CN111952590A - Lithium ion battery positive electrode material for improving safety and cycle performance and preparation method thereof - Google Patents
Lithium ion battery positive electrode material for improving safety and cycle performance and preparation method thereof Download PDFInfo
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- CN111952590A CN111952590A CN202010650978.8A CN202010650978A CN111952590A CN 111952590 A CN111952590 A CN 111952590A CN 202010650978 A CN202010650978 A CN 202010650978A CN 111952590 A CN111952590 A CN 111952590A
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 title claims description 70
- 239000011572 manganese Substances 0.000 claims abstract description 47
- 239000011258 core-shell material Substances 0.000 claims abstract description 40
- 239000010406 cathode material Substances 0.000 claims abstract description 18
- 239000010405 anode material Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims description 75
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 238000005245 sintering Methods 0.000 claims description 47
- 239000013078 crystal Substances 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 44
- 239000002243 precursor Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 238000013329 compounding Methods 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 230000004927 fusion Effects 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 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
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 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 claims description 2
- FYWUVDVZWURZJH-UHFFFAOYSA-E [OH-].[Al+3].[Mn+2].[Co+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Al+3].[Mn+2].[Co+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] FYWUVDVZWURZJH-UHFFFAOYSA-E 0.000 claims description 2
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 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
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 53
- 229910052759 nickel Inorganic materials 0.000 abstract description 13
- 229910052748 manganese Inorganic materials 0.000 abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 abstract description 4
- 239000010941 cobalt Substances 0.000 abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011162 core material Substances 0.000 abstract description 2
- -1 nickel-cobalt-manganese-aluminum Chemical compound 0.000 description 29
- 229910001428 transition metal ion Inorganic materials 0.000 description 17
- 239000002131 composite material Substances 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 239000002002 slurry Substances 0.000 description 10
- 238000007873 sieving Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 6
- 229940044175 cobalt sulfate Drugs 0.000 description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 6
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 6
- 229940099596 manganese sulfate Drugs 0.000 description 6
- 239000011702 manganese sulphate Substances 0.000 description 6
- 235000007079 manganese sulphate Nutrition 0.000 description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 6
- 229940053662 nickel sulfate Drugs 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 229910013716 LiNi Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910011624 LiNi0.7Co0.1Mn0.2O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0422—Cells or battery with cylindrical casing
- H01M10/0427—Button cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a lithium ion battery anode material for improving safety and cycle performance and a preparation method thereof, and the general formula is LiNi1‑x‑y‑z‑uCoxMnyAlzZuO2@MaOb@LiNi1‑c‑ dCocMndO2Wherein x is more than 0 and less than or equal to 0.10, y is more than 0 and less than or equal to 0.05, z is more than 0 and less than or equal to 0.05, u is more than 0 and less than or equal to 0.05, a is more than 0 and less than or equal to 2, b is more than 0 and less than or equal to 3, c is more than 0 and less than or equal to 0.3, and 0D is less than or equal to 0.3. The prepared cathode material with the core-shell structure taking nickel, cobalt and manganese as the core and nickel, cobalt, manganese and aluminum as the shell has the advantages that the DSC shows that the heat release temperature is increased, the heat release area is reduced, and the thermal stability of the cathode material is improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium ion battery anode material for improving safety and cycle performance and a preparation method thereof.
Background
In recent years, with the rapid development of new energy automobile market in China, the demand of power lithium ion batteries is greatly increased, and with the continuous improvement of the energy density requirement of the lithium ion batteries, the requirements of safety performance and cycle life of the lithium ion batteries are increasingly increased, and as the anode material of the key component part of the lithium ion batteries, high nickel is changed into the inevitable trend of the development of the power lithium ion battery material. The high nickel content enables the energy density of the power battery to be remarkably improved, means that the battery with the same weight can provide more charged electricity, the light weight is achieved, the electricity consumption of hundreds of kilometers is reduced, the endurance mileage of the new energy automobile is remarkably improved, and meanwhile, the safety performance and the cycle life are also reduced to some extent. The nickel-cobalt-manganese-aluminum anode material mainly containing nickel has many anode material manufacturers to develop the NCMA anode material at present, and theories show that: the Al and Mn codoping of the NCMA material well inhibits the volume expansion of the material in the charging process, simultaneously reduces the generation of internal cracks of secondary particles and the corrosion of electrolyte to the secondary particles, thereby obviously improving the cycle performance, well maintaining the characteristic of high energy density, and greatly improving the thermal stability compared with NCM and NCA materials.
Disclosure of Invention
The invention aims to provide a lithium ion battery anode material capable of improving safety and cycle performance on the basis of improving energy density and a preparation method thereof.
In order to achieve the purpose, the invention has the following technical scheme:
the invention relates to a lithium ion battery anode material with improved safety and cycle performance, and the general formula of the material is LiNi1-x-y-z-uCoxMnyAlzZuO2@MaOb@LiNi1-c-dCocMndO2Wherein x is more than 0 and less than or equal to 0.10, y is more than 0 and less than or equal to 0.05, z is more than 0 and less than or equal to 0.05, u is more than 0 and less than or equal to 0.05, a is more than 0 and less than or equal to 2, b is more than 0 and less than or equal to 3, c is more than 0 and less than or equal to 0.3, and d is more than 0 and less than or equal.
