CN114715957B - 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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- CN114715957B CN114715957B CN202210514181.4A CN202210514181A CN114715957B CN 114715957 B CN114715957 B CN 114715957B CN 202210514181 A CN202210514181 A CN 202210514181A CN 114715957 B CN114715957 B CN 114715957B
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- 239000010955 niobium Substances 0.000 title claims abstract description 64
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002243 precursor Substances 0.000 title claims abstract description 61
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 36
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 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
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 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
- 229910052748 manganese Inorganic materials 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
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 230000002572 peristaltic effect Effects 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
- 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
- 239000012466 permeate Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 15
- 239000010405 anode material Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
- 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
- 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
- 239000010406 cathode material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000005253 cladding Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- 238000011161 development Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000227 grinding 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
- 230000008569 process Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000010586 diagram Methods 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
- 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
- 238000001816 cooling Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 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
- 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000080590 Niso Species 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- 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
- 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
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000001704 evaporation 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
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 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
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 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
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000001556 precipitation Methods 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
- 150000003608 titanium Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of lithium ion batteries, and provides a niobium-coated nickel-cobalt-manganese ternary precursor, a preparation method and application thereof. The preparation method comprises the following steps: injecting a transition metal ion solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle of a coprecipitation method, 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 the solution is connected from the reaction kettle, the niobium-coated nickel-cobalt-manganese ternary precursor is obtained after washing, filtering and drying, and the dried precursor is mixed with lithium salt and calcined to obtain the niobium-modified nickel-cobalt-manganese ternary anode material. According to the method, 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 positive electrode 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, a preparation method and application thereof.
Background
Currently, rapid development of the electric automobile industry promotes development and application of power batteries, and lithium ion batteries are the first choice of power batteries as secondary batteries with optimal comprehensive performance at present. In order to meet the requirements of the market on the long endurance mileage of the electric automobile, the nickel-cobalt-manganese ternary material with high specific capacity is adopted as the positive electrode, which is an important way for improving the energy density of the power battery. However, the nickel element has high activity and strong oxidizing property in a charged state, so that the surface of the nickel-cobalt-manganese ternary anode material is easy to generate oxidation-reduction side reaction with electrolyte, and irreversible phase change and cycle performance are reduced. In addition, in the charge and discharge process of the nickel-cobalt-manganese ternary positive electrode material, the crystal has obvious volume change, and cracks are easy to generate on the surface of particles, so that the invasion of electrolyte and the integrity of the particles are damaged. The method reduces the exposure of the high-reactivity surface of the nickel-cobalt-manganese ternary cathode material, enhances the interface stability, and is an important starting 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 coated, and substances such as oxides, phosphates or ion conductors with higher stability 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 (CN 113871583 a) discloses a preparation method of a coated ternary precursor, which comprises dissolving a ternary precursor in water in the presence of a solubilizing agent to obtain a precursor solution, mixing an alcohol coating solution containing 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 (CN 114057235A) discloses a method for coating LATP by nickel-cobalt-manganese ternary precursor, adding mixed solution of lithium and aluminum with pH of 4-5 into a reaction kettle, adding NCM precursor powder, ammonium bicarbonate solution, ammonium dihydrogen phosphate solution and titanium salt solution, centrifuging, washing and drying slurry after reaction to obtain LATP-coated NCM ternary precursor material; chinese patent (CN 114005984A) discloses a high-nickel ternary positive electrode material modified by coupling of lithium niobate cladding and niobium doping, a preparation method and application thereof, wherein the high-nickel ternary material is added into an ethanol solution containing niobium and lithium, and the mixture is heated and evaporated to dryness to realize cladding.
However, the nickel-cobalt-manganese ternary cathode material prepared by the method in the prior art has poor interface stability, and the cycle performance of the battery needs to be improved. The existing coating process is independent of the conventional precursor and cathode material synthesis flow, and requires additional coating equipment and auxiliary materials, so that the production cost is increased. In addition, the added coating procedure prolongs the production time of the product, the change of the coating condition improves the operation complexity of the production, and the method is unfavorable for popularization and application of the coating process of the nickel-cobalt-manganese ternary cathode material.
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 synthesis flow of the existing nickel-cobalt-manganese ternary positive electrode material, so that the interface stability of the nickel-cobalt-manganese ternary positive electrode material is improved, the electrochemical performance is improved, the production time of a product is shortened, and the process flow is simplified.
