CN111233051B - Method for preparing submicron spherical cobalt carbonate - Google Patents
Method for preparing submicron spherical cobalt carbonate Download PDFInfo
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- CN111233051B CN111233051B CN202010141217.XA CN202010141217A CN111233051B CN 111233051 B CN111233051 B CN 111233051B CN 202010141217 A CN202010141217 A CN 202010141217A CN 111233051 B CN111233051 B CN 111233051B
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- 229910021446 cobalt carbonate Inorganic materials 0.000 title claims abstract description 33
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 46
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 23
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229920002125 Sokalan® Polymers 0.000 claims description 11
- 239000004530 micro-emulsion Substances 0.000 claims description 11
- 239000004584 polyacrylic acid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 239000004064 cosurfactant Substances 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 abstract description 6
- 239000010941 cobalt Substances 0.000 abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000000593 microemulsion method Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 241000257465 Echinoidea Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
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Abstract
The invention discloses a method for preparing submicron spherical cobalt carbonate, which comprises the steps of firstly preparing spherical calcium carbonate with the particle size of 500 nm-1 mu m by adopting a reverse micro-emulsion method, then simply and efficiently preparing the submicron spherical cobalt carbonate with regular appearance, uniform size and the particle size of 500 nm-1 mu m by adopting a precipitation conversion method by taking the spherical calcium carbonate as a template and cobalt chloride as a cobalt source. The preparation method is simple, safe and nontoxic, has low cost, and the obtained spherical cobalt carbonate has a unique structure and good stability, has good OER catalytic activity and stability in an alkaline potassium hydroxide solution, and has good application prospect in electrochemistry.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a method for preparing spherical cobalt carbonate by using self-made spherical calcium carbonate as a template.
Background
The noble metals such as platinum, silver, rhodium, palladium, ruthenium and the like have many advantages such as high temperature resistance, corrosion resistance, oxidation resistance and the like, and the catalytic activity of the noble metals is high, so that the noble metals are extremely important catalyst materials. However, with the continuous progress of science and technology, since precious metal resources are very rare and expensive, people begin to make a lot of researches on non-precious metals.
At present, the application of cobalt is mainly in the aspects of battery materials, hard alloys, tool steel, magnetic materials and the like; and cobalt in the form of a compound is mainly used as a catalyst, a reagent, a drying agent, a dye, a pigment, and the like. It is worth mentioning that the cobalt nanosheet has large specific surface area and high stability, has good oxygen evolution electrocatalytic performance under alkaline conditions, can save energy, and has important application prospect in the electrolysis industry. At present, the cobalt-containing nano material is mostly obtained by an electrochemical deposition method, and the method is more complex.
Disclosure of Invention
The invention aims to provide a preparation method of submicron spherical cobalt carbonate with regular appearance, uniform size and particle size of 500 nm-1 mu m.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. preparation of spherical calcium carbonate template
Dissolving calcium chloride solid in deionized water, adding polyacrylic acid, stirring uniformly, and then adding sodium dodecyl benzene sulfonate to obtain a calcium source solution with the calcium ion concentration of 0.5-3.5 mol/L; adding the obtained calcium source solution into a mixed solution of cyclohexane, a compound surfactant and a cosurfactant, uniformly mixing, standing, taking supernatant to obtain reverse microemulsion, wherein the total volume of the reverse microemulsion is 100%, the calcium source solution accounts for 1-7%, the compound surfactant accounts for 0.5-1.5%, the cosurfactant accounts for 0.5-2%, and the balance is cyclohexane; dropwise adding ammonia water into the obtained reverse microemulsion, adjusting the pH value to 8-10, and then continuously introducing CO2Reacting the gas at 25-28 ℃ for 0.5-1.5 hours, centrifuging and washing to obtain the submicron spherical calcium carbonate with porous surface.
2. Preparation of submicron spherical cobalt carbonate
And (2) adding the calcium carbonate prepared in the step (1) into a cobalt chloride aqueous solution, wherein the molar ratio of the calcium carbonate to the cobalt chloride is 1: 1-1: 60, vacuumizing for 10-30 minutes at normal temperature, stirring for 8-24 hours at room temperature-60 ℃, centrifuging, washing and drying after the reaction is finished, and thus obtaining the submicron spherical cobalt carbonate.
In the step 1, preferably, the concentration of calcium ions in the obtained calcium source solution is 1.0-3.0 mol/L, the concentration of polyacrylic acid is 0.16-0.24 g/L, and the concentration of sodium dodecyl benzene sulfonate is 0.02-0.03 mol/L, wherein the number average molecular weight of the polyacrylic acid is 5000.
In the step 1, based on the total volume of the reverse microemulsion as 100%, the calcium source solution accounts for 2% -5%, the compound surfactant accounts for 0.7% -1.0%, the cosurfactant accounts for 1.5% -2.0%, and the balance is cyclohexane.
The compound surfactant is a mixture of polyoxyethylene castor oil and span-80 in a mass ratio of 55: 45-65: 35, and the cosurfactant is ethanol.
