CN115676906A - Bimetal alternately-doped cobaltosic oxide and preparation method and application thereof - Google Patents
Bimetal alternately-doped cobaltosic oxide and preparation method and application thereof Download PDFInfo
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 21
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims abstract description 14
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims 3
- 239000000243 solution Substances 0.000 description 78
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 6
- 229910000484 niobium oxide Inorganic materials 0.000 description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 4
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a bimetal alternately doped cobaltosic oxide and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Taking a cobalt source solution as a solution A, an ammonium carbonate solution as a solution B, an aluminum source solution as a solution C, and a magnesium source solution as a solution D; (2) Respectively adding the solution A and the solution B into the base solution at the same time for reaction, and alternately adding the solution A, the solution B and the solution C or the solution A, the solution B and the solution D after the median particle diameter D50 of the system particles reaches 4-6 mu m; (3) And (3) washing and drying the material obtained in the step (2) to obtain the bimetal alternately-doped cobalt carbonate, and calcining the bimetal alternately-doped cobalt carbonate in a rotary kiln to obtain the bimetal alternately-doped cobaltosic oxide.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and relates to a bimetal alternately-doped cobaltosic oxide, and a preparation method and application thereof.
Background
The cobaltosic oxide is a main raw material of lithium cobaltate and is mainly applied to the field of 3C electronic products. Lithium cobalt oxide has problems in current use, mainly in that the theoretical voltage is at least 4.2V and the theoretical specific capacity is 260hA/kg, but the actual average voltage is only 3.6V and not more than 4.0V at present, and the actual capacity decreases with the increase of the cycle number. Lithium cobaltate is developing towards a high voltage of 4.5V in order to release higher energy in a smaller space, because more lithium ions can be extracted from the crystal structure at a high voltage, but the conventional lithium cobaltate cathode material LiCoO 2 Belongs to a hexagonal crystal system, has an R-3m space group, and the two-dimensional layered structure belongs to alpha-NaFeO 2 And (4) molding. During higher voltage charging, the lithium ions are switched from ordered to disordered, followed by a transition of the unit cell from hexagonal to monoclinic phase. The generation of monoclinic phase causes the battery capacity to be sharply attenuated.
At present, the structural stability of the lithium cobaltate material during high-voltage charging and discharging is generally improved by a doping mode, and common doping elements comprise transition metal elements.
CN113087024A discloses a preparation method of niobium oxide coated zirconium aluminum co-doped large-particle cobaltosic oxide. A preparation method of niobium oxide coated zirconium-aluminum co-doped large-particle cobaltosic oxide comprises the following steps: preparing a feed liquid solution A: adding aluminum chloride and zirconium chloride into the cobalt chloride solution; solution B: an ammonium bicarbonate solution; (2) Performing synthesis preparation of zirconium-aluminum co-doped cobalt carbonate, and performing suction filtration and oil removal on the solution A and the solution B respectively; the mixture is introduced into a reaction kettle in a parallel flow manner for constant-temperature synthesis; (3) Sintering and preparing cobaltosic oxide coated with niobium oxide, and performing suction filtration, washing and drying on the doped cobalt carbonate to obtain cobalt carbonate powder doped with zirconium and aluminum; then mixing the powder with nano-grade niobium oxide, putting the mixture into a sintering furnace, sintering and sieving the mixture to obtain the coated cobaltosic oxide.
CN108217753A discloses a gradient doped cobaltosic oxide material and a preparation method thereof, the method comprises mixing a cobalt salt solution with a precipitant to obtain a pre-precipitate A, adding a salt solution containing a doping element into the reaction system to obtain a doped precipitate B, and finally calcining the doped precipitate B at a specific temperature to obtain the gradient doped cobaltosic oxide.
The cobaltosic oxide prepared by the method of the scheme has the problems that doping elements are not uniformly distributed, and the circulation performance is reduced due to redistribution of the elements in the calcining process.
Disclosure of Invention
The invention aims to provide a bimetal alternately-doped cobaltosic oxide and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a bimetal alternately doped cobaltosic oxide, wherein the preparation method comprises the following steps:
(1) Taking a cobalt source solution as a solution A, an ammonium carbonate solution as a solution B, an aluminum source solution as a solution C and a magnesium source solution as a solution D;
(2) Respectively adding the solution A and the solution B into the base solution at the same time for reaction, and alternately adding the solution A, the solution B and the solution C or the solution A, the solution B and the solution D after the median particle diameter D50 of the system particles reaches 4-6 mu m;
(3) And (3) washing and drying the material obtained in the step (2) to obtain the bimetal alternately-doped cobalt carbonate, and calcining the bimetal alternately-doped cobalt carbonate in a rotary kiln to obtain the bimetal alternately-doped cobaltosic oxide.
