CN110436530A - A kind of yolk shell structure cobalt acid manganese porous microsphere and preparation method thereof - Google Patents
A kind of yolk shell structure cobalt acid manganese porous microsphere and preparation method thereof Download PDFInfo
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- CN110436530A CN110436530A CN201910647822.1A CN201910647822A CN110436530A CN 110436530 A CN110436530 A CN 110436530A CN 201910647822 A CN201910647822 A CN 201910647822A CN 110436530 A CN110436530 A CN 110436530A
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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
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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
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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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The present invention discloses a kind of yolk shell structure cobalt acid manganese porous microsphere and preparation method thereof.Microballoon is prepared by cobalt salt, manganese salt, polyvinylpyrrolidone and ethylene glycol, and about 2.1 μm of the diameter of microballoon, BET specific surface area 20.45m2g‑1.Preparation method is: polyethylene pyrrole lattice alkanone being added in ethylene glycol and is stirred continuously until all dissolutions；Cobalt salt and manganese salt are added in the ethylene glycol solution of polyvinylpyrrolidone again and are stirred continuously until forming homogeneous solution；Mixed solution is transferred in autoclave again after heating a period of time under certain temperature and is cooled to room temperature, by being centrifugated and washing the precipitating generated and drying with ethyl alcohol and deionized water, after the precipitating after then roasting is dry.Yolk shell structure cobalt acid manganese porous microsphere material prepared by the present invention can be used as electrode material applied to lithium ion battery.Do not need certain moduli plate agent, preparation process is simple, favorable reproducibility, it is easy to implement, be suitble to large-scale production.
Description
Technical field
The invention belongs to field of nano material preparation more particularly to a kind of yolk shell structure cobalt acid manganese porous microsphere and its systems
Preparation Method.
Background technique
Due to cobalt acid manganese (MnCo2O4) have good chemical property, corrosion-resistant, preparation process is simple, nontoxic, price
The advantages that cheap and distribution is wide, so, in lithium ion battery, photocatalysis, information storage, plastics, coating and gas sensing etc.
It is widely paid close attention to and is applied in field.Since the structure and pattern of cobalt acid manganese have important influence to its performance.In order to mention
Its high performance, scientific worker have synthesized nanometer rods, nano wire, nanotube, nanoparticle, nanobelt, nanometer sheet, multi-panel
The yolk shell structure cobalt acid manganese of the different structures such as body, cube and porous core-shell particles structure and pattern.However so far,
It yet there are no using a kind of solvent heat wet chemistry method and prepare the uniform yolk of morphology controllable, particle diameter distribution in conjunction with subsequent heat treatment
The report of shell structure cobalt acid manganese porous microsphere nano material.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of yolk shell structure cobalt acid manganese porous microsphere and its controlledly synthesis
Preparation method to reduce cost, reduce environmental pollution, and makes product BET surface area with higher.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of yolk shell structure cobalt acid manganese porous microsphere, by the preparation of cobalt salt, manganese salt, polyvinylpyrrolidone and ethylene glycol
At the average diameter of porous microsphere is 2.1 μm, BET specific surface area 20.45m2 g-1。
Further, the cobalt salt is a variety of of one of cobalt acetate, cobalt nitrate or cobaltous sulfate or any mass ratio；Institute
The manganese salt stated is a variety of of one of manganese acetate, manganese nitrate or manganese sulfate or any mass ratio.
Further, the ratio between amount of substance of the cobalt salt and manganese salt is 2:1；Concentration of the cobalt salt in ethylene glycol be 7.63~
10.21g/L；
Further, concentration of the polyvinylpyrrolidone in ethylene glycol is 1.28~2.51g/L.
In order to achieve the above-mentioned object of the invention, the present invention also provides following technical schemes:
A kind of preparation method of yolk shell structure cobalt acid manganese porous microsphere, comprising the following steps:
(1) polyvinylpyrrolidone is added in ethylene glycol, and be stirred continuously until all dissolutions；The polyethylene pyrrole
Concentration of the pyrrolidone in ethylene glycol is 1.28~2.51g/L.
