CN112777649A - Nickel-cobalt-manganese ternary precursor and preparation method and application thereof - Google Patents
Nickel-cobalt-manganese ternary precursor and preparation method and application thereof Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 76
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 87
- 239000000243 solution Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 27
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000000975 co-precipitation Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000000120 microwave digestion Methods 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 230000035484 reaction time Effects 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 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 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000000875 high-speed ball milling Methods 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims description 7
- 229910001453 nickel ion Inorganic materials 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 239000012798 spherical particle Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 13
- 239000011572 manganese Substances 0.000 abstract description 10
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000011363 dried mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 2
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021311 NaFeO2 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
Abstract
The invention discloses a nickel-cobalt-manganese ternary precursor and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding a nickel-cobalt-manganese soluble salt aqueous solution into a sodium hydroxide solution, mixing and controlling the pH value of the solution to be 10-10.5; and (3) carrying out coprecipitation reaction in a microwave digestion instrument, drying the obtained solid-liquid mixture, annealing in a muffle furnace, and cooling to obtain the target nickel-cobalt-manganese ternary precursor. The nickel-cobalt-manganese ternary precursor has the average particle size of 10-50 mu m and the specific surface area of 10-20m2(ii) in terms of/g. The application is the application of the nickel-cobalt-manganese ternary precursor in preparing nickel-cobalt-lithium manganate ternary materials and lithium ion battery anode materials. Nickel-cobalt-manganese ternary precursor structure prepared by using methodThe nickel-based composite material is stable and almost free of impurities, and the problem that the specific capacity of a high-nickel material is improved and the structural stability is poor is solved; the nickel-cobalt-manganese ternary cathode material prepared by the method has good cycling stability, overcomes the defects of poor stability and poor discharge capacity of high-nickel materials, and greatly improves the electrochemical performance of the high-nickel-manganese ternary cathode material.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a nickel-cobalt-manganese ternary precursor and a preparation method and application thereof.
Background
Due to its high specific capacity and high specific power density, lithium ion batteries are widely used as main power supply devices for portable electronic devices. Compared with the graphite cathode with the characteristics of high actual specific capacity, good structural stability and low cost, the anode has become a main factor for restricting the improvement of the energy density, the cycle life and the safety performance of the lithium ion battery, so that the search for a novel anode material with high capacity, high multiplying power and long cycle life is gradually called as a research hotspot.
The nickel-cobalt-manganese ternary positive electrode material has certain application and development due to relatively low cost, high specific capacity and low toxicity. Along with the increase of the nickel content, the specific capacity of the nickel-cobalt-manganese ternary cathode material is gradually increased, and meanwhile, the cycle stability, the thermal stability and the safety performance of the material are obviously reduced. Therefore, it is very important to develop a nickel-cobalt-manganese ternary cathode material with high specific capacity, good cycling stability, good thermal stability and good safety performance. The positive electrode material has inheritance to the precursor, so the appearance of the nickel-cobalt-manganese ternary precursor directly influences the performance of the positive electrode material.
At present, the preparation of nickel-cobalt-manganese ternary precursor generally adopts a coprecipitation method. The effect of the coprecipitation method for preparing the nickel-cobalt-manganese ternary precursor is influenced by various factors such as the pH value of a coprecipitation reaction solution, the reaction temperature, the reaction time and the like. The yield of the precursor is reduced due to the excessively low pH value of the coprecipitation reaction solution, and the growth of the precursor crystal is not facilitated due to the excessively high pH value; in a certain reaction time, the granularity of the precursor is in direct proportion to the reaction time, and the excessive reaction time causes the granularity of the precursor to be too large, thereby generating adverse effect on the quality; the reaction temperature has a major influence on the reaction rate of the chemical reaction, but too high a temperature may cause oxidation of the precursor, so that the chemical reaction rate needs to be increased on the premise of not affecting the quality of the precursor. At present, no method with good repeatability and simple operation is available for solving the problems, and the prepared product has poor stability, so that the application of the nickel-cobalt-manganese ternary precursor in the industry is limited to a certain extent; therefore, it is necessary to provide a preparation method of the nickel-cobalt-manganese ternary precursor with simple operation and stable structure.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a nickel-cobalt-manganese ternary precursor, and the second purpose of the invention is to provide a nickel-cobalt-manganese ternary precursor; the third purpose of the invention is to provide a preparation method of the nickel cobalt lithium manganate ternary material; the fourth purpose of the invention is to provide an application of the nickel cobalt lithium manganate ternary material.
