CN101618861B - Method for preparing hollow micron sulfur balls - Google Patents
Method for preparing hollow micron sulfur balls Download PDFInfo
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- CN101618861B CN101618861B CN2009100603012A CN200910060301A CN101618861B CN 101618861 B CN101618861 B CN 101618861B CN 2009100603012 A CN2009100603012 A CN 2009100603012A CN 200910060301 A CN200910060301 A CN 200910060301A CN 101618861 B CN101618861 B CN 101618861B
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- hollow
- hollow micron
- sulfur balls
- balls
- micron sulfur
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Abstract
The invention relates to a method for preparing hollow micron sulfur balls, which comprises the following steps: (a) a flaky substrate is put at the bottom of a container containing water, and then 0.00625mol/L of sodium thiosulfate pentahydrate, 0.00625mol/L of zinc nitrate hexahydrate and 0.095mol/L of hexamethylene tetramine are added in the container to prepare a mixed solution; (b) 7-30 parts by volume of oleic acid is taken and heated to 40-60 DEG C, and then the oleic acid is added into 100 parts by volume of the mixed solution of the step (a), then the mixed solution is allowed to stand for 15-25 days, and hollow micron sulfur balls grow on the substrate; and (c) the hollow micron sulfur balls are taken out and dried. The method has simple equipment and low energy consumption and is suitable for mass production. When the prepared hollow micron sulfur balls are used as a template and a reaction medium, the hollow micron sulfur balls can be used for directly synthesizing other inorganic hollow spherical micron sulphide materials with simple synthesizing operations, and the prepared material has good performance.
Description
Technical field
The present invention relates to a kind of preparation method of hollow micron sulfur balls.
Background technology
Non-metallic element sulphur is typical electronic and ion isolator, and the Oxidation Number of element sulphur can from-2 to+7, suppose that each sulphur atom electron transfer number is 2, utilize Li
2Reversible transformation between S and the S can be widely used in the Li/S secondary cell.Its specific capacitance is up to 1675mAh/g, theoretical voltage 2.287V, and theoretical energy density reaches 3824Wh/kg, is that specific storage is the highest in the positive electrode material of being understood at present.
The material of micro-nano hollow structure has characteristics such as low density, high-specific surface area, high stable and surface seepage, has special nature at aspects such as electricity, calorifics, optics and surfaces.Micro-nano hollow structure is as a kind of " housing ", and its inner hollow partly can be used as carrier, holds guest molecule or large size object, produces " encapsulation " effect based on microcosmic.Micro-nano hollow structure can be used as " cage " and makes and be reflected at limited space and carry out, or the carrier that transmits as guest species.The material of micro-nano hollow structure can be used for making catalyzer, makeup, sorbent material, charging (secondary) battery.
Therefore, prepare the sulphur of micro-nano hollow structure simply and effectively, be with a wide range of applications in fields such as Li/S battery, dyestuff, gunpowder, medicament slow release, vulcanized rubbers.Simultaneously, hollow micron sulfur balls also can be used as masterplate and reaction medium and is used for directly synthetic other inorganic spherical hollow ball shape micron sulfide material.
Summary of the invention
The object of the invention just provides a kind of preparation method of hollow micron sulfur balls, and this method equipment is simple, and energy consumption is low, is fit to scale operation; The hollow micron sulfur balls that makes can be directly used in the sulphur that substitutes other form, and is with a wide range of applications in fields such as Li/S battery, dyestuff, gunpowder, medicament slow release, vulcanized rubbers.Simultaneously, the hollow micron sulfur balls that makes also can be used as masterplate and reaction medium is used for directly synthetic other inorganic spherical hollow ball shape micron sulfide material, and synthesis step is few, and is simple to operate, and making rerum natura can be good.
The present invention realizes that the technical scheme that order adopted of its invention is: a kind of preparation method of hollow micron sulfur balls, and its concrete practice is:
A, preparation mixing solutions
Put into sheet form base at the container bottom that is filled with water; In container, add Sodium Thiosulfate Pentahydrate, zinc nitrate hexahydrate and hexamethylenetetramine, be mixed with mixing solutions; The concentration of Sulfothiorine is that the concentration of 0.00625mol/L, zinc nitrate hexahydrate is that the concentration of 0.00625mol/L, hexamethylenetetramine is 0.095mol/L in the mixing solutions;
B, the acid of adding deep fat
After the oleic acid of getting 3-30 part volume is heated to 40-60 ℃, join in the mixing solutions of 100 parts of volumes in a step, left standstill 15-25 days, promptly in substrate, grow hollow micron sulfur balls;
C, oven dry
Hollow micron sulfur balls taking-up, the oven dry of substrate in the container and substrate grown are got final product.