The invention relates to a preparation method of a lithium ion battery anode material for improving safety and cycle performance, which is characterized by comprising the following steps:
(1) preparing a salt solution: dissolving soluble nickel salt, cobalt salt and manganese salt in a certain molar ratio in deionized water to form a mixed solution A, and dissolving soluble nickel salt, cobalt salt, manganese salt and aluminum salt in a certain molar ratio in deionized water to form a mixed solution B, wherein the nickel salt, cobalt salt, manganese salt and aluminum salt are any one of sulfate, chloride, nitrate and acetate;
(2) preparing an alkali solution: respectively dissolving a certain amount of NaOH and ammonia water in deionized water to respectively form a mixed solution C and a mixed solution D;
(3) preparing a nickel-cobalt-manganese-aluminum hydroxide precursor with a core-shell structure: adding the mixed solution A prepared in the step (1) into an intermittent reaction container, controlling the stirring frequency within a reasonable range, respectively adding the mixed solution C and the mixed solution D in the step (2) into the intermittent reaction container, adjusting the pH of the solution to a proper range, controlling the reaction temperature and the stirring rate, introducing inert gas for protection in the whole reaction process, adding the solution B in the step (1) after a crystal nucleus D50 grows to a certain size for a reaction period, continuing stirring for reaction growth, finishing the reaction after a crystal D50 grows to a certain size, filtering and washing the obtained precipitate, and drying at 80-200 ℃ for 4-8 hours to prepare a precursor with a core-shell structure;
(4) the heat treatment method comprises the following steps: pre-sintering the precursor with the core-shell structure obtained in the step (3) at a certain temperature;
(5) respectively and uniformly mixing the pre-sintered precursor in the step (4) with a lithium source and a metal compound Z in a mixer according to a certain molar ratio and a certain mass ratio, sintering the uniformly mixed material in a high-temperature furnace, wherein the atmosphere is an oxygen-containing atmosphere, heating the material to a sintering temperature at a certain heating rate by the high-temperature furnace, preserving heat for a plurality of times, and crushing the material after cooling along with the furnace;
(6) washing and drying the crushed material in the step (5) at a certain water temperature and material ratio;
(7) uniformly mixing the dried material in the step (6) and an M compound accounting for 0.01-1% of the mass ratio of the positive electrode material, wherein M is one or more of B, Zr, Ti, La, V, Mo and Cr in a mixer, and then carrying out secondary sintering in an oxygen atmosphere;
(8) and (4) compounding the material obtained in the step (7) with a monocrystal nickel cobalt lithium manganate positive electrode material, then sintering for three times in an oxygen atmosphere, and finally screening to obtain the final positive electrode material.
Wherein the molar concentration of the mixed solution A and the mixed solution B in the step (1) is 0.1-2 mol/L.
Wherein the concentration of the solution C in the step (2) is 0.4-10 mol/L.
Wherein the stirring rate in the step (3) is controlled so that the power obtained per unit volume of the solution is 0.3 to 6kW/m3Controlling the pH range to be 9.5-13, controlling the reaction temperature to be 50-80 ℃, controlling the D50 for crystal nucleus growth to be 0.5-10 mu m, and controlling the D50 for crystal growth to be 2-30 mu m.
Wherein the pre-sintering temperature in the step (4) is 200-600 ℃.
Wherein, in the step (5), the lithium source is any one or more of lithium carbonate, lithium hydroxide, lithium nitrate and lithium chloride, the metal compound Z is any one or more of metal Mg, Ca, Sr, Ba, Zr, Nb, Ti, V and Mo compounds, the molar ratio of the lithium source to the precursor is 0.95-1.5, the mass ratio of the alkali metal compound to the precursor is 0.01-1%, the volume fraction of the oxygen content in the oxygen-containing atmosphere is 20-99.99%, the temperature rise rate ranges from 1-10 ℃/min, the sintering temperature is 600-.
Wherein the mass ratio of the washing water to the materials in the step (6) is 0.3-10:1, the washing time is 5-60min, and the washing temperature is 15-60 ℃; the dehydration time is 5-60min, and the water content of the dehydrated material is less than or equal to 10 percent; the drying temperature is 60-100 ℃, the drying atmosphere is atmosphere or vacuum, and the moisture content of the dried material is less than or equal to 1 percent.
Wherein, in the step (7), the M compound is one or more of B, Zr, Ti, La, V, Mo and Cr, and calculated according to the content of M, the coating amount of M is 0.01-1 wt%, the secondary sintering temperature is 200-700 ℃, the sintering time is 3-20h, and the oxygen content is 30-99.9%.
Wherein, in the step (8), the single crystal lithium nickel cobalt manganese oxide cathode material is at least one or more of single crystals 523, 551530, 622, 651520, 712 and 811, the particle size is 0.5-5 μm, the compounding amount is 0.01-1 wt%, and the compounding method comprises the following steps: any one or more of dry coating, wet coating, mechanical fusion and spray granulation methods, wherein the three-time sintering temperature is 300-800 ℃, the sintering time is 3-20h, and the oxygen content is 30-99.9%.
Advantageous effects
(1) According to the prepared cathode material with the core-shell structure, which takes nickel, cobalt and manganese as the core and nickel, cobalt, manganese and aluminum as the shell, DSC shows that the heat release temperature is increased, the heat release area is reduced, and the thermal stability of the cathode material is improved;
(2) the nickel-cobalt-manganese-aluminum cathode material with the composite single crystal core-shell structure prepared by the invention has good high-temperature cycle performance, and the capacity retention rate can reach 90% after 1C/1C charge and discharge for 600 weeks at a high temperature of 45 ℃, and is improved by about 3-10% compared with the prior art.
