CN115745012A - Preparation method of low-magnetism high-aluminum-doped small-granularity cobaltosic oxide - Google Patents
Preparation method of low-magnetism high-aluminum-doped small-granularity cobaltosic oxide 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 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims abstract description 56
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims abstract description 56
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 45
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 44
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 44
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000002893 slag Substances 0.000 claims abstract description 14
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 30
- 239000002585 base Substances 0.000 claims description 26
- 230000006911 nucleation Effects 0.000 claims description 24
- 238000010899 nucleation Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 17
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000004570 mortar (masonry) Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 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 2
- 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
- 229940011182 cobalt acetate Drugs 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
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000012066 reaction slurry Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000009827 uniform distribution Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 5
- -1 aluminum ions Chemical class 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005056 compaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- IWRAVVYDORMLAM-UHFFFAOYSA-L C([O-])([O-])=O.[Co+2].[Al+3] Chemical compound C([O-])([O-])=O.[Co+2].[Al+3] IWRAVVYDORMLAM-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
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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)
Abstract
The invention discloses a preparation method of low-magnetism high-aluminum-doped small-granularity cobaltosic oxide, which comprises the following steps of: (1) Adding soluble aluminum salt into the cobalt salt solution, and uniformly mixing to prepare a cobalt-aluminum mixed solution; adding the ammonium bicarbonate crystals into deionized water to prepare an ammonium bicarbonate solution; (2) Adding the ammonium bicarbonate solution prepared in the step 1 and deionized water into a reaction kettle to be used as a base solution; (3) Simultaneously adding a cobalt-aluminum solution and an ammonium bicarbonate solution into the base solution obtained in the step (2) for precipitation reaction, and concentrating and removing iron from the slurry in the reaction process; (4) filtering and washing the cobalt carbonate slurry prepared in the step (3); (5) And (4) drying, calcining, sieving and removing iron from the wet cobalt carbonate slag in the step (4) to prepare the low-magnetism high-aluminum-doped small-granularity cobaltosic oxide. The cobaltosic oxide has the outstanding advantages of uniform distribution of aluminum elements, uniform particle size distribution, good sphericity, high tap density, good fluidity, low magnetic foreign matter and the like, and has wide application range.
Description
Technical Field
The invention relates to the technical field of lithium ion battery material preparation, in particular to a preparation method of low-magnetism high-aluminum-doped small-granularity cobaltosic oxide.
Background
With the trend of the 3C battery products towards light weight and durability, the updating and upgrading are more frequent, higher requirements are put on the energy density of the lithium ion battery, and the energy density of the lithium cobalt oxide battery is mainly improved by improving the cut-off voltage. Positive electrode material lithium cobaltate (LiCoO) 2 ) The lithium ion battery anode material has the advantages of high specific energy, stable charging and discharging voltage platform, high working voltage, excellent cycle performance and the like, and is the lithium ion battery anode material with the highest industrialization degree. However, liCoO is hindered by the problem of reduced cycling performance of the material due to the breakdown of the layered structure of the material at high charge cut-off voltages (4.4V or 4.5V) due to phase transition 2 Is widely applied.
Aiming at the problems of commercial lithium cobaltate cathode materials, the traditional process method adopts a solid-phase mixing method to prepare doped lithium cobaltate, namely, a lithium source, cobalt oxide and a dopant are mixed in a solid-phase form and then sintered at high temperature to realize doping. Therefore, the doping uniformity is influenced by the form of the dopant and the mixing state, and is influenced by the thermal diffusion of metal ions during high-temperature reaction, so that the uniform doping of the material is difficult to realize. Under the condition of high-voltage charging, the phase change of the high-delithiation state occurs, the crystal lattice loses oxygen, the structure is unstable, the doping amount of doping elements of the 4.5V lithium cobaltate cobaltosic oxide material is gradually increased, the problem of uneven doping is more obvious along with the increase of the doping amount of the doping elements, and the high-voltage characteristic of the lithium cobaltate anode material is seriously influenced.
