CN108950875A - A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base - Google Patents
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base Download PDFInfo
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- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
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- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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- D04H1/4391—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
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Abstract
The invention discloses a kind of preparation methods of epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, the following steps are included: phenols, aldehyde compound and epoxy alkyl halide are reacted under the action of catalyst, epoxy-modified high adjacent position phenolic resin is made；It is dissolved in alcohols and is reacted under the action of catalyst with aldehyde compound, epoxy-modified high ortho position thermosetting phenolic resin is made；As carbon precursor solution, using coaxial electrostatic spinning, it is heating and curing to obtain the epoxy-modified high ortho position thermosetting phenolic tunica fibrosa of core-skin partial miscibility；Then it is carbonized and is activated under inert gas protection, obtain the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base.Compared with prior art, this method has the advantages that simple process, environmental-friendly, structure-controllable, stoste good spinnability, solidification rate be fast, high mechanical properties.
Description
Technical field
The invention belongs to the preparation fields of extraordinary Carbon Materials, and in particular to utilize epoxy-modified high ortho position thermosetting phenolic tree
Rouge obtains the epoxy-modified high hollow nanometer of ortho position phenolic aldehyde base as carbon precursor, through coaxial electrostatic spinning, solidification, carbonization, activation
The preparation method of activated carbon fiber film.
Background technique
The high hollow activated carbon fibre of ortho position thermosetting phenolic base is due to hollow structure, having than common phenolic aldehyde base activity
The higher specific surface area of Carbon fibe, better absorption property, chemical property, mechanical property and heat-proof quality, and solve heat
The problem of plastic phenolic resin curing time is long, process is more, with high costs and pollution environment, thermosetting phenolic resin molecular weight
Low, the problem of spinnability difference becomes one of extremely important developing direction of Material Field.In order to obtain mechanical property it is better in
Hollow fiber, this patent on this basis, propose a kind of epoxy-modified high hollow nanometer gradient active carbon of ortho position thermosetting phenolic base
The preparation method of tunica fibrosa improves its molecular structure, further improves the spinnability and work of high ortho position thermosetting phenolic resin
The mechanical property of property Carbon fibe.
The method for preparing epoxy-modified thermoplastic resin at present is existing very much, wherein Jiao Mingli (application number
201310375098.4 the preparation method of epoxy chloropropane toughened high-ortho phenolic fiber) just synthesize a kind of epoxychloropropane
Toughening high adjacent position phenolic resin, and melt spinning is carried out, solidify by solution, it is fine to obtain the high ortho position phenolic aldehyde of epoxychloropropane toughening
Dimension.It is compared with other methods with easy reaction, the advantages of stoste good spinnability, solidification rate is fast, high mechanical properties.This
Patent will be modified high ortho position thermosetting phenolic resin by further synthesizing epoxy on this basis, by coaxial electrostatic spinning, thermosetting
Change, carbonization and activation are prepared for a kind of epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, letter
Change preparation process, improve curing efficiency, while absorption property and chemical property can be further increased etc..
Summary of the invention
The present invention thermoplastic phenolic resin curing time is long, process is more, with high costs and pollution environment aiming at the problem that, it is hot
Solidity phenolic resin molecular weight is low, and the problem of spinnability difference, the hollow activated carbon fibre of phenolic aldehyde base prepares cumbersome, at high cost, environment
Pollution weight is difficult to the problem of large-area applications, and further increases the hollow activated carbon fibre mechanical property of phenolic aldehyde base, utilizes phenol
Class, aldehydes, epoxy alkyl halide react under the action of catalyst, obtain epoxy-modified high adjacent position phenolic resin, and react with aldehydes
Epoxy-modified high ortho position thermosetting phenolic resin is obtained, a kind of continuous, flexible epoxy is prepared for by coaxial electrostatic spinning method and is changed
The preparation method of the high hollow activated carbon nano fiber of ortho position thermosetting phenolic base of property.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, including it is following
Step:
(1) phenols, aldehydes and epoxy alkyl halide are heated to (92-115 DEG C) reaction 1-6h of boiling under the first catalyst action,
Decompression dehydration, dewatering vacuum degree are 8000-500Pa, this stage is first cooled to 30-70 DEG C, is then constantly warming up to 120-160 DEG C
Constant temperature 0.2-3h afterwards removes water and other small molecules that in solution and reaction generates, obtains epoxy-modified high adjacent position phenolic resin；
(2) epoxy-modified high adjacent position phenolic resin is dissolved in ethyl alcohol, aldehyde compound and the second catalyst is added, in 45-90
DEG C reaction 2.5-9h, is down to room temperature, adjusts pH=5-7.5, suctions filtration, removing impurity；Then decompression dehydration, dewatering vacuum degree are 8000-
500Pa, isothermal reaction 0.2-3h after being warming up to 40-85 DEG C remove water and other small molecules that in solution and reaction generates, are made
Epoxy-modified high ortho position thermosetting phenolic resin；
(3) epoxy-modified high ortho position thermosetting phenolic resin and Linear Polymer polymer are dissolved in solvent and shell liquid is made, it will
Linear Polymer polymer, which is dissolved in solvent, is made core liquid, and the mass fraction ratio of shell liquid each component is epoxy-modified high ortho position thermosetting
Property phenolic resin: Linear Polymer polymer: solvent=(10-70): (10-0): (80-30), the mass fraction of core liquid each component
Than for macromolecule linear polymer: solvent=(1-15): (99-85)；Using coaxial electrostatic spinning, it is heating and curing to obtain core-skin portion
Divide the epoxy-modified high ortho position thermosetting phenolic tunica fibrosa to dissolve each other；Then in N2It is carbonized and is activated under protection, obtain epoxy
The modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base.
In the step (1), phenolic compound be at least one of phenol, m-cresol, aldehyde compound be formaldehyde,
At least one of acetaldehyde, paraformaldehyde, epoxy alkyl halide be epoxychloropropane, epoxy bromopropane, in epoxy chlorobutane extremely
Few one kind, the first catalyst are zinc acetate, zinc oxide or manganese oxide.
In the step (1), the molar ratio of phenolic compound and aldehyde compound (based on contained aldehyde functions) are 1:
The mass ratio of (0.8-2), phenolic compound and epoxy alkyl halide is 100:(5-45), the matter of phenolic compound and the first catalyst
Amount is than being 100:(0.5-3).
In the step (1), phenols, aldehydes and epoxy alkyl halide are heated to boiling reaction under the first catalyst action
1-6h, acid catalyst is then added, and the reaction was continued that 0.5-4h carries out decompression dehydration again；The acid catalyst is oxalic acid, hydrochloric acid
Or the sulfuric acid that mass fraction is 98%.
In the step (2), alcohol compound is one of methanol, ethyl alcohol, and aldehyde compound is formaldehyde, acetaldehyde, more
At least one of polyformaldehyde, catalyst are one of triethanolamine, barium carbonate or barium acetate；Adjust pH used in acid be hydrochloric acid,
One of the sulfuric acid that acetic acid, simple mass fraction are 98%.
