CN110424154A - A kind of the hydrogen storage method and product of active carbon fiber felt surface metalation and application - Google Patents
A kind of the hydrogen storage method and product of active carbon fiber felt surface metalation and application Download PDFInfo
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- CN110424154A CN110424154A CN201910707255.4A CN201910707255A CN110424154A CN 110424154 A CN110424154 A CN 110424154A CN 201910707255 A CN201910707255 A CN 201910707255A CN 110424154 A CN110424154 A CN 110424154A
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- carbon fiber
- fiber felt
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- carbonization
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 81
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000001257 hydrogen Substances 0.000 title claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000003860 storage Methods 0.000 title claims abstract description 23
- 238000006263 metalation reaction Methods 0.000 title claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 87
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 238000012545 processing Methods 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 30
- 239000012530 fluid Substances 0.000 claims abstract description 20
- 239000010410 layer Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000003475 lamination Methods 0.000 claims description 16
- 238000003763 carbonization Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 229920000297 Rayon Polymers 0.000 claims description 12
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- 238000001465 metallisation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 230000006855 networking Effects 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000012423 maintenance Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 41
- 238000001994 activation Methods 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 230000004913 activation Effects 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000005255 carburizing Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- DITXJPASYXFQAS-UHFFFAOYSA-N nickel;sulfamic acid Chemical compound [Ni].NS(O)(=O)=O DITXJPASYXFQAS-UHFFFAOYSA-N 0.000 description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 3
- 230000001360 synchronised effect Effects 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001467 acupuncture Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 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
- 210000001520 comb Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000009952 needle felting Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- -1 Hydrogen compound Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- VWFLTHZUCYHIEC-UHFFFAOYSA-N cobalt sulfamic acid Chemical compound [Co].S(N)(O)(=O)=O VWFLTHZUCYHIEC-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Inorganic Fibers (AREA)
Abstract
The present invention provides the method and product and application of a kind of hydrogen storage active carbon fiber felt surface metalation, this method includes carrying out carbonization-activation to carbon fiber felt to obtain active carbon fiber felt, metalized is carried out to the active carbon fiber felt, is ultrasonically treated including placing it in the metal treatment fluid for be passed through electric current.Present invention process is simple, operation is convenient, low in cost, the processing uniformity coefficient on monfil surface is preferable, the type and thickness degree of fiber surface metal layer can be effectively controlled by this method, the treated active carbon fiber felt with metal layer can be applied in hydrogen storage field.
Description
Technical field
The present invention relates to hydrogen storage carbonaceous material fields, and in particular to a kind of hydrogen storage active carbon fiber felt surface metalation
Method and product and application.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
The application of hydrogen energy source becomes the main direction of development of current new energy revolution, and the storage of hydrogen energy source becomes current
Sciences problems urgently to be solved, wherein solid hydrogen storage material is obtained because of its higher safety, less energy consumption characteristic
The attention of researcher, the solid hydrogen storage material researched and developed at present mainly include alloy metal material, carbon material, composite chemical
Hydrogen compound material and metal organic framework compound material etc..Wherein carbonaceous material has hydrogen-sucking amount big, light weight, antitoxin
Change the excellent characteristics such as performance is strong, it is most promising that hydrogen physisorption ability is also considered as current new energy deposit field
, wherein comparing, have development includes that hydrogen storage adsorbs carbonaceous material, such as activated carbon fiber, carbon nanotube, graphene.But it invents
People's discovery, these materials still have defect, such as carbon nano-fiber hydrogen storage although hydrogen storage content is larger at present, hydrogen storage media at
This is very high, and desorption rate is unsuitable for large scale storage and transport compared with slow, cycle life is short.
Summary of the invention
Activated carbon fiber is shown stronger characterization of adsorption, is become a kind of economy with its excellent porous surface characteristic
It is applicable in, hydrogen storage content is high, it is fast to desorb, hydrogen storage adsorbent material that is can recycling and last a long time.The present invention has found under study for action
Active carbon fiber felt surface progress metalized can play the monfil surface micropore gap structure of activated carbon-fiber felt simultaneously
The intrinsic hydrogen storage property of characterization of adsorption and hydrogen storage metal, more effectively improves hydrogen storage ability.Therefore, the present invention provides a kind of storages
The method of hydrogen active carbon fiber felt surface metalation, this method carry out metalized in carbon fiber activity felt monofilament surface,
Easy to operate, feasibility is strong, is suitable for production application.
