CN111533176A - Preparation method of layered alkali metal cobalt oxide crystal - Google Patents
Preparation method of layered alkali metal cobalt oxide crystal Download PDFInfo
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- CN111533176A CN111533176A CN202010214505.3A CN202010214505A CN111533176A CN 111533176 A CN111533176 A CN 111533176A CN 202010214505 A CN202010214505 A CN 202010214505A CN 111533176 A CN111533176 A CN 111533176A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
The invention discloses a preparation method of a layered alkali metal cobalt oxide crystal, which comprises the following steps: cobalt nitrate, carbonate and chloride are fully ground and mixed, and then the mixture is put into a muffle furnace to be heated according to the specified reaction temperature and time, and the layered alkali metal cobalt oxide crystal can be directly obtained after simple treatment, so that the layered alkali metal cobalt oxide crystal is a novel thermoelectric material with great potential.
Description
Technical Field
The invention relates to preparation of a layered alkali metal cobalt oxide crystal, in particular to a method for preparing a layered alkali metal cobalt oxide crystal by a molten salt growth method.
Technical Field
Recently, with the emphasis on environmental issues and energy issues, thermoelectric materials have become a hot point of research. At present, thermoelectric materials which are widely applied are alloy materials, but have certain limitation in application aspects due to the characteristics of instability, easy oxidation and the like at high temperature, high cost of raw materials and often containing heavy metals harmful to human bodies. The oxide thermoelectric material is a novel thermoelectric material with great potential, and has the biggest advantages of stable performance under high temperature, most of the thermoelectric materials are nontoxic and pollution-free. As a novel thermoelectric material, the alkali metal cobalt oxide crystal is generally prepared by adopting a chemical solution coprecipitation method, but the prepared alkali metal cobalt oxide has poor crystallinity and an unstable structure.
Disclosure of Invention
The invention aims to provide a preparation method of a layered alkali metal cobalt oxide crystal aiming at the defects of the prior art, which is characterized in that cobalt nitrate, carbonate and chloride are fully and uniformly ground, then the ground cobalt nitrate, carbonate and chloride are placed in an alumina crucible and then are placed in a muffle furnace for reaction at high temperature, and the layered alkali metal cobalt oxide crystal is prepared by a gradient cooling method.
The specific technical scheme for realizing the purpose of the invention is as follows:
a preparation method of layered alkali metal cobalt oxide crystals comprises the following specific steps:
step 1: weighing cobalt nitrate, carbonate and chloride, putting into a mortar, fully grinding and uniformly mixing to obtain a raw material, and transferring into an alumina crucible; wherein the mass ratio of the cobalt nitrate to the carbonate to the chloride is 1:1-5: 1-5; the carbonate and the chloride salt are taken as cosolvent;
step 2: putting the alumina crucible into a muffle furnace, raising the temperature to 900-;
and step 3: taking out the crucible from the muffle furnace, immersing the crucible in a container filled with water for 5-72 hours, pouring out the water after the carbonate and the chloride which do not participate in the reaction in the crucible are completely dissolved and crystal substances are precipitated in the water, keeping the crucible and the crystal substances in the container, taking out the crucible, adding the water into the container again, stirring for 5 minutes, re-precipitating the crystal substances, pouring out the water, adding the water into the container again, stirring for 5 minutes, re-precipitating the crystal substances, and pouring out the water; repeating the steps for several times until the solution is clear, taking out the crystal, and drying the crystal in a forced air drying oven to obtain the layered alkali metal cobalt oxide crystal; wherein the water is deionized water.
The carbonate is sodium carbonate, potassium carbonate, rubidium carbonate or cesium carbonate.
The chlorine salt is sodium chloride, potassium chloride, rubidium chloride or cesium chloride.
The invention provides a simple and low-cost method for preparing layered alkali metal cobalt oxide crystals, namely, a molten salt method is used for generating the layered alkali metal cobalt oxide crystals by using cobalt nitrate, carbonate and chloride as reactants.