In the step 2, the concentration of the cobalt chloride in the aqueous solution of the cobalt chloride is preferably 0.2-0.4 mol/L, and the molar ratio of the calcium carbonate to the cobalt chloride is preferably 1: 10-1: 30.
In the step 2, it is more preferable to stir the mixture at room temperature to 60 ℃ for 10 to 12 hours.
The invention has the following beneficial effects:
the invention firstly adopts a reverse microemulsion method to prepare spherical calcium carbonate with the grain diameter of 500 nm-1 mu m, then adopts the spherical calcium carbonate as a template and cobalt chloride as a cobalt source, adopts a precipitation conversion method and adopts Ca2+And Co2+And the concentration between the two is controlled so that Ca is present2+Complete conversion to Co2+And the spherical structure of the calcium carbonate is kept from being damaged, and the submicron spherical cobalt carbonate with regular appearance, uniform size and narrow distribution of the particle size of 500 nm-1 mu m is simply and efficiently prepared. The preparation method is simple, safe and nontoxic, has low cost, and the obtained spherical cobalt carbonate has a unique structure and good stability, has good OER catalytic activity and stability in an alkaline potassium hydroxide solution, and has good application prospect in electrochemistry.
Drawings
FIG. 1 is a scanning electron micrograph of the spherical calcium carbonate obtained in example 1.
FIG. 2 is a scanning electron micrograph of spherical cobalt carbonate obtained in example 1.
Fig. 3 is a partially enlarged view of fig. 2.
FIG. 4 is a transmission electron micrograph of spherical cobalt carbonate obtained in example 1.
FIG. 5 is the EDS spectrum of spherical cobalt carbonate obtained in example 1.
FIG. 6 is a scanning electron micrograph of spherical cobalt carbonate obtained in example 2.
FIG. 7 is a scanning electron micrograph of spherical cobalt carbonate obtained in example 3.
FIG. 8 is the spherical cobalt carbonate and commercial RuO of example 12Test chart of oxygen evolution reaction performance of the catalyst.
Detailed Description
The invention will be further explained in more detail below with reference to the drawings and examples, but the scope of protection of the invention is not limited to these examples.
Example 1
1. Preparation of spherical calcium carbonate template
Dissolving 1.11g of calcium chloride solid with the purity of more than 99 percent in 8mL of deionized water, adding 2mL of 1.0g/L polyacrylic acid aqueous solution with the number average molecular weight of 5000, stirring for 0.5 hour, adding 0.0871g of sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a calcium source solution, wherein the calcium ion concentration is 1.0mol/L, the polyacrylic acid concentration is 0.2g/L, and the sodium dodecyl benzene sulfonate concentration is 0.025 mol/L. 0.6g of polyoxyethylene castor oil and 0.4g of span-80 are uniformly mixed, 1.0mL of ethanol is added into the mixture, after uniform mixing, the obtained mixture is dropwise added into 100mL of cyclohexane under the state of stirring at normal temperature, 5mL of calcium source solution is dropwise added into the mixture, the mixture is uniformly stirred and stands for 2 hours, and supernatant is taken to obtain the reverse microemulsion. Dropwise adding ammonia water into the reverse microemulsion, adjusting the pH value to 9.4, and then continuously introducing CO into the reverse microemulsion2Standing the gas at 25 ℃ for 40 minutes for reaction, centrifugally separating, washing with ethanol for 3 times, washing with water for 1 time, and finally drying in vacuum at 70 ℃ to obtain the submicron spherical calcium carbonate. As shown in figure 1, the obtained calcium carbonate is spherical, has regular appearance, uniform size and narrow particle size distribution, has the particle size of about 500nm, is composed of 10-20 nm microcrystalline spherical particles, and has a rough surface and a porous shape.
2. Preparation of submicron spherical cobalt carbonate
0.01g (0.1mmol) of the spherical calcium carbonate obtained in step 1 was added to 5mL of 0.2mol/L CoCl2Dispersing in water solution, vacuum drying in a vacuum drying oven to 0.8MPa for 20 min, taking out quickly, stirring at room temperature for 12 hr, and centrifugingAnd washing with ethanol and water for many times to obtain the submicron spherical cobalt carbonate. As can be seen from the graphs in FIGS. 2 to 4, the obtained cobalt carbonate is spherical, has regular appearance, uniform size and narrow particle size distribution, has the particle size of about 500nm, is composed of 10 to 20nm dendritic microcrystals, and has a rough surface in the shape of sea urchins. The EDS of fig. 5 shows that the resulting sample consists of three elements, Co, C, O.
Example 2
In this example, 0.01g (0.1mmol) of the spherical calcium carbonate obtained in step 1 was added to 5mL of 0.4mol/L CoCl2After the aqueous solution was evacuated to 0.8MPa and allowed to stand for 20 minutes, it was quickly taken out and stirred at room temperature for 12 hours, and centrifuged and washed with ethanol and water several times to obtain submicron spherical cobalt carbonate having a particle size of about 1 μm (see FIG. 6).