The first purpose of the invention is realized by the following steps:
1) preparing a sodium hydroxide solution and a nickel-cobalt-manganese soluble salt aqueous solution;
2) adding the nickel-cobalt-manganese soluble salt aqueous solution into a sodium hydroxide solution, uniformly mixing to obtain a reaction solution, and controlling the pH value of the reaction solution to be 10-10.5;
3) putting the reaction solution into a microwave digestion instrument for coprecipitation reaction to obtain a solid-liquid mixture;
4) and drying the solid-liquid mixture to obtain a nickel-cobalt-manganese hydroxide, placing the nickel-cobalt-manganese hydroxide in a muffle furnace for annealing, and cooling to obtain the target nickel-cobalt-manganese ternary precursor.
The second purpose of the invention is realized by the nickel-cobalt-manganese ternary precursor prepared by the preparation method, wherein the nickel-cobalt-manganese ternary precursor is highly agglomerated spherical particles, the average particle diameter is 10-50 mu m, and the specific surface area is 10-20m2/g。
The third purpose of the invention is realized in such a way that the preparation method of the nickel cobalt lithium manganate ternary material is as follows: and mixing the nickel-cobalt-manganese ternary precursor with lithium carbonate in a proportion of 1-1.05: and (2) placing the mixture in a ball milling tank according to the molar ratio of 1-1.1, carrying out high-speed ball milling to obtain a mixed material, placing the mixed material in a muffle furnace for high-temperature oxygen sintering, and naturally cooling to room temperature along with the furnace to obtain the nickel cobalt lithium manganate ternary material.
The fourth purpose of the invention is realized by applying the nickel cobalt lithium manganate ternary material to the preparation of a lithium ion battery anode material.
The method prepares the nickel-cobalt-manganese ternary precursor by a microwave-coprecipitation method, and controls the morphology of the nickel-cobalt-manganese ternary precursor by regulating and controlling the concentration of a precipitator, namely sodium hydroxide, the reaction temperature and the reaction time.
Compared with the prior art, the invention has the following advantages:
1) the invention only adopts sodium hydroxide as a precipitator, not only has low cost, but also has uniform precipitation of nickel, cobalt and manganese in the sodium hydroxide solution; in the reaction process, a microwave digestion instrument is adopted to heat the reaction solution, the heating is uniform, the reaction temperature is stable, the temperature rise is fast, the formability of the nickel-cobalt-manganese ternary precursor is improved, and the subsequent reaction is facilitated;
2) the nickel-cobalt-manganese ternary precursor prepared by the method is highly agglomerated primary spherical particles, the crystallinity is good, and nickel, cobalt and manganese elements are uniformly distributed;
3) the nickel-cobalt-manganese ternary precursor prepared by the method has a stable structure and almost no impurities, the problem of poor structural stability when the specific capacity of a high-nickel material is improved is solved, and the safety performance of the product is improved;
4) the method is simple to operate, the time for preparing the nickel-cobalt-manganese ternary precursor is only 30-60min, the time is greatly shortened by 6 hours compared with that of the traditional coprecipitation process, the production efficiency is improved, and the energy is saved;
5) the nickel cobalt manganese acid lithium ternary material further prepared from the nickel cobalt manganese acid ternary precursor has the advantages of large specific surface area and good crystallinity, is beneficial to full contact of electrolyte and active substances, and increases the active sites of reaction.