Drawings
FIG. 1 shows NaCo prepared in examples 17, 18, 19 and 20 of the present invention2O4、KCo2O4、RbCo2O4、CsCoO3XRD pattern of (a);
FIG. 2 shows NaCo prepared in example 17 of the present invention2O4Scanning electron microscope images of;
FIG. 3 is a diagram showing a sample taken from a crucible after the muffle furnace is heated in example 9 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings, and the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1
2.5 g NaCl, 2.5 g Na2CO3And 0.873 g Co (NO)3)2·6H2Sequentially adding O into a mortar, fully grinding and mixing uniformlyAfter homogenization, the mixture was transferred to an alumina crucible.
Example 2
2.5 g of KCl, 2.5 g K2CO3And 0.873 g Co (NO)3)2·6H2And sequentially adding O into a mortar, fully grinding and uniformly mixing, and transferring to an alumina crucible.
Example 3
2.5 g RbCl, 2.5 g Rb2CO3And 0.873 g Co (NO)3)2·6H2And sequentially adding O into a mortar, fully grinding and uniformly mixing, and transferring to an alumina crucible.
Example 4
2.5 g CsCl, 2.5 g Cs2CO3And 0.873 g Co (NO)3)2·6H2And sequentially adding O into a mortar, fully grinding and uniformly mixing, and transferring to an alumina crucible.
Example 5
3.5g NaCl, 3.5g Na2CO3And 0.5g Co (NO)3)2·6H2And sequentially adding O into a mortar, fully grinding and uniformly mixing, and transferring to an alumina crucible.
Example 6
5g of KCl, 5g K2CO3And 0.873 g Co (NO)3)2·6H2And sequentially adding O into a mortar, fully grinding and uniformly mixing, and transferring to an alumina crucible.
Example 7
2.5 g RbCl, 2.5 g Rb2CO3And 2.5 g Co (NO)3)2·6H2And sequentially adding O into a mortar, fully grinding and uniformly mixing, and transferring to an alumina crucible.
Example 8
5g CsCl, 5g Cs2CO3And 2.5 g Co (NO)3)2·6H2And sequentially adding O into a mortar, fully grinding and uniformly mixing, and transferring to an alumina crucible.
Example 9
The mixture prepared in example 1 was put into a muffle furnace, the temperature was raised to 1000 ℃ at a rate of 3.7 ℃/min, held at constant temperature for 300 minutes, then slowly lowered to 850 ℃ at a rate of 0.17 ℃/min, the temperature was then changed to 650 ℃ over 200 minutes, and finally naturally lowered to room temperature.
Example 10
The mixture prepared in example 2 was put into a muffle furnace, the temperature was raised to 1000 ℃ at a rate of 3.7 ℃/min, held at constant temperature for 300 minutes, then slowly lowered to 850 ℃ at a rate of 0.17 ℃/min, the temperature was then changed to 650 ℃ over 200 minutes, and finally naturally lowered to room temperature.
Example 11
The mixture prepared in example 3 was put into a muffle furnace, the temperature was raised to 1000 ℃ at a rate of 3.7 ℃/min, held at constant temperature for 300 minutes, then slowly lowered to 850 ℃ at a rate of 0.17 ℃/min, then changed to 650 ℃ over 200 minutes, and finally naturally cooled to room temperature.
Example 12
The mixture prepared in example 4 was put into a muffle furnace, the temperature was raised to 1000 ℃ at a rate of 3.7 ℃/min, held at constant temperature for 300 minutes, then slowly lowered to 850 ℃ at a rate of 0.17 ℃/min, the temperature was then changed, lowered to 650 ℃ over 200 minutes, and finally naturally lowered to room temperature.
Example 13
The mixture prepared in example 5 was put into a muffle furnace, the temperature was raised to 900 ℃ at a rate of 4.5 ℃/min, held at constant temperature for 400 minutes, then slowly lowered to 700 ℃ at a rate of 0.15 ℃/min, then changed, lowered to 500 ℃ over 150 minutes, and finally naturally cooled to room temperature.
Example 14
The mixture prepared in example 6 was put into a muffle furnace, the temperature was raised to 950 ℃ at a rate of 4.5 ℃/min, held at constant temperature for 350 minutes, then slowly lowered to 750 ℃ at a rate of 0.17 ℃/min, then changed to 550 ℃ over 150 minutes, and finally naturally cooled to room temperature.
