CN114715957A - Niobium-coated nickel-cobalt-manganese ternary precursor, and preparation method and application thereof - Google Patents
Niobium-coated nickel-cobalt-manganese ternary precursor, and preparation method and application thereof Download PDFInfo
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- CN114715957A CN114715957A CN202210514181.4A CN202210514181A CN114715957A CN 114715957 A CN114715957 A CN 114715957A CN 202210514181 A CN202210514181 A CN 202210514181A CN 114715957 A CN114715957 A CN 114715957A
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- niobium
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- 239000002243 precursor Substances 0.000 title claims abstract description 64
- 239000010955 niobium Substances 0.000 title claims abstract description 60
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 55
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- 239000007774 positive electrode material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 8
- 238000006138 lithiation reaction Methods 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 4
- 229910012599 Li3NbO4 Inorganic materials 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 229910015450 Ni1-x-yCoxMny(OH)2 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
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 26
- 239000002245 particle Substances 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 2
- 159000000002 lithium salts Chemical class 0.000 abstract description 2
- 230000004224 protection Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 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 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 14
- 230000008569 process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 4
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019792 NbO4 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- -1 niobium modified nickel-cobalt-manganese Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/485—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
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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
- H01M4/62—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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- 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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Abstract
The invention belongs to the field of lithium ion batteries, and provides a niobium-coated nickel-cobalt-manganese ternary precursor, and a preparation method and application thereof. The preparation method comprises the following steps: and (3) injecting the transition metal ion solution, the sodium hydroxide solution and the ammonia water solution into a coprecipitation reaction kettle, introducing nitrogen for protection, and regulating and controlling reaction conditions to synthesize the nickel-cobalt-manganese hydroxide precursor. And after the feeding of the transition metal ion solution is finished, injecting a niobium source solution into the reaction kettle. And then taking the solution out of the reaction kettle, washing, filtering and drying to obtain a niobium-coated nickel-cobalt-manganese ternary precursor, and mixing and calcining the dried precursor and a lithium salt to obtain the niobium-modified nickel-cobalt-manganese ternary cathode material. According to the invention, the precursor synthesis step and the coating step are combined, coating is realized in the reaction kettle, the prepared niobium-coated nickel-cobalt-manganese ternary precursor has uniform particle size and good consistency, the interface stability of the lithiated and calcined anode material is high, the residual alkali amount is less, and the cycle stability at normal temperature and high temperature is improved.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a niobium-coated nickel-cobalt-manganese ternary precursor, and a preparation method and application thereof.
Background
At present, the rapid development of the electric automobile industry promotes the development and application of power batteries, and lithium ion batteries become the first choice of power batteries as secondary batteries with the best comprehensive performance at present. In order to meet the requirement of the market on the long endurance mileage of the electric automobile, the nickel-cobalt-manganese ternary material with high specific capacity is used as the anode, which is an important way for improving the energy density of the power battery. However, since nickel has high activity and strong oxidizability in a charged state, the surface of the nickel-cobalt-manganese ternary positive electrode material is easy to generate redox side reaction with electrolyte, resulting in irreversible phase change and reduced cycle performance. In addition, in the process of charging and discharging, the nickel-cobalt-manganese ternary cathode material has obvious volume change of crystals, and cracks are easily generated on the surfaces of particles, so that the invasion of electrolyte and the integrity of the particles are damaged. The exposure of the high-reactivity surface of the nickel-cobalt-manganese ternary cathode material is reduced, the interface stability is enhanced, and the method is an important key point for improving the performance of the nickel-cobalt-manganese ternary cathode material.