6) The anode material prepared from the nickel cobalt lithium manganate ternary material has good cycling stability, overcomes the defects of poor stability and poor discharge capacity of a high nickel material, greatly improves the electrochemical performance of the high nickel material, and is beneficial to realizing commercial application.
Drawings
FIG. 1 is a scanning electron microscope image of a nickel-cobalt-manganese ternary precursor in example 1;
FIG. 2 is the XRD pattern of the Ni-Co-Mn ternary precursor of example 1;
FIG. 3 is an EDS (scanning electron microscope) image of the Ni-Co-Mn ternary precursor in example 1, wherein the EDS image is a distribution diagram of Mn, Ni, Co and each element on the surface of a sample from left to right;
FIG. 4 is a scanning electron microscope image of the lithium nickel cobalt manganese oxide ternary material in example 1;
FIG. 5 is a graph showing the specific surface area of the ternary material of nickel cobalt lithium manganate in example 1;
FIG. 6 is a particle size volume frequency distribution diagram of a nickel cobalt lithium manganate ternary material in example 1;
FIG. 7 is the XRD pattern of the ternary precursor of nickel cobalt lithium manganate in example 2;
FIG. 8 is the XRD pattern of the ternary precursor of nickel cobalt lithium manganate in example 3;
fig. 9 is XRD patterns of the ternary precursor of nickel-cobalt-manganese hydroxide in examples 1-3, wherein the XRD patterns are from top to bottom for example 1, example 2, and example 3, respectively.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.
The invention relates to a preparation method of a nickel-cobalt-manganese ternary precursor, which comprises the following steps:
1) preparing a sodium hydroxide solution and a nickel-cobalt-manganese soluble salt aqueous solution;
2) adding the nickel-cobalt-manganese soluble salt aqueous solution into a sodium hydroxide solution, uniformly mixing to obtain a reaction solution, and controlling the pH value of the reaction solution to be 10-10.5;
3) putting the reaction solution into a microwave digestion instrument for coprecipitation reaction to obtain a solid-liquid mixture;
4) and drying the solid-liquid mixture to obtain a nickel-cobalt-manganese hydroxide, placing the nickel-cobalt-manganese hydroxide in a muffle furnace for annealing, and cooling to obtain the target nickel-cobalt-manganese ternary precursor.
In the step 1, the preparation method of sodium hydroxide is as follows: adding sodium hydroxide into deionized water, and mixing and stirring at the speed of 200-300r/min for 10-15 min; the concentration of the sodium hydroxide solution is 0.15-0.25 mol/L; the total concentration of nickel, cobalt and manganese ions in the nickel-cobalt-manganese soluble salt aqueous solution is 0.08-0.12 mol/L; the nickel-cobalt-manganese soluble salt aqueous solution is a mixed solution of cobalt nitrate, manganese nitrate and nickel nitrate; the molar ratio of the nickel nitrate to the cobalt nitrate to the manganese nitrate is 5-6:2-3: 2-3.
In the step 3, the coprecipitation reaction time is 30-60min, and the reaction temperature is 120-180 ℃.
In the step 4, the solid-liquid mixture is dried in a drying oven, the drying temperature is 60-80 ℃, and the drying time is 10-12 hours.
In the step 4, the nickel-cobalt-manganese hydroxide is calcined in air in a muffle furnace, the calcining temperature is 250-300 ℃, the heating rate is 3-5 ℃/min, and the heat preservation time is 1-3 h.
The nickel-cobalt-manganese ternary precursor is highly agglomerated spherical particles, the average particle size is 10-50 mu m, and the specific surface area is 10-20m2/g。
The invention relates to a preparation method of a nickel cobalt manganese acid lithium ternary material, which comprises the following steps of mixing a nickel cobalt manganese ternary precursor and lithium carbonate by a ratio of 1-1.05: and (2) placing the mixture in a ball milling tank according to the molar ratio of 1-1.1, carrying out high-speed ball milling to obtain a mixed material, placing the mixed material in a muffle furnace for high-temperature oxygen sintering, and naturally cooling to room temperature along with the furnace to obtain the nickel cobalt lithium manganate ternary material.
