CN112174224A - Preparation method of in-situ doped high-nickel cathode material - Google Patents
Preparation method of in-situ doped high-nickel cathode material Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 82
- 239000010406 cathode material Substances 0.000 title claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- 239000010941 cobalt Chemical class 0.000 claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000002019 doping agent Substances 0.000 claims abstract description 18
- 238000007873 sieving Methods 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [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 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 30
- 239000011572 manganese Substances 0.000 claims description 27
- 238000004321 preservation Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- -1 manganese cations Chemical class 0.000 claims description 10
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910006504 ZrSO4 Inorganic materials 0.000 claims description 2
- 229910052925 anhydrite Inorganic materials 0.000 claims description 2
- 229910052923 celestite Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 25
- 239000010405 anode material Substances 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
- 238000005056 compaction Methods 0.000 abstract description 4
- 239000011164 primary particle Substances 0.000 abstract description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 18
- 229940099596 manganese sulfate Drugs 0.000 description 18
- 239000011702 manganese sulphate Substances 0.000 description 18
- 235000007079 manganese sulphate Nutrition 0.000 description 18
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 18
- 239000000243 solution Substances 0.000 description 14
- 229940073644 nickel Drugs 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 9
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 8
- 229940053662 nickel sulfate Drugs 0.000 description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 8
- 230000032683 aging Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
- 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
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- 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
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- 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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Abstract
The invention relates to a preparation method of an in-situ doped high-nickel anode material, which comprises the following steps: (1) preparing spherical NCM ternary precursor from soluble salts of nickel, cobalt and manganese, a doping agent A and ammonia water with a certain concentration according to a certain proportion; (2) uniformly mixing the precursor and a lithium source, sintering at 800-950 ℃ for the first time, and then carrying out jaw crushing, roller pair crushing and sieving to obtain a single crystal high nickel material; (3) and (3) carrying out dry coating on the primary sintering material and a certain amount of coating agent B, then carrying out secondary sintering under the condition of oxygen enrichment, wherein the sintering temperature is 550-750 ℃, and crushing and sieving to obtain the high-nickel single crystal NCM ternary cathode material. The method adopts the precursor in-situ doping, can promote the rapid growth of primary particles in the sintering process, obtain large-size single crystals, improve the compaction density of the material, and have excellent high-temperature cycle performance in the electrochemical process.
Description
Technical Field
The invention relates to the technical field of lithium ion power batteries for new energy automobiles, in particular to a preparation method of an in-situ doped high-nickel anode material.
Background
High capacity, high voltage, long cycle and low cost are the development trend of the ternary lithium ion power battery at present, and although the preparation technology of the system products such as the NCM111, the NCM424, the NCM523, the NCM622 and the like is mature, the product capacity and the production cost are difficult to form competitiveness in the high-end technical field. The trend of the current ternary lithium ion battery is to reduce the cobalt content and improve the nickel content.
The high-nickel ternary positive electrode material has some inevitable defects, poor high-temperature cycle performance, low electronic conductivity and reduced multiplying power caused by Li/Ni mixed discharge, and measures such as doping, surface coating and the like are generally adopted to improve the electrochemical performance of the material. In actual production, dry mixing doping of a precursor and a dopant is generally adopted, and uniform mixing is difficult to achieve to a certain extent by the method. Precursor in-situ doping is a hotspot of current research, and the method can uniformly dope the dopant in the precursor in the preparation process of the precursor.
At present, the NCM ternary lithium ion battery anode material is mainly in single crystal and secondary sphere particle forms, the NCM anode material in the secondary sphere particle form is low in compaction density and poor in high-temperature cycle performance, the phenomena of secondary sphere particle breakage and structure collapse are easy to occur in the charging and discharging processes, the side reaction inside the battery is aggravated, and the battery performance is poor.
Aiming at the problems of the high-nickel ternary material, the invention develops the in-situ doped high-nickel single crystal anode material which has the advantages of stable structure, high compaction density, good cycle performance, low surface free lithium content and the like, so that the product has stronger competitive advantage in the market.
