CN107265517B - A kind of hollow pearl cotton like cobaltosic oxide and preparation method thereof - Google Patents
A kind of hollow pearl cotton like cobaltosic oxide and preparation method thereof Download PDFInfo
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
This application discloses a kind of hollow pearl cotton like cobaltosic oxides and preparation method thereof, which includes the following steps：In water by salt solubility, it is configured to cobalt salt solution, under agitation, glycine is added in cobalt salt solution, then adds isoniazid, ethyl alcohol is added in the above solution, until obtaining aubergine jelly, three times through deionized water washing, drying obtains cobalt precursor；Resulting aubergine glue complex cobalt precursor will be dried to be placed in porcelain boat, high-temperature calcination is carried out with tube furnace, pearl cotton like cobaltosic oxide is obtained after natural cooling.The hollow hollow structure of cobaltosic oxide of the invention carries the fields such as medicine and suffers from potential application in lithium battery.
Description
Technical field
The application belongs to inorganic functional material technical field, specifically, being related to a kind of hollow oxidation of pearl cotton like four three
Cobalt and preparation method thereof.
Background technique
Cobaltosic oxide has excellent magnetics and chemical property, therefore about Co3O4 nanometer material preparation side
Method and property research etc. become one of current hot subject.Since hollow nano-material has large specific surface area, biggish inside
The features such as space, Surface Permeability and thermal stability are good is widely used in lithium ion battery electrode material, catalyst, sensing
With carry the various fields such as medicine.
It at present for the synthesis of hollow structure cobaltosic oxide, is mainly prepared using hydro-thermal method, such as：1) patent is a kind of
Preparation method (the publication number of cobaltosic oxide hollow sub-microsphere：105036203 A of CN, the applying date：2015-07-04), the system
Preparation Method is to react 4h~obtain four oxidations for 24 hours under conditions of 120 DEG C~240 DEG C using hydro-thermal method with raw materials such as cobaltous sulfates
Three cobalt hollow sub-microspheres.2) patent cobaltosic oxide multi-shell hollow sphere cathode material for lithium ion battery and preparation method thereof
(publication number：CN10324777A, the applying date：2013-05-03), it needs to prepare carbon with hydro-thermal method first in the preparation method
Then ball is template using carbon ball, allows carbon ball adsorbing metal cobalt salt under hydrothermal conditions.Four oxygen are obtained finally by high-temperature roasting
Change three cobalt Multi-layer hollow microballoons.Water-heat process is used in above all of document report, since hydro-thermal method needs high temperature, height
It is carried out under the conditions of pressure, to equipment requirement harshness, complicated for operation, energy consumption is higher, therefore is unfavorable for industrialized production and application.
Hollow structure is constructed in traditional preparation process, uses hydro-thermal method substantially, hydro-thermal method complex process, energy consumption is high, no
Easy mass production hinders its industrial applications.Therefore, it develops and the hollow structure of electrode material has been realized based on new mechanism and path
A significant challenge project as correlative study.
Summary of the invention
In view of this, the application is directed to above-mentioned problem, a kind of hollow pearl cotton like cobaltosic oxide and its system are provided
Preparation Method.
In order to solve the above-mentioned technical problem, this application discloses a kind of preparation sides of hollow pearl cotton like cobaltosic oxide
Method includes the following steps：
Step 1, by salt solubility in water, configuration obtain cobalt salt solution；
Step 2, under agitation, glycine is added in cobalt salt solution, then adds isoniazid；
Ethyl alcohol is added in the solution that step 2 obtains in step 3, until obtaining aubergine jelly, washs through deionized water
Three times, drying obtains aubergine glue cobalt precursor；
Step 4, gained cobalt precursor are placed in porcelain boat, are carried out high-temperature calcination with tube furnace, are obtained pearl after natural cooling
Cotton like cobaltosic oxide.
Further, the concentration of the cobalt salt solution in step 1 is 0.5-1.0mol/L.
Further, the cobalt salt solution in step 1 is in cobalt nitrate aqueous solution, cobalt acetate aqueous solution or cobalt sulfate solution
One kind.
Further, cobalt salt and glycine molar ratio are 1 in the cobalt salt solution in step 2:2-1:2.5, isoniazid with it is sweet
Propylhomoserin molar ratio is 1:1.8-1:2.2.
Further, the speed of agitator in step 2 is 180-220r/min.
Further, the drying temperature in step 3 is 50-70 DEG C.