At present, the surface interface of the nickel-cobalt-manganese ternary positive electrode material is mainly modified by means of coating, and substances with high stability, such as oxides, phosphates or ionic conductors, are coated on the surfaces of precursor particles or positive electrode particles, so that direct contact between electrolyte and the surfaces of high-activity positive electrode particles is reduced, and the circulation stability is improved. For example, chinese patent (CN113871583A) discloses a method for preparing a coated ternary precursor, which comprises dissolving a ternary precursor in water in the presence of a solubilizer to obtain a precursor solution, mixing an alcohol coating solution containing a metal salt with the precursor solution, performing solid-liquid separation on the obtained mixture, washing with water, and vacuum-drying to obtain a coated ternary precursor; chinese patent (CN114057235A) discloses a method for coating a nickel-cobalt-manganese ternary precursor with LATP, which comprises the steps of adding a mixed solution of lithium and aluminum with the pH value of 4-5 into a reaction kettle, adding NCM precursor powder, an ammonium bicarbonate solution, an ammonium dihydrogen phosphate solution and a titanium salt solution, centrifuging, washing and drying slurry after reaction to obtain a LATP-coated NCM ternary precursor material; chinese patent (CN114005984A) discloses a lithium niobate-coated and niobium-doped coupling modified high-nickel ternary cathode material, and a preparation method and application thereof.
However, the nickel-cobalt-manganese ternary cathode material prepared by the prior art method has poor interface stability, and the cycle performance of the battery needs to be improved. The existing coating process is independent of the synthesis process of the conventional precursor and the anode material, and additional coating equipment and auxiliary materials are needed, so that the production cost is increased. In addition, the added coating process prolongs the production time of the product, and the change of the coating conditions improves the operation complexity of the production, thus being unfavorable for the popularization and the application of the nickel-cobalt-manganese ternary cathode material coating process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a niobium-coated nickel-cobalt-manganese ternary precursor, wherein the coating process is integrated into the existing synthesis process of a nickel-cobalt-manganese ternary cathode material, so that the interface stability of the nickel-cobalt-manganese ternary cathode material is improved, the electrochemical performance is improved, the production time of a product is shortened, and the process flow is simplified.
The invention provides a preparation method of a niobium-coated nickel-cobalt-manganese ternary precursor, which comprises the following synthesis steps:
s1, injecting the transition metal ion solution, the sodium hydroxide solution and the ammonia water solution into a container, controlling the reaction conditions in the nitrogen atmosphere, and carrying out precipitation reaction to obtain a nickel-cobalt-manganese ternary precursor;
s2, after the transition metal ion solution, the sodium hydroxide solution and the ammonia water solution are fed, feeding the niobium source solution into the container, coating the precursor, and washing and filtering after the feeding of the niobium source solution is finished to obtain a niobium-coated nickel-cobalt-manganese ternary precursor;
the invention combines the synthesis step and the coating step of the precursor, realizes coating in a container (synthesis reaction kettle), omits the equipment for secondary treatment of the precursor or the anode material particles in the conventional coating process, does not need to take out the precursor from the coprecipitation reaction kettle and transfer the precursor to other devices for coating operation, and simplifies the coating process. The prepared niobium-coated nickel-cobalt-manganese ternary precursor has uniform particle size and good consistency, the interface stability of the anode material obtained after lithiation and calcination is high, the residual alkali amount is less, the cycling stability at normal temperature and high temperature is improved, and a good coating effect is shown.
The transition metal ion solution is a water solution formed by mixing nickel salt, cobalt salt and manganese salt according to a certain proportion.
The molar ratio of nickel, cobalt and manganese is 0.33-0.95: 0.33 to 0.025: 0.33 to 0.025; preferably 0.6-0.9: 0.2-0.05: 0.2 to 0.05; more preferably 0.8 to 0.9: 0.1-0.05: 0.1 to 0.05.
The concentration of the transition metal ion aqueous solution is 0.1-10 mol/L; preferably 0.5-5 mol/L; further preferably 1 to 3 mol/L.
The niobium source solution is a niobium water solution, and the concentration is 0.001-1 mol/L; preferably 0.05-0.5 mol/L; further preferably 0.01 to 0.2 mol/L.
The concentration of the sodium hydroxide solution is 0.1-10 mol/L, preferably 0.5-5 mol/L; further preferably 1 to 3 mol/L.
The concentration of the ammonia water solution is 0.002-5 mol/L, preferably 0.01-2 mol/L; further preferably 0.1 to 1 mol/L.
Further, the nickel salt, the cobalt salt and the manganese salt are one or a mixture of more than two of sulfate, carbonate, nitrate and chloride. Preferably, the nickel salt is nickel sulfate or nickel nitrate or nickel chloride; preferably, the cobalt salt is cobalt sulfate or cobalt nitrate or cobalt chloride; preferably, the manganese salt is manganese sulfate or manganese nitrate or manganese chloride.