The first aspect of the invention provides a preparation method of a niobium-coated nickel-cobalt-manganese ternary precursor, which comprises the following synthesis steps:
s1, injecting a transition metal ion solution, a sodium hydroxide solution and an ammonia water solution into a container, controlling reaction conditions under a nitrogen atmosphere, and carrying out precipitation reaction to obtain a nickel-cobalt-manganese ternary precursor;
s2, after the feeding of the transition metal ion solution, the sodium hydroxide solution and the ammonia water solution is finished, the niobium source solution starts to be fed into the container, the precursor is coated, and after the feeding of the niobium source solution is finished, the precursor is washed and filtered, so that the niobium-coated nickel-cobalt-manganese ternary precursor is obtained;
the method combines the precursor synthesis step and the coating step, realizes coating in a container (synthesis reaction kettle), omits equipment for secondary treatment of precursor or positive electrode material particles in the conventional coating process, does not need to take out and transfer the precursor from the coprecipitation reaction kettle 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 positive electrode material obtained after lithiation and calcination has high interface stability, less residual alkali amount and improved cycle stability at normal temperature and high temperature, and good coating effect is shown.
The transition metal ion solution is an aqueous solution of nickel salt, cobalt salt and manganese salt mixed according to a certain proportion.
The mole ratio of nickel, cobalt and manganese is 0.33-0.95: 0.33 to 0.025:0.33 to 0.025; preferably 0.6 to 0.9:0.2 to 0.05:0.2 to 0.05; more preferably 0.8 to 0.9:0.1 to 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 to 5mol/L; further preferably 1 to 3mol/L.
The niobium source solution is an aqueous solution of niobium, and the concentration is 0.001-1 mol/L; preferably 0.05 to 0.5mol/L; further preferably 0.01 to 0.2mol/L.
The concentration of the sodium hydroxide solution is 0.1 to 10mol/L, preferably 0.5 to 5mol/L; further preferably 1 to 3mol/L.
The concentration of the aqueous ammonia solution is 0.002 to 5mol/L, preferably 0.01 to 2mol/L; further preferably 0.1 to 1mol/L.
Further, the nickel salt, cobalt salt and manganese salt are one or 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 nitrate or chloride; preferably, the manganese salt is manganese sulfate or nitrate or chloride.
Further, the niobium source is one or a mixture of more than two of niobium oxalate, niobium chloride and niobate.
Further, the nickel-cobalt-manganese ternary precursor has the following molecular formula: ni (Ni) 1-x-y Co x Mn y (OH) 2 Wherein x is more than 0 and less than or equal to 0.33,0, and y is more 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, a step of; 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 peristaltic pumps, 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. After the transition metal ion solution is fed, the niobium oxalate solution is fed at the speed of 1-3 ml/min until the reaction is finished. And (3) receiving out the solution after the reaction, filtering, washing and drying to obtain the niobium-coated nickel-cobalt-manganese ternary precursor.
Mixing the dried precursor powder with lithium hydroxide in a mortar, grinding, loading into a tube furnace,introducing O 2 Heating to 450-600 ℃, preserving heat for 2-6 h, then heating to 700-850 ℃ in the second stage, preserving heat for 10-14 h, naturally cooling to room temperature, grinding, pulverizing and sieving the sintered material to obtain the niobium-modified nickel-cobalt-manganese ternary anode material. The first stage calcination temperature influences the mixing degree of lithium salt and precursor, and the second stage calcination temperature influences the development condition of the layered structure of the positive electrode material.
The second aspect of the invention provides the niobium-coated nickel-cobalt-manganese ternary precursor prepared by the method. The particle size is uniform and the uniformity is good.
The third aspect of the invention provides a positive electrode material prepared by lithiation and calcination of the niobium-coated nickel-cobalt-manganese ternary precursor. The surface layer of the material is Li 3 NbO 4 Part of niobium element permeates into the material to play a role in stabilizing doping. The positive electrode material has high interface stability, less residual alkali, improved cycling stability at normal temperature and high temperature and good coating effect.
A fourth aspect of the present invention provides an application of the above positive electrode material in the field of lithium ion batteries.