The rotation speed of the ball milling is 350-550 r/min, and the ball milling time is 1-3 h; the temperature of the high-temperature oxygen sintering is 680-880 ℃, the heating rate is 3-5 ℃/min, the sintering is carried out for 3-9 h, then the temperature is kept for 6-8 h, and then the furnace is cooled naturally.
The invention relates to an application of a nickel cobalt lithium manganate ternary material in the preparation of a lithium ion battery anode material.
Example 1
In a stoichiometric ratio n (Ni): n (Co): n (Mn) =6:2:2 dissolving 60mmol nickel nitrate, 20mmol cobalt nitrate and 20mmol manganese nitrate in 100ml deionized water to obtain nitrate solution with total concentration of transition metal nickel, cobalt and manganese ions of 0.1 mol/L; putting 8.33g of sodium hydroxide into 1L of deionized water, mixing and stirring to obtain 0.2mol/L sodium hydroxide solution, wherein the mixing and stirring time is 15min, and the stirring speed is 250 r/min; adding a nitrate solution into a sodium hydroxide solution, uniformly mixing, controlling the pH =10 of a reaction solution, placing the reaction solution into a microwave digestion instrument for coprecipitation reaction, wherein the reaction time is 30min, and the reaction temperature is 150 ℃, so as to obtain a solid-liquid mixture; putting the solid-liquid mixture into a drying oven for drying, putting the dried mixture into a muffle furnace for annealing at 300 ℃ for 1h, and cooling at the heating rate of 5 ℃/min to obtain a nickel-cobalt-manganese oxide precursor;
weighing 0.202g of nickel-cobalt-manganese oxide precursor and 0.262g of lithium carbonate, and carrying out high-speed ball milling and mixing for 2 hours, wherein the ball milling rotation speed is 400r/min, and the ball milling time is 2 hours; and sintering the powder obtained by ball milling in a rapid heating and cooling heating furnace at 680 ℃ for 3h by using oxygen at the heating rate of 3 ℃/min, then preserving heat for 6h, and naturally cooling along with the furnace to obtain the nickel cobalt lithium manganate ternary material.
Scanning electron microscope testing and crystal diffraction testing are carried out on the nickel-cobalt-manganese ternary precursor prepared in the embodiment, and as can be seen from fig. 1, the nickel-cobalt-manganese ternary precursor prepared in the embodiment is highly agglomerated primary spherical particles; from the XRD chart (fig. 2), no impurity peaks other than the characteristic diffraction peaks (003), (101), (105), and (104) were observed, indicating that the crystallinity of the synthesized precursor was good; the EDS analysis chart shows that the nickel, cobalt and manganese elements of the precursor are uniformly distributed (figure 3).
The lithium nickel cobalt manganese ternary material prepared in the embodiment is subjected to a scanning electron microscope test (the morphology of the lithium nickel cobalt manganese ternary material in the embodiment is shown in fig. 4, and the specific surface area and the particle size distribution diagram are respectively shown in fig. 5 and fig. 6): as can be seen from FIGS. 5 to 6, the lithium nickel cobalt manganese oxide ternary material prepared in the embodiment has a large specific surface area and uniform particle size distribution.
The nickel cobalt lithium manganate ternary material prepared in the embodiment is prepared into a positive electrode material and subjected to electrical property detection, and the result is shown in table 1: in the voltage range of 3.0-4.3V, the discharge capacity of the positive electrode material 1C obtained in the embodiment is as high as 110.4mAh/g, and after 10 cycles, the capacity retention rate is still as high as 97.01%.