The properties of the cobaltosic oxide in all aspects determine the performance of the lithium cobaltosic oxide positive electrode material and a downstream lithium ion battery, the small-particle cobaltosic oxide can obviously improve the compaction density of the lithium cobaltosic oxide, and the small-particle cobaltosic oxide is beneficial to the rapid embedding of lithium ions and the rapid embedding of the lithium ions and the rapid preparation of the lithium cobaltosic oxide
Instruction book
The battery performance is greatly improved by the low cation mixed-exclusion and stable layered crystal structure.
If magnetic foreign matters exist in the lithium ion battery, the diaphragm is perforated, the internal short circuit of the battery is caused, and the battery is self-discharged, even ignited and exploded. At present, the metal foreign matters of battery materials applied in industry need to be controlled at the level of dozens of ppb, and the content of the magnetic foreign matters also becomes an important standard for measuring the quality of the lithium ion battery anode materials.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method of low-magnetism high-aluminum-doped small-granularity cobaltosic oxide, which has the advantages of low content of magnetic foreign matters, uniform distribution of doping elements, high compaction density, high charging voltage and good particle sphericity.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of low-magnetism high-aluminum-doped small-granularity cobaltosic oxide comprises the following steps:
s1, weighing cobalt salt and aluminum salt, dissolving the cobalt salt and the aluminum salt in deionized water, and uniformly stirring to prepare a cobalt-aluminum mixed solution;
s2, preparing an ammonium bicarbonate solution with the concentration of 220 to 260g/L in deionized water;
s3, adding deionized water and the ammonium bicarbonate solution obtained in the step S2 into a reaction kettle to serve as a base solution, and simultaneously adding a cobalt-aluminum mixed solution to perform a synthesis reaction to obtain cobalt carbonate slurry;
s4, filtering and washing the cobalt carbonate slurry obtained in the step S3 to obtain cobalt carbonate wet slag;
s5, drying, calcining, screening and removing iron from the wet cobalt carbonate slag obtained in the step S4 to obtain low-magnetism high-aluminum-doped small-granularity cobaltosic oxide; the sieving and iron removal means that the calcined material is sieved by a vibrating sieve and then is removed by a powder iron remover.
As a further improvement of the technical solution of the present invention, in the step S1:
the cobalt salt is one or more of cobalt sulfate, cobalt acetate, cobalt nitrate and cobalt chloride;
the aluminum salt is one or a mixture of more than two of aluminum sulfate, aluminum nitrate and aluminum chloride.
In step S1, the concentration of the cobalt salt solution is 100 to 140g/L, and the concentration of the aluminum salt solution is 0.82 to 1.9g/L.
Further, in step S3, the synthesis reaction is divided into a nucleation stage and a crystal nucleus growth stage, the nucleation stage is ended when the crystal nucleus D50 is 2.2 to 2.8 μm, and the reaction is completed when the cobalt carbonate D50 is 4.0 to 5.0 μm, so as to obtain the cobalt carbonate slurry.
Further, the cobalt-aluminum mixed solution and the ammonium bicarbonate solution are added into a reaction kettle in a parallel flow mode in the nucleation stage, the addition amount of a base solution in the nucleation stage is 15-70% of the volume of the reaction kettle, the concentration of ammonium bicarbonate in the base solution is 45-80g/L, the flow rate of the cobalt-aluminum solution is 100-400L/h, the flow rate of the ammonium bicarbonate solution is 200-800L/h, the pH of a reaction system is 7.0-8.0, the stirring speed is 160-300r/min, the reaction temperature is 35-50 ℃, and the grain size growth speed in the nucleation stage is 0.02-0.06 μm/h.
Furthermore, the flow rate of the cobalt-aluminum solution in the crystal nucleus growth stage is 200-500L/h, the flow rate of the ammonium bicarbonate solution is 300-1000L/h, the pH of the reaction system is 7.0-7.4, the stirring speed is 150-200r/min, the reaction temperature is 40-55 ℃, and the growth speed of the crystal nucleus granularity is 0.05-0.08 mu m/h.
