CN103350994A - Preparation method of mesoporous carbon material with controllable specific surface area and pore volume, and mesoporous carbon material - Google Patents
Preparation method of mesoporous carbon material with controllable specific surface area and pore volume, and mesoporous carbon material Download PDFInfo
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Abstract
The invention discloses a preparation method of a mesoporous carbon material with controllable specific surface area and pore volume, and a mesoporous carbon material prepared from the method. The method comprises the following steps of: heating a polysiloxane precursor and then enabling the polysiloxane precursor to perform a cross-linking reaction, and then performing crushing, pyrolysis and ball-milling to obtain a carbon precursor; then performing chlorination etching by a method of deriving carbon from carbides, so as to obtain a mesoporous carbon material with Cl; finally performing aftertreatment by ammonia gas or hydrogen, so as to obtain a mesoporous carbon material without Cl. The mesoporous carbon material disclosed by the invention has a specific surface area of 1016-2950 m<2>/g, an average pore diameter of 1.8-9.4 mm, a pore volume of 0.521-2.567 cc/g, a microporous content of 0.160-1.125 cc/g, and a mesoporous content of 0.035-2.110 cc/g. The method and the mesoporous carbon material disclosed by the invention have the advantages of being low in cost, simple and convenient in process steps, low in preparation temperature, good in formability, controllable in product performance, and the like.
Description
Technical field
The present invention relates to a kind of preparation of carbon material, relate in particular to a kind of little meso-porous carbon material product and preparation method thereof.
Background technology
Nanoporous carbon materials (Nanoporous Carbon is called for short " NPC ") refers to have a class carbon material of nano pore structure, and the aperture is generally less than 100nm.Porous carbon can be divided into microporous carbon (Micropore according to pore size, ≤ 2nm), mesoporous carbon (Mesopore, 2nm～50nm) and grand hole carbon material (Macropore, 〉=50nm), wherein microporous carbon can be divided into again the one-level microporous carbon (＜0.8nm) and secondary microporous carbon (0.8nm～2nm).Porous carbon materials mainly is comprised of the C atom, but also usually contains some micro-impurity atomss, comprises O, H, N, S etc.Nanoporous carbon materials had both had carbonaceous material low density, high strength, conductivity and the strong characteristics of workability of good biocompatibility, chemical stability (non-oxygenated environment), excellence, also have the porosity characteristics such as specific surface area is high, pore volume is large, pore passage structure is abundant, thereby have wide application background in fields such as electrode materials, sorbent material, lagging material, support of the catalyst.
In order to cater to the growing application demand of different field, develop a kind of cost not high and can either regulate on a large scale microtextures such as porous carbon specific surface area, pore volume, apertures, preparation technology that again can meticulous control, become an important development trend.
The method that is usually used at present preparing nanoporous carbon mainly contains carbide-derived carbon method (Carbide derived carbon is called for short the CDC method), activation method (comprising Physical and chemical activation method), template (comprising hard template method and soft template method), catalytic activation method, mixed with polymers carborization and organic gel carbonization method.Wherein, the CDC ratio juris be by chlorine (Cl2) thus etc. etching agent the non-carbon etching in the carbide is out obtained porous carbon (Carbide derived carbons, with " CDCs " expression), because it has the carbon matrix precursor wide material sources, pore size distribution is narrower and keep the advantage such as the original form of carbon matrix precursor, caused gradually this area researchist's extensive concern over past ten years and developed rapidly.
