CN108832121B - High-nickel positive electrode material and preparation method thereof - Google Patents
High-nickel positive electrode material and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910013716 LiNi Inorganic materials 0.000 claims abstract 2
- 238000005245 sintering Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 238000007873 sieving Methods 0.000 claims description 16
- 239000010406 cathode material Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 150000001844 chromium Chemical class 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 150000002751 molybdenum Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical group [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical group [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000005056 compaction Methods 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- HMPRYWSTSPTPFI-UHFFFAOYSA-N [Li].[F] Chemical compound [Li].[F] HMPRYWSTSPTPFI-UHFFFAOYSA-N 0.000 description 3
- -1 molybdenum ions Chemical class 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 description 1
- GJCNZQUZWSHFHP-UHFFFAOYSA-N [Li].O=S=O Chemical compound [Li].O=S=O GJCNZQUZWSHFHP-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/50—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a high-nickel anode material and a preparation method thereof, wherein the anode material is made of LiNi with a general formula0.25aCr2‑0.75aX1‑ 0.5aMo0.4aMn1.5‑0.2aO4The X element is at least one of Ti, Ba, Al, Mn and Ge, wherein 0<a<2. The positive electrode material has high wear resistance and high temperature resistance, and the surface of the positive electrode material is provided with particles matched with large and small particles, so that the compaction density of the material is improved.
Description
Technical Field
The invention belongs to the technical field of lithium battery equipment, and particularly relates to a high-nickel positive electrode material and a preparation method thereof.
Background
Along with the development of social economy, people have higher and higher requirements on the performance of mobile power supplies, and the matching power supplies of various portable electronic products develop towards high specific energy, high power, long storage life and high safety. Lithium primary batteries are widely used in various civil and military fields such as sensors, cameras, cardiac pacemakers, and airplanes because of their excellent performance. Currently, common lithium primary batteries include lithium manganese dioxide batteries, lithium thionyl chloride batteries, lithium sulfur dioxide batteries, lithium fluorine batteries, lithium iron batteries, and the like. Among them, the lithium manganese dioxide battery is most widely used, and has the advantages of high discharge voltage, smooth discharge, low cost of active materials, and the like, but the specific energy is lower; the carbon fluoride is the highest theoretical specific energy in the positive electrode material of the lithium primary battery, the practical specific energy of the lithium fluorine battery can reach 250-800 Wh/kg, but the practicability of the lithium fluorine battery is limited due to the high cost of the carbon fluoride material, the low-temperature performance of the battery and the non-ideal high-current working performance of the battery.
The main constituent materials of the lithium ion battery include electrolyte, isolating material, anode and cathode materials and the like. The positive electrode material occupies a large proportion (the mass ratio of the positive electrode material to the negative electrode material is 3:1-4:1), because the performance of the positive electrode material directly influences the performance of the lithium ion battery, the cost directly determines the cost of the battery. However, the particle size of the surface of the anode material of the existing lithium battery is consistent and loose, and the anode material is easy to absorb water; the high temperature resistance and the wear resistance are poor.
Disclosure of Invention
The invention aims to solve the problems and provide a high-nickel cathode material and a preparation method thereof, wherein the high-nickel cathode material has high wear resistance and high temperature resistance, and particles matched with large and small particles are arranged on the surface of the cathode material, so that the compaction density of the material is improved.
The invention realizes the purpose through the following technical scheme:
a high-nickel anode material is prepared from LiNi0.25aCr2-0.75aX1-0.5aMo0.4aMn1.5-0.2aO4The X element is at least one of Ti, Ba, Al, Mn and Ge, and the content is 0<a<2。
A preparation method of a high-nickel cathode material comprises the following steps:
a) preparing a precursor, namely mixing a nickel salt solution, a cobalt salt solution and a manganese salt solution, wherein the sum of the concentrations of three ions of nickel, cobalt and manganese in the mixed solution is 0.5-2.0 mol/L, adding a chromium salt solution and a molybdenum salt solution into the mixed solution, wherein the concentrations of chromium and molybdenum ions are 0.01-0.02 mol/L, adding a complexing agent solution, a precipitator solution and the mixed solution into a reaction kettle in a concurrent flow manner, heating and stirring for precipitation reaction, starting solid-liquid separation on overflowed slurry after full reaction, and washing and drying the separated solid product;
b) calcining the synthesized precursor for the first time, introducing non-reducing gas, cooling, crushing, calcining for the second time, simultaneously introducing non-reducing gas, cooling and grinding;
c) and (3) mixing the ground mixture and a lithium salt according to the molar ratio of the metal cations to the Li ions of 1: 1.3-1.5, uniformly mixing, sintering, introducing non-reducing gas in the sintering process, cooling along with a furnace after sintering, and then crushing and sieving.
d) Adding the substances obtained in the step, a detergent solution and a coating solution into a mixer for mixing for 0.3-1.5h, performing suction filtration on a solid-liquid mixture after mixing, drying, sieving and mixing;
e) and sintering the product obtained after sieving and mixing in the steps at the sintering temperature of 500-900 ℃ for 6-20 h, cooling the product along with the furnace after sintering is finished, and sieving the product to obtain the lithium-rich high-nickel cathode material.