Further, the calcination temperature in step 4 is 450-600 DEG C, and calcination time is 1-3 hours, the heating speed of calcining
Rate is 1-5 DEG C/minute.
Hollow pearl cotton like cobaltosic oxide is prepared by above-mentioned preparation method the invention also discloses a kind of.
Compared with prior art, the application can be obtained including following technical effect：
1) preparation process of the present invention is simple, obtains gluey presoma by one-step method, then high temperature sintering obtains product.
2) precursor preparation of the present invention carries out at normal temperature, without heating.
3) preparation method of the present invention is normal pressure liquid phase method, without complex processes such as hydro-thermals.
4) feed stock conversion of the present invention is high, and etoh solvent recycling is easy.Certainly, any product for implementing the application must be different
It is fixed to need while reaching all the above technical effect.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present application, constitutes part of this application, this Shen
Illustrative embodiments and their description please are not constituted an undue limitation on the present application for explaining the application.In the accompanying drawings：
Fig. 1 is the stereoscan photograph of the hollow pearl cotton like cobaltosic oxide of the application；
Fig. 2 is the XRD spectra of the hollow pearl cotton like cobaltosic oxide of the application.
Specific embodiment
Presently filed embodiment is described in detail below in conjunction with accompanying drawings and embodiments, thereby how the application is applied
Technological means solves technical problem and reaches the realization process of technical effect to fully understand and implement.
The present invention provides a kind of preparation method of hollow pearl cotton like cobaltosic oxide, includes the following steps：
Step 1, by salt solubility in water, configure the cobalt salt solution of 0.5-1.0mol/L, cobalt salt solution is cobalt nitrate water
Solution, cobalt acetate aqueous solution and cobalt sulfate solution.
Step 2, in the case where revolving speed is 180-220r/min stirring condition, be added glycine in cobalt salt solution, cobalt salt and sweet
Propylhomoserin molar ratio is 1:2-1:2.5, isoniazid is then added, isoniazid and glycine molar ratio are 1:1.8-1:2.2, different cigarette
The ratio of hydrazine and glycine is the key that experiment, under suitable conditions, forms aubergine glue complex.
Ethyl alcohol is added in step 3 in the above solution, until aubergine jelly is obtained, three times through deionized water washing,
50-70 DEG C of drying obtains aubergine glue cobalt precursor；
Step 4, gained cobalt precursor are placed in porcelain boat, carry out high-temperature calcination, calcination temperature 450-600 with tube furnace
DEG C, the time is 1-3 hours, and heating rate is 1-5 DEG C/minute, and pearl cotton like cobaltosic oxide is obtained after natural cooling.
In this preparation method, 1, glycine solution be faintly acid, isoniazid aqueous solution be alkalescent, the two generating unit
Point neutralization reaction, while adjustment effect is played to the pH of solution, be conducive to ligand glycine, isoniazid and the cobalt of higher concentration from
It is competed when son coordination with hydroxyl in aqueous solution (hydroxyl).
2, isoniazid molecule it is larger and be multidentate ligand, usually as on bridge ligand end group carbonyl O and diazanyl N with
Metal ion-chelant, at the same on molecule other end pyridine ring N atom and another metallic ion coordination, and then formed and one-dimensional matched
Position polymer chain, and metal ion other coordination sites can only be by the relatively small glycine of volume due to the influence of steric hindrance
And inorganic anion occupies.With in the water-soluble solution of polymers, after ethyl alcohol (step 3) is added, solvent is replaced, coordination polymerization
Object solubility reduces, and forms micella and further reunites and form colloid, dries or be dried into vitreum.
3, nickel salt can be cobalt nitrate, nickel acetate and cobaltous sulfate, it is not possible to be cobalt chloride.Chloride ion, which exists, then forms octahedral
Body cannot get hollow foam shape structure.The molar ratio of glycine and isoniazid is 1:1.8-1:2.2, it is more than or less than this range
It cannot get vitreous substance.
4, isoniazid plays a crucial role to hollow foam shape structure is formed, and isoniazid is decomposed at high temperature generates a large amount of gas
Body, to form hollow structure.In addition the gel-like vitreous body generated also plays a crucial role to hollow foam shape structure, and vitreum does not have
There is definite melting point, slowly melts decomposition in heating condition.
