CN107445213A - A kind of hollow six-membered cyclic hydroxy cobalt oxide nano material and preparation method thereof - Google Patents
A kind of hollow six-membered cyclic hydroxy cobalt oxide nano material and preparation method thereof Download PDFInfo
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- CN107445213A CN107445213A CN201610382883.6A CN201610382883A CN107445213A CN 107445213 A CN107445213 A CN 107445213A CN 201610382883 A CN201610382883 A CN 201610382883A CN 107445213 A CN107445213 A CN 107445213A
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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
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- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
- C01P2004/20—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 present invention relates to a kind of hollow six-membered cyclic hydroxy cobalt oxide nano material and preparation method thereof, belong to field of inorganic materials.The length on six sides of the hollow six-membered cyclic hydroxy cobalt oxide is 50 150nm, and longitudinal thickness is 10 20nm, and wall thickness is 20 30nm, and its preparation method detailed process is as follows：(1) cobalt saline solution and strong alkali aqueous solution cocurrent are instilled in three-necked flask, reacts certain time under inert atmosphere and stirring condition；(2) protection gas is removed, adds a certain amount of strong oxidizer, continues to be aged；(3) gained suspension is filtered after ageing terminates, washs, dries, and obtains a kind of hollow six-membered cyclic hydroxy cobalt oxide nano material.The present invention has the advantages that technological process is simple, reaction condition is gentle, easy extensive preparation, products obtained therefrom narrow particle size distribution, morphology controllable, favorable reproducibility, is expected to be applied in fields such as ultracapacitor, lithium ion battery and catalysis.
Description
Technical field
The invention belongs to field of inorganic materials, and in particular to a kind of hollow six-membered cyclic hydroxyl oxidation
Cobalt nano material and preparation method thereof.
Technical background
As the fast development of China's economic society, Energy situation are increasingly serious with environmental problem.
Lithium ion battery because with energy consumption is low, specific capacity and it is higher than energy, operating voltage is high, the circulation longevity
Life is long, self discharge is small, advantages of environment protection, is widely used in notebook computer, movement
The portable electric appts such as phone, camera.Flourishing due to electric automobile in recent years,
Lithium ion battery as electric powered motor source receives widely concern and research.It is logical
Often, performance of lithium ion battery depends primarily on the electrode material and electrolyte material of composition battery.
For negative pole, the research of anode material for lithium-ion batteries relatively lags behind.Cobalt acid lithium is because of tool
Have the advantages that discharge voltage is high, charging/discharging voltage is steady, higher than energy, be current lithium-ion electric
The most commonly used positive electrode in pond.Hydroxy cobalt oxide as production cobalt acid lithium common cobalt source it
One, its structure and properties has to the chemical property of cobalt acid lithium to be significantly affected.Therefore, develop
High-performance hydroxy cobalt oxide nano material and preparation technology have broad application prospects.
Research finds that the performance of nano material depends primarily on its size and pattern.Nano material
Controllable preparation, i.e. the controllable preparation of size and pattern is the mesh that association area researcher pursues
Mark.From the paper published with from the point of view of patent, relative to cobalt hydroxide and cobaltosic oxide,
Research on hydroxy cobalt oxide is less, and its preparation technology is scarcely out of swaddling-clothes.Patent
CN201310375503.2 discloses a kind of synthesis technique of nano cobalt oxyhydroxide, passes through
Solution is prepared, reacted, nano cobalt oxyhydroxide is prepared in ageing and post-treating and other steps.