In the step (2), the mass ratio of epoxy-modified high adjacent position phenolic resin and alcohols is 1:(1-3), it is epoxy-modified
High adjacent position phenolic resin: aldehydes aldehydes (based on contained aldehyde functions) molar ratio is 1:(1-10), epoxy-modified high ortho position phenol
Urea formaldehyde: the mass ratio of catalyst is 100:(1-6).
In the step (3), Linear Polymer polymer is PVB, PVA or PVP, and solvent is ethyl alcohol, methanol, tetrahydrofuran
(THF), at least one of distilled water, N.N- dimethylformamide (DMF)；Coaxial electrostatic spinning parameter is temperature T=15-30
DEG C, relative humidity RH=35-70%, receive distance d=12-25cm, spinning voltage U=13-28kV, axis spinning speed inside and outside interior outer shaft
Vin:Vout=1:1-3。
In the step (3), the temperature that is heating and curing is 120-200 DEG C, curing time 0.5-3h, and Curing environment is sky
Gas, nitrogen or vacuum；The activator used is activated as vapor, CO2、KOH、ZnCl2, KCl, one of phosphoric acid.
In the step (3), when a step activates, the mass ratio of solid activating agent and phenolic fibre is (0.5-8): 1；First carbon
When change, post activation, the mass ratio of solid activating agent and phenolic aldehyde base carbon fibre is (0.5-8): 1；Using gas activator is lived
When change, flow 10-30ml/min.
In the step (3), carbonization and activation heating rate are 1-10 DEG C/min, and carburizing temperature is 400-1000 DEG C, carbon
Change time 0.5-2.5h, activation temperature is 400-850 DEG C, activation time 0.1-2h.
Beneficial effects of the present invention: 1, epoxy-modified high adjacent position phenolic resin and common thermoplastic's phenolic aldehyde prepared by the present invention
Resin is compared, and be joined epoxy alkyl halide, is increased long-chain in phenolic structure, is increased the flexibility of phenolic aldehyde molecule, is improved
The final toughness for obtaining fiber；It is with high ortho position structure because the contraposition activity of high ortho position phenolic aldehyde is high, be conducive to further with
Formaldehyde reaction, generates epoxy-modified high ortho position thermosetting phenolic resin.And the addition of epoxy alkyl halide, increase in phenolic structure
Long-chain, improves the final toughness for obtaining fiber, at the same remaining contraposition also can in as-spun fibre solidification faster response, mention
High reaction efficiency reduces energy consumption, has the characteristics that green high-efficient.2, when the present invention synthesizes high ortho position thermosetting phenolic resin,
Use triethanolamine, barium carbonate and barium acetate as catalyst, when adjusting pH value, be conducive to catalyst removal (precipitating or
Volatilization), catalyst/reaction product content in resin is reduced, the stability in resin use is improved；The epoxy-modified height of preparation
Ortho position thermosetting phenolic resin had both had thermoplastic phenolic resin molecular weight high, and the high feature of spinnability has both thermosetting phenolic
Resin only need to simply be heating and curing can direct carbonization the characteristics of, it is low to solve thermosetting phenolic aldehyde molecular weight, spinnability difference and thermoplastic
The problem of phenolic cure time is long, curing process is more, with high costs and pollution environment.3, the present invention uses coaxial electrostatic spinning method
The epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base of preparation has preparation process simple, green
Environmental protection, the features such as low energy consumption, controlled diameter, and degree of hollowness can design；Due in curing process, core-skin layer phase counterdiffusion, by table
Phenolic aldehyde concentration gradient is produced towards center, to produce the gradient in phenolic aldehyde aperture after activation, remoter from surface, macropore increases
It is more.4, compared with the common hollow activated carbon fibre of phenolic aldehyde base, with higher mechanical property, chemical property and thermal insulation
Can, with more the micro-or nano size that doughnut is uniform, and cortex bore diameter gradient is distributed, while make it have it is complete it is continuous in
Hollow structure is greatly promoted the development of micro-nano hollow Gradient Materials preparation.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, step is such as
Under:
(1) phenol, formaldehyde, epoxychloropropane are heated to 92 DEG C, are added second after reacting 1h under the effect of catalyst acetic acid zinc
Catalyst oxalic acid, then react 1h；Decompression dehydration, vacuum degree first drop to 30 DEG C, are gradually warming up in 8000Pa, this phase temperature
100 DEG C, constant temperature 0.2h, obtain the epoxy-modified hot phenolic resin in high ortho position；Wherein phenol: the molar ratio of formaldehyde is 1:0.8, phenol
Class: the mass ratio of epoxychloropropane is 100:5, and phenol: zinc acetate: the mass ratio of oxalic acid is 100:0.5:0.5；
(2) the epoxy-modified high adjacent position phenolic resin obtained is dissolved in methanol, and formaldehyde is then added in the work of catalyst triethanolamine
In 45 DEG C of reaction 2.5h under, it is down to room temperature, hydrochloric acid, which is added dropwise, makes pH=5, filters.Decompression dehydration, vacuum degree 8000Pa, heating
To 40 DEG C, constant temperature 0.2h, epoxy-modified high ortho position thermosetting phenolic resin is obtained；Wherein epoxy-modified high adjacent position phenolic resin:
The mass ratio of methanol is 1:1, and epoxy-modified high adjacent position phenolic resin: the molar ratio of formaldehyde is 1:1, epoxy-modified high ortho position phenolic aldehyde
Resin: the mass ratio of triethanolamine is 100:1；
(3) coaxial electrostatic spinning is used, the epoxy-modified high ortho position thermosetting phenolic for being heating and curing to obtain core-skin partial miscibility is fine
Tie up film；The wherein mass fraction ratio of shell liquid each component are as follows: epoxy-modified high ortho position thermosetting phenolic resin: ethyl alcohol=70:30, core
The mass fraction ratio of liquid each component be PVB: ethyl alcohol=1:99, coaxial electrostatic spinning parameter be T=15 DEG C, RH=35%, d=12cm, U=
13kV, Vin:Vout=1:1, and in 120 DEG C of air set 0.5h, it is heated up under nitrogen protection with the heating rate of 1 DEG C/min
To 400 DEG C, carbonization 0.5h, being passed through vapor flow is 30ml/min, obtains epoxy-modified high ortho position thermosetting property after activating 2h
The hollow nanometer gradient activated carbon fiber film of phenolic aldehyde base.
The Residual carbon of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base obtained is
93%, activated carbon fibre diameter distribution be 700-2200nm, internal diameter 350-1120nm, thermal coefficient 175W/mK, than
Surface area is 2450m2/ g, iodine number 168mg/g, average micro-pore diameter 1.1nm, internal mesopore diameter are 5nm, and ladder occurs in aperture
Degree distribution.Specific capacitance is 280F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/ by 50mA/g
After g, specific capacitance is still able to maintain 273F/g.