Specifically, the present invention has technical solution as described below:
In the first aspect of the present invention, the present invention provides a kind of hydrogen storage sides of active carbon fiber felt surface metalation
Method comprising carbonization-activation is carried out to carbon fiber felt and obtains active carbon fiber felt, which is carried out at metallization
Reason, is ultrasonically treated including placing it in the metal treatment fluid for be passed through electric current.
In embodiments of the present invention, metal treatment fluid needs to preheat, and can be realized by way of heating water bath, preheating
It is 50-60 DEG C to temperature.Processing activity optimization treatment effect can be improved in the processing.
In embodiments of the present invention, after metal treatment fluid is preheated to certain temperature, active carbon fiber felt is added and carries out
Metalized.
In embodiments of the present invention, in the metallizing process, current density 0.1-10A/dm2, processing
Time is 5-150 minutes.
In embodiments of the present invention, the supersonic frequency is 16.5-40KHz, ultrasonic power 1000-4000W, is surpassed
The voltage of acoustic generator is 220V.
In some embodiments of the present invention, carbon fiber felt of the present invention is high performance preoxidized fiber felt,
Monfil using pre-oxidized polyacrylonitrile fiber felt and/or viscose base preoxidized fiber felt as raw material, in preoxidized fiber felt
Tensile strength be not less than 200MPa, such as 260-300MPa, tensile modulus is not less than 1.0GPa, such as 1.4-1.6GPa, fine
It ties up volume density and is not less than 1.3g/cm3, carbon felt density is not less than 0.07g/m3, such as 0.07-0.085g/cm3, fiber phosphorus content
It not less than 65wt%, for example is 55-75wt%.
In some embodiments of the present invention, the carbonisation in the activation process uses high-purity nitrogen,
Purity is passed through pressure not less than 0.2MPa 99.99999% or more；Heating carbonization heating rate control is in 5-15 DEG C/min model
In enclosing, final carburizing temperature control is passed through the rate control of vapor in 3- within the scope of 1000-1500 DEG C under carburizing temperature
15g/min, final activation time control after the completion of 20-50min, activation processing, cooling temperature control under nitrogen protection
System is within the scope of 150-200 DEG C.The surface apertures of finally obtained carbon felt fiber control within the scope of 0.6-0.7nm.
In some embodiments of the present invention, the carbon fiber felt includes the net tire of at least two layers alternative stacked, and
Needle thorn is through the needling fiber to be connected and fixed adjacent laminates between net tire alternative stacked；In some embodiments, the carbon fiber
The density for tieing up felt is 0.05-0.09g/m3。
In certain embodiments of the present invention, the surface apertures of the active carbon fiber felt be not higher than 0.7nm, or
Not higher than 0.65nm, to be perhaps not higher than 0.6nm or being 0.6-0.7nm.
In certain embodiments of the present invention, the net tire is using pre-oxidized fibers as raw material；Wherein, the pre-oxidation is fine
The tensile strength of dimension is not less than 200MPa, and tensile modulus is not less than 1.0GPa, and fiber volume density is not less than 1.3g/cm3, fiber contains
Carbon amounts is not less than 65wt%.
In certain embodiments of the present invention, the pre-oxidized fibers are pre-oxidized polyacrylonitrile fiber and/or viscose
Base preoxidized fiber.
In certain embodiments of the present invention, the grammes per square metre of the monolayer net tire is 10-50g/m2。
In certain embodiments of the present invention, the needling fiber is to run through stacking perpendicular to the pointing needle of stromatolith thorn
Net tire.
In some embodiments of the present invention, the preparation method of active carbon fiber felt of the present invention includes with pre- oxygen
Chemical fibre dimension is raw material, is combed networking tire using comb net process；Net tire by lamination procedure lamination, lamination with needling fiber into
The hand-manipulating of needle pierces to obtain fibrofelt, and cooling obtains active carbon fiber felt after the processing of fibrofelt carbonization-activation.
In embodiments of the present invention, the present invention uses high-performance pre-oxidized fibers for raw material first, using comb net work
Sequence combs networking tire；Later by net tire using mixing lamination procedure lamination and carrying out needle felting, acupuncture course controls thickness side
To needling density and needling fiber mix ratio；Eventually by activating process, to control the stream of activated media in activation process
Amount and temperature are prepared with reaching control active carbon fiber felt monfil surface apertures purpose (aperture is not more than 0.7nm)
The active carbon fiber felt body material of controlled surface pore structure properties.