Disclosure of Invention
The invention has the core of market competition of the ternary lithium ion battery anode material at present, high capacity, long cycle and low cost, reduces the sintering temperature by doping the precursor A, thereby reducing the cost, improving the material capacity by low-temperature sintering, and the dopant A is beneficial to improving the cycle performance of the material, Ni0.83Co0.07Mn0.1O2The secondary sintering coating additive B is a high-capacity single crystal anode material and has good cycle performance, and the cycle performance of the material can be obviously improved by the secondary sintering coating additive B.
Based on the prior art, the invention aims to provide a preparation method of an in-situ doped high-nickel cathode material, which is a cathode material with high capacity, long cycle, high safety and low cost,
in order to achieve the above purpose, the invention adopts the technical scheme that:
a preparation method of an in-situ doped high-nickel cathode material comprises the following steps:
(1) mixing soluble salts of nickel, cobalt and manganese, a dopant A and ammonia water for coprecipitation reaction to prepare a spherical NCM ternary precursor;
(2) uniformly mixing the high-nickel precursor and lithium hydroxide by using a single-shaft coulter mixer, performing primary sintering on the mixed powder, and then performing jaw crushing, roller pair crushing and sieving to obtain a primary sintered material;
(3) and (3) carrying out dry coating on the primary sintering material and the coating agent B, then carrying out secondary sintering under the oxygen-enriched condition, and crushing and sieving after sintering to obtain the high-nickel NCM ternary cathode material.
In order to better realize the method, further, the total concentration of nickel ions, cobalt ions and manganese ions in the step (1) is 0.4-2.5 mol/L; ammonia water concentration: 0.1-0.5 mol/L; the dopant A is ZrSO4、SrSO4、MgSO4、CaSO4At least one of; wherein the dosage of the dopant is as follows: dopant metal cation: the molar ratio of the nickel, cobalt and manganese cations is 1 (100-1000).
In order to better realize the invention, further, in the step (1), the soluble salt solution of nickel, cobalt and manganese is proportioned according to the molar ratio of metal cations of 0.83:0.07: 0.1; the NCM ternary precursor is Ni0.83Co0.07Mn0.1(OH)2The average particle diameter D50 of the ternary precursor is as follows: 4 +/-1 mu m; the specific surface area BET is 7 to 15m2(ii)/g; bulk density>1.0g/cm3Tap density>1.8g/cm3。
In order to better implement the invention, further, the amount of lithium hydroxide in the step (2) is Li: me (Me ═ Ni + Co + Mn) molar ratio: 1: (1.01-1.10).
In order to better implement the invention, further, the mixing time in the step (2): 2-5 h; mixing frequency: 20-100 Hz; the distance between the double-roll crack of the jaw crusher is 0.2-0.8 mm; the induced air frequency is 10-50 Hz; the grading frequency is 50-200 Hz.
In order to better implement the invention, further, the conditions of the primary sintering in the step (2) are as follows: the temperature is 800-950 ℃, the heating rate is 1-8 ℃/min, the heat preservation time is 8-20 h, and the volume concentration of the oxygen atmosphere is 20-99.9%.
In order to better realize the invention, further, in the step (3), the coating agent B is a metal oxide or a metal hydroxide, and the metal is at least one of Al, Mg, Ti, Sr, Zr; the dosage of the coating agent B is as follows: weight of metal cation in the coating agent B: the primary sintering material is (500-3000) ppm: 1.
In order to better implement the invention, further, the secondary sintering conditions in the step (3) are as follows: the temperature is 550-750 ℃, the heating rate is 1-8 ℃/min, the heat preservation time is 5-10 h, and the volume concentration of the oxygen atmosphere is 20-99.9%.