The invention has the advantages and beneficial effects that:
1. the invention integrates the synthesis flow and the coating process of the nickel-cobalt-manganese ternary positive electrode material, and completes the process continuously in the same reaction kettle, and the surface layer of the prepared material is Li 3 NbO 4 Meanwhile, part of Nb element is doped into a material lattice, and the internal and external synergistic effect improves the performance of the anode material. The results of the assembled button cell test show that the retention rates of the assembled button cell at 25 ℃ and 1C multiplying power for 200 weeks are 91.5% respectively, which indicates that the improvement of the interface stability of the materials improves the cycle performance of the battery.
2. The niobium-coated nickel-cobalt-manganese ternary positive electrode material disclosed by the invention has the advantages that the contact between the high-activity surface and the electrolyte is blocked by the niobium coating, the interface side reaction is inhibited, the dissolution of transition metal ions is reduced, and the structure and the cycling stability of the material are enhanced.
3. The niobium-coated nickel-cobalt-manganese ternary precursor prepared by the method has uniform particle size and good consistency, the positive electrode material obtained after lithiation and calcination has high interface stability, less residual alkali amount and improved cycle stability at normal temperature and high temperature, and good coating effect is shown.
4. The invention integrates the coating process into the existing nickel-cobalt-manganese ternary cathode material synthesis flow, does not add an additional reaction container, does not need auxiliary materials except coating solution, simplifies the coating flow and reduces the production cost.
Drawings
FIG. 1 is a schematic diagram of a synthesis flow of a niobium-coated nickel-cobalt-manganese ternary precursor and a positive electrode material according to the present invention;
fig. 2 (a) is an SEM image of a niobium-coated nickel-cobalt-manganese ternary precursor in example 2, and (b) is a Nb element distribution diagram on the particle surface;
FIG. 3 is an XRD pattern for a niobium-coated nickel cobalt manganese ternary precursor of example 2;
fig. 4 (a) is an SEM image of a cathode material synthesized from a 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 a positive electrode material synthesized from a niobium-coated nickel-cobalt-manganese ternary precursor in example 2;
FIG. 6 is a TEM image of a cathode material synthesized from the niobium-coated nickel-cobalt-manganese ternary precursor of example 2;
FIG. 7 is a 0.1C charge-discharge curve of the cathode material synthesized from the ternary precursor of niobium-coated nickel cobalt-manganese in example 2;
FIG. 8 (a) is a comparison of the cycling performance of the positive electrode material synthesized from the niobium-coated nickel-cobalt-manganese ternary positive electrode material precursor of example 2 and the positive electrode material of comparative example 1 in the voltage range of 2.7-4.3V at 25deg.C; (b) The cycle performance of the high-nickel ternary positive electrode material modified by coupling the lithium niobate cladding and the niobium doping in comparative example 2; (c) The cycling performance of the nickel-cobalt-manganese ternary material doped with the niobium concentration gradient in comparative example 3;
fig. 9 shows the cycle performance at 55 ℃ of the cathode material synthesized from the niobium-coated nickel-cobalt-manganese ternary precursor in example 2.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1
NiSO is carried out 4 、CoSO 4 、MnSO 4 According to the molar ratio of Ni to Co to Mn=0.9 to 0.05, respectively weighing a certain mass, dissolving the mass in deionized water, preparing 5L of transition metal ion solution, preparing 1L of niobium oxalate solution with the solubility of 2mol/L, and preparing 0.01mol/L of concentration, 0.5mol/L of ammonia water and 2mol/L of sodium hydroxide solution. Adopting a reaction flow shown in figure 1, adding ammonia water with the concentration of 0.1mol/L into a reaction kettle as a base solution, respectively adding a transition metal ion solution and an ammonia water solution into the reaction kettle by using peristaltic pumps, wherein the flow rates are 2ml/min, keeping the temperature in the reaction kettle at 55 ℃, the rotating speed of a stirrer at 800rpm/min, and simultaneously adding a sodium hydroxide solution, wherein the flow rate is adjustable within 0.1-10 ml/min so as to keep the pH value of the solution at 10.7. After the transition metal ion solution is fed, the niobium oxalate solution is fed at a rate of 2ml/min until the reaction is completed. And (3) receiving out the solution after the reaction, filtering, washing and drying to obtain the niobium-coated nickel-cobalt-manganese ternary precursor.
Mixing 1g of dried precursor powder with lithium hydroxide according to the molar ratio of Li (Ni+Co+Mn) =1.03:1 in a mortar, grinding, loading into a tube furnace, and introducing O 2 Heating to 500 ℃, preserving heat for 4 hours, then heating to 820 ℃ in the second stage, preserving heat for 12 hours, naturally cooling to room temperature, grinding, pulverizing and sieving the sintered material to obtain the niobium-modified nickel-cobalt-manganese ternary anode material. Electrochemical performance test data are shown in table 1.