Embodiment 2
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, step is such as
Under:
(1) m-cresol, acetaldehyde, epoxy bromopropane are heated to 98 DEG C, are added after reacting 2h under the effect of catalyst acetic acid zinc
Second catalyst sulfuric acid, then react 1h；Decompression dehydration, vacuum degree first drop to 40 DEG C, gradually rise in 6000Pa, this phase temperature
For temperature to 110 DEG C, constant temperature 1h obtains epoxy-modified high adjacent position phenolic resin；Wherein m-cresol: the molar ratio of acetaldehyde is 1:1.2,
Phenols: the mass ratio of epoxy bromopropane is 100:10, m-cresol: zinc acetate: sulfuric acid 100:0.5:0.5；
(2) the epoxy-modified high adjacent position phenolic resin obtained is dissolved in ethyl alcohol, and acetaldehyde is then added in the effect of catalyst acetic acid barium
Under in 50 DEG C of reaction 4h, be down to room temperature, sulfuric acid, which is added dropwise, makes pH=5.5, filters.Decompression dehydration, vacuum degree 6000Pa, is warming up to
55 DEG C, constant temperature 1h, obtain epoxy-modified high ortho position thermosetting phenolic resin；Wherein epoxy-modified high adjacent position phenolic resin: ethyl alcohol
Mass ratio be 1:1.5, epoxy-modified high adjacent position phenolic resin: the molar ratio of acetaldehyde be 1:2, epoxy-modified high ortho position phenolic aldehyde tree
Rouge: the mass ratio of barium acetate is 100:6；
(3) coaxial electrostatic spinning is used, the epoxy-modified high ortho position thermosetting phenolic for being heating and curing to obtain core-skin partial miscibility is fine
Tie up film；The wherein mass fraction ratio of shell liquid each component are as follows: epoxy-modified high ortho position thermosetting phenolic resin: PVB: ethyl alcohol=70:
0.05:29.95, the mass fraction ratio of core liquid each component are PVB: ethyl alcohol=2:98, coaxial electrostatic spinning parameter be T=20 DEG C, RH=
40%, d=16cm, U=15kV, Vin:Vout=1:1, and solidify 1h in 140 DEG C of nitrogen, under nitrogen protection with 2 DEG C/min's
Heating rate is warming up to 600 DEG C, is carbonized after 0.7h, is passed through CO2Flow is 20ml/min, is obtained after activation 1.5h epoxy-modified
The high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base.
The Residual carbon of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base obtained is
85%, activated carbon fibre diameter distribution is 500-1010nm, and internal diameter 250-510nm, thermal coefficient 160W/mK compare table
Area is 2600m2/ g, iodine number 172mg/g, average micro-pore diameter 1.6nm, internal mesopore diameter are 15nm, and ladder occurs in aperture
Degree distribution.Specific capacitance is 315F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/ by 50mA/g
After g, specific capacitance is still able to maintain 294F/g.
Embodiment 3
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, step is such as
Under:
(1) phenol, m-cresol, paraformaldehyde and epoxy chlorobutane are heated to 105 DEG C under the effect of catalyst zinc oxide,
The second catalyst sulfuric acid is added after reaction 3h, then reacts 1.5h；Decompression dehydration, vacuum degree in 4000Pa, this phase temperature first under
50 DEG C are dropped to, is gradually warming up to 120 DEG C, constant temperature 2h obtains epoxy-modified high adjacent position phenolic resin；Wherein phenol: m-cresol:
Paraformaldehyde (based on contained aldehyde functions) molar ratio is 0.5:0.5:01.4, and phenols: the mass ratio of epoxy chlorobutane is
100:20, m-cresol: zinc oxide: the mass ratio of sulfuric acid is 50:0.8:0.4；
(2) the epoxy-modified high adjacent position phenolic resin obtained is dissolved in methanol, and paraformaldehyde is then added in catalyst barium carbonate
In 55 DEG C of reaction 5h under effect, it is down to room temperature, acetic acid, which is added dropwise, makes pH=6, filters.Decompression dehydration, vacuum degree 4000Pa, heating
To 60 DEG C, constant temperature 1.5h, epoxy-modified high ortho position thermosetting phenolic resin is obtained；Wherein epoxy-modified high adjacent position phenolic resin:
The mass ratio of methanol is 1:2, and epoxy-modified high adjacent position phenolic resin: paraformaldehyde (based on contained aldehyde functions) molar ratio is
1:3, epoxy-modified high adjacent position phenolic resin: the mass ratio of barium carbonate is 100:2；
(3) coaxial electrostatic spinning is used, the epoxy-modified high ortho position thermosetting phenolic for being heating and curing to obtain core-skin partial miscibility is fine
Tie up film；The wherein mass fraction ratio of shell liquid each component are as follows: epoxy-modified high ortho position thermosetting phenolic resin: PVB: methanol=50:
0.1:49.9, the mass fraction ratio of core liquid each component are PVB: methanol=3:97, coaxial electrostatic spinning parameter be T=25 DEG C, RH=
45%, d=19cm, U=20kV, Vin:Vout=1:1.2, and solidify 1.5h under 160 DEG C of vacuum conditions, under nitrogen protection with 3
DEG C/heating rate of min is warming up to 700 DEG C, after carbonization 0.9h, obtain the epoxy-modified high hollow nanometer of ortho position thermosetting phenolic base
Gradient carbon-fiber film weighs the hollow nanometer gradient carbon-fiber film of epoxy-modified high ortho position thermosetting phenolic base and KOH, wherein epoxy
The modified high hollow nanometer gradient carbon-fiber film of ortho position thermosetting phenolic base: the mass ratio of KOH is 1:0.5, adds distilled water immersion 1h
And after drying, after being warming up to 700 DEG C with the heating rate of 3 DEG C/min under nitrogen protection, activate 1h, obtain epoxy-modified high adjacent
The position hollow nanometer gradient activated carbon fiber film of thermosetting phenolic base.
The Residual carbon of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base obtained is
76%, activated carbon fibre diameter distribution is 310-800nm, and internal diameter 110-450nm, thermal coefficient 140W/mK compare table
Area is 2750m2/ g, iodine number 249mg/g, average micro-pore diameter 1.6nm, internal mesopore diameter are 18nm, and ladder occurs in aperture
Degree distribution.Specific capacitance is 339F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/ by 50mA/g
After g, specific capacitance is still able to maintain 320F/g.
Embodiment 4
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, step is such as
Under:
(1) phenol, formaldehyde, epoxychloropropane, epoxy bromopropane are heated to 105 DEG C, reaction under the effect of catalyst acetic acid zinc
The second catalyst sulfuric acid is added after 4h, then reacts 2h；Decompression dehydration, vacuum degree first drop to 60 DEG C, gradually heat up in 2000Pa
To 140 DEG C, constant temperature 2.5h obtains epoxy-modified high adjacent position phenolic resin；Wherein phenol: the molar ratio of formaldehyde is 1:1.6, phenol
Class: epoxy bromopropane: the mass ratio of epoxychloropropane is 100:10:15, and phenol: zinc acetate: the mass ratio of sulfuric acid is 100:1:
0.5。
(2) the epoxy-modified high adjacent position phenolic resin obtained is dissolved in ethyl alcohol, and formaldehyde and acetaldehyde is then added in catalyst three
In 60 DEG C of reaction 6h under the action of ethanol amine, it is down to room temperature, hydrochloric acid, which is added dropwise, makes pH=6.5, filters.Decompression dehydration, vacuum degree are
3000Pa is warming up to 65 DEG C, constant temperature 2h, obtains epoxy-modified high ortho position thermosetting phenolic resin；Wherein epoxy-modified high ortho position
Phenolic resin: the mass ratio of ethyl alcohol is 1:2.5, and epoxy-modified high adjacent position phenolic resin: formaldehyde: the molar ratio of acetaldehyde is 1:3:2,
Epoxy-modified high adjacent position phenolic resin: the mass ratio of triethanolamine is 100:3.5.
