CN107445213B - Hollow hexahydric cyclic cobalt oxyhydroxide nano material and preparation method thereof - Google Patents

Hollow hexahydric cyclic cobalt oxyhydroxide nano material and preparation method thereof Download PDF

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CN107445213B
CN107445213B CN201610382883.6A CN201610382883A CN107445213B CN 107445213 B CN107445213 B CN 107445213B CN 201610382883 A CN201610382883 A CN 201610382883A CN 107445213 B CN107445213 B CN 107445213B
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cobalt
aqueous solution
hexahydric
hollow
cobalt oxyhydroxide
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CN107445213A (en
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陈光文
陈会会
杨梅
陶莎
任明月
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • C01G51/04—Oxides; Hydroxides
    • 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
    • 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
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape

Abstract

The invention relates to a hollow hexahydric cyclic cobalt oxyhydroxide nano material and a preparation method thereof, belonging to the field of inorganic materials. The length of six edges of the hollow hexahydric annular cobalt oxyhydroxide is 50-150nm, the longitudinal thickness is 10-20nm, the wall thickness is 20-30nm, and the preparation method comprises the following specific processes: (1) co-current-flow dropping cobalt salt water solution and strong alkali water solution into a three-neck flask, and reacting for a certain time under the conditions of inert atmosphere and stirring; (2) removing the protective gas, adding a certain amount of strong oxidant, and continuing aging; (3) and filtering, washing and drying the turbid liquid obtained after the ageing is finished to obtain the hollow hexahydric annular cobalt oxyhydroxide nano material. The method has the advantages of simple process flow, mild reaction conditions, easy large-scale preparation and the like, and the obtained product has narrow particle size distribution, controllable morphology and good reproducibility, and is expected to be applied to the fields of supercapacitors, lithium ion batteries, catalysis and the like.