Yet existing preparation technology, comprise the CDC method, all the microtextures such as very difficult specific surface area to carbon material, pore volume, aperture are regulated on a large scale, this is main because the carbon matrix precursor that present most of CDC technical study personnel use is preferably binary or double carbide of crystallinity, it obtains by modes such as sintering, and mainly exist with the form of powder particle, such as SiC, TiC and Ti3SiC2 etc.And these carbide structures are more single, are difficult to CDCs is regulated on a large scale.In addition, these ceramic operability are relatively poor, are unfavorable for moulding or preparation complex component.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide that a kind of cost is low, processing step is easy, preparation temperature is low, good moldability, specific surface area and the controlled little meso-porous carbon material preparation method of pore volume that lower to the processing unit requirement, product performance are controlled, and little meso-porous carbon material that the performance that provides this preparation method to make is better, microtexture is controllable.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is the controlled little meso-porous carbon material preparation method of a kind of specific surface area and pore volume, may further comprise the steps:
(1) preparation of carbon matrix precursor (Si (O) C): will make it that crosslinking reaction occur after the heating of polysiloxane precursor, cross-linking products is carried out fragmentation, then the cross-linking products particle after the fragmentation is placed Pintsch process under inert atmosphere or the vacuum atmosphere, product cool to room temperature after the cracking obtains the carbon matrix precursor that particle size range is 0.1 μ m～50 μ m through behind the ball milling;
(2) chlorination etching: utilize carbide-derived carbon method (CDC method) that the carbon matrix precursor that above-mentioned steps (1) obtains is carried out the chlorination etching, obtain containing the little meso-porous carbon material of Cl;
(3) aftertreatment: adopt NH
3Or H
2The little meso-porous carbon material of Cl that contains that above-mentioned steps (2) is obtained carries out aftertreatment (reaction principle is: 4NH
3+ 6Cl
Surf→ 2NH
4Cl+N
2+ 4HCl or
, until the Cl element is removed, do not contained little meso-porous carbon material of Cl.
The technical scheme of the invention described above provides a kind of novel little meso-porous carbon material that can obtain superhigh specific surface area, large pore volume, and by adopting above-mentioned technique of the present invention, can regulate on a large scale the specific surface area of little meso-porous carbon material product, pore volume etc., can also realize the Precise control to little meso-porous carbon material product aperture and degree of crystallinity.Controllability specifically can realize by following three aspects: 1) by the kind of step (1) Raw, cracking temperature, cracking atmosphere, temperature rise rate, particle diameter etc. are controlled; 2) by the etching temperature in the step (2), time etc. are controlled; 3) by the atmosphere kind of aftertreatment in the step (3), time, temperature etc. are controlled.By the processing parameter of these three aspects is adjusted, just can realize the aperture of final CDCs and the control of carbon degree of crystallinity, specific surface area and pore volume, and regulate on a large scale.For example will obtain the product of small-bore, atmosphere can be adopted vacuum, Pintsch process is controlled at more than 1500 ℃, and etching temperature need be controlled more than 800 ℃; For example will obtain the product of super large specific surface area, then adopt atmosphere protection, cracking temperature to be controlled at 1000 ℃～1300 ℃ during cracking, etching temperature need be controlled at more than 900 ℃.
Above-mentioned little meso-porous carbon material preparation method, in the described step (1), described polysiloxane precursor is preferably the silicone resin that contains the Si-OH group.Polysiloxane among the present invention mainly is formed superpolymer take-Si-O-Si-as main chain, take R as side chain; Its molecular formula can be expressed as:
Wherein, the R group can be saturated group (as: CH
3, C
2H
5, C
3H
7Deng); Also can be unsaturated group (as: C
2H
3, C
6H
5Deng); It also can be OH group etc.In the preparation process of precursor, can be by the chain length of control R group, the character of group and the quantity of group are regulated carbon content wherein.
Above-mentioned little meso-porous carbon material preparation method, in the described step (1), the temperature of described crosslinking reaction is preferably 150 ℃～300 ℃, and the time of crosslinking reaction is preferably 2h～6h.
Above-mentioned little meso-porous carbon material preparation method, in the described step (1), the particle size distribution range of the cross-linking products particle after the fragmentation preferably is controlled at 150 μ m～250 μ m.