(3) coaxial electrostatic spinning is used, is heating and curing to obtain the epoxy-modified high ortho position thermosetting property phenol of core-skin partial miscibility
Aldehyde tunica fibrosa；The wherein mass fraction ratio of shell liquid each component are as follows: epoxy-modified high ortho position thermosetting phenolic resin: PVB:THF=
30:0.5:69.5, the mass fraction ratio of core liquid each component are PVB:THF=4:96, coaxial electrostatic spinning parameter be T=30 DEG C, RH=
50%, d=21cm, U=23kV, Vin:Vout=1:1.6, and solidify 2h in 180 DEG C of nitrogen, under nitrogen protection with 4 DEG C/min
Heating rate be warming up to 800 DEG C, carbonization 1h after, obtain the epoxy-modified hollow nanometer gradient carbon fiber of high ortho position thermosetting phenolic base
Film is tieed up, the hollow nanometer gradient carbon-fiber film of epoxy-modified high ortho position thermosetting phenolic base and phosphoric acid are weighed, wherein epoxy-modified height
The mass ratio of the hollow nanometer gradient carbon-fiber film of ortho position thermosetting phenolic base and phosphoric acid is 1:2, adds distilled water immersion 3h and drying
Afterwards, after being warming up to 800 DEG C with the heating rate of 4 DEG C/min under nitrogen protection, activate 0.7h, epoxy-modified high ortho position heat is obtained
The hollow nanometer gradient activated carbon fiber film of solidity phenolic aldehyde base.
The Residual carbon of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base obtained is
66%, activated carbon fibre diameter distribution is 206-450nm, internal diameter 70-186nm, thermal coefficient 111W/mK, specific surface
Product is 3290m2/ g, iodine number 331mg/g, average micro-pore diameter 1.6nm, internal mesopore diameter are 21nm, and gradient occurs in aperture
Distribution.Specific capacitance is 356F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/g by 50mA/g
Afterwards, specific capacitance is still able to maintain 314F/g.
Embodiment 5
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, step is such as
Under:
(1) m-cresol, formaldehyde, acetaldehyde, epoxychloropropane are heated to 110 DEG C, react 5h under the effect of catalyst manganese oxide
After the second hydrochloric is added, then react 4h；Decompression dehydration, vacuum degree first drop to 60 DEG C, are gradually warming up in 1000Pa
150 DEG C, constant temperature 2.5h obtains epoxy-modified high adjacent position phenolic resin；Wherein phenol: formaldehyde: the molar ratio of acetaldehyde is 1:0.9:
0.9, phenols: the mass ratio of epoxychloropropane is 100:35, and phenol: zinc acetate: the mass ratio of sulfuric acid is 100:1.5:0.5；
(2) the epoxy-modified high adjacent position phenolic resin obtained is dissolved in methanol, and formaldehyde is then added in the effect of catalyst barium carbonate
Under in 70 DEG C of reaction 7h, be down to room temperature, sulfuric acid, which is added dropwise, makes pH=7, filters.Decompression dehydration, vacuum degree 2000Pa, is warming up to 70
DEG C, constant temperature 2h obtains epoxy-modified high ortho position thermosetting phenolic resin；Wherein epoxy-modified high adjacent position phenolic resin: methanol
Mass ratio is 1:2.5, epoxy-modified high adjacent position phenolic resin: the molar ratio of formaldehyde is 1:7, epoxy-modified high ortho position phenolic aldehyde tree
Rouge: the mass ratio of barium carbonate is 100:4；
(3) coaxial electrostatic spinning is used, the epoxy-modified high ortho position thermosetting phenolic for being heating and curing to obtain core-skin partial miscibility is fine
Tie up film；Wherein the mass fraction ratio of shell liquid each component is epoxy-modified high ortho position thermosetting phenolic resin: PVB: ethyl alcohol: THF=
20:1:16:63, the mass fraction ratio of core liquid each component are PVB: ethyl alcohol: THF=5:76:19, coaxial electrostatic spinning parameter be T=
30 DEG C, RH=55%, d=23cm, U=25kV, Vin:Vout=1:2, and solidify 2.5h in 200 DEG C of vacuum, under nitrogen protection with
The heating rate of 5 DEG C/min is warming up to 900 DEG C, after carbonization 1.2h, obtains that epoxy-modified high ortho position thermosetting phenolic base is hollow to be received
Rice gradient carbon-fiber film, weighs the epoxy-modified high hollow nanometer gradient carbon-fiber film KCl of ortho position thermosetting phenolic base2, middle ring
The modified high hollow nanometer gradient carbon-fiber film of ortho position thermosetting phenolic base of oxygen: the mass ratio of KCl is 1:3, adds distilled water immersion 5h
And after drying, after being warming up to 800 DEG C with the heating rate of 5 DEG C/min under nitrogen protection, activate 0.8h, epoxy-modified height is obtained
The hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base.
The Residual carbon of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base obtained is
57%, activated carbon fibre diameter distribution is 110-190nm, internal diameter 59-142nm, thermal coefficient 100W/mK, specific surface
Product is 3645m2/ g, iodine number 546mg/g, average micro-pore diameter 1.8nm, internal mesopore diameter are 24nm, and gradient occurs in aperture
Distribution.Specific capacitance is 394F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/g by 50mA/g
Afterwards, specific capacitance is still able to maintain 364F/g.