Table 1 specific charge-discharge capacity data of ni-co-mn ternary positive electrode material in example 1
In conclusion, the ternary precursor sample prepared in the embodiment 1 has good crystallinity, stable structure and almost no impurities, and the problem of poor structural stability when the specific capacity of the high-nickel material is improved is solved. The cathode material prepared by the embodiment has good cycling stability, uniform distribution of nickel, cobalt and manganese, good crystallinity and stable structure, and improves the safety performance of the battery.
Example 2
In a stoichiometric ratio n (Ni): n (Co): n (Mn) =6:2:2 dissolving 60mmol nickel nitrate, 20mmol cobalt nitrate and 20mmol manganese nitrate in 100ml deionized water to obtain nitrate solution with total concentration of transition metal nickel, cobalt and manganese ions of 0.1 mol/L; putting 8.33g of sodium hydroxide into 1L of deionized water, mixing and stirring to obtain 0.2mol/L sodium hydroxide solution, wherein the mixing and stirring time is 15min, and the stirring speed is 250 r/min; adding a nitrate solution into a sodium hydroxide solution, uniformly mixing to obtain a reaction solution, controlling the pH =10 of the reaction solution, placing the reaction solution in a microwave digestion instrument for coprecipitation reaction, wherein the reaction time is 45min, and the reaction temperature is 120 ℃, so that a solid-liquid mixture is obtained; putting the solid-liquid mixture into a drying oven for drying, putting the dried mixture into a muffle furnace for annealing at 300 ℃ for 1h, and cooling at the heating rate of 5 ℃/min to obtain a nickel-cobalt-manganese ternary precursor;
weighing 0.202g of nickel-cobalt-manganese ternary precursor and 0.262g of lithium carbonate, and mixing by high-speed ball milling for 2 hours, wherein the rotating speed of the ball milling is 400r/min, and the ball milling time is 2 hours; and sintering the powder obtained by ball milling in a rapid heating and cooling furnace at 680 ℃ for 6h by using oxygen, wherein the heating rate is 3 ℃/min, then preserving heat for 6h, and naturally cooling along with the furnace to obtain the nickel cobalt lithium manganate ternary material.
The nickel-cobalt-manganese ternary precursor prepared in this example was subjected to a crystal diffraction test, and as can be seen from fig. 7, the characteristic peak of the nickel-cobalt-manganese ternary precursor in this example increased with the increase of the reaction time, and the characteristic peak was strengthened, indicating that the precursor of this example formed good α -NaFeO2A layered structure.
Example 3
In a stoichiometric ratio n (Ni): n (Co): n (Mn) =6:2:2 dissolving 60mmol nickel nitrate, 20mmol cobalt nitrate and 20mmol manganese nitrate in 100ml deionized water to obtain nitrate solution with total concentration of transition metal nickel, cobalt and manganese ions of 0.1 mol/L; putting 8.33g of sodium hydroxide into 1L of deionized water, mixing and stirring to obtain 0.2mol/L sodium hydroxide solution, wherein the mixing and stirring time is 15min, and the stirring speed is 250 r/min; adding a nitrate solution into a sodium hydroxide solution, uniformly mixing to obtain a reaction solution, controlling the pH =10 of the reaction solution, placing the reaction solution in a microwave digestion instrument for coprecipitation reaction, wherein the reaction time is 30min, and the reaction temperature is 180 ℃ to obtain a solid-liquid mixture; putting the solid-liquid mixture into a drying oven for drying, putting the dried mixture into a muffle furnace for annealing at 300 ℃ for 1h, and cooling at the heating rate of 5 ℃/min to obtain a nickel-cobalt-manganese ternary precursor;
weighing 0.202g of nickel-cobalt-manganese ternary precursor and 0.262g of lithium carbonate, and carrying out high-speed ball milling and mixing for 2 hours, wherein the rotating speed of the ball milling is 400r/min, and the ball milling time is 2 hours; and sintering the powder obtained by ball milling in a rapid heating and cooling furnace at 680 ℃ for 9h by using oxygen, wherein the heating rate is 3 ℃/min, then preserving heat for 6h, and naturally cooling along with the furnace to obtain the nickel cobalt lithium manganate ternary material.
