CN100400415C - Nano porous vitreous carbon and its preparing method - Google Patents
Nano porous vitreous carbon and its preparing method Download PDFInfo
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- CN100400415C CN100400415C CNB021589763A CN02158976A CN100400415C CN 100400415 C CN100400415 C CN 100400415C CN B021589763 A CNB021589763 A CN B021589763A CN 02158976 A CN02158976 A CN 02158976A CN 100400415 C CN100400415 C CN 100400415C
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Abstract
The present invention relates to a nano porous vitreous carbon and a preparing method of the carbon. The preparing method comprises the steps: using phenolic resin, or furan resin, or furfural resin or the mixture of the three substances as a raw material; solidifying the raw material at low temperature in the mode of adding firming agents and mechanically mixing the firming agents to form solidified substances with certain crosslinking degree and high volatile components; grinding the solidified substances into powder which is then shaped by pressing. Certain holes are kept among the granules of the pressed bodies so as to achieve the purposes of fast temperature rise, carbonization and activation, and obtain the nano porous vitreous carbon which has about 2 nm of average hole size and high specific surface area. The preparing method has the advantages of simple steps, short period and low cost, and the obtained nano porous vitreous carbon which has about 2 nm of average hole size and high specific surface can be used as an electrode material for super capacitors.
Description
Affiliated technical field
The present invention relates to a kind of preparation method of nanoporous vitrescence charcoal, specifically prepare the method for a kind of resin-base nano hole vitrescence charcoal, this nanoporous vitrescence charcoal can be used as high conductivity, the high-energy-density electrode materials of electrochemical capacitor.
Background technology
Vitrescence charcoal (GC) has the characteristic of carbon and glass concurrently, specific conductivity height (can reach 200S/cm), and good mechanical property, resistance to oxidation and chemical corrosion, air penetrability is extremely low, and structural models is thought the micropore that contains closed shell.The vitrescence charcoal is difficult to whole activation owing to air penetrability is extremely low, can not become the good electrode materials of electrochemical capacitor.For example, the J.Miklos of Germany in 1980 attempts with the vitrescence carbon plate of the warm air oxidation polarizing electrode as double layer capacitor, but its top layer can only be activated into vesicular structure.The twentieth century end, the human electrochemical processes such as Sullivan of Sweden PSI institute are with the activation of vitrescence charcoal top layer, and the cell capaciator of assembling is 2F only.Afterwards, A.Braun etc. carry out the gas thermooxidizing with the vitrescence charcoal thin slice of thick only 55um, but the specific energy of electrical condenser fails to improve, and this technology is difficult to practicality.Recently, we adopt the constant potential electrochemical oxidation process, do one's utmost to prolong oxidization time in the hope of improving the thickness of vitrescence charcoal active layer, though the power characteristic of gained charcoal layer is good, but active layer thickness has only 16 μ m, and the ratio electric capacity of whole vitrescence charcoal or specific energy are still quite low.Therefore it is contemplated that if whole closed pores of vitrescence charcoal can be opened, make its integral body be nano level open-celled structure, then specific surface area will improve a lot, and be expected to become comparatively ideal superpower electric capacity raw material of wood-charcoal material.So far, the report that relevant integral body is vesicular structure mainly contains: nineteen eighty-three the bright grade in Yamamoto of Japan resol or furane resin microballon are added in the homogeneous tree lipoprotein solution, making mean pore size is the wide-aperture porous GC of 40～230um.The people such as jealous woman paddy of Japan in 1996 adopt resol and Resins, epoxy and solidifying agent blended method thereof, and the mean pore size of porous GC is reduced to below the 7.5um, but still in micron-sized wide aperture scope.Therefore, these two kinds of material apertures are excessive, all are not suitable for electrochemical capacitor (or claiming ultracapacitor) electrode.