(2) it in the ethylene glycol solution for the polyvinylpyrrolidone that cobalt salt and manganese salt are added in step (1), and constantly stirs
It mixes until all dissolutions；The ratio between amount of substance of the cobalt salt and manganese salt is 2:1；Concentration of the cobalt salt in ethylene glycol be 7.63~
10.21g/L；
(3) mixed aqueous solution in step (2) is placed in autoclave, is then placed in baking oven and carries out at hydro-thermal
Reason, cooled to room temperature after being kept for 12~24 hours at a temperature of 160 DEG C~190 DEG C；
(4) it by the sample after hydro-thermal in step (3), is centrifuged with the revolving speed of 5000~6000r/min and uses second
Pure and mild deionized water is successively washed 3 times；Finally precipitating is put into vacuum oven and is dried；
(5) precipitating of step (4) after dry is placed in tube furnace, sky is passed through with the air inflow of 0.15~0.5 L/min
Gas shielded gas, heating rate are 1~2.5 DEG C/min, are warming up to 550~600 DEG C and naturally cool to after keeping the temperature 3~5 hours
Room temperature obtains yolk shell structure cobalt acid manganese porous microsphere material.
Preferably, in above-mentioned steps (2), the cobalt salt is one of cobalt acetate, cobalt nitrate or cobaltous sulfate or appoints
Anticipate a variety of of mass ratio；The manganese salt is a variety of of one of manganese acetate, manganese nitrate or manganese sulfate or any mass ratio.
Preferably, in above-mentioned steps (5), the average diameter of the porous microsphere is 2.1 μm, and BET specific surface area is
20.45m2 g-1。
Compared with the prior art, the present invention has the advantage that and has the beneficial effect that:
Using solvent-thermal method and the yolk shell structure cobalt acid manganese porous microsphere of combination subsequent heat treatment preparation, particle diameter distribution
And pattern reaches controllably, preparation method is simple, at low cost, favorable reproducibility, easy to implement, be suitble to large-scale production, preparation it is more
Hole microballoon has broad application prospects.
Detailed description of the invention
Fig. 1 is the X-ray diffraction result of yolk shell structure cobalt acid manganese porous microsphere material prepared by the embodiment of the present invention 1
Figure.
Fig. 2 is the transmission electron microscope picture of yolk shell structure cobalt acid manganese porous microsphere material prepared by the embodiment of the present invention 1.
Fig. 3 is the BET curve of yolk shell structure cobalt acid manganese porous microsphere material prepared by the embodiment of the present invention 1.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is described in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention,
It is not intended to limit the present invention.
Embodiment 1
A kind of preparation method of yolk shell structure cobalt acid manganese porous microsphere, the specific steps of which are as follows:
(1) 0.1g polyvinylpyrrolidone is added in 60mL ethylene glycol, and be stirred continuously until all dissolutions；
(2) tetra- acetate hydrate cobalt of 0.498g and tetra- acetate hydrate manganese of 0.251g are added to the polyethylene pyrrole in step (1)
In the ethylene glycol solution of pyrrolidone, and it is stirred continuously until all dissolutions；
(3) mixed aqueous solution in step (2) is placed in 100mL autoclave, is then placed in baking oven and carries out
Hydro-thermal process, cooled to room temperature after being kept for 12 hours at a temperature of 180 DEG C；
(4) it by the sample after hydro-thermal in step (3), is centrifuged with the revolving speed of 6000r/min and with ethyl alcohol and going
Ionized water successively washs 3 times；Finally precipitating is put into vacuum oven and is dried；
(5) precipitating of step (4) after dry is placed in tube furnace, air conservation is passed through with the air inflow of 0.2 L/min
Gas, heating rate are 2 DEG C/min, and cooled to room temperature after being warming up to 600 DEG C and keeping the temperature 3 hours obtains yolk shell structure
Cobalt acid manganese porous microsphere material.About 2.1 μm of the diameter of gained porous microsphere.