Example 2
The difference from example 1 is that the concentration of the niobium oxalate solution is 0.03mol/L; the lithiation calcination two-stage is heated to 780 ℃.
FIG. 2 is an SEM image of a niobium-coated nickel-cobalt-manganese ternary precursor and a distribution of Nb elements on the surface of the particles of example 2, where a uniform distribution of Nb elements on the surface of the precursor can be observed; FIG. 3 is an XRD pattern of the niobium-coated nickel cobalt manganese ternary precursor of example 2, showing only characteristic peaks of the hydroxide precursor on the pattern due to the small coating amount; FIG. 4 is an SEM image and a particle surface Nb element distribution plot of a cathode material synthesized from a niobium-coated nickel-cobalt-manganese ternary precursor of example 2, showing after calcinationNb element is uniformly distributed on the surface of the positive electrode material; FIG. 5 is an XRD pattern of the positive electrode material synthesized by the niobium-coated nickel-cobalt-manganese ternary precursor in example 2, showing that the synthesized positive electrode material has small cation mixing and arrangement, good lamellar structure development and no characteristic peak of Nb compound; FIG. 6 is a TEM image of a cathode material synthesized from the niobium-coated nickel-cobalt-manganese ternary precursor of example 2, showing the presence of Li at the edges of the cathode material particles 3 NbO 4 The lattice stripes of the X-ray diffraction pattern (XRD) have the thickness of about 20-30 nanometers, and are coated in an embedded lamellar structure, so that the X-ray diffraction pattern cannot be displayed on XRD due to the small content; 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 the voltage range of 2.7-4.3V. Fig. 9 shows the cycle performance of the cathode material synthesized from the niobium-coated nickel-cobalt-manganese ternary precursor in example 2 at 55 ℃, showing better stability at high temperature. Electrochemical performance test data are shown in table 1.
Example 3
The difference from example 1 is that niobium oxalate is replaced with niobium chloride; the concentration of the niobium chloride solution is 0.05mol/L; the lithiation calcination is carried out by heating to 450 ℃ in one stage, preserving heat for 2h, heating to 750 ℃ in the second stage, and preserving heat for 14h. Electrochemical performance test data are shown in table 1.
Example 4
Unlike example 1, the concentration of the niobium oxalate solution was 0.1mol/L, and the lithiation calcination two-stage temperature was raised to 750 ℃. Electrochemical performance test data are shown in table 1.
Comparative example 1
Unlike example 2, the coating step was not performed after the completion of the feeding of the transition metal ion solution. Electrochemical performance test data are shown in table 1.
Comparative example 2
Chinese patent CN114005984A discloses a high-nickel ternary cathode material modified by coupling of lithium niobate cladding and niobium doping, a preparation method and application thereof, wherein the high-nickel ternary material is added into an ethanol solution containing niobium and lithium, and the cladding is realized by heating and evaporating, and the cladding process is adopted outside a synthesis reaction kettle. The reported properties are compared with the examples of this patent.
Comparative example 3
SCI journal Ionics publication article "Improving electrochemical performance and thermal stability of LiNi 0.8 Co 0.1 Mn 0.1 O 2 via a concentration gradient Nb doping "(DOI: 10.1007/s 11581-020-03758-4), where a concentration gradient doping is achieved in a nickel cobalt manganese ternary material using niobium element. As a control, the reported properties were compared with the examples of this patent.
The embodiment of the invention and the comparative example adopt button half batteries for testing, the negative electrode is a metal lithium sheet, and the preparation process is as follows:
firstly, uniformly mixing 80wt% of positive electrode material powder, 10wt% of acetylene black conductive agent and 10wt% of polyvinylidene fluoride binder, then adding a proper amount of N-methyl pyrrolidone into the mixed powder, homogenizing for 25 minutes, uniformly scraping the obtained slurry on an aluminum foil by using a scraper, and drying in vacuum for 12 hours, cutting into wafers, thus obtaining the tested positive electrode plate.
Then, in a glove box filled with argon (oxygen content is less than or equal to 0.1ppm, water content is less than or equal to 0.1 ppm), the positive electrode plate and the LiPF are arranged 6 And assembling the electrolyte, the Celgard 2325 diaphragm and the lithium metal negative plate into a 2032 type button battery, and thus obtaining the half battery for test.