In the preparation of vitrescence charcoal, in order to prevent problems such as bubbling, fracture, distortion, the curing of resinite material, carbonization process must be controlled the per hour extremely slow temperature rise rate about 1 ℃, thereby its preparation cycle is long, and be with high costs.Be head it off, 1971 in the Swansea city, Kawamura and Jenkins are from excessive phenol and hexamethylenetetramine, be heated to 300～330 ℃ crosslinked and preliminary charing takes place, through pulverizing and compression moulding, can be rapidly heated and make density to 1000 ℃ of charings is 1.35～1.5g/cm again
3Sheet vitrescence charcoal.This method is easy, quick, and the preparation cycle of vitrescence charcoal is shortened dramatically, and is referred to as " Swansea method " by people.The density of this vitrescence carbon plate approaches the vitrescence charcoal of classical way preparation, is the microvoid structure of closed shell still, does not see that the someone is used as the polarizing electrode of ultracapacitor.
Summary of the invention
The purpose of this invention is to provide a kind of simple and direct, low-cost and whole preparation method who is the nanoporous vitrescence charcoal of open-celled structure, and use it for the polarizing electrode of ultracapacitor.
The present invention realizes like this, utilize resol, furane resin, furfuryl resin or their mixture to be raw material, by adding solidifying agent and the mode mixed mutually with solidifying agent machinery, make it 300 ℃ of following primary solidification and not charing, regulate the crosslinking degree of solidification value, form and have certain degree of crosslinking and keep cured article than high volatile with the control tridimensional network; Cured article is suitably pressurization compression moulding after pulverizing, make and in press body, leave certain hole between the particle, so that being easy to diffusion, the volatile matter during charing discharges, and stress greatly weakens, and can make activated gas can infiltrate the body phase, activated reactant can diffuse out, and reaches can be rapidly heated charing and activatory purpose, thereby prepares the vitrescence charcoal that functional, production process shortening, low production cost, integral body contain the nanometer perforate.
Preparation method of the present invention comprises the steps:
1. resol, furane resin, furfuryl resin or their mixture are mixed with solidifying agent, by weight the proportioning ball milling mixing of portions of resin solidifying agent=1: 0.03～0.3; Solidifying agent is dispersed in the resin, and places air, carry out heating solid-state reaction, make high porosity, loose, foaming shape cured article at 150～300 ℃.Cured article ball milling 1～48h is become powder, obtain the powdery cured article.Solidifying agent is hexamethylenetetramine, formaldehyde, tosic acid, benzene sulfonyl chloride, sulfuric acid or phosphoric acid etc.
2. on oil press, high pressure is pressed into the powdery cured article resin press body of desired shape.
3. gained resin press body is under protection of inert gas, is warmed up to 500～1100 ℃ with the speed of 1～20 ℃/min and carries out charing and handle time 10～300min.
4. the carbon plate after the charing is under 500～1200 ℃, the mixture that utilizes rare gas elementes such as carbonic acid gas, water vapor, air or they and nitrogen is as the gas activation agent, carry out activation treatment, soak time 10～300min obtains the resin-base nano hole vitrescence charcoal of desired shape.
The preparation method of a kind of nanoporous vitrescence of the present invention charcoal has following characteristics:
1. step is simple, and preparation cycle is short, and cost is low.
2. can obtain mean pore size is about 2nm, and high-specific surface area, electroconductibility are good, the nanoporous vitrescence charcoal of desired shape.
3. but straight forming is used as the electrode materials of electrochemical capacitor.
Description of drawings
Figure: the electronic scanning sem image of resol base nano pore vitrescence charcoal
Embodiment
Embodiment 1
1. 10g lacquer resins and 0.1g hexamethylenetetramine are put into ball grinder together, at room temperature, make the complete uniform mixing of lacquer resins and hexamethylenetetramine with the rotating speed ball milling 60min of 500 commentaries on classics/min.
2. mixture is placed the nickel boat, be put in the retort furnace, be heated to 150 ℃ with the speed of 4 ℃/min and be cured, obtain harder glassy yellow cured article.And then use ball mill grinding 12h, obtain the finely powdered cured article.
3. on oil press, apply 7.6 * 10
7Kg/m
2Pressure, the powdery cured article is pressed into the circular press body of the resol of thickness between 0.6～0.8mm.
