CN103130210A - Preparation method of nano natural crystalline flake graphite supported carbon hollow sphere - Google Patents
Preparation method of nano natural crystalline flake graphite supported carbon hollow sphere Download PDFInfo
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- CN103130210A CN103130210A CN2013100902862A CN201310090286A CN103130210A CN 103130210 A CN103130210 A CN 103130210A CN 2013100902862 A CN2013100902862 A CN 2013100902862A CN 201310090286 A CN201310090286 A CN 201310090286A CN 103130210 A CN103130210 A CN 103130210A
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Abstract
The invention provides a preparation method of a nano natural crystalline flake graphite supported carbon hollow sphere, relates to a preparation method of a hollow sphere and solves the technical problem that the existing carbon composite hollow sphere preparation method is low in yield and is not suitable for large-scale production. The method comprises the following steps: 1, preparing a phenolic resin solution; 2 preparing a mixed solution; and 3, dropwisely adding the phenolic resin solution into the mixed solution, stirring at a constant temperature of 60-85 DEG C for 48 hours, washing, centrifuging, drying the solid phase after centrifuging, heating the dried powder in a nitrogen protective atmosphere at a heating rate of 5 DEG C/min from room temperature to 800-1000 DEG C, and keeping the temperature for 2 hours. The nano natural crystalline flake graphite supported carbon hollow sphere material provided by the invention is large in specific surface area, low in cost, high in yield and favorable in operability, and can be widely used for electrode materials, hydrogen storage materials, catalyst carriers and the like. The invention belongs to the field of preparation of carbon hollow spheres.
Description
Technical field
The present invention relates to a kind of preparation method of hollow ball.
Background technology
The carbon hollow ball material is because its density is low, heat insulation, the electroconductibility high is widely used in drug delivery, support of the catalyst, biomass cells and various capacitor material.The carbon composite of preparation because it has netted space structure and abundant pore structure, has a wide range of applications at aspects such as Chu Qing field and electrode materialss take phenol and furfural as presoma.Therefore, the carbon hollow ball of exploitation take phenol-furfural as raw material becomes the focus that people pay close attention to.Prior art also can prepare carbon hollow ball, but complicated to prepared carbon hollow ball equipment, processing condition are strict, complicated, yield poorly to be not suitable for scale operation, so the prepared carbon hollow ball of prior art all is not suitable for large-scale application.
Summary of the invention
To the objective of the invention is to have in order solving the technical problem that the method for preparing carbon hollow ball yields poorly and is not suitable for scale operation now, a kind of preparation method of nanometer natural flake graphite load carbon hollow ball to be provided.
The preparation method of nanometer natural flake graphite load carbon hollow ball carries out according to following steps:
One, with 0.05～0.1g nano level natural flake graphite, 1～2mol phenol, 0.5～1mol furfural, 0.001～0.002mol sodium carbonate and 20～30mL water mix, then the HCl that is 0.5mol/L with concentration regulates pH value to 1, obtains phenol resin solution;
Two, get 60～90mL kerosene and 0.005～0.012mol Span～80 and mix, obtain mixing solutions;
Three, phenol resin solution is splashed in mixing solutions, stir 48h under 60～85 ℃ of constant temperatures, then washing, centrifugal;
Four, the solid phase dry 24h under 60～100 ℃ of conditions after step 3 is centrifugal; again dried powder speed with 5 ℃/min under the nitrogen protection condition is warming up to 800～1000 ℃ by room temperature; and be incubated 2h under 800～1000 ℃ of conditions, namely get nanometer natural flake graphite load carbon hollow ball.
Nanometer natural flake graphite load carbon hollow ball material specific surface area of the present invention is large, and cost is low, and productive rate is high, and operability is good, can be widely used in electrode materials, hydrogen storage material and support of the catalyst etc.
Nanometer natural flake graphite load carbon hollow ball material method of the present invention is simple, namely adopt the compound mode of nanometer scale graphite original position, make it at phenol and formed spatial network situ of furfural initial stage " pinning ", due to the good dispersity of nanometer scale graphite in aqueous solution, thereby make nanometer scale graphite can be distributed to uniformly by in the middle of phenol and the formed gelling system network of furfural, along with further going deep into of reaction, nanometer scale graphite is solidificated in the middle of the network structure of resol uniformly.By further carbonization, just obtained nanometer natural flake graphite load carbon hollow ball matrix material.The present invention does not need traditional method technological processs such as surface modification to load in preparation charcoal composite hollow ball process, reaction times and preparation cycle have greatly been shortened, improved the production efficiency of charcoal composite hollow ball, for the preparation of other Hollow Sphere Composites provides technical support.