The high-nickel single crystal NCM ternary cathode material obtained by the invention has the characteristics that the average grain diameter D50: 4-6 μm; specific surface area BET: 0.5 to 1.0m2Per g, free lithium<1500ppm。
Advantageous effects
The invention has the advantages and beneficial effects that:
(1) the doped A in the precursor is beneficial to promoting the growth of primary particles in the process of primary sintering, the doped A is 0.2-0.8 mu m larger than the primary sintering material single crystal particles without the doped A under the same condition, and the relative sintering temperature of the doped A in the precursor is 10-20 ℃ lower than that of the doped A in the same average particle size, so that the production cost is greatly reduced, and the material capacity is effectively improved.
(2) The prepared high-nickel single crystal material has the advantages of clean and smooth surface, higher compaction density, high mechanical strength and good cycle performance.
(3) The coating agent B uniformly coats the surface of the material, so that the side reaction between the material and the electrolyte is reduced, the problems of side reaction gas generation and the like are effectively solved, and the cycle performance of the material is greatly improved.
Drawings
FIG. 1 is an SEM image of a sintered sample of a high-nickel single-crystal positive electrode material in example 1 of the present invention;
FIG. 2 is an XRD diffraction pattern of the high nickel single crystal anode material in example 1 of the present invention;
FIG. 3 is one of the charateristic cycle diagrams of the high nickel single crystal positive electrode material in example 1 of the present invention;
FIG. 4 is a second schematic diagram of the charging cycle of the high nickel single crystal positive electrode material in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The embodiment provides a preparation method of an in-situ doped high-nickel cathode material, which comprises the following steps:
preparing nickel sulfate, cobalt sulfate and manganese sulfate according to the metal cation molar ratio of 0.83:0.07:0.1Forming a nickel, cobalt and manganese sulfate solution with the total concentration of nickel, cobalt and manganese cations being 2mol/L, and mixing a zirconium sulfate dopant with the concentration of nickel, cobalt and manganese sulfate solution and zirconium ions being 0.0042mol/L and ammonia water with the concentration of 0.2mol/L according to the volume ratio of 1: 1: 1, performing complex coprecipitation, and aging, centrifuging and drying to obtain the product with the average particle size of D50: 4.08 μm, specific surface area BET: 9.3m2(g), apparent density 1.2g/cm3Tap density: 1.8g/cm3Ni of (2)0.83Co0.07Mn0.1(OH)2High nickel precursor of (2).
And (3) mixing the high-nickel precursor and lithium hydroxide by a single-shaft coulter mixer according to the proportion of Li: me (Me ═ Ni + Co + Mn) molar ratio: 1: 1.05, mix for 2 hours, compounding frequency 100Hz, after the misce bene, carry out the sintering once with mixed powder under 45% oxygen atmosphere, sintering temperature is 860 ℃, the rate of rise: 2 ℃/min and the heat preservation time is 12 h. And (3) carrying out jaw crushing and roll pair on the sintered sample, wherein the gap between the cracks is 0.2mm, and then crushing and sieving to obtain a primary sintered material.
And (3) placing the primary sintering material in a single-shaft coulter mixer, and uniformly mixing the primary sintering material with a coating agent magnesium hydroxide for 3 hours in a dry method, wherein the content of the coating agent is the weight of magnesium ions: the primary sinter was 1500ppm: 1. Then, secondary sintering is carried out in an oxygen atmosphere of 45%, the sintering temperature is 650 ℃, and the heating rate is as follows: 2 ℃/min, the heat preservation time is 9h, and the high-nickel single crystal NCM ternary positive electrode material with the surface covered with a layer of magnesium oxide is obtained after crushing and sieving, the average grain diameter D50 is 5.03 mu m, and the specific surface area BET: 0.6m2(ii) in terms of/g. 1450ppm free lithium.