Further, in the step S3, when the liquid level of the reaction kettle is 30-70% of the volume of the reaction kettle in the synthesis process, concentrating the reaction slurry, making overflow liquid flow to a microporous filter for filtration in the concentration process, conveying the concentrated slurry to a pipeline iron remover, and then flowing to the reaction kettle, wherein the frequency of a mortar pump is 10-20HZ, and controlling the slurry density in the reaction kettle to be 1.0-1.4 g/ml.
Further, in step S4, the washing water is microporous filtration filtrate and is combined with deionized water for washing, and the washing temperature is 40 to 70 ℃.
Further, in the step S5, the drying temperature of the cobalt carbonate wet slag is 90-120 ℃, the drying time is 2-8h, and the water content in the cobalt carbonate is controlled to be less than 10%.
Further, in the step S5, the cobalt carbonate is calcined in a rotary kiln, wherein the temperature of the rotary kiln in a low-temperature area is 190-300 ℃, and the temperature of the rotary kiln in a high-temperature area is 700-760 ℃.
The invention has the following beneficial effects:
1. the low-magnetism high-aluminum-doped small-granularity cobaltosic oxide prepared by the method has the advantages of low content of magnetic foreign matters, uniform distribution of doping elements, high compaction density, high charging voltage, good particle sphericity, fine and uniform primary particles and stable structure;
2. the preparation method is simple in process and applicable to large-scale production, the recovery rate of cobalt metal is effectively improved after the overflow mother liquor and the washing mother liquor are subjected to microfiltration, the mother liquor after microfiltration washes cobalt carbonate, and impurity ions such as sodium ions and chloride ions have good washing effect, so that soluble impurities in finally generated washing wastewater are saturated, the treatment capacity of the washing wastewater is reduced, and meanwhile, the problem of uneven surface aluminum distribution caused by hydrolysis of surface aluminum precipitates is solved, the product quality is effectively improved, and the production cost is reduced;
3. the cobalt carbonate synthesis stage is divided into a nucleation stage and a crystal nucleus growth stage, the uniformity of nucleation and growth conditions among cobalt carbonate particles is maintained through precise process control, the controllability of the particle size and the appearance quality of a cobalt carbonate product is improved, and when the aluminum doping amount is higher than 0.6-1%, uniform cobalt-aluminum element coprecipitation can be realized by controlling the pH value in the synthesis process;
4. in the process of concentrating the slurry in the synthesis stage, the slurry is circularly demagnetized without interruption, the calcined product powder is demagnetized by a deironing device, and the magnetic foreign matter of the obtained product is low after two times of demagnetization;
5. in the calcining process, different temperature intervals are controlled through low-temperature predecomposition and high-temperature thermal decomposition, so that aluminum migration and precipitation and surface enrichment in the calcining process are prevented, and the aluminum element is uniformly distributed in the cobaltosic oxide.
Drawings
FIG. 1 is a process flow diagram of the preparation method of low-magnetic high-aluminum-doped small-granularity cobaltosic oxide of the invention;
FIG. 2 is a scanning electron micrograph of cobalt carbonate after drying in example 1;
FIG. 3 is a scanning electron microscope image of low-magnetic, highly aluminum-doped, small-particle-size cobaltosic oxide in example 1;
FIG. 4 is a graph showing the particle size distribution of cobalt carbonate in example 1;
FIG. 5 is a scanning electron microscope image of low-magnetic high-aluminum-doped small-particle size cobaltosic oxide in example 2;
FIG. 6 is a scanning electron micrograph of cobalt carbonate in the comparative example.
Detailed Description
To facilitate an understanding of the invention, the invention is described more fully hereinafter with reference to the accompanying examples and drawings. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value and various modifications of equivalent form will occur to those skilled in the art upon reading the relevant disclosure of the invention and are intended to be included within the scope of the present application, the exemplary embodiments of the present invention and their descriptions are for illustration only and not for the purpose of limiting the invention.
The technological process chart of the preparation method of low-magnetism high-aluminum-doped small-granularity cobaltosic oxide is shown in figure 1.