(3) The nickel-cobalt-manganese-aluminum cathode material with the core-shell structure prepared by the invention has low surface residual alkali content and Li on the surface of the material2CO3The residual content is less than or equal to 0.25 percent, the LiOH residual content on the surface is less than or equal to 0.2 percent, and the processing performance of the battery slurry is improved;
(4) according to the nickel-cobalt-manganese-aluminum cathode material with the core-shell structure, the first charge-discharge efficiency of a button cell at normal temperature at 0.1C can reach 92.0%, and is improved by about 3-4% compared with the prior art;
drawings
Fig. 1 is a DSC comparison graph of a core-shell structure nickel-cobalt-manganese-aluminum positive electrode material of a composite single crystal material prepared in example 1 of the present invention and comparative examples 1 and 2, and a core-shell structure nickel-cobalt-manganese-aluminum positive electrode material of an uncomplexed single crystal material, and a conventional nickel-cobalt-manganese-aluminum positive electrode material of an uncomplexed single crystal material;
fig. 2 is a comparison graph of charge and discharge cycles of 18650 batteries at a high temperature of 45 ℃ and 1C/1C of a nickel-cobalt-manganese-aluminum positive electrode material with a core-shell structure of the composite single crystal material prepared in example 1 of the present invention and comparative examples 1 and 2, a nickel-cobalt-manganese-aluminum positive electrode material with a core-shell structure of the non-composite single crystal material, and a conventional nickel-cobalt-manganese-aluminum positive electrode material without the composite single crystal material.
Detailed Description
For a further understanding of the invention, reference is made to the following description and specific preferred embodiments, which are given by way of illustration, but do not limit the scope of the invention.
Example 1
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the proportion of Ni: co: the Mn molar ratio is 90: 6: 4 preparing a uniform mixed solution, wherein the total mole number of three transition metal ions of Ni, Co and Mn is 0.5mol/L, then simultaneously adding 2mol/L NaOH solution, 0.5mol/L transition metal ion solution with the total mole number and 2mol/L ammonia water into a batch type reaction container, controlling the feeding rates of the ammonia water, the NaOH solution and the transition metal ion solution to be 200ml/h, 100ml/h and 50ml/h respectively, and controlling the obtained power per unit volume to be 1.3kW/m3Controlling the pH value of the reaction system to be 10.5 and the reaction temperature to be 60 ℃, and adding 0.5mol/L of Ni when the crystal nucleus grows to 3 mu m of D50: co: mn: the Al molar ratio is 89: 6: 4:1, controlling the feeding rate, pH, ammonia water and reaction time of a NaOH solution and a transition ion solution, continuing to react and grow until crystals grow to 12um D50, then filtering and washing the obtained precipitate, drying at 120 ℃ for 12 hours to obtain a precursor with a D50 of 12um and a core-shell structure, raising the temperature of the obtained precursor to 400 ℃ at the heating rate of 1 ℃/min in a high-temperature sintering furnace, preserving the temperature for 6 hours to obtain a presintered precursor, and respectively setting the presintered precursor to be 1.01 in molar ratio and mass ratio of Li/(Ni + Co + Mn + Al) and 1.01 in Zr/Ni0.89Co0.06Mn0.04Al0.01(OH)2Weighing Ni in a ratio of 0.2%0.89Co0.06Mn0.04Al0.01(OH)2Nickel-cobalt-manganese hydroxide precursor, nano-ZrO2And LiOH H2Adding O into a high-speed mixer, mixing for 1h, uniformly mixing, performing primary sintering at 650 ℃ for 20h in 95% oxygen-enriched atmosphere, cooling a sintered product, crushing, sieving, and mixing the primary sintered material with 15 ℃ deionized water according to the weight ratio of water to the material of 1: 2, washing, continuously stirring and washing in the reaction kettle for 10min, transferring the slurry into a centrifuge for high-speed dehydration for 20min to obtain a material with the water content of 6%, transferring the dehydrated material into a vacuum oven, and drying at 120 ℃ for 5h to obtain the material with the water content of 0.3%. H is respectively weighed according to the mass ratio of B/core-shell structure nickel-cobalt-manganese-aluminum positive electrode material being 0.15 percent3BO3Adding the dried positive electrode material into a high-speed mixer, mixing for 0.5h, uniformly mixing, sintering for 10h at 400 ℃ under the oxygen content of 80%, respectively weighing 811 single crystal positive electrode material and the twice-sintered positive electrode material according to the mass ratio of 811 single crystal positive electrode material/nickel cobalt manganese aluminum positive electrode material with a core-shell structure of 0.2%, sintering for 7.5h at 445 ℃ under the oxygen content of 80%, and sieving to obtain the final composite single crystal positive electrode material with 0.2% and nickel cobalt aluminum positive electrode material LiNi with a core-shell structure coated with 0.15% B0.89Co0.06Mn0.04Al0.01O2@LiNi0.8Co0.1Mn0.1O2And mixing the synthesized ternary cathode material, acetylene black, KS-6 and PVDF according to the mass ratio of 9.0: 0.5: 0.2: 0.3, adding a proper amount of NMP, and stirring to prepare uniform slurry; uniformly coating the slurry on an aluminum foil, drying the aluminum foil in a forced air drying oven, and then vacuum drying the aluminum foil in a vacuum drying oven at 120 ℃ for 12 hours; and naturally cooling, punching a wafer with the diameter of 16mm by using a sheet punching machine, and compacting the wafer on a sheet pressing machine by using the pressure of 10MPa to obtain the positive plate. Taking a self-made positive plate as a positive electrode, a lithium plate as a negative electrode, a Celgard2400 polypropylene microporous membrane as a diaphragm and 1mol/L LiPF6The electrolyte solution is prepared by assembling CR2016 type experimental electricity in an argon-filled glove box with water content and oxygen content below 0.1ppmAnd performing charge and discharge tests in a voltage range of 2.75-4.25V at a multiplying power of 0.1C in the cell, wherein the first discharge capacity of the material reaches 214 mAh/g.