Example 2
The embodiment provides a preparation method of an in-situ doped high-nickel cathode material, which comprises the following steps:
preparing nickel sulfate, cobalt sulfate and manganese sulfate into nickel, cobalt and manganese sulfate solution with the total concentration of nickel, cobalt and manganese cations being 2mol/L according to the metal cation molar ratio of 0.83:0.07:0.1, mixing the nickel, cobalt and manganese sulfate solution, magnesium sulfate dopant with the concentration of 0.0042mol/L and ammonia water with the concentration of 0.2mol/L according to the volume ratio of 1: 1: 1, carrying out complex coprecipitation, aging, centrifuging and drying to obtain average particlesDiameter D50: 4.10 μm, specific surface area BET: 8.9m2(g), apparent density 1.1g/cm3Tap density: 1.8g/cm3Ni of (2)0.83Co0.07Mn0.1(OH)2High nickel precursor of (2).
And (3) mixing the high-nickel precursor and lithium hydroxide by a single-shaft coulter mixer according to the proportion of Li: me (Me ═ Ni + Co + Mn) molar ratio: 1: 1.05, mix for 3 hours, compounding frequency 80Hz, after the misce bene, carry out the sintering once with mixed powder under 65% oxygen atmosphere, sintering temperature is 860 ℃, the rate of rise: 2 ℃/min and the heat preservation time is 12 h. And carrying out jaw crushing on the sintered sample, wherein the gap between the cracks is 0.3mm, and then crushing and sieving to obtain a primary sintered material.
And (3) placing the primary sintering material in a single-shaft coulter mixer, and uniformly mixing the primary sintering material with a coating agent magnesium hydroxide for 3 hours in a dry method, wherein the content of the coating agent is the weight of magnesium ions: 1: 1500ppm of calcined material. Then, secondary sintering is carried out in 65% oxygen atmosphere, the sintering temperature is 650 ℃, and the heating rate is as follows: 2 ℃/min, and the heat preservation time is 9 h. And obtaining the high-nickel single crystal NCM ternary cathode material after crushing and sieving, wherein the average particle size D50 is 4.46 mu m, and the specific surface area BET: 0.9m2G, 1400ppm of free lithium. .
Example 3
The embodiment provides a preparation method of an in-situ doped high-nickel cathode material, which comprises the following steps:
preparing nickel sulfate, cobalt sulfate and manganese sulfate into nickel, cobalt and manganese sulfate solution with the total concentration of nickel, cobalt and manganese cations being 2mol/L according to the metal cation molar ratio of 0.83:0.07:0.1, mixing nickel, cobalt and manganese sulfate solution, strontium sulfate dopant with the concentration of 0.0063mol/L and ammonia water with the concentration of 0.2mol/L according to the volume ratio of 1: 1: 1, performing complex coprecipitation, and aging, centrifuging and drying to obtain the product with the average particle size of D50: 4.11 μm, specific surface area BET: 8.7m2(g), apparent density 1.1g/cm3Tap density: 1.8g/cm3Ni of (2)0.83Co0.07Mn0.1(OH)2High nickel precursor of (2).
And (3) mixing the high-nickel precursor and lithium hydroxide by a single-shaft coulter mixer according to the proportion of Li: me (Me ═ Ni + Co + Mn) molar ratio: 1: 1.05, mixing for 4 hours, mixing at a mixing frequency of 70Hz, uniformly mixing, sintering the mixed powder at 860 ℃ in a 75% oxygen atmosphere, and increasing the temperature rate: 2 ℃/min and the heat preservation time is 12 h. And carrying out jaw crushing on the sintered sample, wherein the gap between the cracks is 0.5mm, and then crushing and sieving to obtain a primary sintered material.
And (3) placing the primary sintering material in a single-shaft coulter mixer, and uniformly mixing the primary sintering material with a coating agent magnesium hydroxide for 3 hours in a dry method, wherein the content of the coating agent is the weight of magnesium ions: 1: 1500ppm of calcined material. Then, secondary sintering is carried out in an oxygen atmosphere of 75%, the sintering temperature is 650 ℃, and the heating rate is as follows: 2 ℃/min, and the heat preservation time is 9 h. And obtaining the high-nickel single crystal NCM ternary cathode material after crushing and sieving, wherein the average particle size D50 is 5.06 mu m, and the specific surface area BET: 0.6m2/g, 1430ppm free lithium. .
