CN102674439A - Method for preparing stannic oxide porous microsphere - Google Patents
Method for preparing stannic oxide porous microsphere Download PDFInfo
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- CN102674439A CN102674439A CN2012101679966A CN201210167996A CN102674439A CN 102674439 A CN102674439 A CN 102674439A CN 2012101679966 A CN2012101679966 A CN 2012101679966A CN 201210167996 A CN201210167996 A CN 201210167996A CN 102674439 A CN102674439 A CN 102674439A
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Abstract
The invention relates to methods for preparing stannic oxide microsphere functional materials with porous structures and particularly relates to a method for preparing a stannic oxide porous microsphere. Stannic chloride pentahydrate is used as a raw material, a mixed liquid of deionized water and alcohol is used as a solvent, and the raw material and the solvent are subjected to mixing stirring, hydro-thermal synthesis, solid-liquid separation, cleaning and drying to obtain a stannic oxide porous microsphere functional material product. The method for preparing the stannic oxide porous microsphere has the advantages that the method is simple, the operation is convenient, the production device is simple, the production cycle is short, the production cost is low, the environment is not polluted, and the method is easy to popularize and apply. By means of the method, the prepared product has remarkable effects of being uniform in structure, good in dispersibility, large in specific surface area which can reach to 87.4 square meters per gram and the like. The method for preparing the stannic oxide porous microsphere can be widely applied to preparing stannic oxide porous microsphere functional materials, widely applicable to new energy devices of lithium ion batteries, solar cells, supercapacitors and the like, and further suitable for the fields of catalyst carriers, gas sensitive elements, hydrogen storage materials and the like.
Description
Technical field
The invention belongs to technical field of function materials, be specifically related to the preparation method of vesicular structure tindioxide microballoon functional materials.
Background technology
Tindioxide is a kind of important wide bandgap N type semiconductor material, and its energy gap Eg=3.6eV (300K) is a kind of important functional material.And the tin dioxide material of vesicular structure is because of having the orderly duct and the property of high-specific surface area, and is widely used in a plurality of fields, aspect such as gas sensor, hydrogen storage material, catalytic material, lithium ion battery, solar cell, ultracapacitor.Therefore, the tindioxide microballoon functional materials of development vesicular structure has received great concern.
The preparation method of existing tindioxide microballoon; Like the patent of the publication number CN102060321A that announces in May, 2011 " preparation method of tindioxide self-assembled nano structures microballoon ", disclosed method is: utilizing hydrothermal method is raw material with the sodium stannate trihydrate, and ethanol and deionized water are solvent; Cetyl trimethylammonium bromide is a tensio-active agent; And to add thanomin be additive, stirs, and carries out hydro-thermal reaction 1～48h; Water and absolute ethyl alcohol centrifuge washing remove the impurity solvent again, and drying has generated tindioxide and independently adorned nanostructured microsphere.The main drawback of this method is: (1) uses cetyl trimethylammonium bromide to be tensio-active agent, is unfavorable for environmental protection and increases cost; (2) in hydrothermal reaction process, add the thanomin additive.This had both increased thanomin additive raw material, had increased production process and production unit again, thereby it is high further to have increased production cost; (3) the hydro-thermal time is 1～48h, and production cycle long production cost is high; (4) it is more serious to adopt the microballoon of the product of this method preparation to reunite, and specific surface is less.
Summary of the invention
The objective of the invention is the deficiency to existing tindioxide method for preparing microsphere, a kind of preparation method of tindioxide porous microsphere is provided, is raw material with the stannic chloride pentahydrate, and deionized water and ethanol are solvent; Do not use tensio-active agent, it is simple to have method, and the hydro-thermal reaction time is short; Good dispersivity, specific surface area is big, and reactions step is few; Characteristics such as production cost is low, and is free from environmental pollution can make the tindioxide microballoon functional materials that is widely used vesicular structure.
The technical scheme that realizes the object of the invention is: a kind of preparation method of tindioxide porous microsphere; With the stannic chloride pentahydrate is raw material; Deionized water and alcoholic acid mixed solution are solvent, make tindioxide porous microsphere functional materials product through mixing stirring, hydro-thermal reaction, solid-liquid separation, exsiccant simple process.The concrete steps of said method are following:
(1) mixes stirring
With the stannic chloride pentahydrate is raw material, uses deionized water and alcoholic acid mixed solution to be solvent.Earlier in deionized water: the alcoholic acid volume ratio is 1: 1～6 ratio, and ethanol is joined in the deionized water, mixes and makes aqueous ethanolic solution.Again in the quality (g) of stannic chloride pentahydrate: the ratio of the volume of aqueous ethanolic solution (ml) is 1: 15～21 ratio, and stannic chloride pentahydrate is joined in the aqueous ethanolic solution, stirs 2～30 minutes, just makes finely dispersed mixing solutions.