Description of drawings
Fig. 1 is the scanning electron photomicrograph of the nanometer natural flake graphite load carbon hollow ball of experiment one preparation;
Fig. 2 is the fracture scanning electron photomicrograph of the nanometer natural flake graphite load carbon hollow ball of experiment two preparations.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of present embodiment nanometer natural flake graphite load carbon hollow ball carries out according to following steps:
One, with 0.05～0.1g nano level natural flake graphite, 1～2mol phenol, 0.5～1mol furfural, 0.001～0.002mol sodium carbonate and 20～30mL water mix, then the HCl that is 0.5mol/L with concentration regulates pH value to 1, obtains phenol resin solution;
Two, get 60～90mL kerosene and 0.005～0.012mol Span～80 and mix, obtain mixing solutions;
Three, phenol resin solution is splashed in mixing solutions, stir 48h under 60～85 ℃ of constant temperatures, then washing, centrifugal;
Four, the solid phase dry 24h under 60～100 ℃ of conditions after step 3 is centrifugal; again dried powder speed with 5 ℃/min under the nitrogen protection condition is warming up to 800～1000 ℃ by room temperature; and be incubated 2h under 800～1000 ℃ of conditions, namely get nanometer natural flake graphite load carbon hollow ball.
Embodiment two: present embodiment is different from embodiment one is that the mol ratio of phenol described in step 1 and furfural is 2: 1.Other is identical with embodiment one.
Embodiment three: present embodiment is different from one of embodiment one or two is that the mol ratio of phenol described in step 1 and sodium carbonate is 1000: 1.Other is identical with one of embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three be in step 2 in the gained mixing solutions mass percent concentration of Span-80 be 0.02%.Other is identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is to stir 48h in step 3 under 60～80 ℃ of constant temperatures.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is that the method for washing in step 3 is: first use washing with acetone 3 times, then use absolute ethanol washing 3 times, use at last distilled water wash 3 times.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to six is to stir 48h in step 3 under 70 ℃ of constant temperatures.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven is solid phase dry 24h under 80 ℃ of conditions after in step 4, that step 3 is centrifugal.Other is identical with one of embodiment one to seven.
Embodiment nine: what present embodiment was different from one of embodiment one to eight is again dried powder speed with 5 ℃/min under the nitrogen protection condition to be warming up to 820～980 ℃ by room temperature in step 4.Other is identical with one of embodiment one to eight.
Embodiment ten: what present embodiment was different from one of embodiment one to nine is again dried powder speed with 5 ℃/min under the nitrogen protection condition to be warming up to 950 ℃ by room temperature in step 4.Other is identical with one of embodiment one to nine.
Adopt following experimental verification effect of the present invention:
Experiment one:
The preparation method of nanometer natural flake graphite load carbon hollow ball carries out according to following steps:
One, with 0.1g nano level natural flake graphite, 2mol phenol, 1mol furfural, 0.001mol sodium carbonate and 30mL water mix, and the HCl that is then 0.5mol/L with concentration regulates pH value to 1, obtains phenol resin solution;
Two, get 90mL kerosene and 0.012mol Span～80 and mix, obtain mixing solutions;
Three, phenol resin solution is splashed in mixing solutions, stir 48h under 65 ℃ of constant temperatures, then washing, centrifugal;
Four, the solid phase dry 24h under 90 ℃ of conditions after step 3 is centrifugal; again dried powder speed with 5 ℃/min under the nitrogen protection condition is warming up to 900 ℃ by room temperature; and be incubated 2h under 900 ℃ of conditions, namely get nanometer natural flake graphite load carbon hollow ball.
As can be seen from Figure 1 by the original position composite principle, can prepare nanometer natural flake graphite load carbon hollow ball composite structure.
Experiment two:
The preparation method of nanometer natural flake graphite load carbon hollow ball carries out according to following steps:
One, with 0.08g nano level natural flake graphite, 1.5mol phenol, 0.7mol furfural, 0.0015mol sodium carbonate and 25mL water mix, and the HCl that is then 0.5mol/L with concentration regulates pH value to 1, obtains phenol resin solution;
Two, get 70mL kerosene and 0.008mol Span-80 and mix, obtain mixing solutions;
Three, phenol resin solution is splashed in mixing solutions, stir 48h under 70 ℃ of constant temperatures, then washing, centrifugal;
Four, the solid phase dry 24h under 80 ℃ of conditions after step 3 is centrifugal, more dried powder speed with 5 ℃/min under the nitrogen protection condition is warming up to 900 ℃ by room temperature, and be incubated 2h under 900 ℃ of conditions, namely get the carbon composite hollow ball.
As can be seen from Figure 2, utilize the method to do the carbon hollow ball structural thickness of preparation even, the nanometer natural flake graphite is coated on the carbon hollow ball surface uniformly.
Experiment three:
The preparation method of nanometer natural flake graphite load carbon hollow ball carries out according to following steps:
One, with 0.1g nano level natural flake graphite, 2mol phenol, 1mol furfural, 0.002mol sodium carbonate and 30mL water mix, and the HCl that is then 0.5mol/L with concentration regulates pH value to 1, obtains phenol resin solution;
Two, get 90mL kerosene and 0.012mol Span-80 and mix, obtain mixing solutions;
Three, phenol resin solution is splashed in mixing solutions, stir 48h under 85 ℃ of constant temperatures, then washing, centrifugal;
Four, the solid phase dry 24h under 100 ℃ of conditions after step 3 is centrifugal, more dried powder speed with 5 ℃/min under the nitrogen protection condition is warming up to 1000 ℃ by room temperature, and be incubated 2h under 900 ℃ of conditions, namely get the carbon composite hollow ball.
