-b,0 < a < 1,0 < b < 1, a + b < 1. The concentration of the metal cations introduced is not limited, and can be adjusted according to actual needs.
The complexing agent is one or more of ammonia, ammonium chloride, ammonium sulfate, ammonium dihydrogen phosphate, ethylene glycol, carboxylic acid, ammonium nitrate, glycerol, 1,3-propylene glycol, urea, N' -dimethyl urea, quaternary ammonium salt, citric acid, glycine and ethylene diamine tetraacetic acid. In some embodiments, the complexing agent is ammonia.
The molar concentration of the first complexing agent in the base solution is 0.2-0.6 mol/L, and further 0.4-0.6 mol/L; the molar concentration of the second complexing agent in the reaction solution is 0.6-1.5 mol/L, and further 0.6-1.2 mol/L; when the reaction is finished, the mol concentration of the complexing agent in the precursor solid-liquid mixture is 0.6-1.4 mol/L, and further 0.8-1.2 mol/L.
Discharging a part of solution out of the reaction kettle by solid-liquid separation in the reaction process to prolong the reaction time, wherein the solid-liquid separation can be carried out by a thickener, the concentrated solution returns to the reaction kettle for continuous reaction, and clear water is discharged out of the reaction kettle; or the solid-liquid separation can also be that the reaction is stopped after a period of time, and the upper clear water is pumped out of the reaction kettle after the solid particles are precipitated. The increase in reaction time of the present application will also be more favorable to the increase in primary particles, and generally, in combination with complexing agent concentration control and initial high pH, the effect will be better. As an embodiment, the reaction time is 40 to 100 hours; further 50 to 80 hours.
The precipitant is one or more of sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, lithium hydroxide or sodium hydroxide, and is preferably sodium hydroxide.
The invention also provides a positive electrode material precursor, which is prepared by the preparation method of the positive electrode material precursor.
The invention also provides a positive electrode material, wherein the positive electrode material precursor is uniformly mixed with lithium salt, and then the mixture is heated to obtain the positive electrode material, wherein the temperature of the heating treatment is 600-1000 ℃.
In one embodiment, the step of heat treating comprises: firstly, heating to 300-550 ℃, preserving heat for 3-8 h, then heating to 600-1000 ℃, and preserving heat for 8-30 h; air, oxygen, a mixed gas of air and oxygen or a mixed gas of nitrogen and oxygen are introduced in the processes of heating and heat preservation, and the air is continuously introduced to be cooled to the room temperature after the heating treatment is finished.
The lithium salt is one or more of lithium hydroxide, lithium carbonate, lithium nitrate and lithium acetate.
The positive electrode material precursor contains metal cations, and the ratio of the mass of the metal cations in the positive electrode material precursor to the mass of lithium in the lithium salt is 1.
The mixing of the positive electrode material precursor and the lithium salt can be carried out by adopting a high-speed mixer, a ball mill, a V-shaped mixer or a colter mixer; the heating treatment can be performed by a roller kiln, a pusher kiln, a box furnace, a rotary kiln or a tubular furnace.
The invention also provides a lithium battery which comprises the cathode material.
The preparation method of the precursor of the cathode material comprises the following steps: providing a base solution, wherein the base solution comprises a first molar concentration C 0 The first complexing agent of (a), the first molarity C 0 Refers to the molarity of the first complexing agent in the base solution; providing a reaction solution, wherein the reaction solution comprises a metal salt, a precipitator and a second molar concentration C 1 Wherein, C is 0 ＜C 1 Said second molar concentration C 1 Means the molar concentration of the second complexing agent in the reaction solution; adding the reaction solution into the base solution to react to form a precursor solid-liquid mixture; and filtering the solid-liquid mixture of the precursor and drying to obtain the precursor of the anode material. The anode material precursor comprises a plurality of primary particles with rod-shaped structures, and the primary particles are radially arranged outside the anode material precursor core. According to the invention, the condition of coprecipitation reaction is adjusted to finally obtain the precursor of the lithium ion battery anode material with the outer part formed by a long radial structure, and the ternary anode material is further prepared by heating treatment.