Example 1
Preparing cobalt chloride solution with cobalt ion concentration of 100g/L in a solution preparation tank by using deionized water, and weighing Al 2 (SO 4 ) 3 ·18H 2 Adding O crystals into the cobalt chloride solution to enable the concentration of aluminum ions in the mixed solution to be 0.82g/L, starting a liquid preparation tank, and uniformly stirring to obtain a cobalt-aluminum mixed solution;
preparing an ammonium bicarbonate solution with the concentration of 220g/L by using deionized water;
adding deionized water and the ammonium bicarbonate solution into a reaction kettle to serve as a base solution, wherein the addition amount of the base solution is 15% of the volume of the reaction kettle, the concentration of ammonium bicarbonate in the base solution is 45g/L, heating the base solution, starting the reaction kettle, and stirring at the stirring speed of 300r/min; when the temperature of the base solution is 35 ℃, adding the prepared cobalt-aluminum mixed solution and ammonium bicarbonate solution into a reaction kettle in a cocurrent flow mode, wherein the flow rate of the cobalt-aluminum mixed solution is 100L/h and is stable, controlling the pH of the system to be 7.6 by adjusting the flow rate of the ammonium bicarbonate solution to be 200L/h, the grain size growth rate of a nucleation stage to be 0.02 mu m/h, completing the nucleation stage when the D50 of a crystal nucleus is 2.2 mu m, and entering the crystal nucleus growth stage; stirring and rotating speed is adjusted to be 200r/min, reaction temperature is 40 ℃, a cobalt-aluminum mixed solution and an ammonium bicarbonate solution are added into a reaction kettle in a parallel flow mode, the flow rate of the cobalt-aluminum mixed solution is 200L/h and is stable, the pH value of the system is controlled to be 7.0 by adjusting the flow rate of the ammonium bicarbonate solution to be 380L/h, and the grain size growth speed in a nucleation stage is 0.05 mu m/h; in the synthesis process, when the liquid level of the reaction kettle is 30% of the volume of the reaction kettle, concentrating, wherein the overflow liquid in the concentrating process flows to a microporous filter for filtering, the concentrated slurry is conveyed to a pipeline iron remover through a mortar pump and then flows to the reaction kettle, the frequency of the mortar pump is 10HZ, the density of the slurry in the reaction kettle is controlled to be 1.2g/ml, and when the crystal nucleus D50 is 4.27 mu m, the reaction is completed to obtain cobalt carbonate slurry;
conveying the cobalt carbonate slurry into a centrifugal machine for filtering and washing, wherein the rotating speed of the centrifugal machine is 300r/min, washing water is used as microporous filter filtrate and is combined with deionized water for washing, and the washing temperature is 40 ℃ to obtain cobalt carbonate wet residue;
the wet cobalt carbonate slag after washing is put intoDrying in an oven for 2h at 90 ℃, controlling the water content in the cobalt carbonate to be less than 10%, calcining the dried cobalt carbonate in a rotary kiln, wherein the temperature of a low-temperature area of the rotary kiln is 190 ℃ and the temperature of a high-temperature area is 760 ℃; sieving the calcined aluminum-doped cobaltosic oxide by a vibrating screen, and then removing iron from the sieved material by a powder iron remover to finally obtain the low-magnetism high-aluminum-doped small-granularity cobaltosic oxide with the specific surface area of 3.6cm 2 The tap density is 2.26g/cm 3 The content of magnetic foreign matter was 18ppb.
FIG. 2 is a scanning electron microscope image of the dried cobalt carbonate in example 1, from which it can be seen that the cobalt carbonate particles have good sphericity, the particle surfaces are blocky and fine, the packing manner is compact, the surfaces are round and dense, the pores are small, and no micropowder exists.
FIG. 3 is a scanning electron microscope image of the low-magnetic high-aluminum-doped small-particle size cobaltosic oxide in example 1, from which it can be seen that the low-magnetic high-aluminum-doped small-particle size cobaltosic oxide has good sphericity, fine and uniform primary particles, and smaller pores among the primary particles.
Fig. 4 is a particle size distribution diagram of cobalt carbonate in example 1, and it can be seen from the diagram that the cobalt carbonate has uniform particle size distribution, small particle size span, and good controllability.