In the step (2), the solution A, the solution B and the solution C are alternately added or the solution A, the solution B and the solution D are added in a cocurrent manner, then the solution A, the solution B and the solution C are added in a cocurrent manner, and then the solution A, the solution B and the solution D are sequentially and alternately added.
Al has no electrochemical activity in the electrochemical window of Lithium Cobaltate (LCO), so that Al is a very stable doping element, can effectively improve the thermal stability and the cycle performance of the material, and Al 3+ (53.5 pm) with Co 3+ The (54.5 pm) radiuses are similar, so the materials are easily doped into a crystal cell under the condition of not influencing the structure, the strength of an Al-O bond is higher than that of a Co-O bond, the crystal lattice size of the materials is reduced in the LCO charging and discharging process, and the working voltage of the battery is improved.
Preferably, the solute of the solution a in the step (1) includes any one of cobalt sulfate, cobalt chloride or cobalt nitrate or a combination of at least two of them.
Preferably, the mass concentration of the solution A is 80-110 g/L, such as: 80g/L, 85g/L, 90g/L, 100g/L, 110g/L, etc.
Preferably, the mass concentration of the solution B is 210-260 g/L, such as: 210g/L, 220g/L, 230g/L, 240g/L, 250g/L, 260g/L, etc.
Preferably, the solute of the solution C includes any one of aluminum sulfate, aluminum chloride or aluminum nitrate or a combination of at least two thereof.
Preferably, the mass concentration of the solution C is 9-13 g/L, for example: 9g/L, 10g/L, 11g/L, 12g/L or 13g/L, etc.
Preferably, the solute of solution D comprises magnesium sulfate and/or magnesium nitrate.
Preferably, the mass concentration of the solution D is 2-5 g/L, such as 2g/L, 2.5g/L, 3g/L, 4g/L or 5g/L.
Preferably, the base solution in the step (2) is obtained by mixing the solution D and deionized water.
Preferably, the temperature of the reaction is between 35 and 70 ℃, for example: 35 deg.C, 40 deg.C, 50 deg.C, 60 deg.C or 70 deg.C.
Preferably, the pH of the reaction is between 7 and 9, for example: 7. 7.5, 8, 8.5 or 9, etc.
Preferably, stirring is performed during the reaction.
Preferably, the stirring speed is between 100 and 300rpm, for example: 100rpm, 150rpm, 200rpm, 250rpm, 300rpm, or the like.
Preferably, the flow ratio of the solution A to the solution B in the step (2) is 1 (2-3), such as: 1.
Preferably, the flow ratio of the solution A, the solution B and the solution C is 1 (2-3) to (0.1-0.2), such as: 1.
Preferably, the flow ratio of the solution A, the solution B and the solution D is 1 (2-3) to (0.1-0.2), such as: 1.
Preferably, the alternating time in step (2) is such that the medium particle diameter D50 of the material in the reaction system is switched every 1.5 to 3 μm (e.g., 1.5 μm, 1.8 μm, 2 μm, 2.5 μm, or 3 μm) of growth in the range of 5 to 15 μm (5 μm, 8 μm, 10 μm, 12 μm, or 15 μm, etc.), and the switching is stopped after the medium particle diameter D50 of the material in the reaction system is greater than 15 μm.
In the process of growing the material, the invention can switch the types of the added solution every 1.5-5 mu m, can realize the alternate doping of different elements, and can improve the structural stability of the material and ensure the capacitance of the material at the same time by doping different elements.
Preferably, the detergent used for the washing in step (3) comprises water having a temperature of 50 to 80 ℃ (e.g., 50 ℃, 55 ℃, 60 ℃, 70 ℃, or 80 ℃, etc.).
Preferably, the temperature of the drying is 50 to 120 ℃, for example: 50 ℃, 60 ℃, 80 ℃, 100 ℃ or 120 ℃ and the like.
Preferably, the calcining device in the step (3) comprises a rotary kiln.
The invention adopts a specific calcining device (rotary kiln), can control calcining conditions in multiple directions, and obtains the high TD and high BET doped cobaltosic oxide material (TD =2.51, BET = 5.76) through the synergistic calcining of multiple conditions.
Preferably, the temperature of the calcination is 550 to 750 ℃, for example: 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or the like.
Preferably, the calcination time is 60 to 150min, for example: 60min, 80min, 100min, 120min or 150min and the like.
Preferably, the drum frequency of the calcination is between 10 and 50Hz, for example: 10Hz, 20Hz, 30Hz, 40Hz or 50Hz, etc.