Firstly, the primary particles arranged in a radial shape enable the insertion and the separation of lithium ions to be easier, and the primary particles in the precursor of the positive electrode material prepared by the method are longer, so that the insertion of the lithium ions is facilitated, the resistance of the positive electrode material is reduced, and higher capacity is obtained.
And secondly, the longer primary particles are beneficial to the stability of the structure of the precursor of the anode material, the external structure is compact, the compaction is more resistant, and the problem of particle crushing in the rolling process of the pole piece can be solved.
Thirdly, the length of the primary particles outside the precursor of the cathode material is large, the structure reduces the exposed area of the surface of the primary particles, namely the specific surface area is reduced, and the contact area of the precursor of the cathode material and the electrolyte is reduced, so that the reaction of the cathode material and the electrolyte is reduced, and the cycle stability of the cathode material is finally improved. The lithium battery prepared from the cathode material has good cycle performance and high safety performance, and the cycle retention rate is more than 85% after 180 times of 1C cycle.
Finally, the preparation method is simple in preparation process flow, good in controllability, low in cost, suitable for large-scale industrial production and capable of meeting the requirements of long service life and safety in markets of electric automobiles and the like.
Drawings
Fig. 1 shows a cross-sectional SEM image of the positive electrode material precursor of example 1 of the present invention.
Fig. 2 shows a cross-sectional SEM image of the positive electrode material precursor of comparative example 1.
Fig. 3 shows a cross-sectional SEM image of the cathode material of example 1 of the present invention compacted to 3.4 (the compacted density of the cathode material after roll pressing was 3.4 g/mL).
Fig. 4 shows a cross-sectional SEM image of the cathode material of comparative example 1 compacted to 3.4 (the compacted density of the cathode material after roll pressing was 3.4 g/mL).
Fig. 5 shows the data of the charging cycle of the positive electrode materials prepared in comparative example 1 and example 1.
Detailed Description
The "ranges" disclosed herein are in the form of lower and upper limits. There may be one or more lower limits, and one or more upper limits, respectively. The given range is defined by the selection of a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this manner are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for particular parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Further, if the minimum range values of 1 and 2 are listed, and if the maximum range values of 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present invention, all embodiments and preferred embodiments mentioned herein may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the steps mentioned herein may be performed sequentially or randomly, if not specifically stated, but preferably sequentially.
Example 1
First, a 20L glass reactor was charged with 5L of an aqueous solution of ammonia having a concentration of 0.5 mol/L. Heating the aqueous solution of ammonia water to 50 ℃, and introducing 5mL/min of N under stirring 2 Gas is introduced for 1h and thenAdding sodium hydroxide solution to adjust the pH value in the reaction kettle to 12.4 to form a base solution. Then, after the stirring speed is adjusted to 300rpm, introducing a reaction solution for reaction, wherein the reaction solution comprises ammonia water, an aqueous solution of NaOH and an aqueous solution of metal sulfate, the aqueous solution of metal sulfate comprises an aqueous solution of nickel sulfate, an aqueous solution of manganese sulfate and an aqueous solution of cobalt sulfate, and the metal cation Ni: mn: the molar ratio of Co is 82:8:10, the total concentration of metal ions in the metal sulfate is 2mol/L; the concentration of ammonia in the reaction liquid is 1.0mol/L, the reaction liquid is continuously introduced in the reaction process, the ammonia concentration in the reaction kettle can be kept to slowly rise, and the concentration of ammonia in the reaction kettle is 0.8mol/L at the end of the reaction. The reaction solution was fed at a rate of 250mL/hr, and the reaction temperature was controlled at 50 ℃. The pH value is maintained at 12.4 by controlling the pumping of the sodium hydroxide aqueous solution through a pH controller in the reaction process. After the reaction is finished for 60 hours, a precursor solid-liquid mixture is formed.