Claims (10)
1. the preparation method of nanometer natural flake graphite load carbon hollow ball is characterized in that the preparation method of nanometer natural flake graphite load carbon hollow ball carries out according to following steps:
One, with 0.05～0.1g nano level natural flake graphite, 1～2mol phenol, 0.5～1mol furfural, 0.001～0.002mol sodium carbonate and 20～30mL water mix, then the HCl that is 0.5mol/L with concentration regulates pH value to 1, obtains phenol resin solution;
Two, get 60～90mL kerosene and 0.005～0.012mol Span～80 and mix, obtain mixing solutions;
Three, phenol resin solution is splashed in mixing solutions, stir 48h under 60～85 ℃ of constant temperatures, then washing, centrifugal;
Four, the solid phase dry 24h under 60～100 ℃ of conditions after step 3 is centrifugal; again dried powder speed with 5 ℃/min under the nitrogen protection condition is warming up to 800～1000 ℃ by room temperature; and be incubated 2h under 800～1000 ℃ of conditions, namely get nanometer natural flake graphite load carbon hollow ball.
2. the preparation method of nanometer natural flake graphite load carbon hollow ball according to claim 1, the mol ratio that it is characterized in that phenol described in step 1 and furfural is 2: 1.
3. the preparation method of nanometer natural flake graphite load carbon hollow ball according to claim 1, the mol ratio that it is characterized in that phenol described in step 1 and sodium carbonate is 1000: 1.
4. the preparation method of nanometer natural flake graphite load carbon hollow ball according to claim 1 is characterized in that in step 2 that in the gained mixing solutions, the mass percent concentration of Span-80 is 0.02%.
5. the preparation method of nanometer natural flake graphite load carbon hollow ball according to claim 1, is characterized in that stirring 48h in step 3 under 60～80 ℃ of constant temperatures.
6. the preparation method of nanometer natural flake graphite load carbon hollow ball according to claim 1, is characterized in that the method for washing in step 3 is: first use washing with acetone 3 times, then use absolute ethanol washing 3 times, use at last distilled water wash 3 times.
7. according to claim 1, the preparation method of 2,3,4,5 or 6 described nanometer natural flake graphite load carbon hollow balls, it is characterized in that stirring 48h in step 3 under 70 ℃ of constant temperatures.
8. according to claim 1, the preparation method of 2,3,4,5 or 6 described nanometer natural flake graphite load carbon hollow balls, it is characterized in that the solid phase dry 24h under 80 ℃ of conditions after in step 4, that step 3 is centrifugal.
9. according to claim 1, the preparation method of 2,3,4,5 or 6 described nanometer natural flake graphite load carbon hollow balls, it is characterized in that again dried powder speed with 5 ℃/min under the nitrogen protection condition being warming up to 820～980 ℃ by room temperature in step 4.
10. according to claim 1, the preparation method of 2,3,4,5 or 6 described nanometer natural flake graphite load carbon hollow balls, it is characterized in that again dried powder speed with 5 ℃/min under the nitrogen protection condition being warming up to 950 ℃ by room temperature in step 4.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843665A (en) * | 2015-03-26 | 2015-08-19 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere and preparation method and application thereof |
| CN107265435A (en) * | 2017-06-29 | 2017-10-20 | 湖南科技大学 | Preparation method of surface micropore carbon hollow ball a kind of of graphene interlayers and products thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101785983A (en) * | 2010-04-08 | 2010-07-28 | 哈尔滨工业大学 | Method for preparing carbon hollow sphere composite material carrying tin oxide |
| CN101798077A (en) * | 2010-04-08 | 2010-08-11 | 哈尔滨工业大学 | Preparation method of hollow carbon sphere with resorcinol and formaldehyde as raw materials |
| CN101927994A (en) * | 2010-01-08 | 2010-12-29 | 大连理工大学 | Method for preparing monodisperse nano hollow carbon sphere with controllable size and shape |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927994A (en) * | 2010-01-08 | 2010-12-29 | 大连理工大学 | Method for preparing monodisperse nano hollow carbon sphere with controllable size and shape |
| CN101785983A (en) * | 2010-04-08 | 2010-07-28 | 哈尔滨工业大学 | Method for preparing carbon hollow sphere composite material carrying tin oxide |
| CN101798077A (en) * | 2010-04-08 | 2010-08-11 | 哈尔滨工业大学 | Preparation method of hollow carbon sphere with resorcinol and formaldehyde as raw materials |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843665A (en) * | 2015-03-26 | 2015-08-19 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere and preparation method and application thereof |
| CN104843665B (en) * | 2015-03-26 | 2017-07-21 | 中国科学院化学研究所 | A kind of individual layer and multi-layer hollow Nano carbon balls, preparation and its application |
| CN107265435A (en) * | 2017-06-29 | 2017-10-20 | 湖南科技大学 | Preparation method of surface micropore carbon hollow ball a kind of of graphene interlayers and products thereof |
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Application publication date: 20130605 |