Above-mentioned little meso-porous carbon material preparation method, in the described step (1), inert atmosphere is preferably N
2Or Ar atmosphere, the cracking temperature of Pintsch process preferably is controlled at 1000 ℃～1700 ℃ under the described inert atmosphere; The cracking temperature of Pintsch process preferably is controlled at 1400 ℃～2000 ℃ under the described vacuum atmosphere; Heat-up rate during Pintsch process is preferably 5 ℃/min～20 ℃/min.
Above-mentioned little meso-porous carbon material preparation method, the time of described Pintsch process preferably is controlled to be 1h～6h, and the time of described ball milling preferably is controlled to be 5h～40h.
Above-mentioned little meso-porous carbon material preparation method, in the described step (2), the etching temperature of chlorination etching is preferably 750 ℃～1200 ℃, and heat-up rate is 5 ℃/min～20 ℃/min, and reaction atmosphere is Cl2, logical N in the whole chlorination etching process
2Or Ar is as carrier gas.
Above-mentioned little meso-porous carbon material preparation method, the time of described chlorination etching is preferably 1h～5h.
Above-mentioned little meso-porous carbon material preparation method, the treatment temp of described aftertreatment are preferably 400 ℃～800 ℃.
Above-mentioned little meso-porous carbon material preparation method, the treatment time of described aftertreatment is preferably 0.5h～4h.
As a total technical conceive, the present invention also provides a kind of little meso-porous carbon material that is made by above-mentioned preparation method, and preferred, the specific surface area of described little meso-porous carbon material is 1056m
2/ g～2950m
2/ g, mean pore size is 1.8nm～4.0nm, and pore capacities is 0.521cc/g～2.567cc/g, and wherein micropore hole content is 0.430cc/g～1.125cc/g, and mesoporous hole content is 0.035cc/g～0.980cc/g.
Compared with prior art, the invention has the advantages that: the present invention adopts polysiloxane as raw material, transforms by cracking and can obtain carbon matrix precursor; By factors such as further control cracking temperature mechanism, cracking atmosphere and polysiloxane kinds, can regulate well ratio and the microtexture of each elemental composition in the carbon matrix precursor, and then regulate, accurately control the microtextures such as specific surface, aperture of CDCs on a large scale, and then realize the preparation of little meso-porous carbon materials such as superhigh specific surface area, large pore volume.The present invention is by introducing the polysiloxane conversion method, not only raw materials cost is cheap, molecule can design, and processing step is simple and easy to do, preparation temperature is lower, formability is better, require lower to processing unit, therefore, technique of the present invention is the easier low-cost complex component that obtains little meso-porous carbon material also, for the Industry Promotion of CDC technique provides guarantee.
Description of drawings
Fig. 1 is the adsorption/desorption curve of little meso-porous carbon material of making in the embodiment of the invention 1.
Fig. 2 is the adsorption/desorption curve of little meso-porous carbon material of making in the embodiment of the invention 2.
Fig. 3 is the adsorption/desorption curve of little meso-porous carbon material of making in the embodiment of the invention 3.
Fig. 4 is the adsorption/desorption curve of little meso-porous carbon material of making in the embodiment of the invention 4.
Fig. 5 is the adsorption/desorption curve of little meso-porous carbon material of making in the embodiment of the invention 5.
Embodiment
The invention will be further described below in conjunction with Figure of description and specific embodiment, but protection domain not thereby limiting the invention.