Example 3
In this example, 0.01g (0.1mmol) of the spherical calcium carbonate obtained in step 1 was added to 5mL of 0.4mol/L CoCl2In the aqueous solution, after evacuation to 0.8MPa and standing for 20 minutes, it was quickly taken out and stirred at 60 ℃ for 12 hours, centrifuged and washed with ethanol and water several times to obtain submicron spherical cobalt carbonate having a particle size of about 1 μm (see FIG. 7).
Example 4
In step 1 of this example, 3.33g of calcium chloride solid with a purity of 99% or higher is dissolved in 8mL of deionized water, 2mL of 1.0g/L polyacrylic acid aqueous solution with a number average molecular weight of 5000 is added thereto, and after uniform stirring, 0.0871g of sodium dodecylbenzenesulfonate is added thereto, and uniform stirring is performed, so as to obtain a calcium source solution, wherein the calcium ion concentration is 3.0mol/L, the polyacrylic acid concentration is 0.2g/L, and the sodium dodecylbenzenesulfonate concentration is 0.025 mol/L. The other steps are the same as the example 1, and the submicron spherical cobalt carbonate with uniform size, narrow particle size distribution, 0.8-1 μm particle size, rough surface and porous shape is obtained.
Example 5
In step 1 of this example, CO was continuously introduced into the reverse microemulsion2Gas, at 25 ℃ for 1 hour, and the other steps were the same as in example 1 to obtain submicron spherical cobalt carbonate having a sizeUniform, narrow particle size distribution, 0.8-1 μm particle size, rough surface, and porous.
To demonstrate the beneficial effects of the present invention, the inventors combined the submicron spherical cobalt carbonate prepared in example 1 with commercial RuO2The catalysts were compared in performance with respect to oxygen evolution reaction. First, 2mg of submicron spherical cobalt carbonate or commercial RuO2The catalyst is added into a mixed solution of 800 mu L of water and 200 mu L of isopropanol, and the mixture is ultrasonically homogenized to prepare a catalyst solution. And uniformly dropwise adding 4 mu L of the catalyst solution on the polished glassy carbon electrode, drying at 60 ℃, dropwise adding 5 mu L of Nafion solution (0.05 wt%) on the surface of the dried glassy carbon electrode, and drying at 60 ℃ to obtain the pretreated glassy carbon electrode. The Linear Sweep Voltammetry (LSV) of the resulting treated glassy carbon electrode was measured at room temperature using the CHI 660D electrochemical workstation in a standard three-electrode system. The results show that in N2In saturated 0.1M KOH solution, the oxygen evolution reaction performance of the submicron spherical cobalt carbonate is higher than that of the commercialized RuO2Catalyst (see fig. 8).
Claims (4)
1. A method for preparing submicron spherical cobalt carbonate is characterized by comprising the following steps:
(1) preparation of spherical calcium carbonate template
Dissolving calcium chloride solid in deionized water, adding polyacrylic acid, stirring uniformly, and then adding sodium dodecyl benzene sulfonate to obtain a calcium source solution with the calcium ion concentration of 0.5-3.5 mol/L; adding the obtained calcium source solution into a mixed solution of cyclohexane, a compound surfactant and a cosurfactant, uniformly mixing, standing, taking supernatant to obtain reverse microemulsion, wherein the total volume of the reverse microemulsion is 100%, the calcium source solution accounts for 2-5%, the compound surfactant accounts for 0.7-1.0%, the cosurfactant accounts for 1.5-2.0%, and the balance is cyclohexane; dropwise adding ammonia water into the obtained reverse microemulsion, adjusting the pH value to 8-10, and then continuously introducing CO2Reacting the gas at 25-28 ℃ for 0.5-1.5 hours, centrifuging and washing to obtain submicron spherical calcium carbonate with a porous surface; calcium ions in the obtained calcium source solutionThe concentration of the polyacrylic acid is 1.0-3.0 mol/L, the concentration of the polyacrylic acid is 0.16-0.24 g/L, the concentration of the sodium dodecyl benzene sulfonate is 0.02-0.03 mol/L, and the number average molecular weight of the polyacrylic acid is 5000; the compound surfactant is a mixture of polyoxyethylene castor oil and span-80 in a mass ratio of 55: 45-65: 35; the cosurfactant is ethanol;
(2) preparation of submicron spherical cobalt carbonate
And (2) adding the calcium carbonate prepared in the step (1) into a cobalt chloride aqueous solution, wherein the molar ratio of the calcium carbonate to the cobalt chloride is 1: 1-1: 60, vacuumizing for 10-30 minutes at normal temperature, stirring for 8-24 hours at room temperature-60 ℃, centrifuging, washing and drying after the reaction is finished, and thus obtaining the submicron spherical cobalt carbonate.
2. The method for preparing submicron spherical cobalt carbonate according to claim 1, characterized in that: in the step (2), the concentration of the cobalt chloride in the cobalt chloride aqueous solution is 0.2-0.4 mol/L.
3. The method for preparing submicron spherical cobalt carbonate according to claim 1 or 2, characterized in that: in the step (2), the molar ratio of the calcium carbonate to the cobalt chloride is 1: 10-1: 30.
4. The method for preparing submicron spherical cobalt carbonate according to claim 1, characterized in that: in the step (2), stirring is carried out for 10-12 hours at room temperature-60 ℃.
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