Example 2
Preparing cobalt chloride solution with cobalt ion concentration of 140g/L in a solution preparation tank by using deionized water, and weighing AlCl 3 ·6H 2 Adding O crystals into the cobalt chloride solution to enable the concentration of aluminum ions in the mixed solution to be 1.9g/L, starting a liquid preparation tank, and uniformly stirring to obtain a cobalt-aluminum mixed solution;
preparing an ammonium bicarbonate solution with the concentration of 260g/L by using deionized water;
adding deionized water and the ammonium bicarbonate solution into a reaction kettle to serve as a base solution, wherein the addition amount of the base solution is 70% of the volume of the reaction kettle, the concentration of ammonium bicarbonate in the base solution is 80g/L, heating the base solution, starting the reaction kettle, and stirring at the stirring speed of 160r/min; when the temperature of the base solution is 50 ℃, adding the prepared cobalt-aluminum mixed solution and ammonium bicarbonate solution into a reaction kettle in a parallel flow mode, wherein the flow rate of the cobalt-aluminum mixed solution is 400L/h and is stable, controlling the pH of the system to be 8.0 by adjusting the flow rate of the ammonium bicarbonate solution to be 800L/h, controlling the grain size growth rate of a nucleation stage to be 0.06 mu m/h, completing the nucleation stage when the grain size D50 of a crystal nucleus is 2.8 mu m, and entering the crystal nucleus growth stage; stirring and rotating speed is adjusted to be 150r/min, reaction temperature is 55 ℃, a cobalt-aluminum mixed solution and an ammonium bicarbonate solution are added into a reaction kettle in a parallel flow mode, the flow rate of the cobalt-aluminum mixed solution is 500L/h and is stable and unchanged, and the particle size growth speed of a nucleation stage is controlled to be 0.08 mu m/h by adjusting the flow rate of the ammonium bicarbonate solution to be 780L/h, wherein the pH of the system is 7.4; in the synthesis process, when the liquid level of the reaction kettle is 70% of the volume of the reaction kettle, the concentration is started, the overflow liquid in the concentration process flows to a microporous filter for filtration, the concentrated slurry is conveyed to a pipeline iron remover through a mortar pump and then flows to the reaction kettle, the frequency of the mortar pump is 20HZ, the density of the slurry in the reaction kettle is controlled to be 1.5g/ml, and when the crystal nucleus D50 is 5.0 mu m, the reaction is completed to obtain cobalt carbonate slurry;
conveying the cobalt carbonate slurry into a centrifuge for filtering and washing, wherein the rotating speed of the centrifuge is 800r/min, washing water is used as microporous filter filtrate and is combined with deionized water for washing, and the washing temperature is 70 ℃, so as to obtain cobalt carbonate wet slag;
drying the washed wet cobalt carbonate slag in an oven for 8 hours at the drying temperature of 120 ℃, controlling the moisture in the cobalt carbonate to be less than 10%, calcining the dried cobalt carbonate in a rotary kiln, wherein the temperature of a low-temperature area of the rotary kiln is 300 ℃, and the temperature of a high-temperature area of the rotary kiln is 700 ℃; sieving the calcined aluminum-doped cobaltosic oxide by a vibrating screen, and then removing iron from the sieved material by a powder iron remover to finally obtain the low-magnetism high-aluminum-doped small-granularity cobaltosic oxide with the specific surface area of 3.9cm 2 (g) tap density of 2.27g/cm 3 The content of the magnetic foreign matter was 20ppb.
FIG. 5 is a scanning electron microscope image of the low-magnetic high-aluminum-doped small-particle size cobaltosic oxide in example 2, from which it can be seen that the low-magnetic high-aluminum-doped small-particle size cobaltosic oxide has good sphericity, fine and uniform primary particles, and smaller pores among the primary particles.