As a further optimized technical scheme of the invention, the chromium salt in the step a is chromium sulfate; the molybdenum salt is molybdenum nitrate.
As a further optimized technical scheme of the invention, the temperature of the first calcination in the step b is 200-280 ℃, the calcination time is 2-3 h, the temperature of the second calcination is 500-700 ℃, and the calcination time is 3-5 h.
As a further optimized technical scheme of the invention, the sintering temperature in the step c is 700-900 ℃, and the sintering time is 9-24 h.
As a further optimized technical scheme of the invention, the detergent solution in the step d is at least one of deionized water, ethanol or a mixed solution thereof, the coating agent contains at least one of Ti, Ba, Al, Mn and Ge, and the content of the coating agent is 0.02-0.04%.
The invention has the beneficial effects that:
1) the wear resistance and the high temperature resistance of the anode material are improved by adding the chromium salt solution and the molybdenum salt solution under the condition of preparing the precursor;
2) according to the invention, the precursor is subjected to twice calcination treatments, and is crushed after the first calcination treatment, so that the moisture of the precursor is removed more thoroughly, and the particles are finer and are convenient for the next reaction by grinding after the second calcination treatment;
3) according to the invention, the high nickel ion product is treated by the coating agent, so that particles matched with large and small particles are arranged on the surface of the anode material, and the compaction density of the material is improved.
Drawings
FIG. 1 is an SEM image of a product of example one of the present invention.
Detailed Description
The present application will now be described in further detail with reference to the drawings, it should be noted that the following detailed description is given for illustrative purposes only and is not to be construed as limiting the scope of the present application, as those skilled in the art will be able to make numerous insubstantial modifications and adaptations to the present application based on the above disclosure.
Example 1
a) Preparing a nickel-cobalt-manganese precursor: uniformly mixing a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution which are used as raw materials, wherein the concentration of metal ions in the mixed solution is 1.0mol/L, adding a chromium sulfate solution and a molybdenum nitrate solution into the mixed solution, wherein the concentration of chromium ions and molybdenum ions is 0.01mol/L, adding a complexing agent solution, a NaOH precipitator solution and the mixed solution into a reaction kettle filled with a base solution in a concurrent flow manner, heating and stirring for precipitation reaction, starting solid-liquid separation on overflowed slurry after full reaction, and washing and drying the separated solid product to obtain a spherical nickel-cobalt-manganese precursor;
b) calcining the precursor of the lithium-rich high-nickel cathode material obtained in the step for the first time at the temperature of 200 ℃ for 3 hours, introducing non-reducing gas, cooling, crushing, calcining for the second time at the temperature of 500 ℃ for 5 hours, introducing non-reducing gas, cooling, and grinding;
c) and (3) mixing the mixture sieved in the step with a lithium salt according to the molar ratio of metal cations to Li ions of 1: 1.3, uniformly mixing, sintering at 750 ℃ for 24 hours, continuously introducing air into the furnace during the sintering, cooling along with the furnace after the sintering is finished, crushing and sieving to obtain an intermediate product of the lithium-rich high-nickel cathode material;
d) adding the product obtained in the step, deionized water and a barium nitrate coating agent solution into a high-speed mixer, mixing for 1.5h, performing suction filtration and drying on a solid-liquid mixture after mixing, and sieving;
e) and sintering the product obtained after sieving and mixing in the steps at the sintering temperature of 500 ℃ for 20 hours, cooling the product in a furnace after sintering, and sieving the product to obtain the lithium-rich high-nickel cathode material.
Through inspection, the tap density of the lithium-rich high-nickel cathode material prepared by the method of the embodiment is 2.56g/cm3Has higher wear resistance and high temperature resistance,the SEM spectrum of the product is shown in figure 1.