And after the reaction is finished, discharging the solid-liquid mixture of the precursor from the reaction kettle, filtering, washing with deionized water, and drying the filter cake at 100 ℃ to obtain the precursor of the cathode material. Mixing the dried precursor of the anode material with LiOH & H 2 O is Li (Ni + Mn + Co) 1.05:1, calcining the mixture in a tube furnace at 500 ℃ for 3 hours in an oxygen atmosphere, then calcining the mixture at 780 ℃ for 10 hours, and naturally cooling and sieving the calcined mixture to obtain the final cathode material.
Preparing a lithium battery: the modified positive electrode material, the conductive carbon black and the polyvinylidene fluoride in the embodiment are dissolved in N-methylpyrrolidone according to the weight ratio of 90. The diaphragm adopts a polypropylene diaphragm, and the electrolyte solvent comprises DMC/EC/DEC =1 (volume ratio), and contains 1mol/L LiPF 6 Lithium salt, and assembling into a button lithium battery in a glove box filled with Ar gas.
Testing the charge and discharge performance for the first time: at room temperature, the battery is charged to 4.4V at 0.1C rate by constant current, then charged at constant voltage until the cut-off current is 0.01C, and then discharged to 2.7V at 0.1C rate by constant current.
Example 2
First, a 20L glass reaction kettle is filled with 5L of 0.4mol/L aqueous ammonia solution. Heating the aqueous solution of ammonia water to 50 ℃, and introducing 5mL/min of N under stirring 2 And (3) introducing gas for 1h, and then introducing a sodium hydroxide solution to adjust the pH value in the reaction kettle to 12.2 to form a base solution. Then, after the stirring speed is adjusted to 300rpm, introducing a reaction solution for reaction, wherein the reaction solution comprises ammonia water, an aqueous solution of NaOH and an aqueous solution of metal sulfate, the aqueous solution of metal sulfate comprises an aqueous solution of nickel sulfate, an aqueous solution of manganese sulfate and an aqueous solution of cobalt sulfate, and the metal cation Ni: mn: molar ratio of Co 82:8:10, the total concentration of metal ions in the metal sulfate is 2mol/L; the concentration of ammonia in the reaction liquid is 0.9mol/L, the reaction liquid is continuously introduced in the reaction process, the ammonia concentration in the reaction kettle can be kept to slowly rise, and the concentration of ammonia in the reaction kettle is 0.7mol/L at the end of the reaction. The reaction solution was fed at a rate of 250mL/hr, and the reaction temperature was controlled at 50 ℃. The pH value is maintained at 12.2 by controlling the pumping of the sodium hydroxide aqueous solution through a pH controller in the reaction process. After the reaction is finished after 40 hours, a precursor solid-liquid mixture is formed.
And after the reaction is finished, discharging the solid-liquid mixture of the precursor from the reaction kettle, filtering, washing with deionized water, and drying the filter cake at 100 ℃ to obtain the precursor of the cathode material. Mixing the dried precursor of the anode material with LiOH & H 2 O is Li (Ni + Mn + Co) 1.03:1, calcining the mixture in a tube furnace at 500 ℃ for 3 hours in an oxygen atmosphere, then calcining the mixture at 780 ℃ for 10 hours, and naturally cooling and sieving the calcined mixture to obtain the final cathode material.
Preparing a lithium battery: the modified positive electrode material, the conductive carbon black and the polyvinylidene fluoride in the embodiment are dissolved in N-methyl pyrrolidone according to a weight ratio of 90. The diaphragm adopts a polypropylene diaphragm, and the electrolyte solvent composition DMC/EC/DEC =1 (volume ratio) contains 1mol/LLIPF 6 Lithium salt, and assembling the lithium salt into a button lithium battery in a glove box filled with Ar gas.
Testing the charge and discharge performance for the first time: at room temperature, the battery is charged to 4.4V at 0.1C rate by constant current, then charged at constant voltage until the cut-off current is 0.01C, and then discharged to 2.7V at 0.1C rate by constant current.