Example 3
Preparing cobalt sulfate solution with cobalt ion concentration of 120g/L in a solution preparation tank by using deionized water, and weighing Al 2 (SO 4 ) 3 ·18H 2 Adding O crystal into the cobalt sulfate solutionEnabling the concentration of aluminum ions in the mixed solution to be 1.5g/L, starting a liquid preparation tank, and uniformly stirring to obtain a cobalt-aluminum mixed solution;
preparing an ammonium bicarbonate solution with the concentration of 250g/L by using deionized water;
adding deionized water and the ammonium bicarbonate solution into a reaction kettle to serve as a base solution, wherein the addition amount of the base solution is 50% of the volume of the reaction kettle, the concentration of ammonium bicarbonate in the base solution is 60g/L, heating the base solution, starting the reaction kettle, and stirring at the stirring speed of 200r/min; when the temperature of the base solution is 47 ℃, adding the prepared cobalt-aluminum mixed solution and ammonium bicarbonate solution into a reaction kettle in a cocurrent flow mode, wherein the flow rate of the cobalt-aluminum mixed solution is 250L/h and is stable, controlling the pH of the system to be 8.0 by adjusting the flow rate of the ammonium bicarbonate solution to be 470L/h, the grain size growth rate of a nucleation stage to be 0.04 mu m/h, completing the nucleation stage when the D50 of a crystal nucleus is 2.5 mu m, and entering the crystal nucleus growth stage; stirring and rotating speed is adjusted to 180r/min, reaction temperature is 50 ℃, a cobalt-aluminum mixed solution and an ammonium bicarbonate solution are added into a reaction kettle in a parallel flow mode, the flow rate of the cobalt-aluminum mixed solution is 320L/h and is stable and unchanged, and the particle size growth speed of a nucleation stage is 0.06 mu m/h by adjusting the pH value of a system to be 7.3 through adjusting the flow rate of the ammonium bicarbonate solution to be 500L/h; in the synthesis process, when the liquid level of the reaction kettle is 55% of the volume of the reaction kettle, concentrating, wherein the overflow liquid in the concentrating process flows to a microporous filter for filtering, the concentrated slurry is conveyed to a pipeline iron remover through a mortar pump and then flows to the reaction kettle, the frequency of the mortar pump is 15HZ, the density of the slurry in the reaction kettle is controlled to be 1.3g/ml, and when the crystal nucleus D50 is 4.0 mu m, the reaction is completed to obtain cobalt carbonate slurry;
conveying the cobalt carbonate slurry into a centrifuge for filtering and washing, wherein the rotating speed of the centrifuge is 600r/min, washing water is used as microporous filter filtrate and is combined with deionized water for washing, and the washing temperature is 60 ℃, so as to obtain cobalt carbonate wet slag;
drying the washed wet cobalt carbonate slag in an oven for 6h at the drying temperature of 110 ℃, controlling the water content in the cobalt carbonate to be less than 10%, calcining the dried cobalt carbonate in a rotary kiln, wherein the temperature of a low-temperature area of the rotary kiln is 280 ℃, and the temperature of a high-temperature area of the rotary kiln is 740 ℃; screening the calcined aluminum-doped cobaltosic oxide by a vibrating screen, and then removing iron from the screened material by a powder iron remover to finally obtain the low-iron oxideThe specific surface area of the magnetic high-aluminum-doped small-granularity cobaltosic oxide is 3.2cm 2 (g) tap density of 2.19g/cm 3 The content of magnetic foreign matter was 24ppb.