Embodiment 1:
Little meso-porous carbon material preparation method that a kind of specific surface area of the present invention and pore volume are controlled may further comprise the steps:
(1) preparation of carbon matrix precursor: polysiloxane precursor (what all use among each embodiment is the silicone resin that contains the Si-OH group) is heated to 250 ℃ makes it that crosslinking reaction occur, behind the crosslinked 4h, cross-linking products is crushed to 150 μ m～250 μ m, then the cross-linking products particle after the fragmentation is placed pyrolyzer, and at N
2Pintsch process under the atmosphere, cracking temperature are 1200 ℃, and heat-up rate is 5 ℃/min, and pyrolysis time 2h, the product furnace cooling after the cracking are to room temperature, and ball milling 10h obtains the carbon matrix precursor particle that particle size range is 0.1 μ m～50 μ m through behind the ball milling again;
(2) chlorination etching: utilize the carbide-derived carbon method that the carbon matrix precursor particle that above-mentioned steps (1) obtains is carried out the chlorination etching, chlorination is etched in the atmosphere tube type stove to be carried out, and etching temperature is 900 ℃, and heat-up rate is 5 ℃/min, etching time is 3h, and reaction atmosphere is Cl
2, logical N in the whole chlorination etching process
2As carrier gas, cool to room temperature obtains containing the little meso-porous carbon material of Cl;
(3) aftertreatment: adopt NH
3The little meso-porous carbon material of Cl that contains that above-mentioned steps (2) is obtained carries out aftertreatment, and treatment temp is 600 ℃, and treatment time 2h until the Cl element is removed, is not contained little meso-porous carbon material of Cl.
Little meso-porous carbon material that above-mentioned the present embodiment is made adopts gas adsorption (BET) method that its pore structure is analyzed, and the adsorption/desorption curve as shown in Figure 1.After testing as can be known, the specific surface area of little meso-porous carbon material of the present embodiment is 2121m
2/ g, mean pore size is 3.1nm, and pore capacities is 1.668cc/g, and wherein micropore hole content is 1.045cc/g, and mesoporous hole content is 0.490cc/g.
Embodiment 2:
Little meso-porous carbon material preparation method that a kind of specific surface area of the present invention and pore volume are controlled may further comprise the steps:
(1) preparation of carbon matrix precursor: the polysiloxane precursor is heated to 250 ℃ makes it that crosslinking reaction occur, behind the crosslinked 4h, cross-linking products is crushed to 150 μ m～250 μ m, then the cross-linking products particle after the fragmentation is placed pyrolyzer, and at N
2Pintsch process under the atmosphere, cracking temperature are 1600 ℃, and heat-up rate is 5 ℃/min, and pyrolysis time 2h, the product furnace cooling after the cracking are to room temperature, and ball milling 10h obtains the carbon matrix precursor particle that particle size range is 0.1 μ m～50 μ m through behind the ball milling again;
(2) chlorination etching: utilize the carbide-derived carbon method that the carbon matrix precursor particle that above-mentioned steps (1) obtains is carried out the chlorination etching, chlorination is etched in the atmosphere tube type stove to be carried out, and etching temperature is 900 ℃, and heat-up rate is 15 ℃/min, etching time is 3h, and reaction atmosphere is Cl
2, logical N in the whole chlorination etching process
2As carrier gas, cool to room temperature obtains containing the little meso-porous carbon material of Cl;
(3) aftertreatment: adopt NH
3The little meso-porous carbon material of Cl that contains that above-mentioned steps (2) is obtained carries out aftertreatment, and treatment temp is 600 ℃, and treatment time 2h until the Cl element is removed, is not contained little meso-porous carbon material of Cl.
Little meso-porous carbon material that above-mentioned the present embodiment is made adopts gas adsorption (BET) method that its pore structure is analyzed, and the adsorption/desorption curve as shown in Figure 2.After testing as can be known, the specific surface area of little meso-porous carbon material of the present embodiment is 1016m
2/ g, mean pore size is 9.4nm, and pore capacities is 2.398cc/g, and wherein micropore hole content is 0.161cc/g, and mesoporous hole content is 2.106cc/g.