Embodiment 2
A kind of preparation method of yolk shell structure cobalt acid manganese porous microsphere, the specific steps of which are as follows:
(1) 0.08g polyvinylpyrrolidone is added in 60mL ethylene glycol, and be stirred continuously until all dissolving
(2) tetra- acetate hydrate cobalt of 0.612g and tetra- acetate hydrate manganese of 0.309g are added to the polyethylene pyrrole in step (1)
In the ethylene glycol solution of pyrrolidone, and it is stirred continuously until all dissolutions；
(3) mixed aqueous solution in step (2) is placed in 100mL autoclave, is then placed in baking oven and carries out
Hydro-thermal process, cooled to room temperature after being kept for 12 hours at a temperature of 160 DEG C；
(4) it by the sample after hydro-thermal in step (3), is centrifuged with the revolving speed of 6000r/min and with ethyl alcohol and going
Ionized water successively washs 3 times；Finally precipitating is put into vacuum oven and is dried；
(5) precipitating of step (4) after dry is placed in tube furnace, air conservation is passed through with the air inflow of 0.2 L/min
Gas, heating rate are 2 DEG C/min, and cooled to room temperature after being warming up to 600 DEG C and keeping the temperature 3 hours obtains yolk shell structure
Cobalt acid manganese porous microsphere material.About 2 μm of the diameter of gained porous microsphere.
Embodiment 3
A kind of preparation method of yolk shell structure cobalt acid manganese porous microsphere, the specific steps of which are as follows:
(1) 0.15g polyvinylpyrrolidone is added in 60mL ethylene glycol, and be stirred continuously until all dissolving
(2) tetra- acetate hydrate cobalt of 0.46g and tetra- acetate hydrate manganese of 0.23g are added to the polyvinyl pyrrole in step (1)
In the ethylene glycol solution of alkanone, and it is stirred continuously until all dissolutions；
(3) mixed aqueous solution in step (2) is placed in 100mL autoclave, is then placed in baking oven and carries out
Hydro-thermal process, cooled to room temperature after being kept for 12 hours at a temperature of 190 DEG C；
(4) it by the sample after hydro-thermal in step (3), is centrifuged with the revolving speed of 6000r/min and with ethyl alcohol and going
Ionized water successively washs 3 times；Finally precipitating is put into vacuum oven and is dried；
(5) precipitating of step (4) after dry is placed in tube furnace, air conservation is passed through with the air inflow of 0.2 L/min
Gas, heating rate are 2 DEG C/min, and cooled to room temperature after being warming up to 600 DEG C and keeping the temperature 3 hours obtains yolk shell structure
Cobalt acid manganese porous microsphere material.About 2 μm of the diameter of gained porous microsphere.
Experiment effect explanation:
Fig. 1 is the X-ray diffraction result of yolk shell structure cobalt acid manganese porous microsphere material prepared by the embodiment of the present invention 1
Figure.Peak corresponds respectively to yolk shell structure cobalt acid manganese MnCo in Fig. 12O4The peak of (JCPDS card: 23-1237).The result shows
Using the cobalt acid manganese porous microsphere purity is high of the yolk shell structure of this method preparation, without other impurities.
Fig. 2 is the transmission electron microscope picture of yolk shell structure cobalt acid manganese porous microsphere material prepared by the embodiment of the present invention 1.Pass through
Fig. 2 can be seen that the diameter of yolk shell structure cobalt acid manganese porous microsphere is about 2.1 μm.
Fig. 3 is the BET curve of yolk shell structure cobalt acid manganese porous microsphere material prepared by the embodiment of the present invention 1.Pass through Fig. 3
It can be seen that the BET specific surface area of yolk shell structure cobalt acid manganese porous microsphere material is 20.45m2g-1。
The foregoing is intended to be a preferred embodiment of the present invention.Certainly, the present invention can also have other a variety of implementations
Example, without deviating from the spirit and substance of the present invention, anyone skilled in the art, when can according to this
Various corresponding equivalent change and modification are made in invention, all should fall within the scope of protection of the appended claims of the present invention.
