CN103014917B - Preparation method of multi-branched carbon fiber - Google Patents
Preparation method of multi-branched carbon fiber Download PDFInfo
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- CN103014917B CN103014917B CN201210567529.2A CN201210567529A CN103014917B CN 103014917 B CN103014917 B CN 103014917B CN 201210567529 A CN201210567529 A CN 201210567529A CN 103014917 B CN103014917 B CN 103014917B
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- carbon fiber
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- reaction tube
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- catalyst precursor
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 54
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 54
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 15
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 9
- 239000000243 solution Substances 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 10
- 230000012010 growth Effects 0.000 description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000007952 growth promoter Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000007773 growth pattern Effects 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Abstract
The invention belongs to the technical field of chemical material preparation, and relates to a preparation method of a multi-branched carbon fiber. The method comprises the steps of preparing an aqueous solution of copper salt as a catalyst precursor by taking deionized water as a solvent at a room temperature, placing the catalyst precursor, namely the solution of copper salt, into a porcelain boat, putting the catalyst precursor into a reaction tube of a tubular reaction furnace, vacuumizing the reaction tube, starting to rise temperature, supplying carbon source gas acetylene at a set temperature to an atmosphere for reaction, exhausting residual gas in the reaction tube after reaction completion, keeping vacuum, turning off a heating power supply, naturally cooling to the room temperature, supplying air to the atmosphere, removing a port cover of the reaction tube, and collecting a product in the porcelain boat, namely the multi-branched carbon fiber. The method is simple to operate and good in experiment repeatability, and the reaction process is simplified.
Description
Technical field:
The invention belongs to chemical material preparing technical field, relate to a kind of preparation method of racemosus shape carbon fiber.
Background technology:
The material with carbon elements such as carbon fiber, because of its unique property at aspects such as physics, chemistry, mechanics, electricity, magnetics, make it in all many-sides such as catalyst carrier, electrode for capacitors, structural reinforcement material, absorbing materials, all have broad application prospects.In recent years, the research of the material such as CNT (carbon nano-tube) and gas-phase growth of carbon fibre aspect has obtained huge energy and input in the world.As everyone knows, particularity on material structure determines the unusual of its performance, have compared with the racemosus shape carbon fiber of labyrinth and be different from simple one dimension material with carbon element, it can particularly be widely used at aspects such as nanometer-grade IC and structural reinforcement materials in many aspects in the future.For racemosus shape carbon fiber, the structure particularity of himself can make it on three dimensions, disperse more uniformly, effectively reduce the mutual winding between carbon fiber, reach higher dispersing uniformity, in structural reinforcement material application aspect, there is intrinsic advantage.At present, the preparation method of racemosus shape carbon fiber has a lot, as chemical vapour deposition technique, arc process, flame method and template etc., wherein, chemical vapour deposition technique is one of modal method of preparation racemosus shape carbon fiber, the method is a kind of low cost, easily expand, simple to operate, very potential preparation method, in this preparation method's process, the general iron that adopts, cobalt, the metal such as nickel and copper or its alloy, organic compound is as catalyst or catalyst precursor, with acetylene, ethene, benzene and dimethylbenzene etc. are as carbon source, under certain reaction temperature condition, utilize the catalytic activity of metal nanoparticle to carry out the preparation of racemosus shape carbon fiber.Prepare in the process of racemosus shape carbon fiber utilizing chemical vapour deposition technique, the selection of catalyst type is a key factor, it can directly have influence on the temperature of carbon fiber synthetic reaction, the speed of growth of carbon fiber etc., for transition-metal catalysts such as traditional iron, cobalt, nickel, its required reaction temperature is generally all higher, at 600 ° more than C; Reaction temperature in chemical vapour deposition technique is high means that energy consumption is high, inconsistent with the main body of the society of current promotion energy-saving and emission-reduction and environmental protection; Secondly, in the process of general preparation racemosus shape carbon fiber, its racemosus shape carbon fiber divides the position of branch growth, the position that is branch node is random, cannot accurately control it, and the proportionate relationship between each branch carbon fiber length is not well solved yet, the very large arbitrariness of same existence; Finally, uncertain in the growth population of minute branch growth Nodes carbon fiber,, at different minute branch growth node locations, may grow and have the carbon fiber of varying number; Above-mentioned these 3 is ubiquitous technical problem in research at present and preparation racemosus shape carbon fiber controllable growth process.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, under lower temperature conditions, utilize chemical vapour deposition technique to prepare the preparation method of a kind of racemosus shape carbon fiber of branch node location positioning, improve the pattern unicity of racemosus shape carbon fiber, realize the controlled preparation of carbon fiber, its technological operation of preparing racemosus shape carbon fiber is simple, do not need to introduce the growth promoters such as sulfide or phosphide to improve the growth of carbon fiber, utilize the aqueous solution of copper salt as catalyst precursor.