Example 15
The mixture prepared in example 7 was placed in a muffle furnace, the temperature was raised to 1000 ℃ at a rate of 4.5 ℃/min, held at constant temperature for 300 minutes, then slowly lowered to 800 ℃ at a rate of 0.17 ℃/min, the rate of lowering was changed, the temperature was lowered to 600 ℃ over 180 minutes, and finally naturally lowered to room temperature.
Example 16
The mixture prepared in example 8 was put into a muffle furnace, the temperature was raised to 1050 ℃ at a rate of 4.5 ℃/min, held at constant temperature for 250 minutes, then slowly lowered to 850 ℃ at a rate of 0.15 ℃/min, then changed to 650 ℃ over 180 minutes, and finally naturally cooled to room temperature.
Example 17
Immersing the product prepared in example 9 in a beaker filled with deionized water for 10 hours as shown in fig. 3, pouring the deionized water after the crystal is precipitated in the deionized water, taking out the empty crucible, only the precipitated crystal is left, pouring the deionized water into the beaker, stirring for 5 minutes, pouring the deionized water after the crystal is precipitated again, repeating the step for five times until the solution is clear, and finally putting the residual crystal into a forced air drying box for drying to obtain the flaky NaCo2O4(ii) a The XRD pattern is shown in figure 1, and the scanning electron micrograph is shown in figure 2.
Example 18
Immersing the product prepared in example 10 in a beaker filled with deionized water for 10 hours to precipitate crystals in the deionized water, pouring the deionized water, taking out the empty crucible to only leave the precipitated crystals, pouring the deionized water into the beaker, stirring for 5 minutes, pouring the deionized water after the crystals are precipitated again, repeating the step for five times until the solution is clear, and finally putting the rest crystals into a blast drying oven to be dried to obtain the flaky KCo2O4(ii) a Its XRD pattern is shown in figure 1。
Example 19
Immersing the product prepared in example 11 in a beaker filled with deionized water for 10 hours to precipitate crystals in the deionized water, pouring the deionized water, taking out the empty crucible to only leave the precipitated crystals, pouring the deionized water into the beaker, stirring for 5 minutes, pouring the deionized water after the crystals are precipitated again, repeating the step for five times until the solution is clear, and finally putting the rest crystals into a blast drying oven to be dried to obtain the flaky RbCo2O4(ii) a The XRD pattern is shown in figure 1.
Example 20
Immersing the product prepared in example 12 in a beaker filled with deionized water for 10 h to precipitate crystals in the deionized water, pouring the deionized water, taking out the empty crucible to only leave the precipitated crystals, pouring the deionized water into the beaker, stirring for 5 min, pouring the deionized water after the crystals are precipitated again, repeating the step for five times until the solution is clear, and finally putting the rest crystals into a forced air drying oven to dry to obtain the flaky CsCoO3(ii) a The XRD pattern is shown in figure 1.
Example 21
Immersing the product prepared in example 13 in a beaker filled with deionized water for 10 hours to precipitate crystals in the deionized water, pouring the deionized water, taking out the empty crucible to only leave the precipitated crystals, pouring the deionized water into the beaker, stirring for 5 minutes, pouring the deionized water after the crystals are precipitated again, repeating the step for five times until the solution is clear, and finally putting the rest crystals into a forced air drying oven to be dried to obtain the flaky NaCo2O4。
Example 22
The product prepared in example 14 was immersed in a beaker with deionized water for 10 h to precipitate the crystals in the deionized water, the deionized water was poured off and the empty crucible was removed leaving only the precipitated crystals, and then the deionized water was poured into the beaker and stirred for 5 minutesPouring out the deionized water after the crystal is precipitated again, repeating the step for five times until the solution is clear, and finally drying the residual crystal in a blast drying oven to obtain the flaky KCo2O4。
Example 23