Example 2
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the proportion of Ni: co: the Mn molar ratio is 88: 9: 3 preparing a uniform mixed solution, wherein the total mole number of three transition metal ions of Ni, Co and Mn is 2mol/L, then simultaneously adding 4mol/L NaOH solution, 2mol/L transition metal ion solution with the total mole number and 3mol/L ammonia water into a batch reaction container, controlling the feeding rates of the ammonia water, the NaOH solution and the transition metal ion solution to be 400ml/h, 150ml/h and 200ml/h respectively, and controlling the obtained power per unit volume to be 5kW/m3Controlling the pH value of the reaction system to be 11.5 and the reaction temperature to be 60 ℃, and adding 2mol/L of Ni when the crystal nucleus grows to 5 mu m of D50: co: mn: the molar ratio of Al is 87: 9: 3: 1, controlling the feeding rate, pH (correct), ammonia water and reaction time of NaOH solution and transition ion solution, continuing reaction growth, finishing reaction when crystal growth reaches 17 mu m of D50, then drying the obtained precipitate at 120 ℃ for 12 hours after filtering and washing to obtain a precursor with a D50 of 12 mu m and a core-shell structure, raising the temperature of the precursor with the core-shell structure to 450 ℃ at a heating rate of 1 ℃/min in a high-temperature sintering furnace, preserving heat for 6 hours to obtain a presintered precursor, and respectively setting the presintered precursor to be Li/(Ni + Co + Mn + Al) ═ 1.05 and Zr/Ni according to the molar ratio and the mass ratio of Li/(Ni + Co + Mn + Al) ═ 1.05 and the mass ratio of Zr/Ni0.87Co0.09Mn0.03Al0.01(OH)2Weighing Ni in a ratio of 0.5%0.87Co0.09Mn0.03Al0.01(OH)2Nickel-cobalt-manganese hydroxide precursor, nano-ZrO2And LiOH H2Adding O into a high-speed mixer, mixing for 1h, uniformly mixing, performing primary sintering for 17h at 730 ℃ in 95% oxygen-enriched atmosphere, cooling a sintered product, crushing, sieving, washing the primary sintered material and 25 ℃ deionized water according to the weight ratio of 2:1 of water to the material, continuously stirring and washing in a reaction kettle for 10min, transferring the slurry into a centrifuge for high-speed dehydration for 20miAnd n, the moisture content of the material is 6%, the dehydrated material is transferred into a vacuum oven and dried for 5 hours at the temperature of 120 ℃, and the moisture content of the material is 0.3%. H is respectively weighed according to the mass ratio of B/core-shell structure nickel-cobalt-manganese-aluminum positive electrode material being 0.1 percent3BO3Adding the dried positive electrode material into a high-speed mixer, mixing for 0.5h, uniformly mixing, performing secondary sintering at 390 ℃ for 10h under the condition of 80% oxygen content, weighing 622 single crystal positive electrode material and the twice-sintered positive electrode material according to the mass ratio of 622 single crystal positive electrode material/core-shell structure nickel cobalt manganese aluminum positive electrode material of 0.4%, respectively compounding the 622 single crystal positive electrode material and the twice-sintered positive electrode material with single crystal nickel cobalt lithium manganate, and screening to obtain the final compounded 0.4% single crystal positive electrode material and the core-shell structure nickel cobalt aluminum positive electrode material LiNi coated with 0.1% B0.89Co0.06Mn0.04Al0.01O2@LiNi0.6Co0.2Mn0.2O2The other steps are the same as in example 1.