The nickel-cobalt-manganese ternary precursor prepared in this example was subjected to a crystal diffraction test, and as can be seen from fig. 8, the characteristics of the nickel-cobalt-manganese oxide precursor in this example are as follows: the characteristic peak increases very little with increasing reaction temperature, indicating that the sample crystallization process has substantially ended.
Fig. 9 is an XRD comparison graph of the nickel-cobalt-manganese hydroxide ternary precursor prepared in examples 1 to 3, which shows that the nickel-cobalt-manganese hydroxide precursor in examples 1 to 3 has good crystallinity, and as the reaction time increases, the reaction temperature increases, the characteristic peak increases, and after the subsequent sintering experiment, the nickel-cobalt-manganese ternary precursor having good crystallinity and no impurity peak is obtained.
Example 4
In a stoichiometric ratio n (Ni): n (Co): n (Mn) =5:3: 250 mmol nickel nitrate, 30mmol cobalt nitrate and 20mmol manganese nitrate are dissolved in 100ml deionized water, and the total concentration of transition metal nickel, cobalt and manganese ions in the obtained nitrate solution is 0.1 mol/L; putting 6.25g of sodium hydroxide into 1L of deionized water, mixing and stirring to obtain 0.15mol/L sodium hydroxide solution, wherein the mixing and stirring time is 10min, and the stirring speed is 200 r/min; adding a nitrate solution into a sodium hydroxide solution, uniformly mixing to obtain a reaction solution, controlling the pH =10.5 of the reaction solution, placing the reaction solution in a microwave digestion instrument for coprecipitation reaction, wherein the reaction time is 30min, and the reaction temperature is 180 ℃ to obtain a solid-liquid mixture; putting the solid-liquid mixture into a drying oven for drying, putting the dried mixture into a muffle furnace for annealing at 300 ℃ for 1h, and cooling at the heating rate of 5 ℃/min to obtain a nickel-cobalt-manganese ternary precursor;
weighing 0.202g of nickel-cobalt-manganese ternary precursor and 0.262g of lithium carbonate, and carrying out high-speed ball milling and mixing for 1h, wherein the rotating speed of the ball milling is 350r/min, and the ball milling time is 3 h; and sintering the powder obtained by ball milling in a rapid heating and cooling furnace at 880 ℃ for 3h by using oxygen, wherein the heating rate is 5 ℃/min, then preserving heat for 6h, and naturally cooling along with the furnace to obtain the nickel cobalt lithium manganate ternary material.
Example 5
In a stoichiometric ratio n (Ni): n (Co): n (Mn) =5:2:4 50mmol nickel nitrate, 20mmol cobalt nitrate and 30mmol manganese nitrate are dissolved in 100ml deionized water, and the total concentration of transition metal nickel, cobalt and manganese ions in the obtained nitrate solution is 0.1 mol/L; 10.31g of sodium hydroxide is put into 1L of deionized water for mixing and stirring to obtain 0.25mol/L sodium hydroxide solution, the mixing and stirring time is 13min, and the stirring speed is 300 r/min; adding a nitrate solution into a sodium hydroxide solution, uniformly mixing to obtain a reaction solution, controlling the pH =10.3 of the reaction solution, placing the reaction solution in a microwave digestion instrument for coprecipitation reaction, wherein the reaction time is 60min, and the reaction temperature is 150 ℃ to obtain a solid-liquid mixture; putting the solid-liquid mixture into a drying oven for drying, putting the dried mixture into a muffle furnace for annealing at 280 ℃ for 2h, and cooling at the heating rate of 4 ℃/min to obtain a nickel-cobalt-manganese ternary precursor;
weighing 0.202g of nickel-cobalt-manganese ternary precursor and 0.262g of lithium carbonate, and carrying out high-speed ball milling and mixing for 3h, wherein the rotating speed of the ball milling is 550r/min, and the ball milling time is 1 h; and (3) sintering the powder obtained by ball milling in a rapid heating and cooling furnace at 780 ℃ for 9h with the heating rate of 3 ℃/min, then preserving heat for 8h, and naturally cooling along with the furnace to obtain the nickel cobalt lithium manganate ternary material.