Embodiment 6
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, step is such as
Under:
(1) phenol, acetaldehyde, epoxy bromopropane are heated to 115 DEG C under the effect of catalyst acetic acid zinc, after reacting 6h, decompression is de-
Water, vacuum degree first drop to 70 DEG C in 400Pa, this phase temperature, are gradually warming up to 165 DEG C, and constant temperature 3h obtains epoxy-modified height
Adjacent position phenolic resin；Wherein phenol: the molar ratio of acetaldehyde is 1:2, phenols: the mass ratio of epoxy bromopropane is 100:45, phenol:
Zinc acetate mass ratio is 100:3；
(2) the epoxy-modified high adjacent position phenolic resin obtained is dissolved in ethyl alcohol, and acetaldehyde is then added in the work of catalyst triethanolamine
In 80 DEG C of reaction 8h under, it is down to room temperature, acetic acid, which is added dropwise, makes pH=7.5, filters.Decompression dehydration, vacuum degree 1000Pa, heating
To 80 DEG C, constant temperature 2.5h, epoxy-modified high ortho position thermosetting phenolic resin is obtained；Wherein epoxy-modified high adjacent position phenolic resin:
The mass ratio of ethyl alcohol is 1:3, and epoxy-modified high adjacent position phenolic resin: the molar ratio of acetaldehyde is 1:8, epoxy-modified high ortho position phenolic aldehyde
Resin: the mass ratio of triethanolamine is 100:5；
(3) coaxial electrostatic spinning is used, the epoxy-modified high ortho position thermosetting phenolic for being heating and curing to obtain core-skin partial miscibility is fine
Tie up film；The wherein mass fraction ratio of shell liquid each component are as follows: epoxy-modified high ortho position thermosetting phenolic resin: PVB: methanol: THF=
10:2:70.4:17.6, the mass fraction ratio of core liquid each component are PVB: methanol: THF=4:76.8:19.2, coaxial electrostatic spinning
Silk parameter is T=15 DEG C, RH=60%, d=25cm, U=28kV, Vin:Vout=1:2.3, and in 160 DEG C of air set 3h, in nitrogen
1000 DEG C are warming up to the heating rate of 6 DEG C/min under gas shielded, after the 1.5h that is carbonized, obtain epoxy-modified high ortho position thermosetting property phenol
The hollow nanometer gradient carbon-fiber film of aldehyde radical, weigh the epoxy-modified high hollow nanometer gradient carbon-fiber film of ortho position thermosetting phenolic base and
KOH, wherein the epoxy-modified hollow nanometer gradient carbon-fiber film of high ortho position thermosetting phenolic base: the mass ratio of KOH is 1:4, adds steaming
After distilled water is impregnated 7h and dried, 850 DEG C are warming up to the heating rate of 6 DEG C/min under nitrogen protection, after activating 1h, obtains ring
The modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base of oxygen.
The Residual carbon of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base obtained is
47%, activated carbon fibre diameter distribution is 90-174nm, internal diameter 40-74nm, thermal coefficient 131W/mK, specific surface area
For 3995m2/ g, iodine number 738mg/g, average micro-pore diameter 2nm, internal mesopore diameter are 31nm, and gradient distribution occurs in aperture.
Specific capacitance is 368F/g in the Et4NBF4/PC electrolyte of 1mol/ L, after current density increases to 10A/g by 50mA/g, than
Capacitor is still able to maintain 333F/g.
Embodiment 7
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, step is such as
Under:
(1) phenol, formaldehyde, epoxychloropropane are heated to 92 DEG C, are added second after reacting 1h under the effect of catalyst acetic acid zinc
Catalyst oxalic acid, then react 1h；Decompression dehydration, vacuum degree first drop to 30 DEG C, are gradually warming up in 8000Pa, this phase temperature
100 DEG C, constant temperature 0.2h, obtain the hot phenolic resin in high ortho position；Wherein phenol: the molar ratio of formaldehyde is 1:0.8, phenols: epoxy chlorine
The mass ratio of propane is 100:5, and phenol: zinc acetate: the mass ratio of oxalic acid is 100:0.5:0.5；
(2) the epoxy-modified high adjacent position phenolic resin obtained is dissolved in methanol, and formaldehyde is then added in the effect of catalyst barium carbonate
Under in 90 DEG C of reaction 9h, be down to room temperature, hydrochloric acid, which is added dropwise, makes pH=7.5, filters.Decompression dehydration, vacuum degree 500Pa, is warming up to 85
DEG C, constant temperature 3h obtains epoxy-modified high ortho position thermosetting phenolic resin；Wherein epoxy-modified high adjacent position phenolic resin: methanol
Mass ratio is 1:2.5, epoxy-modified high adjacent position phenolic resin: the molar ratio of formaldehyde is 1:10, epoxy-modified high ortho position phenolic aldehyde tree
Rouge: the mass ratio of barium carbonate is 100:6；
(3) coaxial electrostatic spinning is used, the epoxy-modified high ortho position thermosetting phenolic for being heating and curing to obtain core-skin partial miscibility is fine
Tie up film；The wherein mass fraction ratio of shell liquid are as follows: epoxy-modified high ortho position thermosetting phenolic resin: PVA: ethyl alcohol=60:5:35 core liquid
Mass fraction ratio be PVA: ethyl alcohol=5:95, coaxial electrostatic spinning parameter be T=15 DEG C, RH=35%, d=14cm, U=16kV,
Vin:Vout=1:1.2, and in 120 DEG C of air set 0.5h, it is warming up under nitrogen protection with the heating rate of 7 DEG C/min
500 DEG C, carbonization 2h after, be passed through vapor flow be 15ml/min, activate 0.5h after obtain epoxy-modified high ortho position thermosetting property
The hollow nanometer gradient activated carbon fiber film of phenolic aldehyde base.
The Residual carbon of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base obtained is
80%, activated carbon fibre diameter distribution is 402-640nm, and internal diameter 145-260nm, thermal coefficient 120W/mK compare table
Area is 2699m2/ g, iodine number 135mg/g, average micro-pore diameter 2nm, internal mesopore diameter are 35nm, and gradient occurs in aperture
Distribution.Specific capacitance is 329F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/g by 50mA/g
Afterwards, specific capacitance is still able to maintain 299F/g.
Embodiment 8
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, step is such as
Under:
(1) m-cresol, acetaldehyde, epoxy bromopropane are heated to 98 DEG C, are added after reacting 2h under the effect of catalyst acetic acid zinc
Second catalyst sulfuric acid, then react 1h；Decompression dehydration, vacuum degree first drop to 40 DEG C, gradually rise in 6000Pa, this phase temperature
For temperature to 110 DEG C, constant temperature 1h obtains epoxy-modified high adjacent position phenolic resin；Wherein m-cresol: the molar ratio of acetaldehyde is 1:1.2,
Phenols: the mass ratio of epoxy bromopropane is 100:10, m-cresol: zinc acetate: sulfuric acid 100:0.5:0.5；
(2) the epoxy-modified high adjacent position phenolic resin obtained is dissolved in methanol, and paraformaldehyde is then added in catalyst barium carbonate
In 55 DEG C of reaction 5h under effect, it is down to room temperature, acetic acid, which is added dropwise, makes pH=6, filters.Decompression dehydration, vacuum degree 4000Pa, heating
To 60 DEG C, constant temperature 1.5h, epoxy-modified high ortho position thermosetting phenolic resin is obtained；Wherein epoxy-modified high adjacent position phenolic resin:
The mass ratio of methanol is 1:2, and epoxy-modified high adjacent position phenolic resin: paraformaldehyde (based on contained aldehyde functions) molar ratio is
1:3, epoxy-modified high adjacent position phenolic resin: the mass ratio of barium carbonate is 100:2；
(3) coaxial electrostatic spinning is used, the epoxy-modified high ortho position thermosetting phenolic for being heating and curing to obtain core-skin partial miscibility is fine
Tie up film；The wherein mass fraction ratio of shell liquid each component are as follows: epoxy-modified high ortho position thermosetting phenolic resin: PVA: distilled water=50:
7:43, the mass fraction ratio of core liquid each component are PVA: distilled water=7:93, and coaxial electrostatic spinning parameter is T=30 DEG C, RH=35%,
D=25cm, U=18kV, Vin:Vout=1:1.4, and solidify 1h in 140 DEG C of nitrogen, under protection of argon gas with the liter of 8 DEG C/min
Warm rate is warming up to 600 DEG C, is carbonized after 1.8h, is passed through CO2Flow is 10ml/min, obtains epoxy-modified height after activating 0.8h
The hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base.