Pre-oxidized polyacrylonitrile fiber and/or the base preoxidized fibre of viscose can be selected in pre-oxidized fibers raw material of the present invention
The tensile strength of dimension, pre-oxidized fibers is not less than 200MPa, for example is 250-300MPa, and tensile modulus is not less than 1.0GPa, than
For example 1.2-2.0GPa, fiber volume density are not less than 1.3g/cm3, for example be 1.3-1.5g/cm3, carbon felt density be not less than
0.07g/m3, such as 0.07-0.085g/cm3, fiber phosphorus content is not less than 65wt%, for example is 55-75wt%.
Comb net process of the present invention uses above-mentioned high-performance pre-oxidized fibers to carry out comb net processing for raw material, combs net
Guarantee the grammes per square metre of monolayer net tire in 10-50g/m2It is further 10-45g/m in range2, for example be 10g/m2、40g/m2Or
45g/m2.When mixing comb net using different types of fiber, comb net mixes ratio according to requiring to be adjusted flexibly, such as when using not
When same pre-oxidized fibers mix comb net, for example mixed with pre-oxidized polyacrylonitrile fiber and viscose base preoxidized fiber,
It, which mixes ratio (mass ratio), to be adjusted flexibly, for example is 1:1-99 or 1-99:1, such as 1:1,1:5 or 4:1.
Net tire of the present invention mix lamination can be used different grammes per square metres net tire mixed it is fine to adjust in different layers
The density gradient of dimension.Lamination needle thorn carries out in the direction (i.e. along Z-direction) perpendicular to lamination surface, and the density domination of needle thorn exists
10-40 needle/cm2In range, needling fiber is selected from pre-oxidized fibers, and needling fiber can be mixing for different pre-oxidized fibers,
Mixing ratio can flexible modulation.For example, needling fiber can be pre-oxidized polyacrylonitrile fiber and viscose base preoxidized fiber
Mix, the ratio (mass ratio) that mixes of the two, that is, pre-oxidized polyacrylonitrile fiber and viscose base preoxidized fiber can be 1-99:1
Or 1:1-99, in the inventive solutions, which is easier to realize skill of the invention when being 1-10:1, especially 3-8:1
Art purpose, such as 3:1,4:1 or 8:1.
Carbonization-activation processing technology of the present invention, at room temperature will be above-mentioned using the progress technique synchronous with activation that is carbonized
The carbon fiber felt of preparation is sent into activation furnace burner hearth, and nitrogen is passed through in burner hearth later, is carbonized using different heating rates
Heating, starts to be passed through vapor after reaching certain temperature, and after reaching predetermined temperature, constant temperature activates certain time, finally in nitrogen
It is cooled to certain temperature under protection, later cooled to room temperature, completes carbon felt activation and carbonization treatment.
In some embodiments of the present invention, needle thorn the direction (i.e. along Z-direction) perpendicular to stromatolith into
Row.
In some embodiments of the present invention, the needling density is 10-50 needle/cm2。
In some embodiments of the present invention, the carbonization treatment includes being warming up to 1000-1500 DEG C and being passed through water steaming
Gas is carbonized to carbon fiber felt.
In embodiments of the present invention, carbonization carries out in nitrogen atmosphere.
In some embodiments of the present invention, carbonization is warming up to 1000-1500 DEG C with the heating rate of 5-15 DEG C/min.
In some embodiments of the present invention, it is passed through vapor after being warming up to 1000-1500 DEG C of carburizing temperature, water steams
The rate that is passed through of gas is 3-15g/min.
In some embodiments of the present invention, carbonization time 20-50min.
In some embodiments of the present invention, 150-200 DEG C is cooled in nitrogen atmosphere after the completion of carbonization；Then natural
It is cooled to room temperature.
Heretofore described nitrogen is high-purity nitrogen, and purity is passed through pressure and is not less than 99.99999% or more
0.2MPa。
Preparation method of the invention can control the surface apertures for the active carbon fiber felt being prepared, and make it in 0.6-
Within the scope of 0.7nm.