The possible mechanism of the inventive method is: after the deep fat acid in b step adds a mixed solution in step, and oleic acid (CH at first
3(CH
2)
7CH=CH (CH
2)
7COOH) discharge H
+(reaction formula: CH
3(CH
2)
7CH=CH (CH
2)
7COOH → CH
3(CH
2)
7CH=CH (CH
2)
7COO
-+ H
+); Na then
2S
2O
35H
2O discharges sulphur (reaction formula: S with the H+ reaction
2O
3 2-+ H
+→ HSO
3 -+ S ↓).Simultaneously, oleic acid molecular forms W/O (water/oil) emulsion in the mixed solution of lower aqueous, and sulphur is adsorbed on the oleic acid molecular in the emulsion, grows into hollow ball, is deposited on the substrate of container bottom.Zine ion and elaidin reaction form tree-shaped zinc-oily mixture and constitute the oil phase on container top.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention adopts liquid-phase precipitation method, is the sulphur source with inorganic salt, is template with oleic acid, adds the hexamethylenetetramine used as stabilizers, at room temperature the reaction promptly get hollow micron sulfur balls, its preparation method is simple, reaction temperature with, it is little to consume energy, and equipment is not had particular requirement, is fit to scale operation.Experiment showed, that the hollow micron sulfur balls that makes is a bright sulfur free from foreign meter, its outside spherical shell diameter is the 1-4 micron, intracavity diameter 0.6-1.2 micron.This hollow micron sulfur balls because it has high specific surface area and specific storage, can be used for substituting the sulphur of other form, and is with a wide range of applications in fields such as Li/S battery, dyestuff, gunpowder, medicament slow release, vulcanized rubbers.
The hollow micron sulfur balls that makes, also can be matrix material hollow ball pattern plate is provided, utilize its inherent hollow structure, directly single hollow inorganic sulphide and Hollow Compound micro-nano structures such as CuS-S, CdS-S, CdS-S, ZnS-S and PbS-S such as synthetic CuS, CdS, ZnS and PbS.Need not remove the operation of template after synthetic the finishing, both make its preparation process simple, make the structure that makes thing definite, controlled, stable performance yet.
The temperature of the oven dry in above-mentioned c step is 70-85 ℃, and the time is 3-10 minute.
Above-mentioned a step substrate is a sheet glass.
Below in conjunction with accompanying drawing and concrete embodiment, the present invention is further detailed explanation.
Description of drawings
Fig. 1 is the X-ray diffractogram (XRD) of the hollow micron sulfur balls of the embodiment of the invention one preparation.Wherein transverse axis 2 θ are diffraction angle, and unit is degree; The longitudinal axis is a response intensity.
Fig. 2 is the X ray energy dispersion analysis (EDA) figure (EDAX) of the hollow micron sulfur balls of the embodiment of the invention one preparation.Wherein transverse axis is an electron energy, and unit is Kev; The longitudinal axis is a response intensity.
Fig. 3 is the stereoscan photograph of the hollow micron sulfur balls of the embodiment of the invention one preparation.
Fig. 4 and Fig. 5 are take a morsel respectively stereoscan photographs after supersound process of the hollow micron sulfur balls of the embodiment of the invention one preparation.
Embodiment
Embodiment one
A kind of embodiment of the present invention is: a kind of preparation method of hollow micron sulfur balls, and its concrete practice is:
A, preparation mixing solutions
Put into sheet glass as substrate in the bottom of the container that is filled with water; In container, add Sodium Thiosulfate Pentahydrate, zinc nitrate hexahydrate and hexamethylenetetramine, be mixed with mixing solutions; The concentration of Sodium Thiosulfate Pentahydrate is that the concentration of 0.00625mol/L, zinc nitrate hexahydrate is that the concentration of 0.00625mol/L, hexamethylenetetramine is 0.095mol/L in the mixing solutions;
B, the acid of adding deep fat
After the oleic acid of getting 15 parts of volumes is heated to 50 ℃, join in the mixing solutions of 100 parts of volumes in a step, left standstill 20 days, promptly in substrate, grow hollow micron sulfur balls;
C, oven dry
Hollow micron sulfur balls taking-up, the oven dry of growing on sheet glass in the container and the sheet glass are got final product, and bake out temperature is 80 ℃, and the time is 5 minutes.