Comparative example
Preparing cobalt chloride solution with cobalt ion concentration of 100g/L in a liquid preparation tank by using deionized water, and weighing Al 2 (SO 4 ) 3 ·18H 2 Adding O crystals into the cobalt chloride solution to enable the concentration of aluminum ions in the mixed solution to be 0.82g/L, starting a liquid preparation tank, and uniformly stirring to obtain a cobalt-aluminum mixed solution;
preparing an ammonium bicarbonate solution with the concentration of 220g/L by using deionized water;
adding deionized water and the ammonium bicarbonate solution into a reaction kettle to serve as a base solution, wherein the addition amount of the base solution is 15% of the volume of the reaction kettle, the concentration of ammonium bicarbonate in the base solution is 45g/L, heating the base solution, starting the reaction kettle, and stirring at the stirring speed of 300r/min; when the temperature of the base solution is 35 ℃, adding the prepared cobalt-aluminum mixed solution and ammonium bicarbonate solution into a reaction kettle in a cocurrent flow mode, wherein the flow rate of the cobalt-aluminum mixed solution is 100L/h and is stable, controlling the pH of the system to be 7.6 by adjusting the flow rate of the ammonium bicarbonate solution to be 200L/h, the grain size growth rate of a nucleation stage to be 0.02 mu m/h, completing the nucleation stage when the D50 of a crystal nucleus is 2.2 mu m, and entering the crystal nucleus growth stage; stirring and rotating speed is adjusted to be 200r/min, reaction temperature is 40 ℃, a cobalt-aluminum mixed solution and an ammonium bicarbonate solution are added into a reaction kettle in a parallel flow mode, the flow rate of the cobalt-aluminum mixed solution is 200L/h and is stable, the pH value of the system is controlled to be 7.0 by adjusting the flow rate of the ammonium bicarbonate solution to be 380L/h, and the grain size growth speed in a nucleation stage is 0.05 mu m/h; in the synthesis process, when the liquid level of the reaction kettle is 30% of the volume of the reaction kettle, the concentration is started, the overflow liquid in the concentration process flows to a microporous filter for filtration, the concentrated slurry is conveyed to a pipeline iron remover through a mortar pump and then flows to the reaction kettle, the frequency of the mortar pump is 10HZ, the density of the slurry in the reaction kettle is controlled to be 1.2g/ml, and when the crystal nucleus D50 is 4.2 mu m, the reaction is completed to obtain cobalt carbonate slurry;
conveying the cobalt carbonate slurry into a centrifuge for filtering and washing, wherein the rotating speed of the centrifuge is 300r/min, washing water is used for washing by deionized water, and the washing temperature is 90 ℃, so as to obtain cobalt carbonate wet slag;
drying the washed wet cobalt carbonate slag in an oven for 2 hours at the drying temperature of 90 ℃, controlling the moisture in the cobalt carbonate to be less than 10%, calcining the dried cobalt carbonate in a rotary kiln, wherein the temperature of a low-temperature area of the rotary kiln is 190 ℃ and the temperature of a high-temperature area of the rotary kiln is 760 ℃; sieving the calcined aluminum-doped cobaltosic oxide by a vibrating screen, and then removing iron from the sieved material by a powder iron remover to finally obtain the low-magnetism high-aluminum-doped small-granularity cobaltosic oxide with the specific surface area of 2.7cm 2 The tap density is 2.12g/cm 3 The content of the magnetic foreign matter was 30ppb.
Fig. 6 is a scanning electron microscope image of cobalt carbonate in a comparative experiment of example 1, from which it can be seen that the washing process has a great influence on the uniformity of cobalt aluminum carbonate distribution and particle surface smoothness during the preparation of low-magnetic high-aluminum-doped small-particle size cobaltosic oxide. And the physicochemical indexes of the low-magnetism high-aluminum-doped small-granularity cobaltosic oxide obtained from the comparative example show that the washing process has great influence on the quality of the cobaltosic oxide product.
Claims (10)
1. A preparation method of low-magnetism high-aluminum-doped small-granularity cobaltosic oxide is characterized by comprising the following steps:
s1, weighing cobalt salt and aluminum salt, dissolving the cobalt salt and the aluminum salt in deionized water, and uniformly stirring to prepare a cobalt-aluminum mixed solution;
s2, preparing an ammonium bicarbonate solution with the concentration of 220 to 260g/L in deionized water;
s3, adding deionized water and the ammonium bicarbonate solution obtained in the step S2 into a reaction kettle to serve as a base solution, and simultaneously adding a cobalt-aluminum mixed solution to perform a synthesis reaction to obtain cobalt carbonate slurry;
s4, filtering and washing the cobalt carbonate slurry obtained in the step S3 to obtain cobalt carbonate wet slag;
s5, drying, calcining, screening and removing iron from the wet cobalt carbonate slag obtained in the step S4 to obtain low-magnetism high-aluminum-doped small-granularity cobaltosic oxide; the sieving and iron removal means that the calcined material is sieved by a vibrating sieve and then is removed by a powder iron remover.
