CN107903575A - A kind of preparation method of electrode for capacitors graphene phenolic-resin based composite fibre film - Google Patents
A kind of preparation method of electrode for capacitors graphene phenolic-resin based composite fibre film Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract
A kind of electrode for capacitors is using biomass active Carbon fibe as skeleton with the preparation method of graphene phenolic-resin based composite fibre film, lotion bead is template, suspension is formed with the in the mixed solvent that water and organic solvent composition are added together with the graphene oxide hydrosol, suspension deposit compound, obtain composite and flexible film, composite and flexible film be coated with vacuumized in graphite fixture or inert atmosphere under, 3D macropore blister composite membranes are obtained through hot-pressing processing, 3D macropore blister composite membranes are coated with prepreg phenolic resin, vacuumize at room temperature, through hot pressing, impregnated in lye, activation, obtain graphene phenolic-resin based composite fibre film.The present invention has the advantages that electrode for capacitors energy storage density height, good cycling stability.
Description
Fields
The invention belongs to new energy materials field, is related to a kind of preparation method of electrode material for super capacitor, specifically
Say the preparation method for being related to a kind of electrode for capacitors graphene phenolic-resin based composite fibre film.
Technical background
Graphene is one kind with individual layer or a small number of layer sp2The two-dimensional structure that carbon is formed.Since 2004 are found, because of it
Good electric conductivity (103-104S ﹒ m-1), high electron mobility (20000cm at room temperature2﹒ V-1﹒ S-1) and high theoretical specific surface area
(2630m2﹒ g-1) etc. good characteristic, people just start to probe into this sp2What the carbonaceous material of structure was applied in ultracapacitor
Possibility (Zhang LL, Zhou R, Zhao XS.Graphene-based materials as supercapacitor
Electrodes. grapheme material electrode of super capacitor [J] .J Mater Chem 2010 are based on;20(29):5983-92)
(Stoller MD, Park SJ, Zhu YW, An JH, Ruoff RS.Graphene-based ultracapacitors. are based on
Ultracapacitor [J] the .Nano Lett 2008 of graphene;8(10):3498-502.).
Currently available technology has obtained extensive research and concern based on graphene-based super capacitor material.Wang Yunfeng
Deng (patent publication No.:103723722 A of CN) carried out in organic solvent by the way that the activated carbon of decontamination is mixed with graphene
High-temperature activation is prepared for the graphene modified active carbon electrode material of high-specific surface area, and which show high specific discharge capacity.Lee
Fine jade (patent publication No.:103253658 A of CN) graphene oxide and activator, carbon source material are sufficiently mixed, in protective atmosphere
Under activated, the graphene of high-volume and capacity ratio has been made.The above-mentioned electrode material based on graphene has given full play to graphite
Alkene two-dimensional surface easily comes into full contact with electrolyte, and macroporous structure can provide sufficient cushion space for electrolyte between its piece, be ion
Migration provides free pathway.In addition, graphene towards conjugated pi electron (high density carrier) can for electric charge transmit low-resistance be provided
Passage, so as to meet the energy storage demand of high current fast charging and discharging.But the above-mentioned electrode material based on graphene is mostly solid
Powder, when applied to ultracapacitor, it is necessary to which first uniform with the material mixing such as acetylene black and binding agent, re-coating is to collecting
On fluid, this process can cause agglomerates to coalesce block, and can reduce the electric conductivity of electrode material, so as to cause the stone prepared
Mertenyl electrode material energy storage density is low, cyclical stability is poor, cannot still meet the requirement of practical application.
The content of the invention
The purpose of the present invention is exactly insufficient existing for above-mentioned existing graphene-based electrode material in order to overcome, there is provided a kind of
Electrode for capacitors energy storage density is high, the system of the electrode for capacitors graphene phenolic-resin based composite fibre film of good cycling stability
Preparation Method.