However, the random pattern of gained hydroxy cobalt oxide, broad particle distribution.Patent
CN201210068153.0 discloses a kind of preparation method of spherical hydroxy cobalt oxide.The system
The shortcomings of long reaction time, preparation process complexity be present in Preparation Method.Patent
CN201310124558.6 discloses a kind of preparation method of hydroxy cobalt oxide, first to alkali soluble
Complexing agent and reducing agent are added in liquid, then reacts with cobalt salt solution, obtains under nitrogen protection
Hydroxide cobalt.The hydroxide cobalt, which is transferred to after filter washing in stills for air blowing, aoxidize instead
Should, hydroxy cobalt oxide is finally prepared.Obviously, this method preparation process is complicated, required to set
Standby huge (stills for air blowing).To sum up, it is not related to hollow six-membered cyclic hydroxy cobalt oxide also at present
The report of nano material and preparation method.The present invention provides a kind of six nanometers of members of nanoscale first
Ring-type hydroxy cobalt oxide material and preparation method thereof.The present invention is simple with technological process, process
Energy consumption is low, product pattern and size tunable, and the advantages that easily large-scale production, gained is hollow hexa-atomic
Ring-type hydroxy cobalt oxide nano material is expected to lead in lithium ion battery, ultracapacitor, catalysis etc.
Domain is applied.
The content of the invention
It is an object of the invention to provide a kind of hollow six-membered cyclic hydroxy cobalt oxide nano material
And preparation method thereof, to applied to fields such as lithium ion battery, ultracapacitor, catalysis.
The hollow six-membered cyclic hydroxy cobalt oxide nano material molecular formula is CoOOH, and this is hollow hexa-atomic
The length on (cross section) six sides of ring-type hydroxy cobalt oxide is 50-150nm, longitudinal thickness
For 10-20nm, wall thickness 20-30nm.Its preparation method specifically comprises the following steps：
(1) cobalt salt and strong alkali aqueous solution are prepared, cobalt ions (Co in the cobalt saline solution2+) rub
Your concentration is 0.05-1.0mol/L, hydroxide ion (OH in the strong alkali aqueous solution-) mole
Concentration is 0.05-5.0mol/L；
(2) cobalt saline solution and strong alkali aqueous solution are instilled in three-necked flask with same traffic cocurrent,
Under inert atmosphere and stirring condition, 0.5-2h is reacted in 30-80 DEG C；
(3) inert gas is removed, adds a certain amount of strong oxidizer, continues to be aged 0.2-4h；
(4) after ageing terminates, gained suspension is filtered, washs, dries, and obtains a kind of hollow
Six-membered cyclic hydroxy cobalt oxide nano material.
Cobalt salt is one in cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt acetate in above-mentioned technical proposal
Kind is several.
Highly basic in above-mentioned technical proposal in strong alkali aqueous solution is lithium hydroxide, sodium hydroxide, hydrogen
One or more in potassium oxide.
Cobalt ions (Co in cobalt saline solution in above-mentioned technical proposal2+) with strong alkali aqueous solution in hydrogen
Oxygen radical ion (OH-) mol ratio be n (Co2+)/n(OH-) scope be 1:1-1:20.
Cobalt saline solution is identical with strong alkali aqueous solution flow in above-mentioned technical proposal, and range of flow is
5-100mL/min。
Inert gas is the one or two of nitrogen and argon gas in above-mentioned technical proposal.
Strong oxidizer is one or both of hydrogen peroxide and sodium hypochlorite in above-mentioned technical proposal,
Its final mass fraction in the solution is 2%-10%.
The invention provides a kind of hollow six-membered cyclic hydroxy cobalt oxide nano material and preparation side
Method, compared with prior art, there is following characteristic：(1) nanoscale hollow six has been synthesized first
First ring-type hydroxy cobalt oxide, this unique pattern be expected to lithium ion battery, ultracapacitor,
The acquirement application such as catalytic field；(2) Granularity Distribution is narrow, reproducible between batch, prepares
Method has the advantages that process energy consumption is low, technological process is simple, easily mass produced.
Brief description of the drawings
Fig. 1 is the TEM photos of the product of the embodiment of the present invention 1.
Fig. 2 is the XRD of the product of the embodiment of the present invention 1.
Fig. 3 is the TEM photos of the product of the embodiment of the present invention 1.
Fig. 4 is the TEM photos of the product of comparative example 1 of the present invention.
Embodiment
Following examples are used to illustrate the present invention.