Example 3
First, a 20L glass reaction kettle is filled with 5L of 0.4mol/L aqueous ammonia solution. Heating the aqueous solution of ammonia water to 50 ℃, and introducing 5mL/min of N under stirring 2 And (3) introducing gas for 1h, and then introducing a sodium hydroxide solution to adjust the pH value in the reaction kettle to 12.4 to form a base solution. Then, after the stirring speed is adjusted to 300rpm, introducing a reaction solution for reaction, wherein the reaction solution comprises ammonia water, an aqueous solution of NaOH and an aqueous solution of metal sulfate, the aqueous solution of metal sulfate comprises an aqueous solution of nickel sulfate, an aqueous solution of manganese sulfate and an aqueous solution of cobalt sulfate, and the metal cation Ni: al: the molar ratio of Co is 82:5:13, the total concentration of metal ions in the metal sulfate is 2mol/L; the concentration of ammonia in the reaction liquid is 1.2mol/L, the reaction liquid is continuously introduced in the reaction process, the ammonia concentration in the reaction kettle can be kept to slowly rise, and the concentration of ammonia in the reaction kettle is 0.9mol/L at the end of the reaction. The reaction solution was fed at a rate of 250mL/hr, and the reaction temperature was controlled at 60 ℃. And in the reaction process, a pH controller controls a pump to pump a sodium hydroxide solution to maintain the pH at 12.4 in the first 8 hours, and the pH is adjusted to 11.6 after 8 hours. And (3) carrying out solid-liquid separation in the reaction process, returning the filtered solid to the reaction kettle, and discharging the liquid out of the reaction kettle. After 80h of reaction, the reaction is finished to form a precursor solid-liquid mixture.
After the reaction, discharging the solid-liquid mixture of the precursor from the reaction kettle, filtering, washing with deionized water, and drying the filter cake at 100 ℃ to obtain the precursor of the cathode material. Mixing the dried precursor of the anode material with LiOH & H 2 O is Li (Ni + Al + Co) 1.05:1, calcining the mixture in a tube furnace at 500 ℃ for 3 hours in an oxygen atmosphere, then calcining the mixture at 780 ℃ for 10 hours, and naturally cooling and sieving the calcined mixture to obtain the final cathode material.
Preparing a lithium battery: the modified cathode material, conductive carbon black and polyvinylidene fluoride described in the exampleEthylene was dissolved in N-methylpyrrolidone at a weight ratio of 90. The diaphragm adopts a polypropylene diaphragm, and the electrolyte solvent composition DMC/EC/DEC =1 (volume ratio) contains 1mol/LLIPF 6 Lithium salt, and assembling into a button lithium battery in a glove box filled with Ar gas.
Testing the charge and discharge performance for the first time: at room temperature, the battery is charged to 4.4V at 0.1C rate by constant current, then is charged at constant voltage until the cut-off current is 0.01C, and then is discharged to 2.7V at 0.1C rate by constant current.
Example 4
First, a 20L glass reaction kettle is filled with 5L of 0.6mol/L ammonia water solution. Heating the aqueous solution of ammonia water to 50 ℃, and introducing 5mL/min of N under stirring 2 And (3) introducing gas for 1h, and then introducing a sodium hydroxide solution to adjust the pH value in the reaction kettle to 12.4 to form a base solution. Then, after the stirring speed is adjusted to 300rpm, introducing a reaction solution for reaction, wherein the reaction solution comprises ammonia water, an aqueous solution of NaOH and an aqueous solution of metal sulfate, the aqueous solution of metal sulfate comprises an aqueous solution of nickel sulfate, an aqueous solution of manganese sulfate and an aqueous solution of cobalt sulfate, and the metal cation Ni: mn: the molar ratio of Co is 82:8:10, the total concentration of metal ions in the metal sulfate is 2mol/L; the concentration of ammonia in the reaction liquid is 1.3mol/L, the reaction liquid is continuously introduced in the reaction process, the ammonia concentration in the reaction kettle can be kept to slowly rise, and the concentration of ammonia in the reaction kettle is 1.0mol/L at the end of the reaction. The feed rate of the reaction solution was 250mL/hr, and the reaction temperature was controlled at 45 ℃. The pH value of the reaction is maintained at 12.4 by controlling a pump to pump sodium hydroxide solution through a pH controller; and carrying out solid-liquid separation in the reaction process, returning the filtered solid to the reaction kettle, and discharging the liquid out of the reaction kettle. After the reaction is finished for 100 hours, a precursor solid-liquid mixture is formed.
