CN104085916B - A kind of calcium germinate hollow micron ball and preparation method thereof - Google Patents
A kind of calcium germinate hollow micron ball and preparation method thereof Download PDFInfo
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- CN104085916B CN104085916B CN201410294381.9A CN201410294381A CN104085916B CN 104085916 B CN104085916 B CN 104085916B CN 201410294381 A CN201410294381 A CN 201410294381A CN 104085916 B CN104085916 B CN 104085916B
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Abstract
The present invention relates to a kind of calcium germinate hollow micron ball, described micron ball inner hollow, described micron ball diameter is 1-10 micron, and described micron ball has bar-shaped projection, and described bar-shaped projection diameter is 20-100 nanometer.The invention still further relates to a kind of preparation method of calcium germinate hollow micron ball, comprise the following steps: urea or urea derivative, germanium dioxide and soluble calcium salt are dissolved in water according to the molar ratio of (2-12): 7:2 by (1), form sample solution; (2) described sample solution is carried out hydrothermal treatment consists.Calcium germinate hollow micron ball of the present invention has the characteristic that specific surface area greatly, is not reunited, can be widely used in fields such as lithium ion battery, ultracapacitor, nano-devices, meanwhile, the preparation method of calcium germinate hollow micron ball of the present invention is simple to operate, can adapt to suitability for industrialized production.
Description
Technical field
The present invention relates to inorganic nano material, be specifically related to a kind of calcium germinate hollow micron ball and preparation method thereof.
Background technology
Metal germanate micro Nano material, because of its special physics and chemical property, is subject to extensive concern both domestic and external as the semiconductor functional material that a class is important.Lead germanium oxide has ferroelectric properties and electroluminescently dazzles photoeffect, and zinc germanate is important luminescent material, and copper germanate has spin Peierls transition characteristic.Over the past two years, the research that calcium germinate was applied to lithium ion battery as negative material receives much concern.Calcium germinate has high theoretical capacity, and therefore, the preparation of calcium germinate has important researching value.
At present, the main preparation methods preparing calcium germinate is hydrothermal synthesis method and solvent-thermal process method, and the nanostructure obtained is nano wire and nanometer rod.When the purposes such as electrode materials or photocatalyst of calcium germinate as lithium ion battery time, the nano material of its hierarchy is particularly crucial.But prior art not yet reports the calcium germinate of three-dimensional hierarchical structure.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of calcium germinate hollow micron ball with three-dimensional hierarchical structure.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
A kind of calcium germinate hollow micron ball, described micron ball inner hollow, described micron ball diameter is 1-10 micron, and described micron ball has bar-shaped projection, and described bar-shaped projection diameter is 20-100 nanometer.
The present invention also discloses a kind of preparation method of calcium germinate hollow micron ball, comprises the following steps:
(1) urea or urea derivative, germanium dioxide and soluble calcium salt are dissolved in water according to the molar ratio of (2-12): 7:2, form sample solution;
(2) described sample solution is carried out hydrothermal treatment consists, obtain the solution containing calcium germinate hollow micron ball.
Beneficial effect of the present invention is:
(1) calcium germinate hollow micron ball of the present invention has hollow spheres structure, and its diameter is 1-10 micron, has the characteristic that specific surface area greatly, is not reunited;
(2) preparation method of calcium germinate hollow micron ball of the present invention is with urea or derivative for alkali source, and obtain calcium germinate hollow micron ball through hydrothermal treatment consists, this preparation method is simple to operate;
(3) calcium germinate hollow micron ball applied range of the present invention, can be applicable in fields such as lithium ion battery, ultracapacitor, nano-devices.
Accompanying drawing explanation
Fig. 1 is 25000 times of SEM figure of the calcium germinate hollow micron ball of the embodiment of the present invention 1;
Fig. 2 is 500000 times of SEM figure of the calcium germinate hollow micron ball of the embodiment of the present invention 1.
Embodiment
By describing technology contents of the present invention, structural attitude in detail, realized object and effect, accompanying drawing is coordinated to be explained in detail below in conjunction with embodiment.