The present invention is to be oriented to ordered fabrication method by hard template to obtain a kind of 3D macropores blister graphene/activated carbon from activated sludge
Composite fiber membrane;Then the composite membrane is coated with prepreg Phenolic resin emulsion, then work is activated through vacuum hot pressing formation, alkali
Graphene phenolic-resin based composite fibre film is made in skill.The film combination graphene, activated carbon from activated sludge and the aspect of phenolic resin three
Advantage, has given full play to the good electric conductivity of graphene, activated carbon from activated sludge fiber multihole structure, high-specific surface area and space
Skeleton structure and the high carbon yield of phenolic resin, so as to effectively put forward the energy stores of ultracapacitor.Meanwhile the composite membrane is flexible
It is good, electrode of super capacitor can be directly used as, powder is effectively prevent and is added in electrode process is prepared caused by binding agent
Internal resistance.
To achieve the above object, the technical scheme is that:
(1) using biomass active Carbon fibe as skeleton, lotion bead is template, is added together with the graphene oxide hydrosol
The in the mixed solvent for entering water and organic solvent composition forms suspension, the mass ratio of graphene oxide and biomass active Carbon fibe
For 1:0.1~20, the mass ratio of graphene oxide and lotion bead is 1:0.5~5, the volume ratio of water and organic solvent is 1:
0.5~10, the mass ratio of biomass active Carbon fibe, the quality sum of lotion bead and graphene oxide and mixed solvent is:
1.6-26:50~500;
(2) the graphene oxide hydrosol, lotion bead and activated carbon from activated sludge fibrous suspension deposit compound, obtained
Obtain composite and flexible film;
(3) gained composite and flexible film in step (2) is coated with vacuumized in graphite fixture or inert atmosphere under, through 500-
1000 DEG C of hot-pressing processing 0.1-15h obtain 3D macropore blister composite membranes;
(4) 3D macropore blister composite membranes prepared in step (3) are coated with prepreg phenolic resin, taken out at room temperature
Vacuum, through 150~180 DEG C of hot pressing 30-120min, and further dipping, activation in lye, obtain graphene phenolic-resin base and answer
Condensating fiber film.
In step (1) as described above organic solvent for absolute ethyl alcohol, acetone, 1-methyl-2-pyrrolidinone, N, N- dimethyl
One kind in formamide, DMAC N,N' dimethyl acetamide.
Activated carbon from activated sludge fiber is included using one in poplar wadding, catkin, cattail, kapok in step (1) as described above
Biomass active Carbon fibe prepared by kind.
The graphene oxide hydrosol in step (1) as described above, graphite oxide is ultrasonically treated in deionized water, is surpassed
The sound time is 10-120min, ultrasonic power 100-800W, obtains the graphene oxide hydrosol of 0.1-10mg/ml.
Lotion bead is polymethyl methacrylate emulsus bead (PMMA) or polystyrene in step (1) as described above
Emulsus bead (PS).
Step (2) as described above is by the graphene oxide hydrosol, lotion bead and activated carbon from activated sludge fibrous suspension
Deposit compound, the spraying of deposition Combined Mining, coating, press filtration or vacuum filtration here.
Inert atmosphere is argon gas, nitrogen, helium or ammonia in step (3) as described above.
Step (4) graphene as described above is 0.5~10 with phenolic resin mass ratio:100.
The mass ratio of film and alkali in being impregnated in step (4) lye as described above is 1: 0.5~6, dip time 6-
12h。
Step (4) activation temperature as described above is 500-900 DEG C, soak time 0.5-6h.
Beneficial effects of the present invention:
A kind of electrode for capacitors graphene phenolic-resin based composite fibre membrane preparation method of the present invention, passes through hard template
It is oriented to ordered fabrication method and obtains a kind of 3D macropores blister graphene/activated carbon from activated sludge composite fiber membrane;Then by the composite membrane
It is coated with prepreg Phenolic resin emulsion, then graphene phenolic-resin base is made and answers through vacuum hot pressing formation, alkali activating process
Condensating fiber film.Composite membrane prepared by this method combines three aspect advantage of graphene, activated carbon from activated sludge and phenolic resin, fully
The good electric conductivity of graphene, activated carbon from activated sludge fiber multihole structure, high-specific surface area and spatial skeleton structure are played
The high carbon yield with phenolic resin, so as to effectively improve the energy stores of ultracapacitor., can meanwhile the composite membrane is flexible
Electrode of super capacitor is directly used as, powder is effectively prevent and internal resistance caused by binding agent is added in electrode process is prepared.