In embodiments of the present invention, activation of the present invention carbonization can by carbonization-activation heating device (such as
Device shown in FIG. 1) it realizes, which includes heat preservation burner hearth, heater and temperature control equipment, is led in entirely heat preservation burner hearth
Inflow-rate of water turbine entrance is passed through high pure nitrogen, controls gas flow with flow quantity control instrument；Activated water is passed through by traffic ingress simultaneously to steam
Gas controls steam activation flow with flow quantity control instrument.Therefore, active carbon fiber felt of the invention is prepared based on the device
Technique is particularly easy to realize technology.
Therefore, in the preparation process in accordance with the present invention, the carbonization-activation processing can be based on above-mentioned carbonization-activation heating dress
It sets or the similar device with above structure comprising: the carbon fiber felt of above-mentioned preparation is sent into heat preservation burner hearth 1 at room temperature
It is interior, nitrogen is passed through in burner hearth by traffic ingress 4 later, and pressure is passed through by the control nitrogen of flow quantity control instrument 5 and is not less than
0.2MPa controls heater 2 by temperature control equipment 3 and is warming up to 1000-1500 DEG C with the heating rate of 5-15 DEG C/min, so
Activation vapor is passed through by traffic ingress 6 afterwards, controlling vapor flow with flow quantity control instrument 7 is 3-15g/min, In
Be carbonized 20-50min at a temperature of 1000-1500 DEG C, then proceedes to be cooled to 150-200 DEG C in nitrogen atmosphere；Then natural cooling
To room temperature, the activation and carbonization treatment of carbon fiber felt are completed, active carbon fiber felt is obtained.
In embodiments of the present invention, metal treatment fluid during ultrasonic vibration uniform deposition in active carbon fiber felt
Monfil surface, formed metal deposition process layer；The metal deposition process layer formed and drying are washed, metal layer is obtained,
The metal layer is attached to active carbon fiber felt surface；In certain embodiments of the present invention, the metal layer thickness 1 μm-
100 μ ms are controllable.
In embodiments of the present invention, metalized of the present invention, metal treatment fluid used is prepared can be with
For conventional monometallic or the treatment fluid of alloying metal, the metal is such as nickel, copper, cobalt, magnesium or combinations thereof.
In embodiments of the present invention, the process of surface metalation processing in metalized surface processing unit into
Row, wherein being configured with metal handling apparatus, ultrasonic generator and electrode.
In certain embodiments of the present invention, the ultrasonic generator uses multiple ultrasonic probe arranged in parallel sides
Formula, ultrasonic probe control the frequency and ultrasonic power of ultrasonic probe by ultrasonic wave generating source, and wherein supersonic frequency and power can
It is adjusted flexibly, wherein the ultrasonic frequency of ultrasonic probe is optional in 16.5~40KHz range, and ultrasonic power is in 1000-4000W model
Enclose interior optional, the voltage of ultrasonic generator is 220V.
In embodiments of the present invention, the metallizing process needs in strict control and selection treatment process
Current density and processing time, in certain embodiments of the present invention, current density is controlled in 0.1-10A/dm2, when processing
Between control at 5-150 minutes or so.After connecting processing power supply, metal treatment fluid is in metal handling apparatus through ultrasound in electric current
Vibration processes form the active carbon fiber felt monfil surface deposits of homogeneous coating to get the carbon of surface adhesion metal layer is arrived
Fibrofelt.
The unstable processing uniformity of current density is bad, and the processing time, the too short 5min that is such as shorter than will lead to treatment effect not
It is good, it is too long, it will lead to fibrous mechanical property loss when such as more than 150min, current density is excessively high, for example is higher than 10A/dm2When
Fiber will receive damage.
After the deposited treatment layer is formed, optionally, is washed and dried in an oven, obtain surface adhesion metal
The carbon fiber felt of layer.
The thickness of metal layer can be by adjusting electric current and processing time etc. because usually controlling, metal layer thickness that treated
It is controllable between 1 μm -100 μm.
In embodiments of the present invention, the present invention can by selection different disposal liquid type and technique obtain it is different at
The process layer divided, method of the present invention can be used for the processing of the process layer of current various metals, and metal layer can be for example
The single metal layers such as nickel, magnesium, copper, cobalt can also be various Bimary and trinary alloys etc., such as nickel cobalt (alloy).