Further, the niobium source is one or a mixture of two or more of niobium oxalate, niobium chloride and niobate.
Further, the nickel cobaltThe manganese ternary precursor has the following molecular formula: ni1-x-yCoxMny(OH)2Wherein x is more than 0 and less than or equal to 0.33, and y is more than 0 and less than or equal to 0.33.
Further, the mass ratio of the niobium element to the transition metal element is 0.001-0.05: 1; preferably, the mass ratio is 0.002-0.03: 1; more preferably 0.003 to 0.01: 1.
adding the transition metal ion solution and the ammonia water solution into a reaction kettle by using a peristaltic pump, wherein the flow rate is 1-3 ml/min, the temperature in the reaction kettle is kept at 50-60 ℃, the rotating speed of a stirrer is 600-1000 rpm/min, the flow rate of the sodium hydroxide solution is regulated, and the pH value of the solution is kept at 10.5-11. And after the feeding of the transition metal ion solution is finished, feeding the niobium oxalate solution at the speed of 1-3 ml/min until the reaction is finished. And taking out the solution after the reaction, filtering, washing and drying to obtain the niobium-coated nickel-cobalt-manganese ternary precursor.
Taking the dried precursor powder and lithium hydroxide, fully mixing and grinding in a mortar, then putting into a tube furnace, and introducing O2And heating to 450-600 ℃, preserving heat for 2-6 h, then heating to 700-850 ℃ for a second period, preserving heat for 10-14 h, naturally cooling to room temperature, grinding the sintered material, pulverizing and sieving to obtain the niobium-modified nickel-cobalt-manganese ternary cathode material. The first stage calcination temperature affects the mixing degree of lithium salt and precursor, and the second stage calcination temperature affects the development condition of the layered structure of the anode material.
The second aspect of the invention provides a niobium-coated nickel-cobalt-manganese ternary precursor prepared by the method. Uniform grain size and good consistency.
The third aspect of the invention provides a positive electrode material, which is prepared by lithiating and calcining the niobium-coated nickel-cobalt-manganese ternary precursor. The surface layer of the material is Li3NbO4Part of niobium element of the embedded coating layer permeates into the material to play a role in stabilizing doping. The cathode material has high interface stability, less residual alkali, improved cycle stability at normal temperature and high temperature, and good coating effect.
The fourth aspect of the invention provides the application of the cathode material in the field of lithium ion batteries.
The invention has the advantages and beneficial effects that:
1. the invention integrates the synthesis process and the coating process of the nickel-cobalt-manganese ternary cathode material, and the synthesis process and the coating process are continuously completed in the same reaction kettle, and the surface layer of the prepared material is Li3NbO4And meanwhile, part of Nb element is doped into material crystal lattices, and the inside and outside synergistic effect improves the performance of the anode material. The test result of the assembled button cell shows that the retention rate of the battery is 91.5% at 25 ℃ under the condition of 1C multiplying power for 200 weeks, which indicates that the improvement of the interface stability of the material improves the cycle performance of the battery.
2. According to the niobium-coated nickel-cobalt-manganese ternary cathode material, the contact between the high-activity surface and the electrolyte is blocked through niobium coating, the interface side reaction is inhibited, the dissolution of transition metal ions is reduced, and the structure and the cycle stability of the material are enhanced.
3. The niobium-coated nickel-cobalt-manganese ternary precursor prepared by the invention has uniform particle size and good consistency, the interface stability of the anode material obtained after lithiation and calcination is high, the residual alkali amount is less, the cycling stability at normal temperature and high temperature is improved, and a good coating effect is shown.
4. The invention integrates the coating process into the existing nickel-cobalt-manganese ternary cathode material synthesis process, does not increase an additional reaction vessel, does not need auxiliary materials except the coating solution, simplifies the coating process and reduces the production cost.