(2) hydro-thermal reaction and solid-liquid separation
After the completion of (1) step; The mixing solutions that earlier (1) step was made moves in the hydrothermal reaction kettle that liner is a tetrafluoroethylene; Under 160～250 ℃ of temperature, carried out hydro-thermal reaction 1～24 hour, again the mixed solution after the hydro-thermal reaction is positioned in the whizzer; Carry out the solid-liquid separation first time, collect primary centrifugate and deposition respectively.To the centrifugation first time of collecting; Again in the quality (g) of centrifugation for the first time: the volume ratio of deionized water (ml) is 1: 60～250 ratio, in the centrifugation first time, adds deionized water again, after mixing; Be positioned in the whizzer once more; Carry out the solid-liquid separation second time once more, collect centrifugate and deposition for the second time once more respectively, so repeat 2～20 times.At last, merge the centrifugate of each time collection, treated back up to standard discharging; To the deposition of last collection, be used for next step drying treatment.
(3) drying
(2) step with last deposition of collecting of (2) step, was positioned in the loft drier after accomplishing, 40～150 ℃ dry 6～48 hours down, just prepare tindioxide porous microsphere functional materials product.
After the present invention adopts technique scheme, mainly contain following effect:
1, the present invention does not use tensio-active agent, and is with low cost.Each step does not produce hazardous and noxious substances in the preparation process, helps environment protection;
2, the present invention does not increase any additives in hydrothermal reaction process.Reduced production process and production unit, and the hydro-thermal time is short, with short production cycle, reduces cost;
3, adopt the structure homogeneous of the tindioxide porous microsphere that the present invention prepares, good dispersivity, and specific surface area is big, can reach 87.4m
2/ g;
5, the inventive method is simple, and is easy and simple to handle, and the plant-scale equipment is simple, is easy to apply.
The inventive method can be widely used in preparing tindioxide porous microsphere functional materials; Adopt the tindioxide porous microsphere functional materials of the present invention's preparation, the preparation method is simple, and is with low cost; Good dispersivity; Advantages such as specific surface is big can be widely used in new energy devices such as lithium ion battery, solar cell, ultracapacitor, also applicable to fields such as support of the catalyst, gas sensor, hydrogen storage materials.
Description of drawings
The XRD figure of the tindioxide porous microsphere that Fig. 1 prepares for this instance 1;
Among Fig. 1: a is SnO
2The diffraction curve of porous microsphere; B is standard SnO
2XRD diffraction peak (existing standard).
The low range SEM Electronic Speculum figure of the tindioxide porous microsphere that Fig. 2 prepares for this instance 1;
The high magnification SEM Electronic Speculum figure of the tindioxide porous microsphere that Fig. 3 prepares for this instance 1;
The BET figure of the tindioxide porous microsphere that Fig. 4 prepares for this instance 1;
Among the figure: 1 is the tindioxide microballoon.
Embodiment
Below in conjunction with embodiment, further specify the present invention.
Embodiment 1
A kind of preparation method of tindioxide porous microsphere, its concrete steps are following:
(1) mixes stirring
Earlier in deionized water: the alcoholic acid volume ratio is l: 5 ratio mixes and makes aqueous ethanolic solution.Again in the quality (g) of stannic chloride pentahydrate: the ratio of the volume of aqueous ethanolic solution (ml) is 1: 17 a ratio, stirs 10 minutes, just makes finely dispersed mixing solutions.
(2) hydro-thermal reaction and solid-liquid separation
After the completion of (1) step; The mixing solutions that earlier (1) step was made moves in the hydrothermal reaction kettle that liner is a tetrafluoroethylene; Under 200 ℃ of temperature, carried out hydro-thermal reaction 12 hours, again the mixed solution after the hydro-thermal reaction is positioned in the whizzer; Carry out the solid-liquid separation first time, collect primary centrifugate and deposition respectively.To the centrifugation first time of collecting; Again in the quality (g) of centrifugation for the first time: the volume ratio of deionized water (ml) is 1: 100 a ratio, in the centrifugation first time, adds deionized water again, after mixing; Be positioned in the whizzer; Carry out the solid-liquid separation second time, collect centrifugate and deposition for the second time once more respectively, so repeat 5 times.At last, merge the centrifugate of each time collection, treated back up to standard discharging; To the deposition of last collection, be used for next step drying treatment.
(3) drying
(2) step with last deposition of collecting of (2) step, was positioned in the loft drier after accomplishing, 80 ℃ dry 12 hours down, just prepare tindioxide porous microsphere functional materials product.
Embodiment 2
A kind of preparation method of tindioxide porous microsphere, with embodiment 1, wherein:
In (1) step, deionized water: the alcoholic acid volume ratio is 1: 1, the quality of stannic chloride pentahydrate (g): the ratio of the volume of aqueous ethanolic solution (ml) is 1: 15.Mixing churning time in container is 2 minutes.
In (2) step, hydrothermal temperature is 160 ℃, and the hydro-thermal reaction time is 24 hours, sedimentary quality (g): the volume ratio of deionized water (ml) is 1: 60, so repeats 20 times.
In (3) step, drying temperature is 40 ℃, and be 48 hours time of drying.
Embodiment 3
A kind of preparation method of tindioxide porous microsphere, with embodiment 1, wherein:
In (1) step, deionized water: the alcoholic acid volume ratio is l: 6, and the quality of stannic chloride pentahydrate (g): the ratio of the volume of aqueous ethanolic solution (ml) is 1: 21 a ratio.In container, mixing churning time is 30 minutes.