After the reaction, the solid-liquid mixture of the precursor is discharged from the reaction kettle, filtered and washed by deionized water, and then the filter cake is dried at 100 ℃ to prepare the precursor of the anode material. Mixing the dried precursor of the anode material with LiOH & H 2 O is Li (Ni + Mn + Co) 1.02:1 in a molar ratioAnd (3) mixing, calcining in a tube furnace at 500 ℃ for 3 hours in an oxygen atmosphere, then calcining at 780 ℃ for 10 hours, naturally cooling and sieving to obtain the final cathode material.
Preparing a lithium battery: the modified positive electrode material, the conductive carbon black and the polyvinylidene fluoride in the embodiment are dissolved in N-methyl pyrrolidone according to a weight ratio of 90. The diaphragm adopts a polypropylene diaphragm, and the electrolyte solvent composition DMC/EC/DEC =1 (volume ratio) contains 1mol/LLIPF 6 Lithium salt, and assembling into a button lithium battery in a glove box filled with Ar gas.
Testing the charge and discharge performance for the first time: at room temperature, the battery is charged to 4.4V at 0.1C rate by constant current, then charged at constant voltage until the cut-off current is 0.01C, and then discharged to 2.7V at 0.1C rate by constant current.
Comparative example 1
First, a 20L glass reaction kettle was charged with 5L of an aqueous ammonia solution having a concentration of 0.8mol/L. The solution was heated to 50 ℃ while passing 5mL/min N with gentle stirring 2 After the gas is used for 1h, sodium hydroxide solution is introduced to adjust the pH value in the kettle to 11.6, and a base solution is formed.
Adjusting the stirring speed to 300rpm, and then adding NaOH and NH 3 ·H 2 O and the metal sulfate solution are fed into the reaction kettle to start the reaction. And introducing an ammonia solution to keep the concentration of the ammonia in the kettle unchanged. Wherein the metal sulfate comprises nickel sulfate, manganese sulfate and cobalt sulfate, and the weight ratio of Ni: mn: co in a molar ratio of 82:8:10, feeding with the total concentration of metal cations of 2mol/L at the feeding speed of 250mL/hr, and controlling the pumping of sodium hydroxide solution by a pH controller to maintain the pH at 11.6 in the reaction process. After 24h of reaction, the reaction is finished to form a precursor solid-liquid mixture.
After the reaction, the solid-liquid mixture of the precursor is discharged from the reaction kettle, filtered and washed by deionized water, and then the filter cake is dried at 100 ℃. Mixing the dried positive electrode material precursor with LiOH & H 2 O is Li (Ni + Mn + Co) 1.05:1, and calcining the mixture in a tube furnace at 500 ℃ for 3 hours in an oxygen atmosphere, and thenCalcining at 780 ℃ for 10 hours, naturally cooling and sieving to obtain the final cathode material.
Preparing a lithium battery: the modified positive electrode material, the conductive carbon black and the polyvinylidene fluoride in the embodiment are dissolved in N-methyl pyrrolidone according to a weight ratio of 90. The diaphragm adopts a polypropylene diaphragm, and the electrolyte solvent comprises DMC/EC/DEC =1 (volume ratio), and contains 1mol/L LiPF 6 Lithium salt, and assembling into a button lithium battery in a glove box filled with Ar gas.
Testing the charge and discharge performance for the first time: at room temperature, the battery is charged to 4.4V at 0.1C rate by constant current, then charged at constant voltage until the cut-off current is 0.01C, and then discharged to 2.7V at 0.1C rate by constant current.