Drawings
FIG. 1 is a schematic diagram of the process for synthesizing a niobium-coated Ni-Co-Mn ternary precursor and a positive electrode material according to the present invention;
fig. 2 (a) is an SEM image of the niobium-coated ni-co-mn ternary precursor in example 2, and (b) is a Nb element distribution diagram on the particle surface;
FIG. 3 is an XRD pattern of the niobium-coated nickel-cobalt-manganese ternary precursor in example 2;
fig. 4 (a) is an SEM image of the positive electrode material synthesized from the niobium-coated nickel-cobalt-manganese ternary precursor in example 2, and (b) is a Nb element distribution diagram on the particle surface;
fig. 5 is an XRD pattern of the cathode material synthesized from the niobium-coated nickel-cobalt-manganese ternary precursor in example 2;
fig. 6 is a TEM image of the positive electrode material synthesized from the niobium-coated nickel-cobalt-manganese ternary precursor in example 2;
fig. 7 is a 0.1C charge-discharge curve of the positive electrode material synthesized from the niobium-coated nickel-cobalt-manganese ternary precursor in example 2;
fig. 8 (a) is a comparison of cycle performance of the positive electrode material synthesized from the precursor of the niobium-coated nickel-cobalt-manganese ternary positive electrode material in example 2 and the positive electrode material in comparative example 1 at 25 ℃ and 1C in a voltage range of 2.7-4.3V; (b) the cycle performance of the lithium niobate-coated and niobium-doped coupling modified high-nickel ternary cathode material in the comparative example 2 is shown; (c) the cycle performance of the Ni-Co-Mn ternary material doped with niobium in a concentration gradient manner in the comparative example 3 is shown;
fig. 9 shows the cycle performance of the positive electrode material synthesized from the niobium-coated nickel-cobalt-manganese ternary precursor in example 2 at 55 ℃.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings and embodiments.
Example 1
Mixing NiSO4、CoSO4、MnSO4Weighing certain mass according to the molar ratio of Ni to Co to Mn of 0.9 to 0.05, dissolving the mass in deionized water to prepare 5L of transition metal ion solution with the solubility of 2mol/L and 1L of niobium oxalate solution with the concentration of 0.01mol/L, the concentration of ammonia water of 0.5mol/L and the concentration of sodium hydroxide solution of 2 mol/L. The method adopts a reaction flow shown in figure 1, ammonia water with the concentration of 0.1mol/L is added into a reaction kettle to serve as base solution, transition metal ion solution and the ammonia water solution are respectively added into the reaction kettle by using peristaltic pumps, the flow rate is 2ml/min, the temperature in the reaction kettle is kept at 55 ℃, the rotating speed of a stirrer is 800rpm/min, and meanwhile, sodium hydroxide solution is added, the flow rate is adjustable within 0.1-10 ml/min, so that the pH value of the solution is kept at 10.7. After the feeding of the transition metal ion solution was completed, the niobium oxalate solution was fed at a rate of 2ml/min until the reaction was completed. And taking out the solution after the reaction, filtering, washing and drying to obtain the niobium-coated nickel-cobalt-manganese ternary precursor.
Taking 1g of dried precursor powder, mixing with lithium hydroxide according to the ratio of Li (Ni + Co + Mn) to 1.03:1Mixing and grinding the mixture in a mortar fully according to the molar ratio, then loading the mixture into a tube furnace, and introducing O2Heating to 500 ℃, preserving heat for 4h, then heating to 820 ℃ for two times, preserving heat for 12h, naturally cooling to room temperature, grinding the sintered material, pulverizing and sieving to obtain the niobium modified nickel-cobalt-manganese ternary cathode material. The electrochemical performance test data are shown in Table 1.
Example 2
Different from the embodiment 1, the concentration of the niobium oxalate solution is 0.03 mol/L; the temperature is raised to 780 ℃ in the second lithiation calcination stage.