Preferably, the draft frequency of the calcination is 10 to 30Hz, for example: 10Hz, 15Hz, 20Hz, 25Hz or 30Hz, etc.
In a second aspect, the present invention provides a bimetallic alternatively doped tricobalt tetroxide prepared by the method of the first aspect.
In a third aspect, the invention provides a lithium ion battery cathode material, which is prepared from the bimetal alternating doping type cobaltosic oxide as described in the second aspect.
In a fourth aspect, the invention provides a lithium ion battery comprising the lithium ion battery cathode material according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
the bimetal alternately doped cobaltosic oxide has the advantages that the elements are uniformly distributed, the controllability of redistribution of the elements is high in the calcining process, the structural stability of lithium cobaltate can be improved in the subsequent application process, the cycle performance and the rate capability of the lithium cobaltate are improved, and the bimetal alternately doped cobaltosic oxide can be used as an excellent precursor of a lithium ion battery anode material.
Drawings
Fig. 1 is a flow chart of a process for preparing bimetal alternately doped cobaltosic oxide according to embodiment 1 of the present invention.
Fig. 2 is an SEM image of the bimetal alternately doped cobaltosic oxide according to example 1 of the present invention.
Fig. 3 is an SEM magnified view of the bimetal alternately doped cobaltosic oxide according to example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
The embodiment provides a bimetal alternately-doped cobaltosic oxide, and a preparation method of the bimetal alternately-doped cobaltosic oxide is as follows, and a process flow chart of the preparation method is shown in fig. 1:
(1) Preparing cobalt sulfate into a solution A with the concentration of Co of 110g/L, preparing a solution B with the concentration of ammonium carbonate of 220g/L, preparing aluminum nitrate into a solution C with the concentration of Al of 10g/L, and preparing magnesium nitrate into a solution D with the concentration of Mg of 2.3 g/L;
(2) Mixing pure water and the solution D to serve as a reaction base solution, controlling the reaction temperature at 42 ℃ and the pH at 8, rotating at a speed of 200rpm, adding the solution A and the solution B into a reaction kettle in a ratio of 1. When the particle size is larger than 15 μm, adding the solutions A, B and C into a reaction kettle for reaction at a flow ratio of 1;
(3) When the particle size of the particles reaches the particle size of the reactor, washing the reacted materials with hot water at 60 ℃, drying at 100 ℃ to prepare the aluminum-magnesium alternately-doped cobalt carbonate, placing the dried aluminum-magnesium alternately-doped cobalt carbonate in a rotary kiln, and calcining under the conditions that: the feeding amount is 10Kg, the calcining temperature is 600 ℃, the calcining time is 100min, the drum frequency is 300Hz, the air draft is 20Hz, and the bimetal alternately doped cobaltosic oxide is prepared after the calcining is finished, wherein an SEM image of the bimetal alternately doped cobaltosic oxide is shown in figures 2-3.
Example 2
The embodiment provides a method for preparing bimetal alternately doped cobaltosic oxide, which comprises the following steps:
(1) Preparing cobalt sulfate into a solution A with the concentration of Co of 100g/L, preparing a solution B of ammonium carbonate of 230g/L, preparing aluminum nitrate into a solution C with the concentration of Al of 11g/L, and preparing magnesium nitrate into a solution D with the concentration of Mg of 2.5 g/L;
(2) Mixing pure water and the solution D to serve as a reaction base solution, controlling the reaction temperature at 44 ℃, the pH at 8.2 and the rotation speed at 200rpm, adding the solution A and the solution B into a reaction kettle in a ratio of 1. When the particle size is larger than 15 μm, adding the solutions A, B and C into a reaction kettle for reaction at a flow ratio of 1;
(3) When the particle size of the particles reaches the particle size of the reactor, washing the reacted materials with hot water at 60 ℃, drying at 100 ℃ to prepare the aluminum-magnesium alternately-doped cobalt carbonate, placing the dried aluminum-magnesium alternately-doped cobalt carbonate in a rotary kiln, and calcining under the conditions that: the feeding amount is 10Kg, the calcining temperature is 650 ℃, the calcining time is 90min, the drum frequency is 300Hz, the air draft is 20Hz, and the bimetal alternately doped cobaltosic oxide is prepared after calcining.