The Residual carbon of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base obtained is
70%, activated carbon fibre diameter distribution is 332-900nm, and internal diameter 150-432nm, thermal coefficient 104W/mK compare table
Area is 2910m2/ g, iodine number 177mg/g, average micro-pore diameter 0.5nm, internal mesopore diameter are 42nm, and ladder occurs in aperture
Degree distribution.Specific capacitance is 343F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/ by 50mA/g
After g, specific capacitance is still able to maintain 327F/g.
Embodiment 9
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, step is such as
Under:
(1) phenol, m-cresol, paraformaldehyde and epoxy chlorobutane are heated to 105 DEG C under the effect of catalyst zinc oxide,
The second catalyst sulfuric acid is added after reaction 3h, then reacts 1.5h；Decompression dehydration, vacuum degree first drop to 50 DEG C in 4000Pa, by
Step is warming up to 120 DEG C, and constant temperature 2h obtains epoxy-modified high adjacent position phenolic resin；Wherein phenol: m-cresol: paraformaldehyde (is pressed
Contained aldehyde functions meter) molar ratio is 0.5:0.5:1.4, phenols: the mass ratio of epoxy chlorobutane is 100:20, toluene
Phenol: zinc oxide: the mass ratio of sulfuric acid is 50:0.8:0.4；
(2) the epoxy-modified high adjacent position phenolic resin obtained is dissolved in ethyl alcohol, and formaldehyde and acetaldehyde is then added in three ethyl alcohol of catalyst
In 60 DEG C of reaction 6h under the action of amine, it is down to room temperature, hydrochloric acid, which is added dropwise, makes pH=6.5, filters.Decompression dehydration, vacuum degree are
3000Pa is warming up to 65 DEG C, constant temperature 2h, obtains epoxy-modified high ortho position thermosetting phenolic resin；Wherein epoxy-modified high ortho position
Phenolic resin: the mass ratio of ethyl alcohol is 1:2.5, and epoxy-modified high adjacent position phenolic resin: formaldehyde: the molar ratio of acetaldehyde is 1:3:2,
Epoxy-modified high adjacent position phenolic resin: the mass ratio of triethanolamine is 100:3.5；
(3) coaxial electrostatic spinning is used, the epoxy-modified high ortho position thermosetting phenolic for being heating and curing to obtain core-skin partial miscibility is fine
Tie up film；Wherein the mass fraction ratio of shell liquid each component is epoxy-modified high ortho position thermosetting phenolic resin: PVA: ethyl alcohol: distilled water
The mass fraction ratio of=40:10:50 core liquid each component is PVA: ethyl alcohol: distilled water=10:78.75:11.25, coaxial electrostatic spinning
Parameter is T=25 DEG C, RH=50%, d=18cm, U=18kV, Vin:Vout=1:1.6, and solidify 1.5h in 160 DEG C of vacuum, in nitrogen
700 DEG C are warming up to the heating rate of 9 DEG C/min under gas shielded, after the 2.5h that is carbonized, obtain epoxy-modified high ortho position thermosetting property phenol
The hollow nanometer gradient carbon-fiber film of aldehyde radical weighs the epoxy-modified high hollow nanometer gradient carbon-fiber film of ortho position thermosetting phenolic base
KOH adds steaming wherein the mass ratio of the hollow nanometer gradient carbon-fiber film of epoxy-modified high ortho position thermosetting phenolic base and KOH are 1:5
After distilled water is impregnated 9h and dried, after being warming up to 700 DEG C with the heating rate of 9 DEG C/min under nitrogen protection, activate 0.5h, obtain
The epoxy-modified hollow nanometer gradient activated carbon fiber film of high ortho position thermosetting phenolic base.
The Residual carbon of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base obtained is
63%, activated carbon fibre diameter distribution is 172-445nm, internal diameter 50-142nm, thermal coefficient 88W/mK, specific surface
Product is 3900m2/ g, iodine number 390mg/g, average micro-pore diameter 2nm, internal mesopore diameter are 31nm, and gradient point occurs in aperture
Cloth.Specific capacitance is 387F/g in the Et4NBF4/PC electrolyte of 1mol/ L, after current density increases to 10A/g by 50mA/g,
Specific capacitance is still able to maintain 349F/g.
Embodiment 10
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, step is such as
Under:
(1) phenol, formaldehyde, epoxychloropropane, epoxy bromopropane are heated to 105 DEG C, reaction under the effect of catalyst acetic acid zinc
The second catalyst sulfuric acid is added after 4h, then reacts 2h；Decompression dehydration, vacuum degree first drop to 60 in 2000Pa, this phase temperature
DEG C, 140 DEG C are gradually warming up to, constant temperature 2.5h obtains epoxy-modified high adjacent position phenolic resin；Wherein phenol: the molar ratio of formaldehyde
For 1:1.6, phenols: epoxy bromopropane: the mass ratio of epoxychloropropane is 100:10:15, phenol: zinc acetate: the quality of sulfuric acid
Than for 100:1:0.5；
(2) the epoxy-modified high adjacent position phenolic resin obtained is dissolved in methanol, and formaldehyde is then added in the effect of catalyst barium carbonate
Under in 70 DEG C of reaction 7h, be down to room temperature, sulfuric acid, which is added dropwise, makes pH=7, filters.Decompression dehydration, vacuum degree 2000Pa, is warming up to 70
DEG C, constant temperature 2h obtains epoxy-modified high ortho position thermosetting phenolic resin；Wherein epoxy-modified high adjacent position phenolic resin: methanol
Mass ratio is 1:2.5, epoxy-modified high adjacent position phenolic resin: the molar ratio of formaldehyde is 1:7, epoxy-modified high ortho position phenolic aldehyde tree
Rouge: the mass ratio of barium carbonate is 100:4；
(3) coaxial electrostatic spinning is used, the epoxy-modified high ortho position thermosetting phenolic for being heating and curing to obtain core-skin partial miscibility is fine
Tie up film；The wherein mass fraction ratio of shell liquid each component are as follows: epoxy-modified high ortho position thermosetting phenolic resin: PVA:DMF=20:15:
65, the mass fraction ratio of core liquid each component is PVA:DMF=15:85, and coaxial electrostatic spinning parameter is T=30 DEG C, RH=55%, d=
20cm, U=22kV, Vin:Vout=1:1.8, and solidify 2h in 180 DEG C of nitrogen, under nitrogen protection with the heating of 10 DEG C/min
Rate is warming up to 800 DEG C, is carbonized after 1.5h, obtains the epoxy-modified hollow nanometer gradient carbon fiber of high ortho position thermosetting phenolic base
Film weighs the epoxy-modified high hollow nanometer gradient carbon-fiber film KOH of ortho position thermosetting phenolic base, and wherein carbon alkali mass ratio is 1:6,
After adding distilled water immersion 11h and drying, 800 DEG C, activation 0.4h are warming up to the heating rate of 10 DEG C/min under nitrogen protection
Afterwards, the epoxy-modified hollow nanometer gradient activated carbon fiber film of high ortho position thermosetting phenolic base is obtained.