Fig. 2 is an SEM image and a Nb element distribution diagram of the surface of the particles of the niobium-coated nickel-cobalt-manganese ternary precursor in example 2, and it can be observed that Nb element is uniformly distributed on the surface of the precursor; FIG. 3 is an XRD pattern of the niobium-coated Ni-Co-Mn ternary precursor in example 2, which shows only the characteristic peak of the hydroxide precursor due to the small coating amount; fig. 4 is an SEM image and a distribution diagram of Nb elements on the surface of particles of the cathode material synthesized from the niobium-coated nickel-cobalt-manganese ternary precursor in example 2, which shows that Nb elements are also uniformly distributed on the surface of the cathode material after calcination; fig. 5 is an XRD chart of the cathode material synthesized from the niobium-coated nickel-cobalt-manganese ternary precursor in example 2, which shows that the synthesized cathode material has small cation mixing, a well-developed layered structure, and no characteristic peak of Nb compound; FIG. 6 is a TEM image of the cathode material synthesized from the niobium-coated Ni-Co-Mn ternary precursor in example 2, and it can be seen that Li is present at the edge of the cathode material particle3NbO4The thickness of the lattice fringes is about 20-30 nanometers, the lattice fringes are in a coating mode of an embedded layered structure, and the content is low, so that the lattice fringes cannot be displayed on XRD; fig. 7 is a charge-discharge curve of the positive electrode material synthesized from the niobium-coated nickel-cobalt-manganese ternary positive electrode material precursor in example 2 at 0.1C in a voltage range of 2.7-4.3V. Fig. 9 shows the cycle performance of the positive electrode material synthesized from the niobium-coated nickel-cobalt-manganese ternary precursor in example 2 at 55 ℃, which shows that the stability at high temperature is good. The electrochemical performance test data are shown in Table 1.
Example 3
The difference from example 1 is that niobium oxalate was replaced with niobium chloride; the concentration of the niobium chloride solution is 0.05 mol/L; the temperature of the lithiation calcination is raised to 450 ℃ for the first time, the temperature is kept for 2 hours, and then the temperature of the lithiation calcination is raised to 750 ℃ for the second time, and the temperature is kept for 14 hours. The electrochemical performance test data are shown in Table 1.
Example 4
The difference from example 1 is that the concentration of niobium oxalate solution is 0.1mol/L, and the temperature is raised to 750 ℃ in the second lithiation calcination step. The electrochemical performance test data are shown in Table 1.
Comparative example 1
The difference from example 2 is that the coating step is not carried out after the completion of the feeding of the transition metal ion solution. The electrochemical performance test data are shown in Table 1.
Comparative example 2
Chinese patent CN114005984A discloses a lithium niobate-coated and niobium-doped coupling modified high-nickel ternary cathode material, and a preparation method and application thereof. The reported properties are compared to the examples of this patent.
Comparative example 3
The article published by Ionics, the periodical journal, "Improving electrochemical performance and thermal stability of LiNi0.8Co0.1Mn0.1O2via a concentration gradient Nb doping (DOI: 10.1007/s 11581-020-. This was used as a control and the reported properties were compared to the examples of this patent.
The embodiment and the comparative example of the invention adopt a button half cell for testing, the negative electrode is a metal lithium sheet, and the preparation process comprises the following steps:
firstly, uniformly mixing 80 wt% of positive electrode material powder, 10 wt% of acetylene black conductive agent and 10 wt% of polyvinylidene fluoride binder, then adding a proper amount of N-methyl pyrrolidone into the mixed powder, homogenizing for 25 minutes, uniformly scraping and coating the obtained slurry on an aluminum foil by using a scraper, drying in vacuum for 12 hours, and cutting into a wafer to obtain the tested positive electrode piece.
Then, in a glove box filled with argon (the oxygen content is less than or equal to 0.1ppm, the water content is less than or equal to 0.1ppm), addingPole piece and LiPF6The electrolyte, the Celgard 2325 diaphragm and the lithium metal negative plate are assembled into a 2032 type button battery for assembly, and then the half battery for testing can be obtained.