Comparative example 1
The comparative example provides a bimetal doped cobaltosic oxide, and the preparation method of the bimetal doped cobaltosic oxide comprises the following steps:
(1) Preparing cobalt sulfate into a solution A with the concentration of Co of 100g/L, preparing a solution B of ammonium carbonate of 230g/L, preparing aluminum nitrate into a solution C with the concentration of Al of 11g/L, and preparing magnesium nitrate into a solution D with the concentration of Mg of 2.5 g/L;
(2) Mixing pure water and the solution D to serve as a reaction base solution, controlling the reaction temperature at 44 ℃, the pH at 8.2 and the rotation speed at 200rpm, and simultaneously adding the solutions A, B, C and D into a reaction kettle for reaction at a flow ratio of 1;
(3) When the particle size of the particles reaches the particle size of the reactor, washing the reacted materials with hot water at 60 ℃, drying at 100 ℃ to prepare the aluminum-magnesium alternately-doped cobalt carbonate, placing the dried aluminum-magnesium alternately-doped cobalt carbonate in a rotary kiln, and calcining under the conditions that: the feeding amount is 10Kg, the calcining temperature is 650 ℃, the calcining time is 90min, the drum frequency is 300Hz, the air draft is 20Hz, and the bimetal alternately doped cobaltosic oxide is prepared after calcining.
It can be seen from the cobaltosic oxide prepared in examples 1-2 and comparative example 1 that, compared with common bimetallic doping, the alternating doping of Al and Mg can reduce the loss of capacity, improve the structural stability of the material, and realize multifunctional modification, so that the binary bimetallic alternating doping can realize the structural stability of lithium cobaltate, improve the cycle performance and rate capability of lithium cobaltate, and can be used as an excellent lithium ion battery anode material.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of bimetal alternate doping type cobaltosic oxide is characterized by comprising the following steps:
(1) Taking a cobalt source solution as a solution A, an ammonium carbonate solution as a solution B, an aluminum source solution as a solution C and a magnesium source solution as a solution D;
(2) Respectively adding the solution A and the solution B into the base solution at the same time for reaction, and alternately adding the solution A, the solution B and the solution C or the solution A, the solution B and the solution D after the median particle diameter D50 of the system particles reaches 4-6 mu m;
(3) And (3) washing and drying the material obtained in the step (2) to obtain the bimetal alternately-doped cobalt carbonate, and calcining the bimetal alternately-doped cobalt carbonate in a rotary kiln to obtain the bimetal alternately-doped cobaltosic oxide.
2. The method according to claim 1, wherein the solute of the solution a in the step (1) comprises any one of cobalt sulfate, cobalt chloride or cobalt nitrate or a combination of at least two thereof;
preferably, the mass concentration of the solution A is 80-110 g/L;
preferably, the mass concentration of the solution B is 210-260 g/L;
preferably, the solute of the solution C comprises any one of aluminum sulfate, aluminum chloride or aluminum nitrate or a combination of at least two of the two;
preferably, the mass concentration of the solution C is 9-13 g/L;
preferably, the solute of solution D comprises magnesium sulfate and/or magnesium nitrate;
preferably, the mass concentration of the solution D is 2-5 g/L.
3. The method according to claim 1 or 2, wherein the base solution in the step (2) is obtained by mixing the solution D with deionized water;
preferably, the temperature of the reaction is 35 to 70 ℃;
preferably, the pH of the reaction is 7 to 9;
preferably, stirring is carried out during the reaction;
preferably, the stirring speed is 100 to 300rpm.
4. The method according to any one of claims 1 to 3, wherein the flow ratio of the solution A to the solution B in the step (2) is 1 (2 to 3);
preferably, the flow ratio of the solution A, the solution B and the solution C is 1 (2-3) to (0.1-0.2);
preferably, the flow ratio of the solution A, the solution B and the solution D is 1 (2-3) to (0.1-0.2).
5. The production process according to any one of claims 1 to 4, wherein the alternation time in the step (2) is such that the species of the solution to be added is switched every 1.5 to 3 μm after the median diameter D50 of the material in the reaction system is grown in the range of 5 to 15 μm, and the switching is stopped after the median diameter D50 of the material in the reaction system is >15 μm.
6. The production method according to any one of claims 1 to 5, wherein the detergent used for washing in step (3) comprises water at a temperature of 50 to 80 ℃;
preferably, the drying temperature is 50-120 ℃.
7. The method according to any one of claims 1 to 6, wherein the calcining apparatus of step (3) comprises a rotary kiln;
preferably, the temperature of the calcination is 550-750 ℃;
preferably, the calcining time is 60-150 min;
preferably, the roller frequency of the calcination is 10 to 50Hz;
preferably, the exhaust frequency of the calcination is 10-30 Hz.
8. A bimetallic alternatively-doped cobaltosic oxide prepared by the method of any one of claims 1 to 7.
9. A lithium ion battery positive electrode material, wherein the lithium ion battery positive electrode material is prepared from the bimetal alternating doping type cobaltosic oxide according to claim 8.
10. A lithium ion battery comprising the positive electrode material for a lithium ion battery according to claim 9.
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