Embodiment 1
Cobalt nitrate is dissolved in deionized water, 0.5mol/L cobalt nitrate solution is obtained；In 200r/min revolving speed stirring bar
Under part, glycine is added in cobalt nitrate solution, cobalt nitrate and glycine molar ratio are 1:2；Then isoniazid, isoniazid is added
It is 1 with glycine molar ratio:2；Ethyl alcohol is added in the above solution, until obtaining aubergine color jelly, is washed through deionization
It washs three times, 60 DEG C of drying obtain cobalt precursor；Gained purple red precipitate is transferred in porcelain boat, with tube furnace high temperature sintering, is risen
Warm rate is 2 DEG C/min, keeps the temperature 2 hours under the conditions of 500 DEG C and obtains product.The stereoscan photograph of products therefrom as shown in Figure 1,
And XRD spectra is as shown in Figure 2.It will be seen from figure 1 that products therefrom is hollow foam shape structure.From Fig. 2 spectrogram and Co3O4Mark
Quasi- spectrogram (JCPDS card no.74-1657) unanimously, occurs without other impurity peaks.
Embodiment 2
Cobalt acetate is dissolved in water, the acetic acid cobalt liquor of 1.0mol/L is configured, under 180r/min revolving speed stirring condition,
Glycine is added in acetic acid cobalt liquor, cobalt acetate and glycine molar ratio are 1：2.5, then add isoniazid, isoniazid
It is 1 with glycine molar ratio:1.8；Ethyl alcohol is added in the above solution, until obtaining aubergine jelly, is washed through deionization
It washs three times, 50 DEG C of drying obtain aubergine glue cobalt precursor；Gained cobalt precursor is placed in porcelain boat, carries out high temperature with tube furnace
Calcining, calcination temperature are 450 DEG C, and the time is 3 hours, and heating rate is 1 DEG C/minute, and four oxygen of pearl cotton like is obtained after natural cooling
Change three cobalts.
Embodiment 3
Cobaltous sulfate is dissolved in water, the cobalt sulfate solution of 0.8mol/L is configured；Under 220r/min revolving speed stirring condition,
Glycine is added in cobalt sulfate solution, cobaltous sulfate and glycine molar ratio are 1:2.2, then add isoniazid, isoniazid
It is 1 with glycine molar ratio:2.2；Ethyl alcohol is added in the above solution, until obtaining aubergine jelly, is washed through deionization
It washs three times, 70 DEG C of drying obtain aubergine glue cobalt precursor；Gained cobalt precursor is placed in porcelain boat, carries out high temperature with tube furnace
Calcining, calcination temperature are 600 DEG C, and the time is 1 hour, and heating rate is 5 DEG C/minute, and four oxygen of pearl cotton like is obtained after natural cooling
Change three cobalts.
Embodiment 4
Cobalt acetate is dissolved in water, the cobalt acetate solution of 0.6mol/L is configured；Under 190r/min revolving speed stirring condition,
Glycine is added in cobalt acetate solution, cobalt acetate and glycine molar ratio are 1:2.1, then add isoniazid, isoniazid
It is 1 with glycine molar ratio:2；Ethyl alcohol is added in the above solution, until obtaining aubergine jelly, is washed through deionized water
Three times, 55 DEG C of drying obtain aubergine glue cobalt precursor；Gained cobalt precursor is placed in porcelain boat, is carried out high temperature with tube furnace and is forged
It burns, calcination temperature is 500 DEG C, and the time is 2.5 hours, and heating rate is 3 DEG C/minute, and four oxygen of pearl cotton like is obtained after natural cooling
Change three cobalts.
Embodiment 5
Cobalt nitrate is dissolved in water, the cobalt nitrate solution of 0.9mol/L is configured；Under 210r/min revolving speed stirring condition,
Glycine is added in cobalt nitrate solution, cobalt nitrate solution and glycine molar ratio are 1:2.4, isoniazid is then added, it is different
Cigarette hydrazine and glycine molar ratio are 1:1.9；Ethyl alcohol is added in the above solution, until aubergine jelly is obtained, through deionization
Three times, 65 DEG C of drying obtain aubergine glue cobalt precursor to water washing；Gained cobalt precursor is placed in porcelain boat, is carried out with tube furnace
High-temperature calcination, calcination temperature are 550 DEG C, and the time is 1.5 hours, and heating rate is 4 DEG C/minute, and pearl cotton is obtained after natural cooling
Shape cobaltosic oxide.