Example 4
Preparing nickel sulfate, cobalt sulfate and manganese sulfate into nickel, cobalt and manganese sulfate solution with the total concentration of nickel, cobalt and manganese cations being 2mol/L according to the molar ratio of metal cations being 0.83:0.07:0.1, mixing the nickel, cobalt and manganese sulfate solution, calcium sulfate dopant with the concentration of 0.0036mol/L and ammonia water with the concentration of 0.2mol/L according to the volume ratio of 1: 1: 1, performing complex coprecipitation, and aging, centrifuging and drying to obtain the product with the average particle size of D50: 4.13 μm, specific surface area BET: 8.4m2(g) apparent density of 1.0g/cm3Tap density: 1.8g/cm3Ni of (2)0.83Co0.07Mn0.1(OH)2High nickel precursor of (2).
And (3) mixing the high-nickel precursor and lithium hydroxide by a single-shaft coulter mixer according to the proportion of Li: me (Me ═ Ni + Co + Mn) molar ratio: 1: 1.05, mix for 4 hours, compounding frequency 60Hz, after the misce bene, carry out the sintering once with mixed powder under 85% oxygen atmosphere, sintering temperature is 860 ℃, the rate of rise: 2 ℃/min and the heat preservation time is 12 h. And (3) carrying out jaw crushing and roll pair on the sintered sample, wherein the gap between the cracks is 0.6mm, and then crushing and sieving to obtain a primary sintered material.
Placing the primary sintering material in a single-shaft coulter mixer to mix with the coating agentAnd (3) uniformly mixing the magnesium hydroxide for 3 hours by a dry method, wherein the content of the coating agent is as follows: the primary sinter was 1500ppm: 1. Then, secondary sintering is carried out in an atmosphere of 85% oxygen, the sintering temperature is 650 ℃, and the heating rate is as follows: 2 ℃/min, the heat preservation time is 9h, and the high-nickel single crystal NCM ternary positive electrode material with the surface covered with a layer of magnesium oxide is obtained after crushing and sieving, the average grain diameter D50 is 5.01 mu m, and the specific surface area BET: 0.6m2/g, free lithium 1450 ppm. .
Example 5
The embodiment provides a preparation method of an in-situ doped high-nickel cathode material, which comprises the following steps:
taking nickel sulfate, cobalt sulfate and manganese sulfate according to a metal cation molar ratio of 0.83:0.07:0.1 to prepare a nickel, cobalt and manganese sulfate solution with the total concentration of nickel, cobalt and manganese cations of 1.8mol/L, and mixing the nickel, cobalt and manganese sulfate solution, a zirconium sulfate dopant with the concentration of 0.0042mol/L and ammonia water with the concentration of 0.2mol/L according to a volume ratio of 1: 1: 1, performing complex coprecipitation, and aging, centrifuging and drying to obtain the product with the average particle size of D50: 4.02 μm, specific surface BET: 9.8m2(g), apparent density 1.3g/cm3Tap density: 1.8g/cm3Ni of (2)0.83Co0.07Mn0.1(OH)2High nickel precursor of (2).
And (3) mixing the high-nickel precursor and lithium hydroxide by a single-shaft coulter mixer according to the proportion of Li: me (Me ═ Ni + Co + Mn) molar ratio: 1: 1.05, mixing for 5h, mixing frequency of 50Hz, uniformly mixing, sintering the mixed powder in an oxygen atmosphere of 95%, wherein the sintering temperature is 860 ℃, and the heating rate is as follows: 2 ℃/min and the heat preservation time is 12 h. And (3) carrying out jaw crushing and roll pair on the sintered sample, wherein the gap between the cracks is 0.7mm, and then crushing and sieving to obtain a primary sintered material.
And (2) carrying out secondary sintering on the primary sintering material in an oxygen atmosphere of 95%, wherein the sintering temperature is 650 ℃, and the heating rate is as follows: 2 ℃/min, the heat preservation time is 9h, and the high-nickel single crystal NCM ternary positive electrode material with the surface covered with a layer of magnesium oxide is obtained after crushing and sieving, the average grain diameter D50 is 4.52 mu m, and the specific surface area BET: 0.8m2,/g, free lithium 1470 ppm. .
