CN103613085A - Carbon hollow sphere material with hierarchical porous structure and preparation method thereof - Google Patents
Carbon hollow sphere material with hierarchical porous structure and preparation method thereof Download PDFInfo
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- CN103613085A CN103613085A CN201310489823.0A CN201310489823A CN103613085A CN 103613085 A CN103613085 A CN 103613085A CN 201310489823 A CN201310489823 A CN 201310489823A CN 103613085 A CN103613085 A CN 103613085A
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Abstract
The invention discloses a carbon hollow sphere material with a hierarchical porous structure, the carbon hollow sphere material is composed of a carbon casing and a hollow inner cavity enclosed by the carbon casing, and a plurality of macropores are formed in the carbon casing. Due to the fact the a plurality of macropores are formed in the carbon casing, matters such as electrolyte and the like can enter the inner cavity of the carbon hollow sphere material, so that the inner cavity of the carbon hollow sphere material is fully utilized.
Description
Technical field
The present invention relates to a kind of carbon hollow ball material and preparation method thereof, refer in particular to a kind of carbon hollow ball material with hierarchical porous structure and preparation method thereof.
Background technology
Porous carbon hollow material has the characteristics such as high porosity, high-specific surface area, good electroconductibility and chemical stability, in catalysis, fractionation by adsorption, ion-exchange and electrochemical energy storage field, has important using value.And carbon hollow ball material has good chemical stability and thermostability, and quality is light, and compressive property is good, is therefore widely used in the fields such as electrode materials, energy storage hydrogen storage material, sorbing material, lubricant and support of the catalyst.
The disclosed carbon hollow ball material of prior art, its carbon shell at hollow ball is formed with micropore, and the quantity of described micropore is a lot, and the aperture in hole is below 4nm.Because the aperture of micropore is very little, make electrolytic solution or other material be difficult to enter in the internal chamber wall of carbon hollow ball material, therefore, the inner chamber of carbon hollow ball material cannot be used.As for lithium ion battery, electrolytic solution is difficult to enter the inner chamber of carbon hollow ball material, makes its discharge-rate lower; As support of the catalyst, catalyzer cannot enter the inner chamber of carbon hollow ball material, the activity of catalyzer a little less than.
Summary of the invention
What the object of the present invention is to provide that a kind of inner chamber can make full use of has carbon hollow ball material of hierarchical porous structure and preparation method thereof.
For reaching above-mentioned purpose, solution of the present invention is:
A carbon hollow ball material with hierarchical porous structure, is comprised of carbon shell and the hollow lumen that surrounded by carbon shell, forms a plurality of macropores on carbon shell.
Further, the aperture of described macropore is more than or equal to 20nm.
Further, the volume of described inner chamber accounts for the 10-90% of cumulative volume.
Further, the carbon content of described carbon shell is more than or equal to 80%.
Further, described macropore is straight hole.
Further, how much total areas of described macropore are the 10-90% of carbon hollow ball material geometrical surface.
A carbon hollow ball material preparation method with hierarchical porous structure, comprises the following steps:
One, use sol-gel method that carbon matrix precursor is coated on to template surface, add pore-forming material simultaneously, dissolve and be scattered in water;
Two, the mixed solution that step 1 is formed is put into baking oven gel and is obtained presoma;
Three, the presoma that step 2 is obtained carries out high temperature sintering, obtains having the carbon hollow ball material of hierarchical porous structure.
Further, template described in step 1 is organic formwork polystyrene (PS), polymethylmethacrylate (PMMA), or is inorganic template SiO2, MnO.
Further, the precursor of carbon described in step 1 is resol, epoxy resin.
Further, pore-forming material described in step 1 is polymkeric substance pore-forming material polyoxyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl butyral acetal (PVB), or be trimethylbenzene between organic pore-forming agents, or be mineral ion pore-forming material molysite, cobalt salt, NH
4hCO
3, (NH4)
2c
2o
4.
Further, in step 3, high temperature sintering temperature is 500-1500 ℃.
Adopt after such scheme, the present invention forms a plurality of macropores (being the micropore below 4nm with respect to prior art aperture) on carbon shell, make other materials such as electrolytic solution can enter the inner chamber of carbon hollow ball material, thereby make full use of the inner chamber of carbon hollow ball material.As for lithium ion battery, because electrolytic solution freely enters inner chamber, spread radius drop by half, be conducive to the discharge-rate of material; As support of the catalyst, because catalyzer enters inner chamber, improved the activity of catalyzer; Because material enters inner chamber, this material also can be used as the carrier of some materials and makes full use of inner chamber.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention;
Fig. 2 is preparation flow figure of the present invention.