Embodiment 3:
Little meso-porous carbon material preparation method that a kind of specific surface area of the present invention and pore volume are controlled may further comprise the steps:
(1) preparation of carbon matrix precursor: the polysiloxane precursor is heated to 250 ℃ makes it that crosslinking reaction occur, behind the crosslinked 4h, cross-linking products is crushed to 150 μ m～250 μ m, then the cross-linking products particle after the fragmentation is placed pyrolyzer, and under vacuum atmosphere Pintsch process, cracking temperature is 1500 ℃, heat-up rate is 5 ℃/min, pyrolysis time 6h, product furnace cooling after the cracking is to room temperature, ball milling 15h obtains the carbon matrix precursor particle that particle size range is 0.1 μ m～20 μ m through behind the ball milling again;
(2) chlorination etching: utilize the carbide-derived carbon method that the carbon matrix precursor particle that above-mentioned steps (1) obtains is carried out the chlorination etching, chlorination is etched in the atmosphere tube type stove to be carried out, and etching temperature is 900 ℃, and heat-up rate is 5 ℃/min, etching time is 3h, and reaction atmosphere is Cl
2, logical Ar is as carrier gas in the whole chlorination etching process, and cool to room temperature obtains containing the little meso-porous carbon material of Cl;
(3) aftertreatment: adopt H
2The little meso-porous carbon material of Cl that contains that above-mentioned steps (2) is obtained carries out aftertreatment, and post-processing temperature is 600 ℃, and treatment time 2h until the Cl element is removed, is not contained little meso-porous carbon material of Cl.
Little meso-porous carbon material that above-mentioned the present embodiment is made adopts gas adsorption (BET) method that its pore structure is analyzed, and the adsorption/desorption curve as shown in Figure 3.After testing as can be known, the specific surface area of little meso-porous carbon material of the present embodiment is 1539m
2/ g, mean pore size is 1.9nm, and pore capacities is 0.726cc/g, and wherein micropore hole content is 0.571cc/g, and mesoporous hole content is 0.076cc/g.
Embodiment 4:
Little meso-porous carbon material preparation method that a kind of specific surface area of the present invention and pore volume are controlled may further comprise the steps:
(1) preparation of carbon matrix precursor: the polysiloxane precursor is heated to 250 ℃ makes it that crosslinking reaction occur, behind the crosslinked 4h, cross-linking products is crushed to 150 μ m～250 μ m, then the cross-linking products particle after the fragmentation is placed pyrolyzer, and under vacuum atmosphere Pintsch process, cracking temperature is 1700 ℃, heat-up rate is 5 ℃/min, pyrolysis time 6h, product furnace cooling after the cracking is to room temperature, ball milling 15h obtains the carbon matrix precursor particle that particle size range is 0.1 μ m～20 μ m through behind the ball milling again;
(2) chlorination etching: utilize the carbide-derived carbon method that the carbon matrix precursor particle that above-mentioned steps (1) obtains is carried out the chlorination etching, chlorination is etched in the atmosphere tube type stove to be carried out, and etching temperature is 900 ℃, and heat-up rate is 5 ℃/min, etching time is 3h, and reaction atmosphere is Cl
2, logical N in the whole chlorination etching process
2As carrier gas, cool to room temperature obtains containing the little meso-porous carbon material of Cl;
(3) aftertreatment: adopt NH
3The little meso-porous carbon material of Cl that contains that above-mentioned steps (2) is obtained carries out aftertreatment, and treatment temp is 600 ℃, and treatment time 2h until the Cl element is removed, is not contained little meso-porous carbon material of Cl.
Little meso-porous carbon material that above-mentioned the present embodiment is made adopts gas adsorption (BET) method that its pore structure is analyzed, and the adsorption/desorption curve as shown in Figure 4.After testing as can be known, the specific surface area of little meso-porous carbon material of the present embodiment is 1168m
2/ g, mean pore size is 1.9nm, and pore capacities is 0.726cc/g, and wherein micropore hole content is 0.571cc/g, and mesoporous hole content is 0.076cc/g.