To achieve these goals, the preparation method of dendritic carbon fiber of the present invention completes according to the following steps:
(1) preparation of catalyst precursor: at ambient temperature, take deionized water as the aqueous solution of solvent configuration concentration as 0.5mol/L～2.0mol/L copper salt, as catalyst precursor;
(2) preparation of racemosus shape carbon fiber: 1. get 1ml～50ml copper salt solution catalyst presoma and be placed in porcelain boat (length * wide * height: 6 * 3 * 1cm), and put it into the reaction tube (internal diameter * length: 9 * 90cm) in tubular react furnace; 2. reaction tube is vacuumized, then start to be warming up to 300～600 ° of C, heating rate is set in 2 ° of C/min～15 ° C/min; At 50 ° of C～200 ° C temperature of setting, pass into carbon-source gas acetylene to atmospheric pressure, and keep reaction time 5min～60min;
(3) collection of racemosus shape carbon fiber: after reaction finishes, the residual gas in reaction tube is taken out, and kept vacuum, turn off heating power supply, after naturally cooling to room temperature, pass into air to atmospheric pressure, open reaction tube port lid, the product of collecting in porcelain boat is racemosus shape carbon fiber.
It is 200nm ~ 1 μ m that the present invention adopts synthetic diameter in the simple environmental system sealing, length reaches the racemosus shape carbon fiber of tens μ m, course of reaction temperature is between 300 ° of C～600 ° C, and do not need the participation of the growth promoters such as phosphide and sulfide or carrier gas, synthetic carbon fiber is impalpable structure, and the carbon fiber with many dendrite morphologies can reach more than 80% in gross product; The carbon fiber of synthesized be take catalyst granules as branch node, and growth morphology and pattern congruity are high, can be applied in capacitor, Chu Qing and composite, and output is large, simple to operate, reproducible, is suitable for expanding as suitability for industrialized production.
The present invention compared with prior art, the one, the aqueous solution of copper salt of take is catalyst precursor, adopts chemical vapour deposition technique to prepare racemosus shape carbon fiber, its reaction temperature is between 300 ° of C～450 ° C, reaction temperature is low, energy consumption is low; The 2nd, the racemosus shape carbon fiber of preparation, take catalyst granules as branch node, and on same catalyst granules, grown carbon fiber, to realize racemosus shape growth pattern, has improved the pattern unicity of racemosus shape carbon fiber simultaneously; The 3rd, without the introducing of the growth promoters such as phosphide or sulfide, simplify course of reaction, simple to operate, and experimental repeatability is good.
Accompanying drawing explanation:
Fig. 1 is the transmission electron microscope photo of the racemosus shape carbon fiber prepared of the present invention, as can be seen from the figure racemosus shape carbon fiber be take catalyst granules and is carried out branching pattern growth as branch node, what catalyst precursor adopted is copper chloride solution, carries out the reaction of 20min under 450 ° of C reaction temperatures.
Fig. 2 is the stereoscan photograph of the racemosus shape carbon fiber prepared of the present invention, and as can be seen from the figure the diameter of each branch's carbon fiber is suitable.
Fig. 3 is the XRD spectra of the racemosus shape carbon fiber prepared of the present invention, by the known racemosus shape of spectrogram carbon fiber by metallic copper catalyst with have that the carbon fiber branch of amorphous carbon forms.
The specific embodiment:
Below by embodiment, be also described further by reference to the accompanying drawings.