Example 6
The embodiment provides a preparation method of an in-situ doped high-nickel cathode material, which comprises the following steps:
preparing nickel sulfate, cobalt sulfate and manganese sulfate solution with the total concentration of nickel, cobalt and manganese cations being 2.2mol/L by taking nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of metal cations being 0.83:0.07:0.1, and mixing the nickel sulfate solution, the cobalt sulfate solution, the manganese sulfate solution, zirconium sulfate doping agent with the concentration of 0.0063mol/L and ammonia water with the concentration of 0.2mol/L according to the volume ratio of 1: 1: 1, performing complex coprecipitation, and aging, centrifuging and drying to obtain the product with the average particle size of D50: 4.07 μm, specific surface area BET: 9.4m2(g), apparent density 1.1g/cm3Tap density: 1.8g/cm3Ni of (2)0.83Co0.07Mn0.1(OH)2High nickel precursor of (2).
And (3) mixing the high-nickel precursor and lithium hydroxide by a single-shaft coulter mixer according to the proportion of Li: me (Me ═ Ni + Co + Mn) molar ratio: 1: 1.05, mixing for 5h, mixing frequency of 30Hz, uniformly mixing, sintering the mixed powder in 65% oxygen atmosphere at 860 ℃ for one time, and increasing the temperature rate: 2 ℃/min and the heat preservation time is 12 h. And (3) carrying out jaw crushing and roll pair on the sintered sample, wherein the gap between the cracks is 0.8mm, and then crushing and sieving to obtain a primary sintered material.
Placing the primary sintering material in a single-shaft coulter mixer to mix with the coating agent AL2O3And (3) uniformly mixing for 3 hours by a dry method, wherein the content of the coating agent is the weight of aluminum ions: the primary sinter was 1500ppm: 1. Then, secondary sintering is carried out in 65% oxygen atmosphere, the sintering temperature is 650 ℃, and the heating rate is as follows: 2 ℃/min, the heat preservation time is 9h, and the high-nickel single crystal NCM ternary positive electrode material with the surface covered with a layer of magnesium oxide is obtained after crushing and sieving, the average grain diameter D50 is 5.10 mu m, and the specific surface area BET: 0.5m2Mg, free lithium 1440 ppm. .
FIG. 1 is an SEM image of a sintered sample of a high-nickel single-crystal positive electrode material in example 1 of the present invention, and it can be observed that the particle compacted density is high and the structure is compact; FIG. 2 is an XRD diffraction pattern of the high nickel single crystal anode material in example 1, and it can be seen that the structure of the high nickel single crystal anode material tends to a hexagonal crystal form, and the mechanical strength is high; fig. 3 and 4 are charateristics of the charging cycle of the high nickel single crystal anode material in example 1 of the present invention, which show that the cycle performance of the material is good.
The high nickel single crystal anode materials obtained by different methods are subjected to electricity deduction assembly and test, and the operation is as follows: and drying the anode material at 120 ℃ for 12h, uniformly mixing the anode material with the conductive agent and the adhesive for 4h, and defoaming on a defoaming machine. And uniformly coating the prepared slurry on an aluminum foil, drying, tabletting, cutting into pole pieces, and assembling the pole pieces, the foam nickel, the lithium piece, the diaphragm, the filter paper, the electrolyte and the like in a glove box in inert atmosphere to form the buckle. And carrying out capacity test (3.0-4.3V, 0.1C/0.1C) and cycle test (3.0-4.5V, 1C/1C) on the assembled withholding power.