Claims (10)
1. The preparation method of the nickel-cobalt-manganese ternary precursor is characterized by comprising the following steps of:
1) preparing a sodium hydroxide solution and a nickel-cobalt-manganese soluble salt aqueous solution with certain concentration;
2) adding the nickel-cobalt-manganese soluble salt aqueous solution into a sodium hydroxide solution, uniformly mixing to obtain a reaction solution, and controlling the pH value of the reaction solution to be 10-10.5;
3) putting the reaction solution into a microwave digestion instrument for coprecipitation reaction to obtain a solid-liquid mixture;
4) and drying the solid-liquid mixture to obtain a nickel-cobalt-manganese hydroxide, placing the nickel-cobalt-manganese hydroxide in a muffle furnace for annealing, and cooling to obtain the target nickel-cobalt-manganese ternary precursor.
2. The method for preparing the ternary nickel-cobalt-manganese precursor according to claim 1, wherein in the step 1, the concentration of the sodium hydroxide solution is 0.15-0.25 mol/L.
3. The method for preparing the nickel-cobalt-manganese ternary precursor according to claim 1, wherein the total concentration of nickel, cobalt and manganese ions in the nickel-cobalt-manganese soluble salt aqueous solution is 0.08-0.12 mol/L; the nickel-cobalt-manganese soluble salt aqueous solution is a mixed solution of cobalt nitrate, manganese nitrate and nickel nitrate; the molar ratio of the nickel nitrate to the cobalt nitrate to the manganese nitrate is 5-6:2-3: 2-3.
4. The method for preparing the nickel-cobalt-manganese ternary precursor according to claim 1, wherein in the step 3, the coprecipitation reaction time is 30-60min, and the reaction temperature is 120-180 ℃.
5. The method for preparing the nickel-cobalt-manganese ternary precursor according to claim 1, wherein in the step 4, the solid-liquid mixture is dried in a drying oven, the drying temperature is 60-80 ℃, and the drying time is 10-12 hours.
6. The method for preparing the nickel-cobalt-manganese ternary precursor according to claim 1, wherein in the step 4, the nickel-cobalt-manganese hydroxide is calcined in air in a muffle furnace, the calcination temperature is 250-300 ℃, the heating rate is 3-5 ℃/min, and the holding time is 1-3 h.
7. The nickel-cobalt-manganese ternary precursor prepared by the preparation method of any one of claims 1 to 6, wherein the nickel-cobalt-manganese ternary precursor is highly agglomerated spherical particles with an average particle diameter of 10 to 50 μm and a specific surface area of 10 to 20m2/g。
8. A preparation method of a nickel cobalt manganese acid lithium ternary material is characterized in that the nickel cobalt manganese acid ternary precursor of claim 7 and lithium carbonate are mixed in a proportion of 1-1.05: and (2) placing the mixture in a ball milling tank according to the molar ratio of 1-1.1, carrying out high-speed ball milling to obtain a mixed material, placing the mixed material in a muffle furnace for high-temperature oxygen sintering, and naturally cooling to room temperature along with the furnace to obtain the nickel cobalt lithium manganate ternary material.
9. The method for preparing the nickel cobalt lithium manganate ternary material of claim 8, characterized in that; the rotation speed of the ball milling is 350-550 r/min, and the ball milling time is 1-3 h; the temperature of the high-temperature oxygen sintering is 680-880 ℃, the heating rate is 3-5 ℃/min, the sintering is carried out for 3-9 h, then the temperature is kept for 6-8 h, and then the furnace is cooled naturally.
10. The use of the nickel cobalt lithium manganate ternary material of claim 8 in the preparation of lithium ion battery positive electrode material.
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