Embodiment 5:
Little meso-porous carbon material preparation method that a kind of specific surface area of the present invention and pore volume are controlled may further comprise the steps:
(1) preparation of carbon matrix precursor: the polysiloxane precursor is heated to 250 ℃ makes it that crosslinking reaction occur, behind the crosslinked 4h, cross-linking products is crushed to 150 μ m～250 μ m, then the cross-linking products particle after the fragmentation is placed pyrolyzer, and at N
2Pintsch process under the atmosphere, cracking temperature are 1200 ℃, and heat-up rate is 5 ℃/min, and pyrolysis time 2h, the product furnace cooling after the cracking are to room temperature, and ball milling 15h obtains the carbon matrix precursor particle that particle size range is 0.1 μ m～50 μ m through behind the ball milling again;
(2) chlorination etching: utilize the carbide-derived carbon method that the carbon matrix precursor particle that above-mentioned steps (1) obtains is carried out the chlorination etching, chlorination is etched in the atmosphere tube type stove to be carried out, and etching temperature is 1200 ℃, and heat-up rate is 15 ℃/min, etching time is 3h, and reaction atmosphere is Cl
2, logical Ar is as carrier gas in the whole chlorination etching process, and cool to room temperature obtains containing the little meso-porous carbon material of Cl;
(3) aftertreatment: adopt H
2The little meso-porous carbon material of Cl that contains that above-mentioned steps (2) is obtained carries out aftertreatment, and treatment temp is 600 ℃, and treatment time 2h until the Cl element is removed, is not contained little meso-porous carbon material of Cl.
Little meso-porous carbon material that above-mentioned the present embodiment is made adopts gas adsorption (BET) method that its pore structure is analyzed, and the adsorption/desorption curve as shown in Figure 5.After testing as can be known, the specific surface area of little meso-porous carbon material of the present embodiment is 2869m
2/ g, mean pore size is 3.2nm, and pore capacities is 1.869cc/g, and wherein micropore hole content is 1.045cc/g, and mesoporous hole content is 0.824cc/g.
Claims (10)
1. a specific surface area and the controlled little meso-porous carbon material preparation method of pore volume may further comprise the steps:
(1) preparation of carbon matrix precursor: will make it that crosslinking reaction occur after the heating of polysiloxane precursor, cross-linking products is carried out fragmentation, then the cross-linking products particle after the fragmentation is placed Pintsch process under inert atmosphere or the vacuum atmosphere, product cool to room temperature after the cracking obtains the carbon matrix precursor that particle size range is 0.1 μ m～50 μ m through behind the ball milling;
(2) chlorination etching: utilize the carbide-derived carbon method that the carbon matrix precursor that above-mentioned steps (1) obtains is carried out the chlorination etching, obtain containing the little meso-porous carbon material of Cl;
(3) aftertreatment: adopt NH
3Or H
2The little meso-porous carbon material of Cl that contains that above-mentioned steps (2) is obtained carries out aftertreatment, until the Cl element is removed, is not contained little meso-porous carbon material of Cl.
2. little meso-porous carbon material preparation method according to claim 1, it is characterized in that: in the described step (1), described polysiloxane precursor is the silicone resin that contains the Si-OH group.
3. little meso-porous carbon material preparation method according to claim 1, it is characterized in that: in the described step (1), the temperature of described crosslinking reaction is 150 ℃～300 ℃, and the time of crosslinking reaction is 2h～6h.
4. according to claim 1,2 or 3 described little meso-porous carbon material preparation methods, it is characterized in that: in the described step (1), the particle size distribution range of the cross-linking products particle after the fragmentation is controlled at 150 μ m～250 μ m.
5. little meso-porous carbon material preparation method according to claim 4, it is characterized in that: in the described step (1), inert atmosphere is nitrogen atmosphere or Ar atmosphere, the cracking temperature of Pintsch process is controlled at 1000 ℃～1700 ℃ under the described inert atmosphere; The cracking temperature of Pintsch process is controlled at 1400 ℃～2000 ℃ under the described vacuum atmosphere; Heat-up rate during Pintsch process is 5 ℃/min～20 ℃/min.