In one embodiment of the invention, the suitable activated carbon fiber felted three-dimensional structure of pore structure is prepared first
Body, suitable according to the requirement of metalized thickness selection on active carbon fiber felt surface later processing current density and surface
The metalized time carries out ultrasonic vibration operation to carbon fiber felt simultaneously during processing, guarantees the uniform for the treatment of process
Stablize, ultimately forms the chopped felted carbon fiber structural of the three-dimensional with homogeneous metal superficial layer, i.e. hydrogen storage activated carbon fiber
Felt.
In the second aspect of the present invention, the present invention also provides the surface metalations being prepared by method as described above
Metal layer is contained on active carbon fiber felt afterwards, the active carbon fiber felt surface, which can between 1 μm -100 μm
Control.
In the third aspect of the present invention, the present invention also provides the active carbon fiber felts after above-mentioned surface metalation in hydrogen
Application in energy storage and/or adsorbing domain.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.Hereinafter, coming in conjunction with attached drawing detailed
Describe bright embodiment of the present invention in detail, in which:
Fig. 1 is the carbonization-activation heating device schematic diagram of active carbon fiber felt, which includes heat preservation burner hearth 1, heater 2
With temperature control equipment 3, high pure nitrogen is passed through by traffic ingress 4 in entirely heat preservation burner hearth 1, with the control of flow quantity control instrument 5
Nitrogen stream；Activation vapor is passed through by traffic ingress 6 simultaneously, vapor flow is controlled with flow quantity control instrument 7.
Fig. 2 is metalized surface processing unit schematic diagram, which includes that (treatment fluid is placed on gold to metal handling apparatus 1
Belong in processing unit 1), ultrasonic generator 2 and electrode 3, wherein 4 be processing sample.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part or according to the normal condition proposed by manufacturer.
Unless otherwise defined, it anticipates known to all professional and scientific terms as used herein and one skilled in the art
Justice is identical.Reagent or raw material used in the present invention can be bought by conventional route and be obtained, unless otherwise specified, institute of the present invention
The reagent or raw material used is used according to this field usual manner or is used according to product description.In addition, any and institute
The similar or impartial method of contents and material can be applied to the method for the present invention.Preferable implementation method described in the text with
Material is for illustrative purposes only.
In embodiments of the present invention, the activation processing can be based on carbonization-activation heating device shown in FIG. 1, living
Chemical industry sequence includes: that carbon fiber felt is sent into heat preservation burner hearth 1 at room temperature, and nitrogen is passed through burner hearth by traffic ingress 4 later
In, and nitrogen is controlled by flow quantity control instrument 5 and is passed through pressure not less than 0.2MPa, heater 2 is controlled by temperature control equipment 3
It is warming up to 1000-1500 DEG C with the heating rate of 5-15 DEG C/min, activation vapor is then passed through by traffic ingress 6, with
It is 3-15g/min that flow quantity control instrument 7, which controls vapor flow, and be carbonized 20-50min at a temperature of 1000-1500 DEG C, then proceedes to
150-200 DEG C is cooled in nitrogen atmosphere；Then cooled to room temperature obtains active carbon fiber felt.The control of its surface apertures
It is being not higher than 0.7nm, either for not higher than 0.65nm or for not higher than 0.6nm or within the scope of 0.6-0.7nm.
In embodiments of the present invention, the metallizing process needs in strict control and selection treatment process
Current density carries out in the metalized surface processing unit that the treatment process can be shown in Fig. 2 with the processing time, metal is handled
Liquid is put into metal handling apparatus 1, and active carbon fiber felt to be processed is also placed in wherein, powers on control current density control
System is in 0.1-10A/dm2, and open ultrasonic generator and carry out sonic oscillation, the metallizing process time controls in 5-150
Minute or so, metal treatment fluid forms the activated carbon of homogeneous coating in metal handling apparatus in electric current through ultrasonic vibration process
Fibrofelt monofilament surface deposit is to get the carbon fiber felt for arriving surface adhesion metal layer.It, can after the deposited treatment layer is formed
Selection of land is washed and is dried in an oven.The thickness of metal layer can be by adjusting electric current and processing time etc. because usually controlling
System, metal layer thickness that treated are controllable between 1 μm -100 μm.