And (3) testing results:
| sample (I) | First discharge capacity mAh/g | Capacity retention at 50 weeks |
| Example 1 | 205.4 | 98.7％ |
| Example 2 | 196.7 | 93.2％ |
| Example 3 | 201.3 | 97.6％ |
| Example 4 | 202.9 | 98.3％ |
| Example 5 | 178.2 | 89.3％ |
| Example 6 | 205.2 | 97.5％ |
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the in-situ doped high-nickel cathode material is characterized by comprising the following steps of:
(1) mixing soluble salts of nickel, cobalt and manganese, a dopant A and ammonia water for coprecipitation reaction to prepare a spherical NCM ternary precursor;
(2) uniformly mixing the high-nickel precursor and lithium hydroxide by using a single-shaft coulter mixer, performing primary sintering on the mixed powder, and then performing jaw crushing, roller pair crushing and sieving to obtain a primary sintered material;
(3) and (3) carrying out dry coating on the primary sintering material and the coating agent B, then carrying out secondary sintering under the oxygen-enriched condition, and crushing and sieving after sintering to obtain the high-nickel NCM ternary cathode material.
2. According to claim 1The preparation method of the in-situ doped high-nickel cathode material is characterized in that the total concentration of nickel ions, cobalt ions and manganese ions in the step (1) is 0.4-2.5 mol/L; ammonia water concentration: 0.1-0.5 mol/L; the dopant A is ZrSO4、SrSO4、MgSO4、CaSO4At least one of; wherein the dosage of the dopant is as follows: dopant metal cation: the molar ratio of the nickel, cobalt and manganese cations is 1 (100-1000).
3. The method for preparing the in-situ doped high-nickel cathode material according to claim 1, wherein in the step (1), soluble salt solutions of nickel, cobalt and manganese are mixed according to a metal cation molar ratio of 0.83:0.07: 0.1; the NCM ternary precursor is Ni0.83Co0.07Mn0.1(OH)2The average particle diameter D50 of the ternary precursor is as follows: 4 +/-1 mu m; the specific surface area BET is 7 to 15m2(ii)/g; bulk density>1.0g/cm3Tap density>1.8g/cm3。
4. The method for preparing an in-situ doped high-nickel cathode material as claimed in claim 1, wherein the amount of lithium hydroxide in the step (2) is Li: me (Me ═ Ni + Co + Mn) molar ratio: 1: (1.01-1.10).
5. The method for preparing an in-situ doped high-nickel cathode material as claimed in claim 1, wherein the mixing time in the step (2): 2-5 h; mixing frequency: 20-100 Hz; the distance between the double-roll crack of the jaw crusher is 0.2-0.8 mm; the induced air frequency is 10-50 Hz; the grading frequency is 50-200 Hz.
6. The method for preparing an in-situ doped high-nickel cathode material according to claim 1, wherein the conditions of the primary sintering in the step (2) are as follows: the temperature is 800-950 ℃, the heating rate is 1-8 ℃/min, the heat preservation time is 8-20 h, and the volume concentration of the oxygen atmosphere is 20-99.9%.
7. The method for preparing an in-situ doped high-nickel cathode material as claimed in claim 1, wherein the coating agent B in the step (3) is a metal oxide or a metal hydroxide, and the metal is at least one of Al, Mg, Ti, Sr and Zr; the dosage of the coating agent B is as follows: weight of metal cation in the coating agent B: the primary sintering material is (500-3000) ppm: 1.
8. The method for preparing the in-situ doped high-nickel cathode material as claimed in claim 1, wherein the secondary sintering conditions in the step (3) are as follows: the temperature is 550-750 ℃, the heating rate is 1-8 ℃/min, the heat preservation time is 5-10 h, and the volume concentration of the oxygen atmosphere is 20-99.9%.
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| CN114349075A (en) * | 2022-01-05 | 2022-04-15 | 合肥国轩高科动力能源有限公司 | Preparation method of coated metal element-doped ternary positive electrode material, prepared positive electrode material and application thereof |
| CN116799188A (en) * | 2023-07-14 | 2023-09-22 | 宁夏大学 | Ca-doped and CaO-coated co-modified ternary positive electrode material and preparation method thereof |
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Application publication date: 20210105 |