Its specific capacity is between 100-300F/g;Capacitance remains to the 90%-98.5% for reaching initial capacity after 2000 circle circulations.
Brief description of the drawings
The adsorption desorption curve and pore size distribution curve of graphene phenolic-resin based composite fibre film prepared by Fig. 1 embodiments 1.
Graphene phenolic-resin based composite fibre film prepared by Fig. 2 embodiments 1 is directly used as electrode assembling ultracapacitor
The cyclic voltammetry curve under speed is swept in difference.
Embodiment
The present invention is further illustrated with embodiment, but protection scope of the present invention is not limited in embodiment below.It is right
The other changes and modifications that those skilled in the art makes in the case of the spirit and scope without departing substantially from the present invention, still
It is included within the scope of the present invention.
Embodiment 1
(1) graphite oxide is ultrasonically treated in deionized water, ultrasonic time 10min, ultrasonic power 800W, obtains
The graphene oxide hydrosol of 10mg/ml;
(2) using the biomass active Carbon fibe wadded a quilt with cotton based on poplar as skeleton, polymethyl methacrylate emulsus bead (PMMA)
For template, the in the mixed solvent that water and absolute ethyl alcohol are added together with the graphene oxide hydrosol forms suspension, aoxidizes stone
The mass ratio of black alkene and biomass active Carbon fibe is 1: 0.1, and the mass ratio of graphene oxide and lotion bead is 1: 0.5, water
Volume ratio with organic solvent is 1: 0.5, and the quality sum of biomass active Carbon fibe, lotion bead and graphene oxide is with mixing
The mass ratio of bonding solvent is:1.6∶50;
(3) suspension is filtered by vacuum, obtains composite and flexible film;
(4) gained composite and flexible film in step (3) is coated with and is vacuumized in graphite fixture, through 500 DEG C of hot-pressing processing 15h
Obtain 3D macropores blister graphene/activated carbon from activated sludge composite fiber membrane;
(5) the 3D macropores blister graphene/activated carbon from activated sludge composite fiber membrane prepared in step (4) is coated with preimpregnation
Expect in phenolic resin that (graphene is 4 with phenolic resin mass ratio:100), vacuumize at room temperature, through 150 DEG C of hot pressing 120min, and
12h (mass ratio of film and alkali is 1: 2), 800 DEG C of activation 1h are further impregnated in lye, it is compound to obtain graphene phenolic-resin base
Tunica fibrosa.
Graphene phenolic-resin based composite fibre film specific surface area prepared by embodiment 1 is 698m2/g.By the graphite of preparation
Alkene phenolic resin based composite fibre film is directly used as electrode assembling ultracapacitor.After tested, which is in current density
1Ag-1When specific discharge capacity be 284Fg-1, capacitance remains to reach initial capacity 98.5% after 2000 circulations.