The Residual carbon of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base obtained is
55%, activated carbon fibre diameter distribution is 72-175nm, internal diameter 20-51nm, thermal coefficient 70W/mK, specific surface area
For 3961m2/ g, iodine number 441mg/g, average micro-pore diameter 1.1nm, internal mesopore diameter are 45nm, and gradient point occurs in aperture
Cloth.Specific capacitance is 401/g in the Et4NBF4/PC electrolyte of 1mol/ L, after current density increases to 10A/g by 50mA/g,
Specific capacitance is still able to maintain 369F/g.
Embodiment 11
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, step is such as
Under:
(1) m-cresol, formaldehyde, acetaldehyde, epoxychloropropane are heated to 110 DEG C, react 5h under the effect of catalyst manganese oxide
After the second hydrochloric is added, then react 4h；Decompression dehydration, vacuum degree first drop to 60 DEG C in 1000Pa, this phase temperature,
150 DEG C are gradually warming up to, constant temperature 2.5h obtains epoxy-modified high adjacent position phenolic resin；Wherein phenol: formaldehyde: mole of acetaldehyde
Than for 1:0.9:0.9, phenols: the mass ratio of epoxychloropropane is 100:35, and phenol: zinc acetate: the mass ratio of sulfuric acid is 100:
1.5:0.5；
(2) the epoxy-modified high adjacent position phenolic resin obtained is dissolved in ethyl alcohol, and acetaldehyde is then added in the work of catalyst triethanolamine
In 80 DEG C of reaction 8h under, it is down to room temperature, acetic acid, which is added dropwise, makes pH=7.5, filters.Decompression dehydration, vacuum degree 1000Pa, heating
To 80 DEG C, constant temperature 2.5h, epoxy-modified high ortho position thermosetting phenolic resin is obtained；Wherein epoxy-modified high adjacent position phenolic resin:
The mass ratio of ethyl alcohol is 1:3, and epoxy-modified high adjacent position phenolic resin: the molar ratio of acetaldehyde is 1:8, epoxy-modified high ortho position phenolic aldehyde
Resin: the mass ratio of triethanolamine is 100:5；
(3) coaxial electrostatic spinning is used, the epoxy-modified high ortho position thermosetting phenolic for being heating and curing to obtain core-skin partial miscibility is fine
Tie up film；The wherein mass fraction ratio of shell liquid each component are as follows: epoxy-modified high ortho position thermosetting phenolic resin: PVP: ethyl alcohol: distillation
Water=35:8:45.6:11.4, the mass fraction ratio of core liquid each component are PVA: ethyl alcohol: distilled water=8:73.6:18.4, coaxial quiet
Electrospun parameter is T=24 DEG C, RH=52%, d=20cm, U=18kV, Vin:Vout=1:3, and solidify 23h in 180 DEG C of vacuum,
900 DEG C are warming up to the heating rate of 4 DEG C/min under nitrogen protection, after the 0.8h that is carbonized, being passed through CO2 flow is 10ml/min,
The epoxy-modified hollow nanometer gradient activated carbon fiber film of high ortho position thermosetting phenolic base is obtained after activation 0.8h.
The Residual carbon of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base obtained is
54%, activated carbon fibre diameter distribution is 69-204nm, internal diameter 6.4-172nm, thermal coefficient 62W/mK, specific surface
Product is 3842m2/ g, iodine number 522mg/g, average micro-pore diameter 1nm, internal mesopore diameter are 36nm, and gradient point occurs in aperture
Cloth.Specific capacitance is 421/g in the Et4NBF4/PC electrolyte of 1mol/ L, after current density increases to 10A/g by 50mA/g,
Specific capacitance is still able to maintain 388F/g.
Embodiment 12
A kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, step is such as
Under:
(1) phenol, acetaldehyde, epoxy bromopropane are heated to 115 DEG C under the effect of catalyst acetic acid zinc, after reacting 6h, decompression is de-
Water, vacuum degree first drop to 70 DEG C in 400Pa, this phase temperature, are gradually warming up to 165 DEG C, and constant temperature 3h obtains epoxy-modified height
Adjacent position phenolic resin；Wherein phenol: the molar ratio of acetaldehyde is 1:2, phenols: the mass ratio of epoxy bromopropane is 100:45, phenol:
Zinc acetate mass ratio is 100:3；
(2) the epoxy-modified high adjacent position phenolic resin obtained is dissolved in ethyl alcohol, and acetaldehyde is then added in the work of catalyst triethanolamine
In 80 DEG C of reaction 8h under, it is down to room temperature, acetic acid, which is added dropwise, makes pH=7.5, filters.Decompression dehydration, vacuum degree 1000Pa, heating
To 80 DEG C, constant temperature 2.5h, epoxy-modified high ortho position thermosetting phenolic resin is obtained；Wherein epoxy-modified high adjacent position phenolic resin:
The mass ratio of ethyl alcohol is 1:3, and epoxy-modified high adjacent position phenolic resin: the molar ratio of acetaldehyde is 1:8, epoxy-modified high ortho position phenolic aldehyde
Resin: the mass ratio of triethanolamine is 100:5；
(3) coaxial electrostatic spinning is used, the epoxy-modified high ortho position thermosetting phenolic for being heating and curing to obtain core-skin partial miscibility is fine
Tie up film；The wherein mass fraction ratio of shell liquid each component are as follows: epoxy-modified high ortho position thermosetting phenolic resin: PVP: methanol: distillation
Water=45:9:40.8:5.2, the mass fraction ratio of core liquid each component are PVA: methanol: distilled water=12:52.8:35.2, coaxial quiet
Electrospun parameter is T=28 DEG C, RH=49%, and d=20cm, U=22kV, Vin:Vout=1:2, and solidify 2h in 170 DEG C of nitrogen claim
Epoxy-modified high ortho position thermosetting phenolic fiber membrane and KOH are measured, wherein epoxy-modified high ortho position thermosetting phenolic fiber membrane:
The mass ratio of KOH is 1:8, after adding distilled water immersion 13h and drying, is heated up under nitrogen protection with the heating rate of 5 DEG C/min
To 600 DEG C, activation 1.5h, the epoxy-modified hollow nanometer gradient activated carbon fiber film of high ortho position thermosetting phenolic base is obtained.
The Residual carbon of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base obtained is
73%, activated carbon fibre diameter distribution is 42-89nm, internal diameter 11-21nm, thermal coefficient 61W/mK, specific surface area
3890m2/ g, iodine number 379mg/g, average micro-pore diameter 1.5nm, internal mesopore diameter are 35nm, and gradient distribution occurs in aperture.