Immersing the product prepared in example 15 in a beaker filled with deionized water for 10 hours to precipitate crystals in the deionized water, pouring the deionized water, taking out the empty crucible to only leave the precipitated crystals, pouring the deionized water into the beaker, stirring for 5 minutes, pouring the deionized water after the crystals are precipitated again, repeating the step for five times until the solution is clear, and finally putting the residual crystals into a blast drying oven to be dried to obtain the flaky RbCo2O4。
Example 24
Immersing the product prepared in example 16 in a beaker filled with deionized water for 10 h to precipitate crystals in the deionized water, pouring the deionized water, taking out the empty crucible to only leave the precipitated crystals, pouring the deionized water into the beaker, stirring for 5 min, pouring the deionized water after the crystals are precipitated again, repeating the step for five times until the solution is clear, and finally putting the rest crystals into a forced air drying oven to dry to obtain the flaky CsCoO3。
Claims (3)
1. A preparation method of layered alkali metal cobalt oxide crystals is characterized by comprising the following specific steps:
step 1: weighing cobalt nitrate, carbonate and chloride, putting into a mortar, fully grinding and uniformly mixing to obtain a raw material, and transferring into an alumina crucible; wherein the mass ratio of the cobalt nitrate to the carbonate to the chloride is 1:1-5: 1-5; the carbonate and the chloride salt are taken as cosolvent;
step 2: putting the alumina crucible into a muffle furnace, raising the temperature to 900-;
and step 3: taking out the crucible from the muffle furnace, immersing the crucible in a container filled with water for 5-72 hours, pouring out the water after the carbonate and the chloride which do not participate in the reaction in the crucible are completely dissolved and crystal substances are precipitated in the water, keeping the crucible and the crystal substances in the container, taking out the crucible, adding the water into the container again, stirring for 5 minutes, re-precipitating the crystal substances, pouring out the water, adding the water into the container again, stirring for 5 minutes, re-precipitating the crystal substances, and pouring out the water; repeating the steps for several times until the solution is clear, taking out the crystal, and drying the crystal in a forced air drying oven to obtain the layered alkali metal cobalt oxide crystal; wherein the water is deionized water.
2. The production method according to claim 1, wherein the carbonate is sodium carbonate, potassium carbonate, rubidium carbonate, or cesium carbonate.
3. The production method according to claim 1, wherein the chlorine salt is sodium chloride, potassium chloride, rubidium chloride, or cesium chloride.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000269560A (en) * | 1999-03-15 | 2000-09-29 | Toshiba Corp | Composite oxide aggregate, manufacture thereof and thermoelectric conversion element |
| JP2004035299A (en) * | 2002-07-01 | 2004-02-05 | National Institute Of Advanced Industrial & Technology | Single crystal of sodium cobalt oxide and its manufacturing method |
| CN101041472A (en) * | 2007-03-16 | 2007-09-26 | 北京化工大学 | Method for preparing perovskite-like composite metallic oxide by lamina |
| CN101412544A (en) * | 2008-11-14 | 2009-04-22 | 哈尔滨工业大学 | Preparation of layered cobalt oxide |
| CN103910388A (en) * | 2014-03-21 | 2014-07-09 | 东风商用车有限公司 | Method for manufacturing nano-scale granular sodium cobaltate thermoelectric material |
| CN109326781A (en) * | 2018-09-29 | 2019-02-12 | 湖南长远锂科有限公司 | A kind of preparation method of high voltage lithium cobalt oxide anode |
-
2020
- 2020-03-24 CN CN202010214505.3A patent/CN111533176A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000269560A (en) * | 1999-03-15 | 2000-09-29 | Toshiba Corp | Composite oxide aggregate, manufacture thereof and thermoelectric conversion element |
| JP2004035299A (en) * | 2002-07-01 | 2004-02-05 | National Institute Of Advanced Industrial & Technology | Single crystal of sodium cobalt oxide and its manufacturing method |
| CN101041472A (en) * | 2007-03-16 | 2007-09-26 | 北京化工大学 | Method for preparing perovskite-like composite metallic oxide by lamina |
| CN101412544A (en) * | 2008-11-14 | 2009-04-22 | 哈尔滨工业大学 | Preparation of layered cobalt oxide |
| CN103910388A (en) * | 2014-03-21 | 2014-07-09 | 东风商用车有限公司 | Method for manufacturing nano-scale granular sodium cobaltate thermoelectric material |
| CN109326781A (en) * | 2018-09-29 | 2019-02-12 | 湖南长远锂科有限公司 | A kind of preparation method of high voltage lithium cobalt oxide anode |
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