In (2) step, hydrothermal temperature is 250 ℃, and the hydro-thermal reaction time is 1 hour, sedimentary quality (g): the volume ratio of deionized water (ml) is 1: 250, so repeats 2 times.
In (3) step, drying temperature is 150 ℃, and be 6 hours time of drying.
Test-results
The tindioxide porous microsphere functional materials of preparing with embodiment 1 is through the XRD figure of XRD diffractometer test gained, and is as shown in Figure 1; The SEM that takes gained through field emission scanning electron microscope schemes like Fig. 2 (1 is the tindioxide microballoon among the figure) shown in 3; Through the BET figure of specific surface area analysis appearance test gained, as shown in Figure 4.
Know that from Fig. 1 adopt the XRD figure spectrum of the prepared sample of the present invention consistent with the tindioxide XRD peak position of standard, sample that makes and standard tindioxide XRD diffraction peak are coincide fine;
Show clearly that from Fig. 2 the tindioxide porous microsphere is the sphere of diameter 1～2.5 μ m, specific surface area is big;
From the clear demonstration tindioxide of Fig. 3 microsphere surface porous, and with adjacent ball good dispersibility;
Know from Fig. 4, according to the classification of lag loop, porous microsphere isothermal adsorption～desorption curve be the H3 type, belong to the platy shaped particle material.The specific surface area of calculating matrix material with BET (Brunauer-Emmmet-Teller) method is 87.4m
2/ g.
Claims (1)
1. preparation method who prepares the tindioxide porous microsphere is characterized in that the concrete steps of said method are following:
(1) mixes stirring
With the stannic chloride pentahydrate is raw material; Use deionized water and alcoholic acid mixed solution to be solvent, earlier in deionized water: the alcoholic acid volume ratio is 1: 1～6 ratio, and ethanol is joined in the deionized water; Mix and make aqueous ethanolic solution; Again in the quality of stannic chloride pentahydrate: the ratio of the volume of aqueous ethanolic solution is the ratio of 1g: 15～21ml, and stannic chloride pentahydrate is joined in the aqueous ethanolic solution, stirs 2～30 minutes;
(2) hydro-thermal reaction and solid-liquid separation
(1) step went on foot the mixing solutions that makes with (1) earlier and moves in the hydrothermal reaction kettle that liner is a tetrafluoroethylene, under 160～250 ℃ of temperature after accomplishing; Carry out hydro-thermal reaction 1～24 hour, and again the mixed solution after the hydro-thermal reaction was positioned in the whizzer, carry out the solid-liquid separation first time; Collect primary centrifugate and deposition respectively, to the centrifugation first time of collecting, again by the quality of the centrifugation first time: the volume ratio of deionized water is the ratio of 1g: 60～250ml; In the centrifugation first time, add deionized water again, after mixing, be positioned in the whizzer once more; Carry out the solid-liquid separation second time once more, collect centrifugate and deposition for the second time once more respectively, so repeat 2～20 times; At last, the centrifugate that merges each time collection;
(3) drying
(2) step with last deposition of collecting of (2) step, was positioned in the loft drier after accomplishing, 40～150 ℃ dry 6～48 hours down.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588242A (en) * | 2013-11-25 | 2014-02-19 | 湛江师范学院 | Preparation method for synthesis of porous SnO2 nanospheres with assistance of biopolymer by adopting one-step hydrothermal method |
| CN103739006A (en) * | 2013-12-12 | 2014-04-23 | 宁夏东方钽业股份有限公司 | Preparation method of superfine highly-pure tin oxide |
| CN105329937A (en) * | 2015-11-09 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing stannic oxide nanometer microspheres through supercritical method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324502A (en) * | 2011-09-14 | 2012-01-18 | 重庆大学 | Preparation method of flower-like tin dioxide and graphene composite material |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324502A (en) * | 2011-09-14 | 2012-01-18 | 重庆大学 | Preparation method of flower-like tin dioxide and graphene composite material |
Non-Patent Citations (2)
| Title |
|---|
| HUA WANG ET AL.: "The self-assembly of porous microspheres of tin dioxide octahedral nanoparticles for high performance lithium ion battery anode materials", 《J. MATER. CHEM.》 * |
| 吕逵弟等: "二氧化锡超细粉体的制备及研究进展", 《无机盐工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588242A (en) * | 2013-11-25 | 2014-02-19 | 湛江师范学院 | Preparation method for synthesis of porous SnO2 nanospheres with assistance of biopolymer by adopting one-step hydrothermal method |
| CN103588242B (en) * | 2013-11-25 | 2015-10-14 | 湛江师范学院 | Biological polymer assists the preparation method of a step hydrothermal synthesis of stephanoporate stannic oxide nanometer ball |
| CN103739006A (en) * | 2013-12-12 | 2014-04-23 | 宁夏东方钽业股份有限公司 | Preparation method of superfine highly-pure tin oxide |
| CN105329937A (en) * | 2015-11-09 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing stannic oxide nanometer microspheres through supercritical method |
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Application publication date: 20120919 |