4. the resol press body that obtains in the step 3 is heated to 700 ℃ and keep 30min to carry out charing with the speed of 4 ℃/min, obtains phenolic resin carbon.
5. the phenolic resin carbon that obtains in the step 4 is heated to 700 ℃ with the speed of 8 ℃/min, feeds activator-CO
2Activation, temperature rise to 900 ℃ of activation and finish, and obtain resol base nano pore vitrescence charcoal.The results are shown in Table 1.
Embodiment 2
1. as step 1 among the embodiment 1 according to a certain ratio, resol and solidifying agent-hexamethylenetetramine are mixed.
2. mixture is placed the nickel boat, be put in the retort furnace, be heated to 225 ℃ with the speed of 4 ℃/min and be cured the cured article of the shape that loosened, foams.And then use ball mill grinding 12h, obtain the finely powdered cured article.
As step 3 among the embodiment 1,4, the 5 pairs of above-mentioned powdery cured articles suppress, charing and activation treatment, obtain resol base nano pore vitrescence charcoal.The results are shown in Table 1.
Embodiment 3
1. mix with its solidifying agent-hexamethylenetetramine as the resol of step 1 among the embodiment 1 certain proportioning.
2. as step 2 among the embodiment 2.
3. as step 3 among the embodiment 1.
4. the resol press body that obtains in the step 3 is heated to 900 ℃ and keep 30min to carry out charing with the speed of 5 ℃/min, obtains phenolic resin carbon.
5. the phenolic resin carbon that obtains in the step 4 is heated to 900 ℃ with the speed of 8 ℃/min, feeds activator-CO
2Activation, temperature rises to 925 ℃ of constant temperature 15min, obtains resol base nano pore vitrescence charcoal.The results are shown in Table 1.The electronic scanning sem image of resol base nano pore vitrescence charcoal is seen accompanying drawing.
Comparative Examples 1
As step 1,2,3 resol and solidifying agent thereof among the embodiment 3 with certain proportioning mix, curing and compression moulding.
2. the resol press body that obtains is heated to 900 ℃ and keep 30min to carry out charing with the speed of 5 ℃/min, obtains phenolic resin carbon.The results are shown in Table 1.
Comparative Examples 2
1. the hexamethylenetetramine that in three mouthfuls of round-bottomed flasks of 250ml, successively adds 40g (0.425mol) phenol and 5g (0.036mol), slowly heating then, temperature rises to more than 40 ℃, the phenol fusing, hexamethylenetetramine begins to be dissolved in the liquid phenol.At this moment, start stirring and backflow.Temperature rises to more than 104 ℃, and NH is arranged
3Overflow, solution colour changes into dark-brown, and liquid viscosity increases, and makes phenol and hexamethylenetetramine mol ratio and be 12 novolac resin.
2. the novolac resin that step 1 is obtained is under nitrogen protection, is heated to 330 ℃ with the speed of 4 ℃/min and carries out pre-treatment, pulverizes then, ball milling 12h, obtains the finely powdered material resin.
As step 3 among the embodiment 1 with the compression moulding of above-mentioned finely powdered material resin.
4. above-mentioned resin press body is heated to 1000 ℃ and keep 30min to carry out charing with the speed of 5 ℃/min, obtains alkyd resin based vitrescence charcoal.