The design of most critical of the present invention is: be hydrolyzed under hydrothermal conditions by urea and derivative thereof and produce ammonia and carbonic acid gas, thus obtain calcium germinate hollow micron ball, this micron ball has the advantage that specific surface area greatly, is not reunited.
Refer to Fig. 1 and Fig. 2, the invention discloses a kind of calcium germinate hollow micron ball, described micron ball inner hollow, described micron ball diameter is 1-10 micron, and described micron ball has bar-shaped projection, and described bar-shaped projection diameter is 20-100 nanometer.
The present invention also discloses a kind of preparation method of calcium germinate hollow micron ball, comprises the following steps:
(1) urea or urea derivative, germanium dioxide and soluble calcium salt are dissolved in water according to the molar ratio of (2-12): 7:2, form sample solution;
(2) described sample solution is carried out hydrothermal treatment consists, obtain calcium germinate hollow micron ball.
The mechanism process that the present invention prepares calcium germinate hollow micron ball is: first, urea and derivative thereof facile hydrolysis under hydrothermal conditions, and hydrolysis produces ammonia or amine and carbonic acid gas.The ammonia produced or amine and carbon dioxide are as the soft template of micron ball; Secondly, calcium germinate is diamond structure, is easy to be grown to one dimension Nano structure; Again, ball-like structure has minimum system free energy, and stability is high.Based on this, by control condition, the hollow micron ball of calcium germinate can be obtained.
From foregoing description, beneficial effect of the present invention is:
(1) calcium germinate hollow micron ball of the present invention has hollow spheres structure, and its diameter is 1-10 micron, has the characteristic that specific surface area greatly, is not reunited;
(2) preparation method of calcium germinate hollow micron ball of the present invention is with urea or derivative for alkali source, and obtain calcium germinate hollow micron ball through hydrothermal treatment consists, this preparation method is simple to operate;
(3) calcium germinate hollow micron ball applied range of the present invention, can be applicable in fields such as lithium ion battery, ultracapacitor, nano-devices.
Further, described micron ball diameter is 2-6 micron, and described bar-shaped projection diameter is 20-35 nanometer.
Further, the hydrothermal treatment consists temperature in described step (2) is 180-240 DEG C, and hydrothermal conditions is 3-36h.
Further, described step (2) is: described sample solution be transferred to polytetrafluoro container and be fixed in stainless steel cauldron, stainless steel cauldron being placed in baking oven and heating.
Further, in step (1), described urea derivative is selected from one or more of MU, ethyl carbamide, propyl group urea and N-Butylurea, and described soluble calcium salt is selected from one or more of calcium chloride, nitrocalcite and lime acetate.
Further, step (3) is also comprised: carried out by described calcium germinate hollow micron ball cooling, removal of impurities.
Further, the impurity-removing method of described step (3) is: to be hocketed washing with water and ethanol respectively by described calcium germinate hollow micron ball, described washing times is more than twice.
Further, step (4) is also comprised: described calcium germinate hollow micron ball is carried out drying treatment.
Further, the drying treatment temperature in described step (4) is 50-80 DEG C, and the drying treatment time is 4-6h.
Experimental technique in following embodiment, if no special instructions, is ordinary method; Used reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment one
Take 1 gram of MU, 0.366 gram of germanium dioxide and 0.111 gram of calcium chloride respectively, be dissolved in 35 ml deionized water, after to be dissolved, to be transferred in the polytetrafluoro container of 50 milliliters and to be fixed in stainless reactor, then baking oven is put into, arranging oven temperature is 240 degrees Celsius, heat after 12 hours and take out, when the temperature of question response still is reduced to room temperature naturally, obtained reactant is replaced repeated washing 3 times with water and ethanol respectively, by the sample after washing in 60 degrees Celsius of baking ovens dry 4 hours, obtain calcium germinate hollow micron ball.Calcium germinate hollow micron ball has hollow structure, its surface has bar-shaped projection (because bar-shaped protruding size is nano level, also nanometer rod is claimed), the diameter of the calcium germinate hollow micron ball of the present embodiment is 2 to 6 microns, and the nanorod diameter on the calcium germinate hollow micron ball of the present embodiment is 20-30 nanometer.