Example 3
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the proportion of Ni: co: the Mn molar ratio is 87: 10: 3 preparing a uniform mixed solution, wherein the total mole number of three transition metal ions of Ni, Co and Mn is 2mol/L, then simultaneously adding a 5mol/L NaOH solution, a 2mol/L transition metal ion solution and 4mol/L ammonia water into a batch reaction container, controlling the feeding rates of the ammonia water, the NaOH solution and the transition metal ion solution to be 300ml/h, 250ml/h and 100ml/h respectively, and controlling the obtained power per unit volume to be 3.5kW/m3Controlling the pH value of the reaction system to be 12 and the reaction temperature to be 60 ℃, and adding 2mol/L of Ni when the crystal nucleus grows to 7 mu m of D50: co: mn: the Al molar ratio is 86: 10: 3: 1, controlling the feeding rate, pH, ammonia and reaction time of a NaOH solution and a transition ion solution, continuing to react and grow, ending the reaction when a crystal grows to 15 mu m of D50, then filtering and washing the obtained precipitate, drying at 120 ℃ for 12 hours to obtain a precursor with a core-shell structure and a D50 of 12 mu m, raising the temperature of the precursor to 540 ℃ at the heating rate of 1 ℃/min in a high-temperature sintering furnace, preserving the heat for 6.5 hours,obtaining a presintered precursor, and respectively setting the presintered precursor as Li/(Ni + Co + Mn + Al) to 1.05 and Zr/Ni according to the molar ratio and the mass ratio0.86Co0.10Mn0.03Al0.01(OH)2Weighing Ni in a ratio of 0.33%0.86Co0.10Mn0.03Al0.01(OH)2Nickel-cobalt-manganese hydroxide precursor, nano-ZrO2And LiOH H2Adding O into a high-speed mixer, mixing for 1h, uniformly mixing, performing primary sintering for 15.5h at 770 ℃ in 95% oxygen-enriched atmosphere, cooling a sintered product, crushing, sieving, washing a primary sintered material and 40 ℃ deionized water according to the weight ratio of water to the material of 2:1, continuously stirring and washing in a reaction kettle for 10min, transferring the slurry into a centrifuge for high-speed dehydration for 30min to obtain a material with 6% of water content, transferring the dehydrated material into a vacuum oven, and drying at 120 ℃ for 5h to obtain the material with 0.3% of water content. H is respectively weighed according to the mass ratio of B/core-shell structure nickel-cobalt-manganese-aluminum positive electrode material being 0.2 percent3BO3Adding the dried positive electrode material into a high-speed mixer, mixing for 0.5h, uniformly mixing, sintering for 10h at 400 ℃ under the oxygen content of 80%, weighing 523 single-crystal positive electrode material and the twice-sintered positive electrode material according to the mass ratio of 523 single-crystal positive electrode material/core-shell structure nickel-cobalt-manganese-aluminum positive electrode material of 0.5%, respectively, compounding, sintering for 12h at 350 ℃ under the oxygen content of 80%, and screening to obtain the final compounded 0.5% single-crystal positive electrode material and the final 0.2% B core-shell structure nickel-cobalt-aluminum positive electrode material LiNi0.89Co0.06Mn0.04Al0.01O2@LiNi0.5Co0.2Mn0.3O2The other steps are the same as in example 1.
Example 4
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the proportion of Ni: co: the Mn molar ratio is 85: 11: 4 preparing a uniform mixed solution, wherein the total mole number of the three transition metal ions of Ni, Co and Mn is 3mol/L, then adding 5mol/L NaOH solution, the total mole number of the transition metal ion solution is 3mol/L and 2.5mol/L ammonia water into the batch reaction simultaneouslyIn the container, the feeding rates of ammonia water, NaOH solution and transition metal ion solution are controlled to be 300ml/h, 200ml/h and 100ml/h respectively, and the obtained power per unit volume is controlled to be 0.8kW/m3Controlling the pH value of the reaction system to be 11 and the reaction temperature to be 60 ℃, and adding 2mol/L of Ni when the crystal nucleus grows to 7 mu m of D50: co: mn: the molar ratio of Al is 84: 11: 4:1, controlling the feeding rate, pH, ammonia and reaction time of a NaOH solution and a transition ion solution, continuing to react and grow until crystals grow to 15 mu m of D50, then filtering and washing the obtained precipitate, drying at 120 ℃ for 12 hours to obtain a precursor with a D50 of 15 mu m and a core-shell structure, raising the temperature of the precursor to 600 ℃ at the heating rate of 1 ℃/min in a high-temperature sintering furnace, preserving the heat for 4 hours to obtain a presintered precursor, and respectively setting the presintered precursor to be 1.07 and Zr/Ni according to the molar ratio and the mass ratio of Li/(Ni + Co + Mn + Al) and 1.07 and the mass ratio of Zr/Ni0.84Co0.11Mn0.04Al0.01(OH)2Weighing Ni in a ratio of 0.3%0.84Co0.11Mn0.04Al0.01(OH)2Nickel-cobalt-manganese hydroxide precursor, nano-ZrO2And LiOH H2Adding O into a high-speed mixer, mixing for 1h, uniformly mixing, performing primary sintering for 10h at 815 ℃ in a 95% oxygen-enriched atmosphere, cooling a sintered product, crushing, sieving, washing the primary sintered material and 35 ℃ deionized water according to the weight ratio of water to the material of 1:1, continuously stirring and washing in a reaction kettle for 10min, transferring the slurry into a centrifuge for high-speed dehydration for 30min to obtain a material with 6% of water content, transferring the dehydrated material into a vacuum oven, and drying for 5h at 120 ℃ to obtain the material with 0.3% of water content. H is respectively weighed according to the mass ratio of B/core-shell structure nickel-cobalt-manganese-aluminum positive electrode material being 0.18 percent3BO3And adding the dried positive electrode material into a high-speed mixer, mixing for 0.5h, uniformly mixing, sintering for 8h at 500 ℃ under the oxygen content of 80%, and weighing 712 the monocrystalline positive electrode material and the secondary sintered positive electrode material according to the mass ratio of 712 to 0.5% of the monocrystalline positive electrode material/nickel-cobalt-manganese-aluminum positive electrode material with the core-shell structureCompounding the positive electrode material, sintering the compounded material for three times at 450 ℃ for 8.5h under the oxygen content of 80%, and screening to obtain the final compound 0.5% single crystal positive electrode material and the core-shell structure nickel-cobalt-aluminum positive electrode material LiNi coated with 0.18% B0.89Co0.06Mn0.04Al0.01O2@LiNi0.7Co0.1Mn0.2O2The other steps are the same as in example 1.