In embodiments of the present invention, the carbon fiber felt body can directly adopt the carbon fiber for meeting requirement of the present invention
Felt is tieed up, i.e., carbon fiber felt of the present invention is high performance preoxidized fiber felt, with pre-oxidized polyacrylonitrile fiber and/or is sticked
Matrix preoxidized fiber felt is raw material, and the tensile strength of the monfil in preoxidized fiber felt is not less than 200MPa, such as
260-300MPa, tensile modulus are not less than 1.0GPa, such as 1.4-1.6GPa, and fiber volume density is not less than 1.3g/cm3。
Alternatively, the carbon fiber felt for meeting requirement of the present invention is prepared by method as follows:
It uses high-performance pre-oxidized fibers for raw material first, networking tire is combed using comb net process；Net tire is used later
Mix lamination procedure lamination and carry out needle felting, acupuncture course controls the needling density and needling fiber hybrid ratio of thickness direction
Example.
Wherein, in above-mentioned preparation process, it is fine that preoxidized polyacrylonitrile can be selected in pre-oxidized fibers raw material of the present invention
The tensile strength of dimension and/or viscose base preoxidized fiber, pre-oxidized fibers is not less than 200MPa, for example is 250-300MPa, resists
Drawing-die amount is not less than 1.0GPa, for example is 1.2-2.0GPa, and fiber volume density is not less than 1.3g/cm3, for example be 1.3-1.5g/
cm3, fiber phosphorus content is not less than 65wt%, for example is 55-75wt%.
Comb net process described in above-mentioned preparation process, use above-mentioned high-performance pre-oxidized fibers (can for Single Fiber or
Assorted fibre) it is that raw material carries out comb net processing, comb net guarantees the grammes per square metre of monolayer net tire in 10-50g/m2In range, further for
10-45g/m2, for example be 10g/m2、40g/m2Or 45g/m2.When mixing comb net using different types of fiber, comb net mixes ratio
According to requiring to be adjusted flexibly, such as when mixing comb net using different pre-oxidized fibers, such as with preoxidized polyacrylonitrile
Fiber and viscose base preoxidized fiber are mixed, and mixing ratio (mass ratio) can be adjusted flexibly, for example, for 1:1-99 or
1-99:1, such as 1:1,1:5 or 4:1.Net tire of the present invention, which mixes lamination the net tires of different grammes per square metres can be used, to be mixed
To adjust the density gradient of fiber in different layers.Lamination needle thorn carries out in the direction (i.e. along Z-direction) perpendicular to lamination surface, needle
The density domination of thorn is in 10-40 needle/cm2In range, needling fiber is selected from pre-oxidized fibers, and needling fiber can be different pre- oxygen
Chemical fibre dimension mixes, and mixing ratio can flexible modulation.For example, needling fiber can be pre-oxidized polyacrylonitrile fiber and viscose base
Pre-oxidized fibers mix, and the two, that is, pre-oxidized polyacrylonitrile fiber and viscose base preoxidized fiber mix ratio (mass ratio)
It can be 1-99:1 or 1:1-99, be easier in the inventive solutions, when which is 1-10:1, especially 3-8:1 real
Existing technical purpose of the invention, such as 3:1,4:1 or 8:1.
Contain the active carbon fiber felt of metal layer, metal thickness in the surface being prepared through above embodiment of the present invention
Spend it is controllable in 1 μm of -100 μ m, compared to without metalized carbon fiber felt body or active carbon fiber felt body to hydrogen
Absorption and hydrogen storage property be increased dramatically, promoted amplitude up to 5-20%.
Specifically, according to above-mentioned preparation method, the present invention provides following preparating examples:
Embodiment 1
The process that carbon fiber felt body is activated is as follows:
Select tensile strength 285MPa, tensile modulus 1.6GPa, carbon felt density 0.08g/cm3, phosphorus content 65% it is poly-
Acrylonitrile preoxidized fiber felt is put into heat preservation burner hearth, is passed through purity 99.99999% or more of the pressure not less than 0.2MPa
High-purity nitrogen synchronizes and is carbonized and is activated, and carburizing temperature is arranged at 1000 DEG C first, and heating rate is 5 DEG C/
Min ought reach carburizing temperature and first be passed through the vapor that rate is 3g/min, later after the activation processing by 20min, in nitrogen
150 DEG C are cooled the temperature under gas shielded, later cooled to room temperature, the surface apertures control of finally obtained carbon felt fiber exists
Within the scope of 0.6nm.