Embodiment 1:
The present embodiment at ambient temperature configuration concentration is 1.0mol/L copper chloride solution catalyst precursor, and get 10ml solution and be placed in porcelain boat, then porcelain boat is put into tubular react furnace, subsequently the reaction tube in tubular react furnace is vacuumized, and starting to be warming up to 350 ° of C, heating rate is set in 5 ° of C/min; When temperature rises to 60 ° of C, pass into carbon-source gas acetylene to atmospheric pressure, keep reaction time 20min; After reaction finishes, the residue reacting gas in reaction tube is taken out, and kept vacuum, turn off heating power supply, after naturally cooling to room temperature, pass into air to atmospheric pressure, open reaction tube port lid, collect the racemosus shape carbon fiber product in porcelain boat.
Embodiment 2:
The present embodiment at ambient temperature configuration concentration is 1.0mol/L copper chloride solution catalyst precursor, and gets 10ml solution and be placed in porcelain boat, then puts it in tubular react furnace; Subsequently the reaction tube in tubular react furnace is vacuumized, then start to be warming up to 450 ° of C, heating rate is set in 8 ° of C/min; When temperature rises to 80 ° of C, pass into carbon-source gas acetylene to atmospheric pressure, and keep reaction time 20min; After reaction finishes, the residue reacting gas in reaction tube is taken out, and kept vacuum, turn off heating power supply, after naturally cooling to room temperature, pass into air to atmospheric pressure, open reaction tube port lid, collect the racemosus shape carbon fiber product in porcelain boat.
Embodiment 3:
The present embodiment at ambient temperature configuration concentration is 1.5mol/L copper chloride solution catalyst precursor, and gets 20ml solution and be placed in porcelain boat, then puts it in tubular react furnace; Subsequently the reaction tube in tubular react furnace is vacuumized, then start to be warming up to 450 ° of C, heating rate is set in 5 ° of C/min; When temperature rises to 80 ° of C, pass into carbon-source gas acetylene to atmospheric pressure, and keep reaction time 20min; After reaction finishes, the residue reacting gas in reaction tube is taken out, and kept vacuum, turn off heating power supply, after naturally cooling to room temperature, pass into air to atmospheric pressure, open reaction tube port lid, collect the racemosus shape carbon fiber product in porcelain boat.
Embodiment 4:
The present embodiment at ambient temperature configuration concentration is 1.0mol/L copper nitrate aqueous solution catalyst precursor, and gets 10ml solution and be placed in porcelain boat, then puts it in tubular react furnace; Subsequently the reaction tube in tubular react furnace is vacuumized, then start to be warming up to 450 ° of C, heating rate is set in 10 ° of C/min; When temperature rises to 60 ° of C, pass into carbon-source gas acetylene to atmospheric pressure, and keep reaction time 20min; After reaction finishes, the residue reacting gas in reaction tube is taken out, and kept vacuum, turn off heating power supply, after naturally cooling to room temperature, pass into air to atmospheric pressure, open reaction tube port lid, collect the racemosus shape carbon fiber product in porcelain boat.
Claims (1)
1. a preparation method for racemosus shape carbon fiber, is characterized in that the preparation method of dendritic carbon fiber completes according to the following steps:
(1) preparation of catalyst precursor: at ambient temperature, take deionized water as the aqueous solution of solvent configuration concentration as 0.5mol/L～2.0mol/L copper salt, as catalyst precursor;
(2) preparation of racemosus shape carbon fiber: 1. get 1mL～50mL copper salt solution catalyst presoma and be placed in the porcelain boat that length * wide * height is 6 * 3 * 1cm, and put it in the reaction tube that the internal diameter * length in tubular react furnace is 9 * 90cm; 2. reaction tube is vacuumized, then start to be warming up to 300～600 ℃, heating rate is set in 2 ℃/min～15 ℃/min; At 50 ℃～200 ℃ temperature of setting, pass into carbon-source gas acetylene to atmospheric pressure, and keep reaction time 5min～60min;
(3) collection of racemosus shape carbon fiber: after reaction finishes, the residual gas in reaction tube is taken out, and kept vacuum, turn off heating power supply, after naturally cooling to room temperature, pass into air to atmospheric pressure, open reaction tube port lid, the product of collecting in porcelain boat is racemosus shape carbon fiber.
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| CN103014917B true CN103014917B (en) | 2014-09-24 |
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| CN109081324B (en) * | 2018-07-27 | 2021-09-17 | 青岛科技大学 | Preparation method of multi-dendritic carbon fiber/amorphous carbon composite material |
| CN109056121B (en) * | 2018-07-27 | 2021-04-27 | 青岛科技大学 | Preparation method of six-branch structure carbon fiber |
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