Fig. 1 is the X-ray diffractogram with the hollow micron sulfur balls of the example method preparation, Fig. 1 as seen, (No.01-074-1465) is consistent with the PDF of sulphur (powdery diffractometry file) standard card for the diffraction peak of the hollow micron sulfur balls of preparation, is the bright sulfur phase.There is no other impurity.Fig. 2 is EDAX (X ray energy dispersion analysis (EDA)) figure, and as seen from Figure 2, prepared product is very pure, has only element sulphur.
Fig. 3 is that prepared product is that diameter is the coccoid of micron dimension as seen from the figure with the sem photograph of the hollow micron sulfur balls of the example method preparation, and diameter of micro ball approximately is 1-4 μ m.
The prepared product that this is routine is respectively scraped and is taken a morsel, and is put in respectively in the water, adopts the ultrasonic power of 100w, and supersound process obtains two width of cloth sem photographs---Fig. 4, Fig. 5 respectively after 5 seconds.Contrast as seen with Fig. 3, through after the supersound process, some microballoons break, and the thickness of disruptive spherical shell is greatly about 0.6-1.2 μ m, and what illustrate that the inventive method obtains is hollow micron sulfur balls.
Embodiment two
This example is basic identical with embodiment one, and different is: the hot oleic volume parts that b added in the step is 3 parts, and hot oleic temperature is 40 ℃, the time of repose of mixed solution these 15 days.The temperature that C was dried in the step is 70 ℃, and the time is 3 minutes.
Embodiment three
This example is basic identical with embodiment one, and different is: the hot oleic volume parts that b added in the step is 30 parts, and hot oleic temperature is 60 ℃, the time of repose of mixed solution these 25 days.The temperature that C was dried in the step is 85 ℃, and the time is 10 minutes.
The effect of the substrate among the present invention be used for adhering to, micron sulfur balls that growth response generates.Obviously, its sheet glass in available embodiment, also can adopt other non-metal plate, if these non-metal plates not with hydration Sulfothiorine, zinc nitrate hexahydrate and hexamethylenetetramine generation chemical reaction.
Claims (3)
1. the preparation method of a hollow micron sulfur balls, its concrete practice is:
A, preparation mixing solutions
Put into sheet form base at the container bottom that is filled with water; In container, add Sodium Thiosulfate Pentahydrate, zinc nitrate hexahydrate and hexamethylenetetramine, be mixed with mixing solutions; The concentration of Sulfothiorine is that the concentration of 0.00625mol/L, zinc nitrate hexahydrate is that the concentration of 0.00625mol/L, hexamethylenetetramine is 0.095mol/L in the mixing solutions;
B, the acid of adding deep fat
After the oleic acid of getting 3-30 part volume is heated to 40-60 ℃, join in the mixing solutions of 100 parts of volumes in a step, left standstill 15-25 days, promptly in substrate, grow hollow micron sulfur balls;
C, oven dry
Hollow micron sulfur balls taking-up, the oven dry of substrate in the container and substrate grown are got final product.
2. the preparation method of a kind of hollow micron sulfur balls as claimed in claim 1 is characterized in that: the temperature of the oven dry in described c step is 70-85 ℃, and the time is 3-10 minute.
3. the preparation method of a kind of hollow micron sulfur balls as claimed in claim 1 is characterized in that: the substrate in described a step is a sheet glass.
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| CN2009100603012A CN101618861B (en) | 2009-08-07 | 2009-08-07 | Method for preparing hollow micron sulfur balls |
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|---|---|---|---|
| CN2009100603012A CN101618861B (en) | 2009-08-07 | 2009-08-07 | Method for preparing hollow micron sulfur balls |
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| CN101618861B true CN101618861B (en) | 2010-12-29 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811673B (en) * | 2010-05-24 | 2012-01-25 | 西南交通大学 | Method for preparing dendritic sulfur nano structure |
| CN101814602B (en) * | 2010-05-24 | 2011-11-16 | 西南交通大学 | Method for preparing nanometer flower-shaped hydrogen-oxygen-zinc sulfate used as anode material of nickel/zinc battery |
| CN102581296A (en) * | 2012-01-12 | 2012-07-18 | 北京理工大学 | Method for improving efficiency of hollow sphere preparation by template dissolving method |
| CN104709936B (en) * | 2014-12-09 | 2016-08-24 | 西南交通大学 | A kind of preparation method of lim solid sulfuration copper ball |
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2009
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