Example 5
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the proportion of Ni: co: the Mn molar ratio is 82: 10: 8, preparing a uniform mixed solution, wherein the total mole number of three transition metal ions of Ni, Co and Mn is 1mol/L, then simultaneously adding 8mol/L NaOH solution, 1mol/L transition metal ion solution and 6.5mol/L ammonia water into a batch reaction container, controlling the feeding rates of the ammonia water, the NaOH solution and the transition metal ion solution to be 230ml/h, 190ml/h and 40ml/h respectively, and controlling the obtained power per unit volume to be 2 kW/m/h3Controlling the pH value of the reaction system to be 10 and the reaction temperature to be 60 ℃, and adding 2mol/L of Ni when the crystal nucleus grows to 5 mu m of D50: co: mn: the molar ratio of Al is 81: 10: 8: 1, controlling the feeding rate, PH, ammonia and reaction time of a NaOH solution and a transition ion solution, continuing to react and grow until crystals grow to 20 mu m of D50, then filtering and washing the obtained precipitate, drying at 120 ℃ for 12 hours to obtain a precursor with a D50 of 20 mu m and a core-shell structure, raising the temperature of the precursor to 350 ℃ at the heating rate of 1 ℃/min in a high-temperature sintering furnace, preserving the heat for 8 hours to obtain a presintered precursor, and respectively setting the presintered precursor to be 1.15 according to the molar ratio and the mass ratio of Li/(Ni + Co + Mn + Al) and Zr/Ni0.81Co0.10Mn0.08Al0.01(OH)2Weighing Ni in a ratio of 0.35%0.81Co0.10Mn0.08Al0.01(OH)2Nickel-cobalt-manganese hydroxide precursor, nano-ZrO2And LiOH H2Adding O into a high-speed mixer, mixing for 1h, uniformly mixing, and heating at 850 deg.C in 95% oxygen-enriched atmosphereAnd carrying out primary sintering for 12 hours, cooling a sintered product, crushing, sieving, washing a primary sintering material and 25 ℃ deionized water according to the weight ratio of water to the material of 1:3, continuously stirring and washing in a reaction kettle for 10 minutes, transferring the slurry into a centrifuge for high-speed dehydration for 30 minutes to obtain a material with the water content of 6%, transferring the dehydrated material into a vacuum oven, and drying at 120 ℃ for 5 hours to obtain the material with the water content of 0.3%. H is respectively weighed according to the mass ratio of B/core-shell structure nickel-cobalt-manganese-aluminum positive electrode material being 0.5 percent3BO3Adding the dried positive electrode material into a high-speed mixer, mixing for 0.5h, uniformly mixing, sintering for 10h at 300 ℃ under the oxygen content of 80%, respectively weighing 622 single crystal positive electrode material and the twice-sintered positive electrode material according to the mass ratio of 622 single crystal positive electrode material/core-shell structure nickel-cobalt-manganese-aluminum positive electrode material of 0.3%, sintering for 6h at 600 ℃ under the oxygen content of 80%, and sieving to obtain the final composite 0.3% single crystal positive electrode material and the final composite 0.5% core-shell structure nickel-cobalt-aluminum positive electrode material LiNi0.89Co0.06Mn0.04Al0.01O2@LiNi0.6Co0.2Mn0.2O2The other steps are the same as in example 1.
Comparative example 1
Similarly to example 1, H was weighed in a proportion of 0.15% by mass of B/core-shell structure nickel-cobalt-manganese-aluminum positive electrode material3BO3And adding the dried positive electrode material into a high-speed mixer, mixing for 0.5h, uniformly mixing, sintering for 10h at 400 ℃ under 80% of oxygen content, and screening to obtain the final core-shell structure nickel-cobalt-aluminum positive electrode material LiNi coated with 0.15% of B0.89Co0.06Mn0.04Al0.01O2The other steps are the same as in example 1.
Comparative example 2
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the proportion of Ni: co: the Mn molar ratio is 89: 6: 4:1, preparing a uniform mixed solution, wherein the total mole number of three transition metal ions of Ni, Co and Mn is 0.5mol/L, and then adding 2mol/L NaOH solution and 0.5mol/L transition metal ionsSimultaneously adding the solution and 2mol/L ammonia water into a batch type reaction container, controlling the feeding rates of the ammonia water, the NaOH solution and the transition metal ion solution to be 200ml/h, 100ml/h and 50ml/h respectively, and controlling the obtained power per unit volume to be 1.3kW/m3Controlling the pH value of a reaction system to be 10.5, controlling the reaction temperature to be 60 ℃, finishing the reaction when the crystal grows to 12 mu m of D50, then filtering and washing the obtained precipitate, drying at 120 ℃ for 12 hours to obtain a precursor with D50 of 12 mu m, raising the temperature of the obtained precursor to 400 ℃ at the heating rate of 1 ℃/min in a high-temperature sintering furnace, preserving the temperature for 6 hours to obtain a presintered precursor, and respectively setting the presintered precursor to be 1.01 and Zr/Ni according to the molar ratio and the mass ratio of Li/(Ni + Co + Mn + Al) ═ 1.01 and Zr/Ni0.89Co0.06Mn0.04Al0.01(OH)2Weighing Ni in a ratio of 0.2%0.89Co0.06Mn0.04Al0.01(OH)2Nickel-cobalt-manganese hydroxide precursor, nano-ZrO2And LiOH H2Adding O into a high-speed mixer, mixing for 1h, uniformly mixing, performing primary sintering at 650 ℃ for 20h in 95% oxygen-enriched atmosphere, cooling a sintered product, crushing, sieving, and mixing the primary sintered material with 15 ℃ deionized water according to the weight ratio of water to the material of 1: 2, washing, continuously stirring and washing in the reaction kettle for 10min, transferring the slurry into a centrifuge for high-speed dehydration for 20min to obtain a material with the water content of 6%, transferring the dehydrated material into a vacuum oven, and drying at 120 ℃ for 5h to obtain the material with the water content of 0.3%. H is respectively weighed according to the mass ratio of B/nickel-cobalt-manganese-aluminum anode material to 0.15 percent3BO3And adding the dried positive electrode material into a high-speed mixer, mixing for 0.5h, uniformly mixing, sintering for 10h at 400 ℃ under 80% oxygen content, and screening to obtain 0.15% B-coated nickel-cobalt-aluminum positive electrode material LiNi0.89Co0.06Mn0.04Al0.01O2The other steps are the same as in example 1.