Metalized: sulfamate metal treatment fluid, nickel sulfamic acid 420g/L, nickel chloride 5g/L, boric acid are used
40g/L is put into metal handling apparatus after configuring treatment fluid, 60 DEG C is heated under water bath condition, later will be active
Carbon fiber felt is placed in metal handling apparatus, is handled using ultrasonic generator it, tune is powered in treatment process
Economize on electricity current density is 0.6A/dm2, the time is handled at 120 minutes.The metal nickel layer activity with a thickness of 1.2 μm or so is prepared
Carbon fiber felt.
Embodiment 2
The process that carbon fiber felt body is activated is as follows:
Select tensile strength 260MPa, tensile modulus 1.5GPa, carbon felt density 0.07g/m3, phosphorus content 75% it is glutinous
Matrix preoxidized fiber felt is put into heat preservation burner hearth, and it is high-purity not less than 99.9999% or more the purity of 0.3MPa to be passed through pressure
Nitrogen to be spent, is synchronized and is carbonized and is activated, carburizing temperature is arranged at 1500 DEG C first, heating rate is 15 DEG C/min,
Carburizing temperature ought be reached later and be first passed through the vapor that rate is 15g/min, after the activation processing by 26min, in nitrogen
150 DEG C are cooled the temperature under protection, later cooled to room temperature, the surface apertures control for finally obtaining carbon felt fiber exists
Within the scope of 0.6nm.
Metalized: sulfamate metal treatment fluid, nickel sulfamic acid 420g/L, nickel chloride 5g/L, boric acid are used
40g/L is put into metal handling apparatus after configuring treatment fluid, 50 DEG C is heated under water bath condition, later will be active
Carbon fiber felt is placed in metal handling apparatus, is handled using ultrasonic generator it, and adjusting current density is 2A/dm2,
The time is handled at 80 minutes.Metal nickel layer active carbon fiber felt of the thickness at 20 μm or so is prepared.
Embodiment 3
The process that carbon fiber felt body is activated is as follows:
Select tensile strength 260MPa, tensile modulus 1.5GPa, carbon felt density 0.07g/m3, phosphorus content 75% it is glutinous
Matrix preoxidized fiber felt is put into heat preservation burner hearth, and it is high-purity not less than 99.99999% or more the purity of 0.4MPa to be passed through pressure
Nitrogen to be spent, is synchronized and is carbonized and is activated, carburizing temperature is arranged at 1400 DEG C first, heating rate is 12 DEG C/min,
Carburizing temperature ought be reached later and be first passed through the vapor that rate is 12g/min, after the activation processing by 30min, in nitrogen
110 DEG C are cooled the temperature under protection, later cooled to room temperature, the surface apertures control for finally obtaining carbon felt fiber exists
Within the scope of 0.65nm.
Metalized: metal sulfate treatment fluid is used, copper sulphate 200g/L, sulfuric acid 70g/L configure treatment fluid
It is put into metal handling apparatus later, 60 DEG C is heated under water bath condition, active carbon fiber felt is placed in metal processing later
In device, it is handled using ultrasonic generator, adjusting current density is 5A/dm2, the time is handled at 40 minutes.
Metal copper layer active carbon fiber felt to thickness at 100 μm or so.
Embodiment 4
The process that carbon fiber felt body is activated is as follows:
Select tensile strength 264MPa, tensile modulus 1.45GPa, carbon felt density 0.085g/m3, phosphorus content 67%
Viscose base preoxidized fiber felt is put into heat preservation burner hearth, is passed through the height of purity 99.99999% or more of the pressure not less than 0.5MPa
Purity nitrogen gas synchronizes and is carbonized and is activated, and carburizing temperature is arranged at 1500 DEG C first, and heating rate is 8 DEG C/min,
Carburizing temperature ought be reached later and be first passed through the vapor that rate is 10g/min, after the activation processing by 33min, in nitrogen
190 DEG C are cooled the temperature under protection, later cooled to room temperature, the surface apertures control for finally obtaining carbon felt fiber exists
Within the scope of 0.7nm.