Example 2
a) Preparing a nickel-cobalt-manganese precursor: uniformly mixing a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution which are used as raw materials, wherein the concentration of metal ions in the mixed solution is 2.0mol/L, adding a chromium sulfate solution and a molybdenum nitrate solution into the mixed solution, wherein the concentration of chromium ions and molybdenum ions is 0.02mol/L, adding a complexing agent solution, a NaOH precipitator solution and the mixed solution into a reaction kettle filled with a base solution in a concurrent flow manner, heating and stirring for precipitation reaction, starting solid-liquid separation on overflowed slurry after full reaction, and washing and drying the separated solid product to obtain a spherical nickel-cobalt-manganese precursor;
b) calcining the precursor of the lithium-rich high-nickel cathode material obtained in the step for the first time at 280 ℃ for 2h, introducing non-reducing gas, cooling, crushing, calcining for the second time at 3h and 700 ℃, introducing non-reducing gas, cooling, and grinding;
c) and (3) mixing the mixture sieved in the step with a lithium salt according to the molar ratio of metal cations to Li ions of 1: 1.5, uniformly mixing, sintering at 900 ℃ for 9h, continuously introducing air into the furnace during the sintering, cooling along with the furnace after the sintering is finished, crushing and sieving to obtain an intermediate product of the lithium-rich high-nickel cathode material;
d) adding the product obtained in the step, deionized water and a chromium nitrate coating agent solution into a high-speed mixer, mixing for 0.3h, filtering, drying and sieving a solid-liquid mixture after mixing;
e) and sintering the product obtained after sieving and mixing in the steps at the sintering temperature of 900 ℃ for 10 hours, cooling the product in a furnace after sintering, and sieving the product to obtain the lithium-rich high-nickel cathode material.
Through inspection, the tap density of the lithium-rich high-nickel cathode material prepared by the method of the embodiment is 2.62g/cm3Has high wear resistance and high temperature resistance.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (4)
1. A preparation method of a high-nickel anode material is characterized in that the anode material is made of LiNi with a general formula0.25aCr2- 0.75aX1-0.5aMo0.4aMn1.5-0.2aO4The X element is at least one of Ti, Ba, Al, Mn and Ge, wherein 0<a<2；
The preparation method comprises the following steps:
a) preparing a precursor, namely mixing a nickel salt solution, a cobalt salt solution and a manganese salt solution, wherein the sum of the concentrations of three ions of nickel, cobalt and manganese in the mixed solution is 0.5-2.0 mol/L, adding a chromium salt solution and a molybdenum salt solution into the mixed solution to prepare a mixed solution, wherein the concentration of the ions of chromium and molybdenum is 0.01-0.02 mol/L, adding a complexing agent solution, a precipitator solution and the mixed solution into a reaction kettle in a concurrent flow manner, heating and stirring for precipitation reaction, carrying out solid-liquid separation on overflowed slurry after full reaction, and washing and drying the separated solid product;
b) calcining the synthesized precursor for the first time, introducing non-reducing gas, cooling, crushing, calcining for the second time after crushing, introducing non-reducing gas, cooling, and grinding, wherein the temperature of the first calcining is 200-280 ℃, the calcining time is 2-3 h, the temperature of the second calcining is 500-700 ℃, and the calcining time is 3-5 h;
c) and (3) mixing the ground mixture and a lithium salt according to the molar ratio of the metal cations to the Li ions of 1: 1.3-1.5, uniformly mixing, sintering, introducing non-reducing gas in the sintering process, cooling along with a furnace after sintering, and then crushing and sieving;
d) c, adding the substance obtained in the step c, a detergent solution and a coating solution into a mixer for mixing for 0.3-1.5h, performing suction filtration on a solid-liquid mixture after mixing, drying, sieving and mixing;
e) and d, sintering the product obtained after sieving and mixing in the step d at the sintering temperature of 500-900 ℃ for 6-20 h, cooling the product along with the furnace after sintering is finished, and sieving the product to obtain the required cathode material.
2. The method for preparing a high nickel positive electrode material according to claim 1, wherein: in the step a, the chromium salt is chromium sulfate; the molybdenum salt is molybdenum nitrate.
3. The method for preparing a high nickel positive electrode material according to claim 1, wherein: the sintering temperature in the step c is 700-900 ℃, and the sintering time is 9-24 h.
4. The method for preparing a high nickel positive electrode material according to claim 1, wherein: the detergent solution is at least one of deionized water, ethanol or a mixed solution thereof, the coating solution contains at least one of Ti, Ba, Al, Mn and Ge, and the content of the coating solution is 0.02-0.04%.
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| CN201810565874.XA CN108832121B (en) | 2018-06-04 | 2018-06-04 | High-nickel positive electrode material and preparation method thereof |
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| CN201810565874.XA CN108832121B (en) | 2018-06-04 | 2018-06-04 | High-nickel positive electrode material and preparation method thereof |
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| Publication Number | Publication Date |
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| CN108832121A CN108832121A (en) | 2018-11-16 |
| CN108832121B true CN108832121B (en) | 2020-12-04 |
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