Evaluation of Positive electrode Material
The obtained positive electrode material was evaluated for a) thermal stability and b) high temperature cycle life at 45 ℃.
a) Thermal stability
Preparing the obtained positive electrode material into a CR2016 button cell, charging and discharging for two weeks at 0.1C, and then charging to 4.3V at 0.1C; disassembling a fully charged battery in a glove box, taking out a pole piece, placing the pole piece in a dry and clean aluminum crucible matched with equipment, enabling a positive electrode material surface to be upward, adding 1uL of electrolyte on the material, covering a crucible cover, sealing, and performing a differential scanning calorimeter test; and (3) in a nitrogen atmosphere, wherein the test temperature range is from room temperature to 400 ℃, the test is carried out in a closed manner, and the heating rate is 2 ℃/min.
b) High temperature cycle performance at 45 DEG C
The obtained positive electrode material is manufactured into a 18650 cylindrical battery, the cylindrical battery is conventionally formed after being prepared, the formed battery is subjected to a cycle test in a constant temperature box at 45 ℃, 1C charging and discharging are selected for cycle multiplying power, data are recorded after the battery is cycled for 500 times, and the capacity retention rate is calculated.
As can be seen from fig. 1, compared with comparative examples 1 and 2, the nickel-cobalt-manganese-aluminum positive electrode material with the core-shell structure of example 1 prepared according to the present invention has the advantages of increased DSC heat release temperature, reduced heat release peak area, and improved thermal stability of the positive electrode material.
As can be seen from fig. 2, compared with comparative examples 1 and 2, the cycle retention rates of 500 cycles of the nickel-cobalt-manganese-aluminum cathode material with the core-shell structure of example 1 prepared according to the invention are respectively increased from 88% and 84% to about 92%.
By comparing the examples with the comparative examples, the increase of the pre-sintering reduces the residual alkali of the cathode material and improves the processability of the battery slurry; doping with metal to reduce Li+、Ni2+Mixed arrangement is adopted, so that the thermal stability of the anode material is improved; the surface is coated and compounded, and the coating B enables the surface to form a fast ion conductor, so that the lithium ion diffusion rate is improved, the first charge-discharge efficiency is improved, meanwhile, the single crystal anode material is compounded, the side reaction between the anode material and the electrolyte is further inhibited, and the high voltage performance and the high temperature cycle performance of the anode material are improved.
And (3) dry coating: the main material and the coated substance are mixed by coating equipment, and the main material and the coated substance are mixed for a certain time until the main material and the coated substance are uniformly mixed, and whether the main material and the coated substance are uniformly mixed can be judged by surface scanning.
And (3) wet coating: the main material and the coated substance are added into a certain water system solvent and stirred for a certain time, and then the mixture is dried by a drying device, and the coating uniformity can be judged by surface scanning.
Mechanical fusion: the mechanical fusion technology is a new composite material processing technology, the basic principle is the mechano-chemical effect generated by the mechanical force action on the particle surface, the material is coated on the particle surface to be modified under the actions of extrusion, friction, shearing stress and the like, so that different materials are prepared into the composite material, and the mechanical fusion can form two or more powder materials into a composite material.
The spray granulation method comprises the following steps: spray granulation refers to adding a certain amount of adhesive into ground powder, uniformly blending to form granular powder, wherein the powder has better fluidity and rolling property, so that tablets with better strength and difficult layering and cracking can be obtained in a tabletting process. The spray drying process is used in industrial production to granulate, and its basic principle is that the powder material with adhesive is sprayed into granulating tower by means of sprayer to atomize, and the fog drops in the tower are dried by hot air flow in the tower to obtain granular powder body, then the granular powder body is discharged from bottom of drying tower.
The applicant states that the present invention is illustrated by the above examples to show the details of the process equipment and process flow of the present invention, but the present invention is not limited to the above, i.e. it is not meant to imply that the present invention must rely on the above details of the process equipment and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A lithium ion battery anode material for improving safety and cycle performance is characterized in that the material has a general formula of LiNi1-x-y-z-uCoxMnyAlzZuO2@MaOb@LiNi1-c-dCocMndO2Wherein x is more than 0 and less than or equal to 0.10, y is more than 0 and less than or equal to 0.05, z is more than 0 and less than or equal to 0.05, u is more than 0 and less than or equal to 0.05, a is more than 0 and less than or equal to 2, b is more than 0 and less than or equal to 3, c is more than 0 and less than or equal to 0.3, and d is more than 0 and less than or equal.