Label declaration
Carbon shell 1 macropore 11
Template 4 pore-forming materials 5
Presoma 6.
Embodiment
Below in conjunction with drawings and the specific embodiments, the invention will be further described.
Consult shown in Fig. 1, a kind of carbon hollow ball material with hierarchical porous structure that the present invention discloses, by carbon shell 1 and the hollow lumen 2 that surrounded by carbon shell 1, formed, on carbon shell 1, form a plurality of macropore 11(for prior art aperture is the micropore below 4nm).Macropore 11 is straight hole, and aperture is more than or equal to 10nm.How much total areas of described macropore 11 are the 10-90% of carbon hollow ball material geometrical surface.Meanwhile, the volume of described inner chamber 2 accounts for the 10-90% of cumulative volume.The carbon content of described carbon shell 1 is more than or equal to 80%.
Consult shown in Fig. 2, described in there is the carbon hollow ball material preparation method of hierarchical porous structure, comprise the following steps:
One, use sol-gel method that carbon matrix precursor 3 is coated on to template 4 surfaces, add pore-forming material 5 simultaneously, dissolve and be scattered in water; Wherein, carbon matrix precursor 3 is resol, epoxy resin; Pore-forming material 5 is polymkeric substance pore-forming material polyoxyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl butyral acetal (PVB), or is trimethylbenzene between organic pore-forming agents, or is mineral ion pore-forming material molysite, cobalt salt, NH
4hCO
3, (NH4)
2c
2o
4.
Two, the mixed solution that step 1 is formed is put into baking oven gel and is obtained presoma 6.
Three, the presoma 6 that step 2 is obtained carries out high temperature sintering, obtains having the carbon hollow ball material of hierarchical porous structure, and high temperature sintering temperature is 500-1500 ℃.
Embodiment mono-
A kind of carbon hollow ball material preparation method with hierarchical porous structure, comprise the following steps: one, the resol of 2g (Resorcinol: formaldehyde mol is than being 1:2), the pore-forming material PEG of the template PMMA microballoon of 1.2g (being made into PMMA emulsion 30ml) and 0.5g, dissolving is dispersed in 10ml water, stirs 10min; Two, sealing is put into 85 ℃ of baking oven gels 3 days, opens to dry to obtain presoma; Three, at 800 ℃, carry out high temperature sintering, PMMA(polymethylmethacrylate in the process of sintering) and PEG(polyoxyethylene glycol) be decomposed to form the macropore of cavity and carbon shell.
The carbon hollow ball material with hierarchical porous structure prepared by described method, the aperture of macropore is 20nm, and how much total areas of macropore are 10% of carbon hollow ball material geometrical surface, and the volume of inner chamber accounts for 27% of cumulative volume, the carbon content 98% of carbon shell.
Embodiment bis-
A kind of carbon hollow ball material preparation method with hierarchical porous structure, comprise the following steps: one, the resol of 2g (Resorcinol: formaldehyde mol is than being 1:2), the pore-forming material PEG of the template PMMA microballoon of 2.1g (being made into PMMA emulsion 70ml) and 0.5g, dissolving is dispersed in 10ml water, stirs 10min; Two, sealing is put into 85 ℃ of baking oven gels 3 days, opens to dry to obtain presoma; Three, at 800 ℃, carry out high temperature sintering, PMMA(polymethylmethacrylate in the process of sintering) and PEG(polyoxyethylene glycol) be decomposed to form the macropore of cavity and carbon shell.
The carbon hollow ball material with hierarchical porous structure prepared by described method, the aperture of macropore is 50nm, and how much total areas of macropore are 40% of carbon hollow ball material geometrical surface, and the volume of inner chamber accounts for 55% of cumulative volume, the carbon content 98% of carbon shell.
Embodiment tri-
A carbon hollow ball material preparation method with hierarchical porous structure, comprises the following steps: the resol of one, 1g (Resorcinol: formaldehyde mol is than being 1:2), the template SiO of 1.2g
2the pore-forming material PVP of ball and 0.5g, dissolves and is dispersed in 10ml water, stirs 10min; Two, sealing is put into 85 ℃ of baking oven gels 3 days, opens to dry to obtain presoma; Three, at 1500 ℃, carry out high temperature sintering, after sintering, with HF pickling, fall template SiO
2.