Embodiment 2
(1) graphite oxide is ultrasonically treated in deionized water, ultrasonic time 120min, ultrasonic power 100W, obtains
To the graphene oxide hydrosol of 0.1mg/ml;
(2) using the biomass active Carbon fibe based on cattail as skeleton, polymethyl methacrylate emulsus bead (PMMA)
For template, suspension is formed in the mixed system for adding water and 1-methyl-2-pyrrolidinone together with the graphene oxide hydrosol,
The mass ratio of graphene oxide and biomass active Carbon fibe is 1: 20, and the mass ratio of graphene oxide and lotion bead is 1: 5,
The volume ratio of water and organic solvent be 1: 10, the quality sum of biomass active Carbon fibe, lotion bead and graphene oxide with
The mass ratio of mixed solvent is:26∶500;
(3) the graphene oxide hydrosol, lotion bead and activated carbon from activated sludge fibrous suspension are coated compound, obtained
Obtain graphene oxide/lotion bead/activated carbon from activated sludge fiber composite flexible membrane;
(4) gained graphene oxide/activated carbon from activated sludge fiber composite flexible membrane in step (3) is coated with graphite fixture
In vacuumize, obtain 3D macropores blister graphene/activated carbon from activated sludge composite fiber membrane through 1000 DEG C of hot-pressing processing 0.1h;
(5) the 3D macropores blister graphene/activated carbon from activated sludge composite fiber membrane prepared in step (4) is coated with preimpregnation
Expect in phenolic resin that (graphene is 2 with phenolic resin mass ratio:100), vacuumize at room temperature, through 180 DEG C of hot pressing 30min, and
6h is further impregnated in lye, and (mass ratio of film and alkali is 1:6), 500 DEG C of activation 2h, it is compound to obtain graphene phenolic-resin base
Tunica fibrosa.
Graphene phenolic-resin based composite fibre film specific surface area prepared by embodiment 2 is 542m2/g.By the graphite of preparation
Alkene phenolic resin based composite fibre film is directly used as electrode assembling ultracapacitor.After tested, which is in current density
1Ag-1When specific discharge capacity be 211Fg-1, capacitance remains to reach initial capacity 90.5% after 2000 circulations.
Embodiment 3
(1) graphite oxide is ultrasonically treated in deionized water, ultrasonic time 30min, ultrasonic power 500W, obtains
The graphene oxide hydrosol of 3mg/ml;
(2) using the biomass active Carbon fibe based on catkin as skeleton, polystyrene emulsus bead (PS) is template, with
The graphene oxide hydrosol adds in water and the mixed system of n,N-Dimethylformamide and forms suspension, graphene oxide together
Be 1: 10 with the mass ratio of biomass active Carbon fibe, the mass ratio of graphene oxide and lotion bead is 1: 3, water with it is organic molten
The volume ratio of agent is 1: 5, the matter of biomass active Carbon fibe, the quality sum of lotion bead and graphene oxide and mixed solvent
Measuring ratio is:14∶300;
(3) the graphene oxide hydrosol, lotion bead and activated carbon from activated sludge fibrous suspension spray compound, obtained
Obtain graphene oxide/lotion bead/activated carbon from activated sludge fiber composite flexible membrane;
(4) gained graphene oxide/activated carbon from activated sludge fiber composite flexible membrane in step (3) is coated with graphite fixture
In vacuumize, obtain 3D macropores blister graphene/activated carbon from activated sludge composite fiber membrane through 800 DEG C of hot-pressing processing 1h;
(5) the 3D macropores blister graphene/activated carbon from activated sludge composite fiber membrane prepared in step (4) is coated with preimpregnation
Expect in phenolic resin that (graphene is 10 with phenolic resin mass ratio:100), vacuumize at room temperature, through 140 DEG C of hot pressing 100min,
And further (mass ratio of film and alkali is 1 to dipping 12h in lye:4), 900 DEG C of activation 0.5h, obtain graphene phenolic-resin base
Composite cellulosic membrane.
Graphene phenolic-resin based composite fibre film specific surface area prepared by embodiment 3 is 980m2/g.By the graphite of preparation
Alkene phenolic resin based composite fibre film is directly used as electrode assembling ultracapacitor.After tested, which is in current density
1Ag-1When specific discharge capacity be 103Fg-1, capacitance remains to reach initial capacity 98.5% after 2000 circulations.
Embodiment 4
(1) graphite oxide is ultrasonically treated in deionized water, ultrasonic time 45min, ultrasonic power 300W, obtains
The graphene oxide hydrosol of 3.5mg/ml.