6. little meso-porous carbon material preparation method according to claim 5, it is characterized in that: the time of described Pintsch process is controlled to be 1h～6h, and the time of described ball milling is controlled to be 5h～40h.
7. according to claim 1,2,3 or 6 described little meso-porous carbon material preparation methods, it is characterized in that: in the described step (2), the etching temperature of chlorination etching is 750 ℃～1200 ℃, heat-up rate is 5 ℃/min～20 ℃/min, reaction atmosphere is Cl
2, logical N in the whole chlorination etching process
2Or Ar is as carrier gas.
8. little meso-porous carbon material preparation method according to claim 7, it is characterized in that: the time of described chlorination etching is 1h～5h.
9. according to claim 1,2,3 or 6 described little meso-porous carbon material preparation methods, it is characterized in that: in the described step (3), the treatment temp of aftertreatment is 400 ℃～800 ℃; The treatment time of described aftertreatment is 0.5h～4h.
10. little meso-porous carbon material that is made by each described preparation method in the claim 1～9, it is characterized in that: the specific surface area of described little meso-porous carbon material is 1016m
2/ g～2950m
2/ g, mean pore size is 1.8nm～9.4nm, and pore capacities is 0.521cc/g～2.567cc/g, and wherein micropore hole content is 0.160cc/g～1.125cc/g, and mesoporous hole content is 0.035cc/g～2.110cc/g.
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| CN104529401A (en) * | 2015-01-14 | 2015-04-22 | 景德镇陶瓷学院 | Preparing method for silica carbon ceramic material with large-specific surface area micropore and mesoporous |
| CN111389357A (en) * | 2020-03-24 | 2020-07-10 | 中国科学院化学研究所 | Mesoporous multilevel structure carbon microsphere and preparation method thereof |
| CN111850600A (en) * | 2020-07-17 | 2020-10-30 | 西安怡速安智能科技有限公司 | Formula of anode coating for removing peculiar smell of electrochemical electrode |
| CN113546584A (en) * | 2021-07-14 | 2021-10-26 | 中天超容科技有限公司 | Mesoporous carbon pressurized fluidization production system and production method |
| CN117120368A (en) * | 2021-03-24 | 2023-11-24 | 斯克莱顿技术有限公司 | Method for producing microporous carbon material |
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| CEKDAR VAKIFAHMETOGLU等: "Enhanced hydrogen and methane gas storage of silicon oxycarbide derived carbon", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| SUN-HWA YEON等: "Carbide-derived-carbons with hierarchical porosity from a preceramic polymer", 《CARBON》 * |
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| CN104058387A (en) * | 2014-07-11 | 2014-09-24 | 武汉工程大学 | Preparation method of hollow mesoporous carbon material |
| CN104529401A (en) * | 2015-01-14 | 2015-04-22 | 景德镇陶瓷学院 | Preparing method for silica carbon ceramic material with large-specific surface area micropore and mesoporous |
| CN111389357A (en) * | 2020-03-24 | 2020-07-10 | 中国科学院化学研究所 | Mesoporous multilevel structure carbon microsphere and preparation method thereof |
| CN111389357B (en) * | 2020-03-24 | 2021-03-23 | 中国科学院化学研究所 | Mesoporous multilevel structure carbon microsphere and preparation method thereof |
| CN111850600A (en) * | 2020-07-17 | 2020-10-30 | 西安怡速安智能科技有限公司 | Formula of anode coating for removing peculiar smell of electrochemical electrode |
| CN117120368A (en) * | 2021-03-24 | 2023-11-24 | 斯克莱顿技术有限公司 | Method for producing microporous carbon material |
| CN113546584A (en) * | 2021-07-14 | 2021-10-26 | 中天超容科技有限公司 | Mesoporous carbon pressurized fluidization production system and production method |
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