Embodiment 1
(1) configuration concentration is 0.1mol/L cobalt chloride solution and 1.0mol/L hydrogen-oxygen
Change each 50mL of sodium water solution；(2) by above two solution respectively via constant-flux pump with phase cocurrent flow
Amount (20mL/min) is squeezed into three-necked flask, nitrogen is passed through in three-necked flask in advance, at 50 DEG C
And react 30min under stirring condition；(3) N is removed2, add the dioxygen that mass fraction is 28%
Water 10ml, it is aged 30min；(4) after ageing terminates, gained suspension is filtered, washing,
Dry, hollow six-membered cyclic hydroxy cobalt oxide is prepared, its TEM photo and XRD spectra
Accompanying drawing 1 and accompanying drawing 2 are seen respectively.It can be seen that the length on six sides of gained sample is
80-100nm, longitudinal thickness 10-15nm, wall thickness 20-25nm.
Embodiment 2
(1) configuration concentration is 0.1mol/L cobalt chloride solution and 0.3mol/L hydrogen-oxygen
Change each 50mL of sodium water solution；(2) by above two solution respectively via constant-flux pump with phase cocurrent flow
Amount (20mL/min) is squeezed into three-necked flask, nitrogen is passed through in three-necked flask in advance, at 50 DEG C
And react 30min under stirring condition；(3) N is removed2, add the dioxygen that mass fraction is 28%
Water 10ml, it is aged 30min；(4) after ageing terminates, gained suspension is filtered, washing,
Dry, hollow six-membered cyclic hydroxy cobalt oxide is prepared, its TEM photo is shown in accompanying drawing 3.Can
To find out that the length on six sides of gained sample is 100-120nm, longitudinal thickness 10-15
Nm, wall thickness 20-25nm.
Embodiment 3
(1) configuration concentration is 0.1mol/L cobalt chloride solution and 1.0mol/L hydroxide
Each 50mL of sodium water solution；(2) by above two solution respectively via constant-flux pump with same traffic
(100mL/min) is squeezed into three-necked flask, is passed through nitrogen in three-necked flask in advance, at 50 DEG C
And react 30min under stirring condition；(3) N is removed2, add the dioxygen that mass fraction is 28%
Water 10ml, it is aged 2h；(4) after ageing terminates, gained suspension is filtered, washs, be dry
It is dry, hollow six-membered cyclic hydroxy cobalt oxide is prepared, the length on six sides of gained sample is equal
For 120-150nm, longitudinal thickness 15-20nm, wall thickness 25-30nm.
Embodiment 4
(1) configuration concentration is 0.1mol/L cobalt sulfate solution and 1.0mol/L hydroxide
Each 50mL of sodium water solution；(2) by above two solution respectively via constant-flux pump with same traffic
(20mL/min) is squeezed into three-necked flask, is passed through nitrogen in three-necked flask in advance, at 50 DEG C
And react 30min under stirring condition；(3) N is removed2, add the dioxygen that mass fraction is 28%
Water 20ml, it is aged 30min；(4) after ageing terminates, gained suspension is filtered, washing,
Dry, hollow six-membered cyclic hydroxy cobalt oxide, the length on six sides of gained sample is prepared
It is 80-100nm, longitudinal thickness 10-15nm, wall thickness 20-25nm.
Embodiment 5
(1) configuration concentration is 0.1mol/L cobalt chloride solution and 1.0mol/L hydroxide
Each 50mL of sodium water solution；(2) by above two solution respectively via constant-flux pump with same traffic
(20mL/min) is squeezed into three-necked flask, is passed through nitrogen in three-necked flask in advance, at 30 DEG C
And react 30min under stirring condition；(3) N is removed2, add the secondary chlorine that mass fraction is 10%
Acid sodium aqueous solution 20ml, it is aged 30min；(4) after ageing terminates, gained suspension passes through
Filter, washing, dry, be prepared hollow six-membered cyclic hydroxy cobalt oxide, the six of gained sample
The length on bar side is 80-100nm, longitudinal thickness 10-15nm, wall thickness 20-25nm.