As used some vocabulary in the specification and claims to censure special component or method.Art technology
Personnel are, it is to be appreciated that different regions may call the same ingredient with different nouns.This specification and claims are not
In such a way that the difference of title is as ingredient is distinguished.As the "comprising" mentioned by throughout the specification and claims is
One open language, therefore should be construed to " including but not limited to "." substantially " refer within the acceptable error range, this field
Technical staff can solve the technical problem within a certain error range, basically reach the technical effect.Specification is subsequent
It is described as implementing the better embodiment of the application, so the description is for the purpose of the rule for illustrating the application, not
To limit scope of the present application.The protection scope of the application is as defined by the appended claims.
It should also be noted that, the terms "include", "comprise" or its any other variant are intended to nonexcludability
Include, so that commodity or system including a series of elements not only include those elements, but also including not clear
The other element listed, or further include for this commodity or the intrinsic element of system.In the feelings not limited more
Under condition, the element that is limited by sentence "including a ...", it is not excluded that in the commodity or system for including the element also
There are other identical elements.
Above description has shown and described several preferred embodiments of invention, but as previously described, it should be understood that invention is not
It is confined to form disclosed herein, should not be regarded as an exclusion of other examples, and can be used for various other combinations, modification
And environment, and can be carried out within that scope of the inventive concept describe herein by the above teachings or related fields of technology or knowledge
Change.And changes and modifications made by those skilled in the art do not depart from the spirit and scope of invention, then it all should be in the appended power of invention
In the protection scope that benefit requires.
Claims (7)
1. a kind of preparation method of hollow pearl cotton like cobaltosic oxide, which is characterized in that include the following steps：
Step 1, by salt solubility in water, configuration obtain cobalt salt solution；
Step 2, under agitation, glycine is added in cobalt salt solution, then adds isoniazid；
Ethyl alcohol is added in the solution that step 2 obtains in step 3, until aubergine jelly is obtained, through deionized water washing three
Secondary, drying obtains aubergine glue cobalt precursor；
Step 4, gained cobalt precursor are placed in porcelain boat, carry out high-temperature calcination with tube furnace, pearl cotton like is obtained after natural cooling
Cobaltosic oxide.
2. preparation method according to claim 1, which is characterized in that the concentration of the cobalt salt solution in step 1 is 0.5-
1.0mol/L。
3. preparation method according to claim 1, which is characterized in that cobalt salt solution in step 1 be cobalt nitrate aqueous solution,
One of cobalt acetate aqueous solution or cobalt sulfate solution.
4. preparation method according to claim 1, which is characterized in that cobalt salt and glycine in the cobalt salt solution in step 2
Molar ratio is 1:2-1:2.5, isoniazid and glycine molar ratio are 1:1.8-1:2.2.
5. preparation method according to claim 1, which is characterized in that the speed of agitator in step 2 is 180-220r/min.
6. preparation method according to claim 1, which is characterized in that the drying temperature in step 3 is 50-70 DEG C.
7. preparation method according to claim 1, which is characterized in that the calcination temperature in step 4 is 450-600 DEG C, is forged
Burning the time is 1-3 hours, and the heating rate of calcining is 1-5 DEG C/minute.
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| CN108470904B (en) * | 2018-03-21 | 2020-03-31 | 淮阴师范学院 | Annular sheet-shaped hexagonal manganous-manganic oxide lithium battery negative electrode material and preparation method thereof |
| CN110156092B (en) * | 2018-11-12 | 2021-07-30 | 淮阴师范学院 | Dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material and preparation method thereof |
| CN111498913A (en) * | 2020-05-12 | 2020-08-07 | 北京林业大学 | Preparation method and application of cobaltosic oxide nanoparticles |
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| CN103241781A (en) * | 2013-04-19 | 2013-08-14 | 浙江大学 | Method for preparing porous Co3O4 powder |
| CN103395846A (en) * | 2013-08-05 | 2013-11-20 | 青岛科技大学 | Preparation method and application of octahedron-shaped cobaltosic oxide anode material for lithium ion battery |
| CN103803663A (en) * | 2012-11-06 | 2014-05-21 | 宁波科博特钴镍有限公司 | Production method of spherical tricobalt tetroxide |
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| CN103803663A (en) * | 2012-11-06 | 2014-05-21 | 宁波科博特钴镍有限公司 | Production method of spherical tricobalt tetroxide |
| CN103241781A (en) * | 2013-04-19 | 2013-08-14 | 浙江大学 | Method for preparing porous Co3O4 powder |
| CN103395846A (en) * | 2013-08-05 | 2013-11-20 | 青岛科技大学 | Preparation method and application of octahedron-shaped cobaltosic oxide anode material for lithium ion battery |
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