The carbon hollow ball material with hierarchical porous structure prepared by described method, the aperture of macropore is 50nm, and how much total areas of macropore are 40% of carbon hollow ball material geometrical surface, and the volume of inner chamber accounts for 85% of cumulative volume, the carbon content 95% of carbon shell.
Embodiment tetra-
Comprise the following steps: the resol of one, 1g (Resorcinol: formaldehyde mol is than being 1:2), the template SiO of 0.6g
2the pore-forming material NH of ball and 1.0g
4hCO
3, dissolve and be dispersed in 10ml water, stir 10min; Two, sealing is put into 85 ℃ of baking oven gels 3 days, opens to dry to obtain presoma; Three, at 1500 ℃, carry out high temperature sintering, after sintering, with HF pickling, fall template SiO
2.
The carbon hollow ball material with hierarchical porous structure prepared by described method, the aperture of macropore is 20nm, and how much total areas of macropore are 20% of carbon hollow ball material geometrical surface, and the volume of inner chamber accounts for 25% of cumulative volume, the carbon content 95% of carbon shell.
The generation of the macropore of carbon shell of the present invention is because added pore-forming material in synthetic process, and the generation of cavity is because added template in synthetic process.After high-temperature calcination, the pore-forming material pyrolysis in the template in chamber and template coating layer is that gas is overflowed, thereby forms the eurypyloue hollow carbon sphere of tool.The macropore that utilizes carbon shell to chisel, can make full use of the inner chamber of ball, can be applied to a plurality of fields.Carbon hollow ball material self can, as the electrode of lithium ion battery and ultracapacitor, can also be applied to a plurality of fields such as solar cell, fuel cell, catalysis, biological medicine and environmental purification as carrier and template.
The foregoing is only preferred embodiment of the present invention, the not restriction to this case design, all equivalent variations of doing according to the design key of this case, all fall into the protection domain of this case.
Claims (10)
1. a carbon hollow ball material with hierarchical porous structure, is characterized in that: carbon shell and the hollow lumen that surrounded by carbon shell, consist of, form a plurality of macropores on carbon shell.
2. a kind of carbon hollow ball material with hierarchical porous structure as claimed in claim 1, is characterized in that: the aperture of described macropore is more than or equal to 10nm.
3. a kind of carbon hollow ball material with hierarchical porous structure as claimed in claim 1, is characterized in that: the volume of described inner chamber accounts for the 10-90% of cumulative volume.
4. a kind of carbon hollow ball material with hierarchical porous structure as claimed in claim 1, is characterized in that: the carbon content of described carbon shell is more than or equal to 80%.
5. a kind of carbon hollow ball material with hierarchical porous structure as claimed in claim 1, is characterized in that: described macropore is straight hole.
6. a kind of carbon hollow ball material with hierarchical porous structure as claimed in claim 1, is characterized in that: how much total areas of described macropore are the 10-90% of carbon hollow ball material geometrical surface.
7. a kind of carbon hollow ball material preparation method with hierarchical porous structure as described in claim 1 to 6 any one, is characterized in that: comprise the following steps:
One, use sol-gel method that carbon matrix precursor is coated on to template surface, add pore-forming material simultaneously, dissolve and be scattered in water;
Two, the mixed solution that step 1 is formed is put into baking oven gel and is obtained presoma;
Three, the presoma that step 2 is obtained carries out high temperature sintering, obtains having the carbon hollow ball material of hierarchical porous structure.
8. a kind of carbon hollow ball material preparation method with hierarchical porous structure as claimed in claim 7, is characterized in that: template described in step 1 is organic formwork polystyrene, polymethylmethacrylate, or is inorganic template SiO2, MnO; Carbon matrix precursor described in step 1 is resol or epoxy resin.
9. a kind of carbon hollow ball material preparation method with hierarchical porous structure as claimed in claim 7, it is characterized in that: pore-forming material described in step 1 is polymkeric substance pore-forming material polyoxyethylene glycol, polyvinylpyrrolidone, polyvinyl butyral acetal, or be trimethylbenzene between organic pore-forming agents, or be mineral ion pore-forming material molysite, cobalt salt, NH
4hCO
3, (NH4)
2c
2o
4.