2. The method for preparing low-magnetic high-aluminum-doped small-granularity cobaltosic oxide according to claim 1, wherein in the step S1:
the cobalt salt is one or a mixture of more than two of cobalt sulfate, cobalt acetate, cobalt nitrate and cobalt chloride;
the aluminum salt is one or a mixture of more than two of aluminum sulfate, aluminum nitrate and aluminum chloride.
3. The preparation method of the low-magnetic high-aluminum-doped small-granularity cobaltosic oxide as claimed in claim 2, wherein in the step S1, the concentration of the cobalt salt solution is 100 to 140g/L, and the concentration of the aluminum salt solution is 0.82 to 1.9g/L.
4. The method for preparing low-magnetism high-aluminum-doped small-granularity cobaltosic oxide as claimed in claim 1, wherein in the step S3, the synthesis reaction is divided into a nucleation stage and a crystal nucleus growth stage, the nucleation stage is finished when the crystal nucleus D50 is 2.2 to 2.8 μm, and the reaction is completed when the cobalt carbonate D50 is 4.0 to 5.0 μm, so as to obtain the cobalt carbonate slurry.
5. The preparation method of the low-magnetic high-aluminum-doped small-granularity cobaltosic oxide as claimed in claim 4, wherein the cobalt-aluminum mixed solution and the ammonium bicarbonate solution are added into the reaction kettle in a cocurrent manner in the nucleation stage, the addition amount of the base solution in the nucleation stage is 15 to 70% of the volume of the reaction kettle, the concentration of the ammonium bicarbonate in the base solution is 45 to 80g/L, the flow rate of the cobalt-aluminum solution is 100 to 400L/h, the flow rate of the ammonium bicarbonate solution is 200 to 800L/h, the pH of the reaction system is 7.0 to 8.0, the stirring speed is 160 to 300r/min, the reaction temperature is 35 to 50 ℃, and the growth speed of the granularity in the nucleation stage is 0.02 to 0.06 μm/h.
6. The method for preparing low-magnetism high-aluminum-doped small-granularity cobaltosic oxide as claimed in claim 5, wherein the cobalt aluminum solution flow rate in the crystal nucleus growth stage is 200-500L/h, and the ammonium bicarbonate solution flow rate
300-1000L/h, the pH value of a reaction system is 7.0-7.4, the stirring speed is 150-200r/min, and the reaction temperature is
40 to 55 ℃, and the growth speed of the crystal nucleus granularity is 0.05 to 0.08 mu m/h.
7. The method for preparing low-magnetic high-aluminum-doped small-granularity cobaltosic oxide as claimed in claim 6, wherein in step S3, when the liquid level of the reaction kettle is 30 to 70% of the volume of the reaction kettle in the synthesis process, the reaction slurry is concentrated, the overflow liquid in the concentration process flows to a microporous filter for filtration, the concentrated slurry is conveyed to a pipeline iron remover and then flows to the reaction kettle, the frequency of a mortar pump is 10 to 20HZ, and the density of the slurry in the reaction kettle is controlled to be 1.0 to 1.4g/ml.
8. The method for preparing low-magnetic high-aluminum-doped small-granularity cobaltosic oxide as claimed in claim 7, wherein in the step S4, the washing water is microporous filter filtrate and is combined with deionized water for washing, and the washing temperature is 40-70 ℃.
9. The method for preparing low-magnetism high-aluminum-doped small-granularity cobaltosic oxide as claimed in any one of claims 1 to 8, wherein in the step S5, the drying temperature of the wet cobalt carbonate slag is 90 to 120 ℃, the drying time is 2 to 8h, and the water content in the cobalt carbonate is controlled to be less than 10%.
10. The method for preparing low-magnetism high-aluminum-doped small-granularity cobaltosic oxide as claimed in claim 9, wherein in the step S5, the cobalt carbonate is calcined in a rotary kiln, and the temperature of the rotary kiln in a low temperature area is 190-300 ℃ and the temperature of the rotary kiln in a high temperature area is 700-760 ℃.
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