Metalized: sulfamate metal treatment fluid, nickel sulfamic acid 600g/L, sulfamic acid cobalt 1.25g/ are used
L, nickel chloride 10g/L boric acid 35g/L are put into metal handling apparatus after configuring treatment fluid, heat under water bath condition
To 60 DEG C, active carbon fiber felt is placed in metal handling apparatus later, it is handled using ultrasonic generator, is adjusted
Current density is 3A/dm2, the time is handled at 25 minutes.Metal nickel layer active carbon fiber felt of the thickness at 2 μm or so.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of hydrogen storage method of active carbon fiber felt surface metalation comprising carry out carbonization-activation to carbon fiber felt and obtain
Active carbon fiber felt carries out metalized to the active carbon fiber felt, the metal treatment fluid of electric current is passed through including placing it in
In be ultrasonically treated.
2. the method according to claim 1, wherein in metallizing process, current density 0.1-10A/
dm2, the processing time is 5-150 minutes.
3. ultrasonic power is the method according to claim 1, wherein the supersonic frequency is 16.5-40KHz
1000-4000W, the voltage of ultrasonic generator are 220V.
4. the method according to claim 1, wherein the method for carrying out carbonization-activation to fibrofelt includes:
It is warming up to 1000-1500 DEG C and is passed through vapor；
Preferably, the heating rate is 5-15 DEG C/min；
Preferably, the rate for being passed through vapor is 3-15g/min；
Preferably, the carbonization time is in 1000-1500 DEG C of maintenance 20-50min；
Preferably, the carbonization carries out under nitrogen atmosphere；
Preferably, 150-200 DEG C is cooled to after the completion of carbonization-activation in nitrogen atmosphere；Then cooled to room temperature is lived
Property carbon fiber felt.
5. the method according to claim 1, wherein the carbon fiber felt includes the net of at least two layers alternative stacked
Tire, and needle thorn runs through the needling fiber to be connected and fixed adjacent laminates between net tire alternative stacked；
Preferably, the density of the carbon fiber felt is 0.05-0.09g/m3；
Preferably, the surface apertures of the active carbon fiber felt are not higher than 0.7nm, either for not higher than 0.65nm or for not
It higher than 0.6nm or is 0.6-0.7nm.
6. according to the method described in claim 5, it is characterized in that, the net tire is using pre-oxidized fibers as raw material；
Preferably, the tensile strength of the pre-oxidized fibers is not less than 200MPa, and tensile modulus is not less than 1.0GPa, and corpus fibrosum is close
Degree is not less than 1.3g/cm3, fiber phosphorus content is not less than 65wt%；
Preferably, the pre-oxidized fibers are pre-oxidized polyacrylonitrile fiber and/or viscose base preoxidized fiber；
Preferably, the grammes per square metre of the monolayer net tire is 10-50g/m2；
Preferably, the needling fiber is with the net tire perpendicular to the pointing needle of stromatolith thorn through stacking.
7. according to the method described in claim 5, it is characterized in that, the preparation method of the active carbon fiber felt includes: with pre-
Oxidized fibre is raw material, is combed networking tire using comb net process；Net tire is by lamination procedure lamination, and lamination is with needling fiber
It carries out needle to pierce to obtain carbon fiber felt, cooling obtains active carbon fiber felt after carbon fiber felt carbonization treatment；
Preferably, the needle thorn is in the direction progress perpendicular to stromatolith；
Preferably, the needling density is 10-40 needle/cm2；
Preferably, the carbonization treatment include under nitrogen atmosphere with the rate of 5-15 DEG C/min be warming up to 1000-1500 DEG C and with
The rate of 3-15g/min is passed through vapor to carbon fiber felt carbonization-activation 20-50min；
Preferably, the preparation method of active carbon fiber felt further includes that the carbonization is cooled to 150-200 in nitrogen atmosphere after the completion
℃；Then cooled to room temperature.
8. the method according to claim 1, wherein metal treatment fluid uniform deposition during ultrasonic vibration exists
The monfil surface of active carbon fiber felt forms metal deposition process layer；
Preferably, the metal deposition process layer of formation and drying are washed, metal layer is obtained, which is attached to activated carbon fiber
Felt surface；
Preferably, the metal layer thickness is controllable at 1 μm -100 μm.
9. the active carbon fiber felt after the surface metalation that method according to any one of claim 1 to 8 is prepared.
10. the active carbon fiber felt after surface metalation as claimed in claim 9 is in hydrogen as energy source storage and/or adsorbing domain
Application.
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