TABLE 1 initial and final Ammonia concentrations and initial and final pH values for the examples and comparative examples
Fig. 1 shows a cross-sectional SEM image of a precursor of a positive electrode material according to example 1 of the present invention, and fig. 2 shows a cross-sectional SEM image of a precursor of a positive electrode material according to comparative example 1, and as can be seen from fig. 1 and 2, the outside of the precursor of a positive electrode material prepared according to example is composed of long primary particles and is radially arranged, and the surface of the precursor of a positive electrode material is very dense, which is advantageous for achieving rapid insertion of lithium ions and reducing the contact area between the surface of the precursor of a positive electrode material and an electrolyte, thereby reducing the reaction between the positive electrode material and the electrolyte, while the primary particles on the surface of comparative example 1 are short and insufficiently dense. From fig. 3 and 4, it can be seen that the positive electrode material precursor of example 1 was hardly crushed, while the positive electrode material precursor of comparative example 1 was largely crushed, by rolling the positive electrode materials prepared in example 1 and comparative example 1 into a pole piece to a density of 3.4 g/mL. This further demonstrates that the materials prepared in the examples have a more robust structure and are more resistant to compaction. Finally, as can be seen from fig. 5, the chargeability cycle performance of example 1 and comparative example 1 is much better than that of comparative example 1, thereby further demonstrating that the long radial structure has more stable electrochemical performance.
In view of the above, the method of the invention has the following advantages:
the preparation method of the precursor of the cathode material comprises the following steps: providing a base solution, wherein the base solution comprises a first molar concentration C 0 A first complexing agent of (a); providing a reaction solution, wherein the reaction solution comprises a second molar concentration C 1 A second complexing agent of (1), wherein, C 0 ＜C 1 (ii) a The base solution reacts with the reaction solution to form a precursor solid-liquid mixture; and filtering the solid-liquid mixture of the precursor and drying to obtain the precursor of the anode material. The anode material precursor comprises a plurality of primary particles with rod-shaped structures, and the primary particles are radially arranged outside the anode material precursor core. According to the invention, the condition of coprecipitation reaction is adjusted to finally obtain the precursor of the lithium ion battery anode material with the outer part formed by a long radial structure, and the ternary anode material is further prepared by heating treatment.
Firstly, the primary particles arranged in a radial shape enable the insertion and the separation of lithium ions to be easier, the primary particles in the precursor of the positive electrode material prepared by the method are longer, the insertion of the lithium ions is more facilitated, and the resistance of the precursor is reduced, so that higher capacity is obtained.
And secondly, the longer primary particles are beneficial to the stability of the structure of the precursor of the anode material, the external structure is compact, the compaction is more resistant, and the problem of particle crushing in the rolling process of the pole piece can be solved.
Thirdly, the external primary particles of the precursor of the cathode material are large, the structure reduces the exposed area of the surface of the primary particles, namely the specific surface area, and the contact area of the precursor of the cathode material and the electrolyte, so that the reaction of the cathode material and the electrolyte is reduced, and the cycle stability of the cathode material is finally improved. The lithium battery prepared from the cathode material has good cycle performance and high safety performance, and the cycle retention rate is more than 85% after 180 times of 1C cycle.
Finally, the preparation method is simple in preparation process flow, good in controllability, low in cost, suitable for large-scale industrial production and capable of meeting the requirements of long service life and safety in markets of electric automobiles and the like.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited by the appended claims.
Claims (15)
1. The precursor of the positive electrode material is characterized by comprising a plurality of primary particles with rod-shaped structures, wherein the primary particles are radially arranged outside a core of the precursor of the positive electrode material.
2. The precursor of a positive electrode material according to claim 1, wherein the particle size of the precursor of a positive electrode material is in a range of 5 to 18um, the length of the primary particles having a rod-like structure is in a range of 2 to 5um, and the volume of the primary particles accounts for 30% or more of the volume of the precursor of a positive electrode material.
3. A preparation method of a precursor of a positive electrode material is characterized by comprising the following steps:
providing a base solution, wherein the base solution comprises a first molar concentration C 0 A first complexing agent of (a); the first molar concentration C 0 Means the molarity of the first complexing agent in the base solution;
providing a reaction solution, wherein the reaction solution comprises a metal salt, a precipitator and a second molar concentration C 1 Wherein, C is 0 ＜C 1 Said second molar concentration C 1 Means the molar concentration of the second complexing agent in the reaction solution;
adding the reaction solution into the base solution to react to form a precursor solid-liquid mixture; and filtering the solid-liquid mixture of the precursor and drying to obtain the precursor of the positive electrode material.