Embodiment two
Take 0.06 gram of urea, 0.366 gram of germanium dioxide and 0.111 gram of calcium chloride respectively, be dissolved in 35 ml deionized water, after to be dissolved, to be transferred in the polytetrafluoro container of 50 milliliters and to be fixed in stainless reactor, then baking oven is put into, arranging oven temperature is 200 degrees Celsius, heat after 24 hours and take out, when the temperature of question response still is reduced to room temperature naturally, obtained reactant is replaced repeated washing 3 times with water and ethanol respectively, by washing after sample in 60 degree baking ovens drying 4 hours.The diameter of calcium germinate hollow micron ball prepared by the present embodiment is 2.5-6 micron, and nanorod diameter is about 40 nanometers.
Embodiment three
Take 0.4 gram of propyl group urea, 0.366 gram of germanium dioxide and 0.158 gram of calcium acetate respectively, be dissolved in 35 ml deionized water, after to be dissolved, to be transferred in the polytetrafluoro container of 50 milliliters and to be fixed in stainless reactor, then baking oven is put into, arranging oven temperature is 200 degrees Celsius, heat after 3 hours and take out, when the temperature of question response still is reduced to room temperature naturally, obtained reactant is replaced repeated washing 3 times with water and ethanol respectively, by washing after sample in 60 degree baking ovens drying 4 hours.The diameter of calcium germinate hollow micron ball prepared by the present embodiment is 3-5.5 micron, and nanorod diameter is 30-60 nanometer.
Embodiment four
Take 0.5 gram of ethyl carbamide, 0.366 gram of germanium dioxide and 0.284 gram of calcium stearate respectively, be dissolved in 35 ml deionized water, after to be dissolved, to be transferred in the polytetrafluoro container of 50 milliliters and to be fixed in stainless reactor, then baking oven is put into, arranging oven temperature is 180 degrees Celsius, heat after 12 hours and take out, when the temperature of question response still is reduced to room temperature naturally, obtained reactant is replaced repeated washing 3 times with water and ethanol respectively, by washing after sample in 60 degree baking ovens drying 4 hours.The diameter of calcium germinate hollow micron ball prepared by the present embodiment is 1-2.5 micron, and nanorod diameter is 25-35 nanometer.
Embodiment five
Take 1.2 grams of propyl group ureas, 0.366 gram of germanium dioxide and 0.111 gram of calcium chloride respectively, be dissolved in 35 ml deionized water, after to be dissolved, to be transferred in the polytetrafluoro container of 50 milliliters and to be fixed in stainless reactor, then baking oven is put into, arranging oven temperature is 200 degrees Celsius, heat after 12 hours and take out, when the temperature of question response still is reduced to room temperature naturally, obtained reactant is replaced repeated washing 3 times with water and ethanol respectively, by washing after sample in 60 degree baking ovens drying 4 hours.The diameter of calcium germinate hollow micron ball prepared by the present embodiment is 3.5-6 micron, and nanorod diameter is 80-100 nanometer.
The calcium germinate hollow micron ball of table 1 prepared by the embodiment of the present invention one to embodiment five and the diameter contrast table of bar-shaped projection thereof.Specific as follows:
Table 1
| Calcium germinate hollow micron ball diameter | Baculum diameter | |
| Embodiment one | 2-6 micron | 20-30 nanometer |
| Embodiment two | 2.5-6 micron | 40 nanometers |
| Embodiment three | 3-5.5 micron | 30-60 nanometer |
| Embodiment four | 1-2.5 micron | 25-35 nanometer |
| Embodiment five | 5-10 micron | 80-100 nanometer |
Scan under calcium germinate hollow micron ball embodiment one to embodiment five obtained carries out Electronic Speculum and take pictures, Electronic Speculum figure can refer to Fig. 1 and Fig. 2.
Fig. 1 is 25000 times of SEM figure of calcium germinate hollow micron ball prepared by the embodiment of the present invention one, Fig. 2 is that 500000 times of SEM of calcium germinate hollow micron ball prepared by the embodiment of the present invention one scheme; As shown in Figure 1, calcium germinate hollow micron ball has hollow structure, and its surface has bar-shaped projection (nanometer rod), and the diameter of the calcium germinate hollow micron ball of embodiment one is 2 to 6 microns; As shown in Figure 2, the nanorod diameter on the calcium germinate hollow micron ball of embodiment one is 20-30 nanometer.