Table 1 is electrochemical performance test data of the battery cathode materials obtained in examples 1 to 4 and comparative example 1.
| Specific discharge capacity (mAhg) of 1C -1 ) | 1C cycle 200 weeks retention | |
| 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 that: the battery prepared from the niobium-coated nickel-cobalt-manganese positive electrode materials obtained in examples 1-4 of the present invention has slightly lower discharge capacity, but the cycle retention rate is far better than that of comparative example 1. Example 2 shows the best performance due to the relatively suitable coating amount and the calcination conditions in the optimized interval. The differences in the coating amount and the calcination conditions determine the effect of the properties as compared with other examples and comparative examples.
FIG. 8 (a) is a comparison of the cycling performance of the positive electrode material synthesized from the niobium-coated nickel-cobalt-manganese ternary positive electrode material precursor of example 2 and the positive electrode material of comparative example 1 in the voltage range of 2.7-4.3V at 25deg.C; (b) The cycle performance of the high-nickel ternary positive electrode material modified by coupling the lithium niobate cladding and the niobium doping in comparative example 2; (c) In order to compare the cycling performance of the nickel-cobalt-manganese ternary material doped with the concentration gradient of niobium in example 3, it can be seen that the discharge capacity and the cycle life of the niobium-coated nickel-cobalt-manganese ternary positive electrode material in example 2 are higher than those of the samples coated and doped with niobium in (b) and (c).
In summary, the above embodiments are merely illustrative of the related principles and embodiments, and various technical features thereof may be arbitrarily combined, and are not intended to limit the invention, but any modification, equivalent replacement, improvement, etc. of the invention should be included in the protection scope of the invention without departing from the principles of the invention.
Claims (8)
1. The preparation method of the niobium-coated nickel-cobalt-manganese ternary precursor is characterized by combining a precursor synthesis step and a coating step, realizing coating in a reaction kettle, and comprising the following synthesis steps of:
under the nitrogen atmosphere, adding a transition metal ion solution and an 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 a sodium hydroxide solution is regulated and controlled, the pH value of the solution is kept at 10.5-11, after the transition metal ion solution is fed, a niobium source solution is fed at the rate of 1-3 ml/min until the reaction is finished, and the mass ratio of niobium element to transition metal element is 0.001-0.05:1; the niobium source is one or a mixture of more than two of niobium oxalate, niobium chloride and niobate;
the transition metal ion solution is an aqueous solution of nickel salt, cobalt salt and manganese salt mixed according to a certain proportion, and 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, manganese salt is one or a mixture of two or more of sulfate, carbonate, nitrate, chloride.
3. 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 to 0.05, and the concentration of the transition metal ion solution is 0.5 to 5 mol/L.
4. The method of claim 3, wherein the molar ratio of nickel, cobalt, manganese is 0.8-0.9: 0.1 to 0.05:0.1 to 0.05, and the concentration of the transition metal ion solution is 1 to 3mol/L.
5. The method according to claim 4, wherein the mass ratio of niobium element to transition metal element is 0.002 to 0.03:1.
6. a niobium-coated nickel cobalt manganese ternary precursor prepared by the method of any one of claims 1-5.
7. A positive electrode material is characterized in that the positive electrode material is prepared by lithiation and calcination of the niobium-coated nickel-cobalt-manganese ternary precursor according to claim 6, wherein the surface layer of the material is Li 3 NbO 4 Part of niobium element permeates into the material.
8. Use of the positive electrode material according to claim 7 in the field of lithium ion batteries.
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| CN113488620A (en) * | 2021-06-28 | 2021-10-08 | 恒大新能源技术(深圳)有限公司 | Ternary positive electrode precursor and preparation method thereof, ternary positive electrode material and preparation method thereof, and lithium ion battery |
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| CN109638232A (en) * | 2018-10-25 | 2019-04-16 | 宁夏汉尧石墨烯储能材料科技有限公司 | A kind of preparation method of cladded type ternary cobalt nickel oxide manganses lithium anode material |
| CN113488620A (en) * | 2021-06-28 | 2021-10-08 | 恒大新能源技术(深圳)有限公司 | Ternary positive electrode precursor and preparation method thereof, ternary positive electrode material and preparation method thereof, and lithium ion battery |
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