Claims (8)
1. a kind of yolk shell structure cobalt acid manganese porous microsphere, it is characterised in that: the porous microsphere is by cobalt salt, manganese salt, polyethylene
Pyrrolidones and ethylene glycol are prepared；2.09-2.11 μm of diameter of the yolk shell structure cobalt acid manganese porous microsphere；It is described
Yolk shell structure cobalt acid manganese porous microsphere BET specific surface area be 20.45m2g-1。
2. a kind of yolk shell structure cobalt acid manganese porous microsphere according to claim 1, it is characterised in that: the cobalt acid manganese is more
The preparation method of hole microballoon is: polyethylene pyrrole lattice alkanone being added in ethylene glycol first and is stirred continuously until all dissolutions；
Then cobalt salt and manganese salt are added in the ethylene glycol solution of polyvinylpyrrolidone and are stirred continuously until forming homogeneous solution；
Then after heating a period of time under certain temperature being transferred in autoclave and is cooled to room temperature by mixed solution, pass through centrifugation point
The precipitating generated and drying are washed from and with ethyl alcohol and deionized water, the precipitating after then roasting is dry obtains yolk shell structure
Cobalt acid manganese porous microsphere material.
3. yolk shell structure cobalt acid manganese porous microsphere material according to claims 1 to 2, it is characterised in that: the poly- second
Concentration of the alkene pyrrolidone in ethylene glycol is 1.28~2.51g/L.
4. yolk shell structure cobalt acid manganese porous microsphere material according to claims 1 to 2, it is characterised in that: the cobalt salt
It is 2:1 with the ratio between the amount of substance of manganese salt；Concentration of the cobalt salt in ethylene glycol is 7.63~10.21g/L.
5. a kind of preparation method of yolk shell structure cobalt acid manganese porous microsphere material, which is characterized in that specifically includes the following steps:
(1) polyvinylpyrrolidone is added in ethylene glycol, and be stirred continuously until all dissolutions；The polyvinylpyrrolidine
Concentration of the ketone in ethylene glycol is 1.28~2.51g/L；
(2) it in the ethylene glycol solution for the polyvinylpyrrolidone that cobalt salt and manganese salt are added in step (1), and is stirred continuously straight
To whole dissolutions；The ratio between amount of substance of the cobalt salt and manganese salt is 2:1；Concentration of the cobalt salt in ethylene glycol be 7.63~
10.21g/L；
(3) mixed solution in step (2) is placed in autoclave, is then placed in baking oven, at 160 DEG C~190 DEG C
At a temperature of kept for 12~24 hours after, cooled to room temperature；
(4) it by the sample after solvent heat in step (3), is centrifuged with the revolving speed of 5000~6000r/min and uses ethyl alcohol
It is successively washed with deionized water 3 times；Finally precipitating is put into vacuum oven and is dried；
(5) precipitating of step (4) after dry is placed in tube furnace, air conservation is passed through with the air inflow of 0.15~0.5L/min
Gas, heating rate are 1~2.5 DEG C/min, and cooled to room temperature after being warming up to 550~600 DEG C and keeping the temperature 3~5 hours obtains
To the cobalt acid manganese porous microsphere material of yolk shell structure.
6. a kind of according to claim 1, yolk shell structure cobalt acid manganese porous microsphere material described in any one of 2,5, special
Sign is: the cobalt salt is a variety of of one of cobalt acetate, cobalt nitrate or cobaltous sulfate or any mass ratio；The manganese salt
For a variety of of one of manganese acetate, manganese nitrate or manganese sulfate or any mass ratio.
7. according to claim 1, yolk shell structure cobalt acid manganese porous microsphere material, feature described in any one of 2,5 exist
In: the solvent of polyethylene dissolving pyrrolidones is ethylene glycol.
8. the preparation method of yolk shell structure cobalt acid manganese porous microsphere according to claim 5, it is characterised in that: the step
Suddenly in (5), the diameter of the yolk shell structure cobalt acid manganese porous microsphere is 2.1 μm, BET specific surface area 20.45m2 g-1。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233048A (en) * | 2020-01-17 | 2020-06-05 | 曲靖师范学院 | Double-shell MnCo2O4Hollow nanosphere material and synthesis method thereof |
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| US20110111327A1 (en) * | 2009-11-09 | 2011-05-12 | Ngk Insulators, Ltd. | Coating body |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111233048A (en) * | 2020-01-17 | 2020-06-05 | 曲靖师范学院 | Double-shell MnCo2O4Hollow nanosphere material and synthesis method thereof |
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