Description

Hollow hexahydric cyclic cobalt oxyhydroxide nano material and preparation method thereof
Technical Field
The invention belongs to the field of inorganic materials, and particularly relates to a hollow hexahydric cyclic cobalt oxyhydroxide nano material and a preparation method thereof.
Technical Field
With the rapid development of economic society in China, the energy situation and environmental problems become more and more severe. Lithium ion batteries have the advantages of low energy consumption, high specific capacity and energy, high working voltage, long cycle life, small self-discharge, environmental friendliness and the like, and are widely applied to portable electronic equipment such as notebook computers, mobile phones, cameras and the like. Due to the vigorous development of electric vehicles in recent years, lithium ion batteries have been receiving more extensive attention and research as power sources for electric vehicles. Generally, the performance of a lithium ion battery depends mainly on the electrode materials and electrolyte materials constituting the battery. The study of positive electrode materials for lithium ion batteries is relatively delayed with respect to negative electrodes. Lithium cobaltate is the most commonly used anode material of the lithium ion battery at present because of the advantages of high discharge voltage, stable charge and discharge voltage, high specific energy and the like. The hydroxyl cobalt oxide is one of common cobalt sources for producing lithium cobaltate, and the structure and the property of the hydroxyl cobalt oxide have obvious influence on the electrochemical performance of the lithium cobaltate. Therefore, the development of the high-performance cobalt oxyhydroxide nano material and the preparation process have wide application prospects.
It is found that the properties of the nanomaterial mainly depend on the size and morphology of the nanomaterial. Controllable preparation of nanomaterials, i.e., size and morphology, is a goal sought by researchers in the relevant field. From the published papers and patents, there is less research on cobalt oxyhydroxide relative to cobalt hydroxide and cobaltosic oxide, and the preparation process thereof is still in the preliminary stage. Patent CN201310375503.2 discloses a synthesis process of nano-scale cobalt oxyhydroxide, which comprises the steps of solution preparation, reaction, aging, post-treatment and the like to obtain the nano-scale cobalt oxyhydroxide. However, the obtained cobalt oxyhydroxide has an irregular shape and a wide particle size distribution. Patent CN201210068153.0 discloses a preparation method of sphere-like cobalt oxyhydroxide. The preparation method has the defects of long reaction period, complex preparation process and the like. Patent CN201310124558.6 discloses a preparation method of cobalt oxyhydroxide, which comprises adding complexing agent and reducing agent into alkaline solution, reacting with cobalt salt solution, and obtaining cobaltous hydroxide under the protection of nitrogen. The cobaltous hydroxide is filtered and washed and then transferred into an oxidation kettle for oxidation reaction, and finally the cobaltous oxyhydroxide is prepared. Obviously, the preparation process of the method is complex, and the required equipment is huge (an oxidation kettle). In summary, no report on hollow hexahydric cyclic cobalt oxyhydroxide nanomaterial and preparation method is available. The invention provides a nano-scale six-nanometer cyclic cobaltous oxyhydroxide material and a preparation method thereof for the first time. The method has the advantages of simple process flow, low process energy consumption, controllable product appearance and particle size, easiness in large-scale production and the like, and the obtained hollow hexahydric cyclic cobalt oxyhydroxide nano material is expected to be applied to the fields of lithium ion batteries, supercapacitors, catalysis and the like.
Disclosure of Invention
The invention aims to provide a hollow hexahydric cyclic cobalt oxyhydroxide nano material and a preparation method thereof, which are expected to be applied to the fields of lithium ion batteries, supercapacitors, catalysis and the like. The molecular formula of the hollow hexahydric annular cobalt oxyhydroxide nano material is CoOOH, the length of six edges (cross section) of the hollow hexahydric annular cobalt oxyhydroxide is 50-150nm, the longitudinal thickness is 10-20nm, and the wall thickness is 20-30 nm. The preparation method specifically comprises the following steps:
(1) preparing cobalt salt and strong alkali aqueous solution, wherein cobalt ions (Co) in the cobalt salt aqueous solution2+) The molar concentration is 0.05-1.0mol/L, and the hydroxide ions (OH) in the strong alkali aqueous solution-) The molar concentration is 0.05-5.0 mol/L;
(2) co-current-flow dropping cobalt salt water solution and strong alkali water solution into a three-neck flask at the same flow rate, and reacting for 0.5-2h at 30-80 ℃ under the conditions of inert atmosphere and stirring;
(3) removing the inert gas, adding a certain amount of strong oxidant, and continuing aging for 0.2-4 h;
(4) and after the ageing is finished, filtering, washing and drying the obtained suspension to obtain the hollow hexahydric cyclic cobaltous oxyhydroxide nano material.
In the technical scheme, the cobalt salt is one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate.
In the technical scheme, the strong alkali in the strong alkali aqueous solution is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide.
In the technical scheme, cobalt ions (Co) in the cobalt salt aqueous solution2+) With hydroxide ions (OH) in an aqueous alkali solution-) N (Co) as the molar ratio of2+)/n(OH-) The range is 1:1-1: 20.
In the technical scheme, the flow rates of the cobalt salt aqueous solution and the strong alkali aqueous solution are the same, and the flow rate range is 5-100 mL/min.
In the technical scheme, the inert gas is one or two of nitrogen and argon.
In the technical scheme, the strong oxidant is one or two of hydrogen peroxide and sodium hypochlorite, and the final mass fraction of the strong oxidant in the solution is 2-10%.
The invention provides a hollow hexahydric cyclic cobalt oxyhydroxide nano material and a preparation method thereof, compared with the prior art, the hollow hexahydric cyclic cobalt oxyhydroxide nano material has the following characteristics: (1) the nano-scale hollow hexahydric annular cobalt oxyhydroxide is synthesized for the first time, and the unique morphology is expected to be applied to the fields of lithium ion batteries, supercapacitors, catalysis and the like; (2) the product has narrow particle size distribution and good repeatability among batches, and the preparation method has the advantages of low process energy consumption, simple process flow, easy large-scale production and the like.
Drawings
FIG. 1 is a TEM photograph of a product of example 1 of the present invention.
Figure 2 is an XRD pattern of the product of example 1 of the invention.
FIG. 3 is a TEM photograph of a product of example 1 of the present invention.
FIG. 4 is a TEM photograph of a comparative example 1 product of the present invention.
Detailed Description
The following examples serve to illustrate the invention.
Example 1
(1) Preparing 50mL of each of 0.1mol/L cobalt chloride aqueous solution and 1.0mol/L sodium hydroxide aqueous solution; (2) pumping the two solutions into a three-neck flask through an advection pump at the same flow rate (20mL/min), introducing nitrogen into the three-neck flask in advance, and reacting for 30min at 50 ℃ under stirring; (3) remove N2Adding 10ml of 28% hydrogen peroxide, and aging for 30 min; (4) after aging, filtering, washing and drying the obtained suspension to obtain the hollow hexahydric annular cobalt oxyhydroxide, wherein TEM photos and XRD spectrograms of the hollow hexahydric annular cobalt oxyhydroxide are respectively shown in the attached figures 1 and 2. It can be seen that the six sides of the obtained sample are all 80-100nm in length, 10-15nm in longitudinal thickness and 20-25nm in wall thickness.
Example 2
(1) Preparing 50mL of each of 0.1mol/L cobalt chloride aqueous solution and 0.3mol/L sodium hydroxide aqueous solution; (2) pumping the two solutions into a three-neck flask through an advection pump at the same flow rate (20mL/min), introducing nitrogen into the three-neck flask in advance, and reacting for 30min at 50 ℃ under stirring; (3) remove N2Adding 10ml of 28% hydrogen peroxide, and aging for 30 min; (4) after aging, the obtained suspension is filtered, washed and dried to prepare the hollow hexahydric cyclic cobaltous oxide, and a TEM picture of the hollow hexahydric cyclic cobaltous oxide is shown in an attached figure 3. It can be seen that the six sides of the obtained sample are all 100-120nm in length, 10-15nm in longitudinal thickness and 20-25nm in wall thickness.
Example 3
(1) Preparing 50mL of each of 0.1mol/L cobalt chloride aqueous solution and 1.0mol/L sodium hydroxide aqueous solution; (2) pumping the two solutions into a three-neck flask through an advection pump at the same flow rate (100mL/min), introducing nitrogen into the three-neck flask in advance, and reacting for 30min at 50 ℃ under stirring; (3) remove N2Adding 10ml of 28% hydrogen peroxide, and aging for 2 h; (4) after the aging is finished, filtering, washing and drying the obtained suspension to prepare the hollow hexahydric annular cobalt oxyhydroxide, wherein the length of six sides of the obtained sample is 120-150nm, the longitudinal thickness is 15-20nm, and the wall thickness is 25-30 nm.
Example 4
(1) 50mL of each of 0.1mol/L cobalt sulfate aqueous solution and 1.0mol/L sodium hydroxide aqueous solution is prepared; (2) pumping the two solutions into a three-neck flask through an advection pump at the same flow rate (20mL/min), introducing nitrogen into the three-neck flask in advance, and reacting for 30min at 50 ℃ under stirring; (3) remove N2Adding 20ml of 28% hydrogen peroxide, and aging for 30 min; (4) and after aging, filtering, washing and drying the obtained suspension to prepare the hollow hexahydric annular cobalt oxyhydroxide, wherein six edges of the obtained sample are all 80-100nm in length, the longitudinal thickness is 10-15nm, and the wall thickness is 20-25 nm.
Example 5
(1) Preparing 50mL of each of 0.1mol/L cobalt chloride aqueous solution and 1.0mol/L sodium hydroxide aqueous solution; (2) pumping the two solutions into a three-neck flask through an advection pump at the same flow rate (20mL/min), introducing nitrogen into the three-neck flask in advance, and reacting for 30min at 30 ℃ under stirring conditions; (3) remove N2Adding 20ml of sodium hypochlorite aqueous solution with the mass fraction of 10%, and aging for 30 min; (4) and after aging, filtering, washing and drying the obtained suspension to prepare the hollow hexahydric annular cobalt oxyhydroxide, wherein six edges of the obtained sample are all 80-100nm in length, the longitudinal thickness is 10-15nm, and the wall thickness is 20-25 nm.
Comparative example 1
(1) Preparing 50mL of each of 0.1mol/L cobalt chloride aqueous solution and 1.0mol/L sodium hydroxide aqueous solution; (2) pumping the two solutions into a three-neck flask through an advection pump at the same flow rate (20mL/min), introducing nitrogen into the three-neck flask in advance, and aging for 2h at 50 ℃ under stirring conditions; (3) after aging, the obtained suspension is filtered, washed and dried to obtain the nanometer hexagonal flaky cobaltous hydroxide, and a TEM picture of the nanometer hexagonal flaky cobaltous hydroxide is shown in an attached figure 4. It can be seen that the six sides of the obtained sample are all 120-150nm in length and 15-20nm in longitudinal thickness.