4. The method for producing a precursor for a positive electrode material according to claim 3, wherein the base solution further comprises an alkali, and the pH of the base solution is 12 to 12.8.
5. The method for preparing a precursor of a positive electrode material according to claim 3, wherein the reaction temperature is 25 ℃ to 90 ℃; the reaction time is 40 to 100 hours; the stirring speed is 100-1000r/min during reaction.
6. The method for producing a precursor of a positive electrode material according to claim 3, wherein the metal cation of the metal salt is selected from one of Mg, ca, ti, V, cr, mn, fe, co, ni, cu, and Al, or any combination thereof.
7. The method for preparing the precursor of the positive electrode material according to claim 3, wherein the complexing agent is one or more of ammonia, ammonium chloride, ammonium sulfate, ammonium dihydrogen phosphate, ethylene glycol, carboxylic acid, ammonium nitrate, glycerol, 1,3-propylene glycol, urea, N' -dimethylurea, quaternary ammonium salt, citric acid, glycine, and disodium ethylenediaminetetraacetate.
8. The method for preparing a precursor of a positive electrode material according to claim 3, wherein the molar concentration of the first complexing agent in the base solution is 0.2 to 0.6mol/L; the molar concentration of the second complexing agent in the reaction liquid is 0.6-1.5 mol/L; and when the reaction is finished, the molar concentration of the complexing agent in the precursor solid-liquid mixture is 0.6-1.4 mol/L.
9. The method for preparing a precursor of a positive electrode material according to claim 3, wherein a part of the solution is discharged from the reaction vessel by solid-liquid separation during the reaction to prolong the reaction time, wherein the solid-liquid separation is performed by a thickener, the concentrated solution is returned to the reaction vessel for continuous reaction, and the clear water is discharged from the reaction vessel; or the solid-liquid separation can also be that the reaction is stopped after a period of time, and the upper clear water is pumped out of the reaction kettle after the solid particles are precipitated.
10. The method for preparing a precursor of a positive electrode material according to claim 3, wherein the precipitant is one or more of sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, lithium hydroxide, and sodium hydroxide.
11. A precursor of a positive electrode material, which is prepared by the method for preparing the precursor of the positive electrode material according to claims 1 to 10.
12. A positive electrode material obtained by mixing a positive electrode material precursor according to claim 11 with a lithium salt and then heating the mixture at a temperature of 600 to 1000 ℃.
13. The positive electrode material according to claim 12, wherein the lithium salt is one or more of lithium hydroxide, lithium carbonate, lithium nitrate and lithium acetate.
14. The positive electrode material according to claim 12, wherein the positive electrode material precursor contains metal cations, and a ratio of the amount of the metal cations to the amount of lithium in the lithium salt in the positive electrode material precursor is 1.90 to 1.5.
15. A lithium battery, characterized in that the positive electrode material of the lithium battery is as defined in any one of claims 12 to 14.
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| CN110492064A (en) * | 2018-05-15 | 2019-11-22 | 三星Sdi株式会社 | For the positive electrode active materials of lithium secondary battery and the lithium secondary battery including anode containing a positive electrode active material |
| CN111634958A (en) * | 2020-06-02 | 2020-09-08 | 格林美股份有限公司 | Precursor for lithium battery, lithium battery positive electrode material and preparation method of lithium battery positive electrode material |
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| CN110492064A (en) * | 2018-05-15 | 2019-11-22 | 三星Sdi株式会社 | For the positive electrode active materials of lithium secondary battery and the lithium secondary battery including anode containing a positive electrode active material |
| CN111634958A (en) * | 2020-06-02 | 2020-09-08 | 格林美股份有限公司 | Precursor for lithium battery, lithium battery positive electrode material and preparation method of lithium battery positive electrode material |
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