In sum, calcium germinate hollow micron ball provided by the invention has hollow spheres structure, its diameter is 1-10 micron, there is the characteristic that specific surface area greatly, is not reunited, can be widely used in fields such as lithium ion battery, ultracapacitor, nano-devices, meanwhile, the preparation method of calcium germinate hollow micron ball of the present invention has simple to operate, can adapt to suitability for industrialized production.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification sheets of the present invention and accompanying drawing content to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (8)
1. a calcium germinate hollow micron ball, is characterized in that, described micron ball inner hollow, and described micron ball diameter is 1-10 micron, and described micron ball has bar-shaped projection, and described bar-shaped projection diameter is 20-100 nanometer.
2. calcium germinate hollow micron ball according to claim 1, is characterized in that, described micron ball diameter is 2-6 micron, and described bar-shaped projection diameter is 20-35 nanometer.
3. a preparation method for calcium germinate hollow micron ball according to claim 1, is characterized in that, comprise the following steps:
(1) urea or urea derivative, germanium dioxide and soluble calcium salt are dissolved in water according to the molar ratio of (2-12): 7:2, form sample solution;
(2) described sample solution is carried out hydrothermal treatment consists, obtain calcium germinate hollow micron ball;
In step (1), described urea derivative is selected from one or more of MU, ethyl carbamide, propyl group urea and N-Butylurea, and described soluble calcium salt is selected from one or more of calcium chloride, nitrocalcite and lime acetate; Hydrothermal treatment consists temperature in described step (2) is 180-240 DEG C, and hydrothermal conditions is 3-36h.
4. the preparation method of calcium germinate hollow micron ball according to claim 3, it is characterized in that, described step (2) is: described sample solution be transferred to polytetrafluoro container and be fixed in stainless steel cauldron, stainless steel cauldron being placed in baking oven and heating.
5. the preparation method of calcium germinate hollow micron ball according to claim 3, is characterized in that, also comprises step (3): carried out by described calcium germinate hollow micron ball cooling, removal of impurities.
6. the preparation method of calcium germinate hollow micron ball according to claim 5, it is characterized in that, the impurity-removing method of described step (3) is: to be hocketed washing with water and ethanol respectively by described calcium germinate hollow micron ball, described washing times is more than twice.
7. the preparation method of calcium germinate hollow micron ball according to claim 5, is characterized in that, also comprises step (4): described calcium germinate hollow micron ball is carried out drying treatment.
8. the preparation method of calcium germinate hollow micron ball according to claim 7, is characterized in that, the drying treatment temperature in described step (4) is 50-80 DEG C, and the drying treatment time is 4-6h.
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| CN104393319B (en) * | 2014-11-19 | 2016-05-11 | 安徽工业大学 | A kind of hollow spheres lanthanum germanate and preparation method thereof |
| CN110615465B (en) * | 2018-06-20 | 2021-09-14 | 天津大学 | Preparation method of amorphous germanium-based nanowire |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101956237A (en) * | 2010-09-30 | 2011-01-26 | 安徽工业大学 | Calcium germinate nanowire and preparation method thereof |
| CN102502789A (en) * | 2011-10-14 | 2012-06-20 | 中国科学院化学研究所 | Alkaline earth metal germanate nanomaterial and preparation method thereof and use thereof as cathode material of lithium ion battery |
| CN103726130A (en) * | 2013-09-12 | 2014-04-16 | 上海大学 | Method for preparing short CaGeO3 fiber with electrostatic spinning technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101956237A (en) * | 2010-09-30 | 2011-01-26 | 安徽工业大学 | Calcium germinate nanowire and preparation method thereof |
| CN102502789A (en) * | 2011-10-14 | 2012-06-20 | 中国科学院化学研究所 | Alkaline earth metal germanate nanomaterial and preparation method thereof and use thereof as cathode material of lithium ion battery |
| CN103726130A (en) * | 2013-09-12 | 2014-04-16 | 上海大学 | Method for preparing short CaGeO3 fiber with electrostatic spinning technology |
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