2. The preparation method of the lithium ion battery anode material for improving the safety and the cycle performance according to claim 1 is characterized by comprising the following steps:
(1) preparing a salt solution: dissolving soluble nickel salt, cobalt salt and manganese salt in a certain molar ratio in deionized water to form a mixed solution A, and dissolving soluble nickel salt, cobalt salt, manganese salt and aluminum salt in a certain molar ratio in deionized water to form a mixed solution B, wherein the nickel salt, cobalt salt, manganese salt and aluminum salt are any one of sulfate, chloride, nitrate and acetate;
(2) preparing an alkali solution: respectively dissolving a certain amount of NaOH and ammonia water in deionized water to respectively form a mixed solution C and a mixed solution D;
(3) preparing a nickel-cobalt-manganese-aluminum hydroxide precursor with a core-shell structure: adding the mixed solution A prepared in the step (1) into an intermittent reaction container, controlling the stirring frequency within a reasonable range, respectively adding the mixed solution C and the mixed solution D in the step (2) into the intermittent reaction container, adjusting the pH of the solution to a proper range, controlling the reaction temperature and the stirring rate, introducing inert gas for protection in the whole reaction process, adding the solution B in the step (1) after a crystal nucleus D50 grows to a certain size for a reaction period, continuing stirring for reaction growth, finishing the reaction after a crystal D50 grows to a certain size, filtering and washing the obtained precipitate, and drying at 80-200 ℃ for 4-8 hours to prepare a precursor with a core-shell structure;
(4) the heat treatment method comprises the following steps: pre-sintering the precursor with the core-shell structure obtained in the step (3) at a certain temperature;
(5) respectively and uniformly mixing the pre-sintered precursor in the step (4) with a lithium source and a metal compound Z in a mixer according to a certain molar ratio and a certain mass ratio, sintering the uniformly mixed material in a high-temperature furnace, wherein the atmosphere is an oxygen-containing atmosphere, heating the material to a sintering temperature at a certain heating rate by the high-temperature furnace, preserving heat for a plurality of times, and crushing the material after cooling along with the furnace;
(6) washing and drying the crushed material in the step (5) at a certain water temperature and material ratio;
(7) uniformly mixing the dried material in the step (6) and an M compound accounting for 0.01-1% of the mass ratio of the positive electrode material, wherein M is one or more of B, Zr, Ti, La, V, Mo and Cr in a mixer, and then carrying out secondary sintering in an oxygen atmosphere;
(8) and (4) compounding the material obtained in the step (7) with a monocrystal nickel cobalt lithium manganate positive electrode material, then sintering for three times in an oxygen atmosphere, and finally screening to obtain the final positive electrode material.
3. The preparation method of the lithium ion battery cathode material with improved safety and cycle performance according to claim 2, characterized in that: the molar concentration of the mixed solution A and the mixed solution B in the step (1) is 0.1-2 mol/L.
4. The method of claim 1, wherein: the concentration of the solution C in the step (2) is 0.4-10 mol/L.
5. The preparation method of the lithium ion battery cathode material with improved safety and cycle performance according to claim 2, characterized in that: the stirring rate in said step (3) is controlled so that the power obtained per unit volume of the solution is 0.3 to 6kW/m3Controlling the pH range to be 9.5-13, controlling the reaction temperature to be 50-80 ℃, controlling the D50 for crystal nucleus growth to be 0.5-10 mu m, and controlling the D50 for crystal growth to be 2-30 mu m.
6. The preparation method of the lithium ion battery cathode material with improved safety and cycle performance according to claim 2, characterized in that: the pre-sintering temperature in the step (4) is 200-600 ℃.
7. The preparation method of the lithium ion battery cathode material with improved safety and cycle performance according to claim 2, characterized in that: in the step (5), the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium nitrate and lithium chloride, the metal compound Z is one or more of metal Mg, Ca, Sr, Ba, Zr, Nb, Ti, V and Mo compounds, the molar ratio of the lithium source to the precursor is 0.95-1.5, the mass ratio of the alkali metal compound to the precursor is 0.01-1%, the volume fraction of the oxygen content in the oxygen-containing atmosphere is 20-99.99%, the temperature rise rate ranges from 1-10 ℃/min, the sintering temperature is 600-1000 ℃, and the heat preservation time is 6-20 h.
8. The preparation method of the lithium ion battery cathode material with improved safety and cycle performance according to claim 2, characterized in that: in the step (6), the mass ratio of the washing water to the materials is 0.3-10:1, the washing time is 5-60min, and the washing temperature is 15-60 ℃; the dehydration time is 5-60min, and the water content of the dehydrated material is less than or equal to 10 percent; the drying temperature is 60-100 ℃, the drying atmosphere is atmosphere or vacuum, and the moisture content of the dried material is less than or equal to 1 percent.
9. The preparation method of the lithium ion battery cathode material with improved safety and cycle performance according to claim 2, characterized in that: in the step (7), the compound M is one or more of B, Zr, Ti, La, V, Mo and Cr, and calculated according to the content of M, the coating amount of M is 0.01-1 wt%, the secondary sintering temperature is 200-700 ℃, the sintering time is 3-20h, and the oxygen content is 30-99.9%.
10. The preparation method of the lithium ion battery cathode material with improved safety and cycle performance according to claim 2, characterized in that: in the step (8), the single-crystal lithium nickel cobalt manganese oxide positive electrode material is at least one or more of single crystals 523, 551530, 622, 651520, 712 and 811, the particle size is 0.5-5 mu m, the compounding amount is 0.01-1 wt%, and the compounding method comprises the following steps: any one or more of dry coating, wet coating, mechanical fusion and spray granulation methods, wherein the three-time sintering temperature is 300-800 ℃, the sintering time is 3-20h, and the oxygen content is 30-99.9%.
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