Comparative example 1
(1) configuration concentration is 0.1mol/L cobalt chloride solution and 1.0mol/L hydrogen-oxygen
Change each 50mL of sodium water solution；(2) by above two solution respectively via constant-flux pump with phase cocurrent flow
Amount (20mL/min) is squeezed into three-necked flask, nitrogen is passed through in three-necked flask in advance, at 50 DEG C
And it is aged 2h under stirring condition；(3) after ageing terminates, gained suspension is filtered, washing,
Dry, a nanometer hexagonal plate hydroxide cobalt is prepared, its TEM photo is shown in accompanying drawing 4.Can
To find out that the length on six sides of gained sample is 120-150nm, longitudinal thickness 15-20
nm。
Claims (8)
1. a kind of hollow six-membered cyclic hydroxy cobalt oxide nano material, its molecular formula is CoOOH, should
The length on six sides of hollow six-membered cyclic hydroxy cobalt oxide is 50-150nm, longitudinal thickness
For 10-20nm, wall thickness 20-30nm.
2. the preparation side of hollow six-membered cyclic hydroxy cobalt oxide nano material according to claim 1
Method, it is concretely comprised the following steps：
(1) cobalt salt and strong alkali aqueous solution are prepared, cobalt ions (Co in the cobalt saline solution2+) rub
Your concentration is 0.05-1.0mol/L, hydroxide ion (OH in the strong alkali aqueous solution-) mole
Concentration is 0.05-5.0mol/L；
(2) cobalt saline solution and strong alkali aqueous solution are instilled in three-necked flask with same traffic cocurrent,
Under inert atmosphere and stirring condition, 0.5-2h is reacted in 30-80 DEG C；
(3) inert gas is removed, adds a certain amount of strong oxidizer, continues to be aged 0.2-4h；Institute
It is 2%-10% to state the final mass fraction of strong oxidizer in the solution；
(4) after ageing terminates, gained suspension is filtered, washs, dries, and obtains a kind of hollow
Six-membered cyclic hydroxy cobalt oxide nano material.
3. the preparation side of hollow six-membered cyclic hydroxy cobalt oxide nano material according to claim 2
Method, it is characterised in that：The cobalt salt is in cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt acetate
It is one or more of.
4. the preparation side of hollow six-membered cyclic hydroxy cobalt oxide nano material according to claim 2
Method, it is characterised in that：Highly basic in the strong alkali aqueous solution is lithium hydroxide, sodium hydroxide,
One or more in potassium hydroxide.
5. the preparation side of hollow six-membered cyclic hydroxy cobalt oxide nano material according to claim 2
Method, it is characterised in that：Cobalt ions (Co in the cobalt saline solution2+) with strong alkali aqueous solution in
Hydroxide ion (OH-) mol ratio be n (Co2+)/n(OH-) scope be 1:1-1:20.
6. the preparation side of hollow six-membered cyclic hydroxy cobalt oxide nano material according to claim 2
Method, it is characterised in that：Cobalt saline solution is identical with strong alkali aqueous solution flow, and range of flow is
5-100mL/min。
7. the preparation side of hollow six-membered cyclic hydroxy cobalt oxide nano material according to claim 2
Method, it is characterised in that：The gas of the inert atmosphere is the one or two of nitrogen and argon gas.
8. the preparation side of hollow six-membered cyclic hydroxy cobalt oxide nano material according to claim 2
Method, it is characterised in that：The strong oxidizer is one or both of hydrogen peroxide and sodium hypochlorite.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110095616A (en) * | 2019-05-23 | 2019-08-06 | 重庆医科大学 | A method of based on cobalt nano material/aptamer combined probe fluorescence " On-Off-On " strategy detection brain natriuretic peptide |
| CN111924890A (en) * | 2020-07-01 | 2020-11-13 | 陕西师范大学 | Preparation method of CoO (OH) nanoflower |
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| JP5017747B2 (en) * | 2001-04-23 | 2012-09-05 | 株式会社豊田中央研究所 | Cobalt oxide hydroxide plate-like particles |
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| CN110095616A (en) * | 2019-05-23 | 2019-08-06 | 重庆医科大学 | A method of based on cobalt nano material/aptamer combined probe fluorescence " On-Off-On " strategy detection brain natriuretic peptide |
| CN111924890A (en) * | 2020-07-01 | 2020-11-13 | 陕西师范大学 | Preparation method of CoO (OH) nanoflower |
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