Claims (6)

1. The preparation method of the cobalt oxyhydroxide nano material is characterized by comprising the following steps of:
(1) preparing cobalt salt and strong alkaline aqueous solution, wherein cobalt ion Co in the cobalt salt aqueous solution2+The molar concentration is 0.05-1.0mol/L, and hydroxyl ions OH in the strong alkali aqueous solution-The molar concentration is 0.05-5.0 mol/L;
(2) co-current-flow dropping cobalt salt water solution and strong alkali water solution into a three-neck flask at the same flow rate, and reacting for 0.5-2h at 30-80 ℃ under the conditions of inert atmosphere and stirring;
(3) removing the inert gas, adding a certain amount of H2O2Continuing to age for 0.2-0.5 h; the final mass fraction of the strong oxidant in the solution is 2-10%;
(4) and after the ageing is finished, filtering, washing and drying the obtained suspension to obtain the hollow hexahydric annular cobalt oxyhydroxide nano material.
2. The method for preparing cobalt oxyhydroxide nanomaterial according to claim 1, wherein the method comprises the steps of: the cobalt salt is one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate.
3. The method for preparing cobalt oxyhydroxide nanomaterial according to claim 1, wherein the method comprises the steps of: the strong base in the strong base aqueous solution is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide.
4. The method for preparing cobalt oxyhydroxide nanomaterial according to claim 1, wherein the method comprisesCharacterized in that: cobalt ion Co in the cobalt salt aqueous solution2+With hydroxide ions OH in an aqueous alkali solution-N (Co) as the molar ratio of2+ )/n( OH-) The range is 1:1-1: 20.
5. The method for preparing cobalt oxyhydroxide nanomaterial according to claim 1, wherein the method comprises the steps of: the flow rates of the cobalt salt aqueous solution and the strong alkali aqueous solution are the same, and the flow rate range is 5-100 mL/min.
6. The method for preparing cobalt oxyhydroxide nanomaterial according to claim 1, wherein the method comprises the steps of: the inert atmosphere gas is one or two of nitrogen and argon.
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