10. a kind of carbon hollow ball material preparation method with hierarchical porous structure as claimed in claim 7, is characterized in that: in step 3, high temperature sintering temperature is 500-1500 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445148A (en) * | 2014-11-19 | 2015-03-25 | 中国科学院长春应用化学研究所 | Preparation method of monodispersed hollow carbon spheres |
| CN104759186A (en) * | 2015-05-04 | 2015-07-08 | 苏州新求是环保科技有限公司 | Activated carbon padding and preparation method thereof |
| WO2016141559A1 (en) * | 2015-03-11 | 2016-09-15 | Xi'an Jiaotong University | Porous carbon hollow spheres and methods for their preparation and use |
| CN107555415A (en) * | 2017-09-26 | 2018-01-09 | 四川大学 | A kind of method that hydro-thermal method prepares PVA-based carbosphere |
| CN111994893A (en) * | 2020-07-24 | 2020-11-27 | 盐城工学院 | Preparation method of nitrogen-doped carbon material |
| CN113081971A (en) * | 2021-05-14 | 2021-07-09 | 江西中医药大学 | Traditional Chinese medicine porous core-shell type composite particle powder and preparation method and application thereof |
| CN114361716A (en) * | 2021-12-29 | 2022-04-15 | 广东国光电子有限公司 | Positive pole piece with safety coating and preparation method and application thereof |
| CN114373949A (en) * | 2020-10-15 | 2022-04-19 | 丰田自动车株式会社 | Porous carbon, catalyst carrier, and method for producing porous carbon |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020268A (en) * | 2011-01-07 | 2011-04-20 | 中国科学院化学研究所 | Hollow carbon sphere and preparation method thereof |
| CN102718205A (en) * | 2012-06-27 | 2012-10-10 | 北京科技大学 | Method for preparing three-dimensional hierarchical porous carbon |
-
2013
- 2013-10-18 CN CN201310489823.0A patent/CN103613085A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020268A (en) * | 2011-01-07 | 2011-04-20 | 中国科学院化学研究所 | Hollow carbon sphere and preparation method thereof |
| CN102718205A (en) * | 2012-06-27 | 2012-10-10 | 北京科技大学 | Method for preparing three-dimensional hierarchical porous carbon |
Non-Patent Citations (1)
| Title |
|---|
| BAIZENG FANG,ET.AL.: "Ordered Hierarchical Nanostructured Carbon as a Highly Efficient Cathode Catalyst Support in Proton Exchange Membrane Fuel Cell", 《CHEM. MATER.》, vol. 21, no. 5, 4 February 2009 (2009-02-04), pages 789 - 796 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445148A (en) * | 2014-11-19 | 2015-03-25 | 中国科学院长春应用化学研究所 | Preparation method of monodispersed hollow carbon spheres |
| WO2016141559A1 (en) * | 2015-03-11 | 2016-09-15 | Xi'an Jiaotong University | Porous carbon hollow spheres and methods for their preparation and use |
| CN107406257A (en) * | 2015-03-11 | 2017-11-28 | 西安交通大学 | Porous carbon hollow ball and its preparation method and application |
| US10259713B2 (en) | 2015-03-11 | 2019-04-16 | Xi'an Jiaotong University | Porous carbon hollow spheres and methods for their preparation and use |
| CN104759186A (en) * | 2015-05-04 | 2015-07-08 | 苏州新求是环保科技有限公司 | Activated carbon padding and preparation method thereof |
| CN107555415A (en) * | 2017-09-26 | 2018-01-09 | 四川大学 | A kind of method that hydro-thermal method prepares PVA-based carbosphere |
| CN107555415B (en) * | 2017-09-26 | 2020-02-14 | 四川大学 | Method for preparing polyvinyl alcohol-based carbon microspheres by hydrothermal method |
| CN111994893A (en) * | 2020-07-24 | 2020-11-27 | 盐城工学院 | Preparation method of nitrogen-doped carbon material |
| CN114373949A (en) * | 2020-10-15 | 2022-04-19 | 丰田自动车株式会社 | Porous carbon, catalyst carrier, and method for producing porous carbon |
| CN113081971A (en) * | 2021-05-14 | 2021-07-09 | 江西中医药大学 | Traditional Chinese medicine porous core-shell type composite particle powder and preparation method and application thereof |
| CN114361716A (en) * | 2021-12-29 | 2022-04-15 | 广东国光电子有限公司 | Positive pole piece with safety coating and preparation method and application thereof |
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Application publication date: 20140305 |