Specific capacitance is 384F/g in the Et4NBF4/PC electrolyte of 1mol/L, after current density increases to 10A/g by 50mA/g, than electricity
Appearance is still able to maintain 359F/g.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (10)
1. a kind of preparation method of the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base, feature
Be the following steps are included:
(1) phenols, aldehydes and epoxy alkyl halide are heated to boiling reaction 1-6h under the first catalyst action, decompression dehydration,
Dewatering vacuum degree is 8000-500Pa, this stage is first cooled to 30-70 DEG C, constant temperature after being then constantly warming up to 120-160 DEG C
0.2-3h obtains epoxy-modified high adjacent position phenolic resin；
(2) epoxy-modified high adjacent position phenolic resin is dissolved in ethyl alcohol, aldehyde compound and the second catalyst is added, in 45-90
DEG C reaction 2.5-9h, is down to room temperature, adjusts pH=5-7.5, suctions filtration, removing impurity；Then decompression dehydration, dewatering vacuum degree are 8000-
Epoxy-modified high ortho position thermosetting phenolic resin is made in 500Pa, isothermal reaction 0.2-3h after being warming up to 40-85 DEG C；
(3) epoxy-modified high ortho position thermosetting phenolic resin and Linear Polymer polymer are dissolved in solvent and shell liquid is made, it will
Linear Polymer polymer, which is dissolved in solvent, is made core liquid, the mass fraction ratio of shell liquid each component are as follows: epoxy-modified high ortho position heat
Solidity phenolic resin: Linear Polymer polymer: solvent=(10-70): (10-0): (80-30), the quality point of core liquid each component
Number is than being macromolecule linear polymer: solvent=(1-15): (99-85)；Using coaxial electrostatic spinning, it is heating and curing to obtain core-skin
The epoxy-modified high ortho position thermosetting phenolic tunica fibrosa of partial miscibility；Then in N2It is carbonized and is activated under protection, obtain ring
The modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base of oxygen.
2. the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base according to claim 1
Preparation method, it is characterised in that: in the step (1), phenolic compound is at least one of phenol, m-cresol, aldehydes
Compound is at least one of formaldehyde, acetaldehyde, paraformaldehyde, and epoxy alkyl halide is epoxychloropropane, epoxy bromopropane, epoxy
At least one of chlorobutane, the first catalyst are zinc acetate, zinc oxide or manganese oxide.
3. the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base according to claim 1
Preparation method, it is characterised in that: in the step (1), the molar ratio of phenolic compound and aldehyde compound is 1:(0.8-2),
The mass ratio of phenolic compound and epoxy alkyl halide is 100:(5-45), the mass ratio of phenolic compound and the first catalyst is
100:(0.5-3).
4. the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base according to claim 1
Preparation method, it is characterised in that: in the step (1), phenols, aldehydes and epoxy alkyl halide are added under the first catalyst action
Then acid catalyst is added the reaction was continued that 0.5-4h carries out decompression dehydration again to boiling reaction 1-6h in heat；The acid based catalyst
Agent is the sulfuric acid that oxalic acid, hydrochloric acid or mass fraction are 98%.
5. the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base according to claim 1
Preparation method, it is characterised in that: in the step (2), alcohol compound is one of methanol, ethyl alcohol, and aldehyde compound is
At least one of formaldehyde, acetaldehyde, paraformaldehyde, catalyst are one of triethanolamine, barium carbonate or barium acetate；Adjust pH institute
It is one of the sulfuric acid that hydrochloric acid, acetic acid or mass fraction are 98% with acid.
6. the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base according to claim 1
Preparation method, it is characterised in that: in the step (2), the mass ratio of epoxy-modified high adjacent position phenolic resin and alcohols is 1:(1-
3), epoxy-modified high adjacent position phenolic resin: aldehydes aldehydes molar ratio is 1:(1-10), epoxy-modified high adjacent position phenolic resin: urge
The mass ratio of agent is 100:(1-6).
7. the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base according to claim 1
Preparation method, it is characterised in that: in the step (3), Linear Polymer polymer be PVB, PVA or PVP, solvent be ethyl alcohol,
At least one of methanol, tetrahydrofuran, distilled water, N.N- dimethylformamide；Coaxial electrostatic spinning parameter is temperature T=15-
30 DEG C, relative humidity RH=35-70% receive distance d=12-25cm, spinning voltage U=13-28kV, axis spinning speed inside and outside interior outer shaft
Spend Vin:Vout=1:1-3.
8. the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base according to claim 1
Preparation method, it is characterised in that: in the step (3), the temperature that is heating and curing is 120-200 DEG C, curing time 0.5-3h, Gu
Change atmosphere is air, nitrogen or vacuum；The activator used is activated as vapor, CO2、KOH、ZnCl2, KCl, one in phosphoric acid
Kind.
9. the epoxy-modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base according to claim 1
Preparation method, it is characterised in that: in the step (3), when a step activates, the mass ratio of solid activating agent and phenolic fibre is
(0.5-8): 1；First when carbonization, post activation, the mass ratio of solid activating agent and phenolic aldehyde base carbon fibre is (0.5-8): 1；Use gas
When body activator is activated, flow 10-30ml/min.
10. the preparation side of the hollow nanometer gradient activated carbon fiber film of high ortho position thermosetting phenolic base according to claim 1
Method, it is characterised in that: in the step (3), carbonization and activation heating rate are 1-10 DEG C/min, carburizing temperature 400-1000
DEG C, carbonization time 0.5-2.5h, activation temperature is 400-850 DEG C, activation time 0.1-2h.
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| CN1816290A (en) * | 2003-03-07 | 2006-08-09 | 弗吉尼亚联邦大学 | Electroprocessed phenolic materials and methods |
| EP1366791B1 (en) * | 2002-05-28 | 2008-03-26 | Hollingsworth & Vose GmbH | Filter material |
| CN101389793A (en) * | 2006-02-13 | 2009-03-18 | 唐纳森公司 | Polymer blend, polymer solution composition and fibers spun from the polymer blend and filtration applications thereof |
| CN102677193A (en) * | 2012-05-03 | 2012-09-19 | 东华大学 | Preparation method of phenolic resin matrix nano activated carbon fiber material |
| CN103225132A (en) * | 2013-02-28 | 2013-07-31 | 江苏竹溪活性炭有限公司 | Bioactive carbon fiber preparation method |
| US8876994B2 (en) * | 2011-09-27 | 2014-11-04 | Samsung Electro-Mechanics Co., Ltd. | Porous sheet and method for manufacturing the porous sheet |
| US20170241049A1 (en) * | 2016-02-24 | 2017-08-24 | Tingying Zeng | Method to Massively Manufacture Carbon Fibers through Graphene Composites and the Use Thereof |
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| EP1366791B1 (en) * | 2002-05-28 | 2008-03-26 | Hollingsworth & Vose GmbH | Filter material |
| CN1816290A (en) * | 2003-03-07 | 2006-08-09 | 弗吉尼亚联邦大学 | Electroprocessed phenolic materials and methods |
| CN101389793A (en) * | 2006-02-13 | 2009-03-18 | 唐纳森公司 | Polymer blend, polymer solution composition and fibers spun from the polymer blend and filtration applications thereof |
| US8876994B2 (en) * | 2011-09-27 | 2014-11-04 | Samsung Electro-Mechanics Co., Ltd. | Porous sheet and method for manufacturing the porous sheet |
| CN102677193A (en) * | 2012-05-03 | 2012-09-19 | 东华大学 | Preparation method of phenolic resin matrix nano activated carbon fiber material |
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| US20170241049A1 (en) * | 2016-02-24 | 2017-08-24 | Tingying Zeng | Method to Massively Manufacture Carbon Fibers through Graphene Composites and the Use Thereof |
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