The character of the made resol base nano pore of table 1 vitrescence charcoal reaches the contrast with phenolic resin carbon, alkyd resin based vitrescence charcoal
| Classification | BET specific surface area (m 2/g) | Micropore specific area (m 2/g) | Total pore volume (cm 3/g) | Micropore pore volume (cm 3/g) | Mean pore size (nm) | Than electric capacity (F/g) |
| Resol base nano pore vitrescence charcoal (150 ℃ of solidification values) among the embodiment 1 | 235 | 203 | 0.13 | 0.094 | 2.17 | 28 |
| Resol base nano pore vitrescence charcoal (225 ℃ of solidification values) among the embodiment 2 | 891 | 798 | 0.44 | 0.37 | 1.98 | 174 |
| Resol base nano pore vitrescence charcoal (carbonization temperature is 900 ℃, soak time 15min) among the embodiment 3 | 935 | 843 | 0.46 | 0.39 | 1.96 | 182 |
| Phenolic resin carbon in the Comparative Examples 1 | 532 | 488 | 0.25 | 0.23 | 1.89 | 130 |
| Alkyd resin based vitrescence charcoal in the Comparative Examples 2 | - | - | - | - | - | 0 |
Claims (1)
1. the preparation method of a nanoporous vitrescence charcoal is characterized in that the preparation method comprises the steps:
(1) after 1: 0.03～0.3 ball milling mixes by weight with solidifying agent with resol, furane resin, furfuryl resin or their mixture, wherein solidifying agent is hexamethylenetetramine, formaldehyde, tosic acid, benzene sulfonyl chloride, sulfuric acid or phosphoric acid, in air, be rapidly heated to 150～300 ℃ of thermofixations, make high porosity, loose, blister cured article, with cured article ball milling 1～48h powdering, obtain the powdery cured article;
(2) the powdery cured article is pressed into the resin press body of desired shape;
(3) the resin press body with the speed of 1～20 ℃/min, is warmed up to 500～1100 ℃ of constant temperature 10～300min under protection of inert gas, carries out charing and handles;
(4) carbon plate after the charing is under 500～1200 ℃, feeds gas activation agent activation 10～300min, and the gas activation agent is the gas mixture of carbonic acid gas, water vapor, air or they and nitrogen or other rare gas element, obtains the nanoporous vitrescence charcoal of desired shape.
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| CNB021589763A CN100400415C (en) | 2002-12-31 | 2002-12-31 | Nano porous vitreous carbon and its preparing method |
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| CNB021589763A CN100400415C (en) | 2002-12-31 | 2002-12-31 | Nano porous vitreous carbon and its preparing method |
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| CN100400415C true CN100400415C (en) | 2008-07-09 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006059923A (en) * | 2004-08-18 | 2006-03-02 | Nippon Oil Corp | Original composition of carbon material for electrode of electric double-layer capacitor |
| CN101299397B (en) * | 2008-03-21 | 2011-08-03 | 中国科学院上海硅酸盐研究所 | Stephanoporate carbon electrode material and preparation method thereof |
| CN101409152B (en) * | 2008-09-16 | 2010-12-01 | 上海第二工业大学 | Preparation method for element-doping manganese bioxide electrode material for super capacitor |
| CN106517158B (en) * | 2016-11-11 | 2019-01-08 | 石家庄世易糠醛糠醇有限公司 | Method, the grapheme foam material and application thereof of grapheme foam material are prepared by chaff ketone resin |
| CN106587047B (en) * | 2016-12-12 | 2019-01-29 | 张家港智电芳华蓄电研究所有限公司 | A kind of preparation method of nano-pore charcoal |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5225296A (en) * | 1989-11-21 | 1993-07-06 | Ricoh Company, Ltd. | Electrode and method of producing the same |
| US5776633A (en) * | 1995-06-22 | 1998-07-07 | Johnson Controls Technology Company | Carbon/carbon composite materials and use thereof in electrochemical cells |
| US5882621A (en) * | 1995-12-07 | 1999-03-16 | Sandia Corporation | Method of preparation of carbon materials for use as electrodes in rechargeable batteries |
| CN1305236A (en) * | 2000-07-07 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Process for preparing C/C composition used for negative electrode of lithium ion bettery |
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2002
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5225296A (en) * | 1989-11-21 | 1993-07-06 | Ricoh Company, Ltd. | Electrode and method of producing the same |
| US5776633A (en) * | 1995-06-22 | 1998-07-07 | Johnson Controls Technology Company | Carbon/carbon composite materials and use thereof in electrochemical cells |
| US5882621A (en) * | 1995-12-07 | 1999-03-16 | Sandia Corporation | Method of preparation of carbon materials for use as electrodes in rechargeable batteries |
| CN1305236A (en) * | 2000-07-07 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Process for preparing C/C composition used for negative electrode of lithium ion bettery |
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