Table 1 shows the data of the electrochemical performance test of the positive electrode materials of the batteries obtained in examples 1 to 4 and comparative example 1.
| Specific discharge capacity of 1C (mAhg)-1) | Retention rate of 200 weeks at 1C | |
| Example 1 | 176.1 | 90.6％ |
| Example 2 | 185.5 | 93.8％ |
| Example 3 | 178.6 | 87.0％ |
| Example 4 | 175.7 | 81.3％ |
| Comparative example 1 | 193.2 | 48.0％ |
From table 1, it can be derived: the discharge capacity of the battery prepared by adopting the niobium-coated nickel-cobalt-manganese positive electrode materials obtained in the embodiments 1 to 4 of the invention is slightly lower, but the cycle retention rate is far better than that of the battery prepared in the comparative example 1. Example 2 shows the best performance due to the relatively proper coating amount and the calcination condition in the optimized interval. The difference in the coating amount and the calcination conditions has a determining effect on the performance as compared with other examples and comparative examples.
Fig. 8 (a) is a comparison of cycle performance of the positive electrode material synthesized from the precursor of the niobium-coated nickel-cobalt-manganese ternary positive electrode material in example 2 and the positive electrode material in comparative example 1 at 25 ℃ and 1C in a voltage range of 2.7-4.3V; (b) the cycle performance of the lithium niobate-coated and niobium-doped coupling modified high-nickel ternary cathode material in the comparative example 2 is shown; (c) for the cycle performance of the ni-co-mn ternary material with gradient doped nb concentration in comparative example 3, it can be seen that the discharge capacity and cycle life of the ni-coated ni-co-mn ternary positive electrode material in example 2 are both higher than those of the samples coated and doped nb in (b) and (c).
In summary, the above embodiments are merely illustrative of the related principles and embodiments, and various technical features can be arbitrarily combined, which is not intended to limit the present invention, and any modifications, equivalents, improvements, etc. made to the present invention without departing from the principles of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the niobium-coated nickel-cobalt-manganese ternary precursor is characterized by comprising the following synthetic steps of:
s1, injecting the transition metal ion solution, the sodium hydroxide solution and the ammonia water solution into a container, controlling reaction conditions under the nitrogen atmosphere, and performing precipitation reaction to obtain a nickel-cobalt-manganese ternary precursor, wherein the nickel-cobalt-manganese ternary precursor has the following molecular formula: ni1-x- yCoxMny(OH)2Wherein x is more than 0 and less than or equal to 0.2, and y is more than 0 and less than or equal to 0.2;
s2, after the transition metal ion solution, the sodium hydroxide solution and the ammonia water solution are fed, feeding the niobium source solution into the container at a certain speed, coating the precursor, washing and filtering the niobium source solution after the feeding is finished to obtain a niobium-coated nickel-cobalt-manganese ternary precursor, wherein the mass ratio of the niobium element to the transition metal element is 0.001-0.05: 1;
the transition metal ion solution is a water solution formed by mixing nickel salt, cobalt salt and manganese salt according to a certain proportion, wherein the molar ratio of nickel to cobalt to manganese is 0.33-0.95: 0.33 to 0.025: 0.33 to 0.025, and the concentration of the transition metal ion solution is 0.1 to 10 mol/L.
2. The method according to claim 1, wherein the nickel salt, cobalt salt, and manganese salt are one or a mixture of two or more of sulfate, carbonate, nitrate, and chloride.
3. The method according to claim 1, wherein the niobium source is one or a mixture of two or more of niobium oxalate, niobium chloride and niobate.
4. The method according to claim 1, wherein the molar ratio of nickel, cobalt and manganese is 0.6-0.9: 0.2-0.05: 0.2-0.05, and the concentration of the transition metal ion solution is 0.5-5 mol/L.
5. The method according to claim 4, wherein the molar ratio of nickel, cobalt and manganese is 0.8-0.9: 0.1-0.05: 0.1-0.05, and the concentration of the transition metal ion solution is 1-3 mol/L.
6. The method according to claim 5, wherein the mass ratio of the niobium element to the transition metal element is 0.002 to 0.03: 1.
7. the method of claim 6, wherein the niobium source solution is fed at a rate of 1 to 3 ml/min.
8. A niobium coated nickel cobalt manganese ternary precursor prepared by the method of any one of claims 1 to 7.
9. A positive electrode material, which is prepared by lithiation and calcination of the niobium-coated nickel-cobalt-manganese ternary precursor of claim 8, wherein the surface layer of the material is Li3NbO4Part of niobium element penetrates into the material.
10. The use of the positive electrode material of claim 9 in the field of lithium ion batteries.
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