(2) using the biomass active Carbon fibe based on kapok as skeleton, polystyrene emulsus bead (PS) is template, with
The graphene oxide hydrosol adds in water and the mixed system of n,N-dimethylacetamide and forms suspension, graphene oxide together
Be 1: 5 with the mass ratio of biomass active Carbon fibe, the mass ratio of graphene oxide and lotion bead is 1: 2, water with it is organic molten
The volume ratio of agent is 1: 1, the matter of biomass active Carbon fibe, the quality sum of lotion bead and graphene oxide and mixed solvent
Measuring ratio is:8∶200;
(3) the graphene oxide hydrosol, lotion bead and activated carbon from activated sludge fibrous suspension are filtered by vacuum, are obtained
Obtain graphene oxide/lotion bead/activated carbon from activated sludge fiber composite flexible membrane;
(4) gained graphene oxide/activated carbon from activated sludge fiber composite flexible membrane in step (3) is coated with graphite fixture
In vacuumize, obtain 3D macropores blister graphene/activated carbon from activated sludge composite fiber membrane through 600 DEG C of hot-pressing processing 4h;
(5) the 3D macropores blister graphene/activated carbon from activated sludge composite fiber membrane prepared in step (4) is coated with preimpregnation
Expect in phenolic resin that (graphene is 8 with phenolic resin mass ratio:100), vacuumize at room temperature, through 170 DEG C of hot pressing 60min, and
8h is further impregnated in lye, and (mass ratio of film and alkali is 1:2), 850 DEG C of activation 1h, it is compound to obtain graphene phenolic-resin base
Tunica fibrosa.
Graphene phenolic-resin based composite fibre film specific surface area prepared by embodiment 4 is 720m2/g.By the graphite of preparation
Alkene phenolic resin based composite fibre film is directly used as electrode assembling ultracapacitor.After tested, the composite membrane in current density
For 1Ag-1When specific discharge capacity be 189Fg-1, capacitance remains to reach initial capacity 95.2% after 2000 circulations.
Embodiment 5
(1) graphite oxide is ultrasonically treated in deionized water, ultrasonic time 60min, ultrasonic power 100W, obtains
The graphene oxide hydrosol of 4mg/ml.
(2) using the biomass active Carbon fibe based on catkin as skeleton, polystyrene emulsus bead (PS) is template, with
The graphene oxide hydrosol adds in the mixed system of water and acetone together forms suspension, graphene oxide and biomass active
The mass ratio of Carbon fibe is 1: 15, and the mass ratio of graphene oxide and lotion bead is 1: 4, and the volume ratio of water and organic solvent is
1: 6, the mass ratio of biomass active Carbon fibe, the quality sum of lotion bead and graphene oxide and mixed solvent is:20∶
400;
(3) the graphene oxide hydrosol, lotion bead and activated carbon from activated sludge fibrous suspension are subjected to press filtration, obtain oxygen
Graphite alkene/lotion bead/activated carbon from activated sludge fiber composite flexible membrane;
(4) gained graphene oxide/activated carbon from activated sludge fiber composite flexible membrane in step (3) is coated with graphite fixture
In vacuumize, obtain 3D macropores blister graphene/activated carbon from activated sludge composite fiber membrane through 600 DEG C of hot-pressing processing 2h;
(5) the 3D macropores blister graphene/activated carbon from activated sludge composite fiber membrane prepared in step (4) is coated with preimpregnation
Expect in phenolic resin that (graphene is 0.5 with phenolic resin mass ratio:100), vacuumize at room temperature, through 170 DEG C of hot pressing 70min,
And further (mass ratio of film and alkali is 1 to dipping 8h in lye:3), 900 DEG C of activation 6h, obtain graphene phenolic-resin base and answer
Condensating fiber film.
Graphene phenolic-resin based composite fibre film specific surface area prepared by embodiment 5 is 685m2/g.By the graphite of preparation
Alkene phenolic resin based composite fibre film is directly used as electrode assembling lithium ion super capacitor.By graphene/biomass of preparation
Activated carbon fibre composite and flexible film is directly used as electrode assembling ultracapacitor.The composite membrane is in current density after tested
1Ag-1When specific discharge capacity be 220Fg-1, capacitance remains to reach initial capacity 95.3% after 2000 circulations.
Claims (10)
1. a kind of electrode for capacitors preparation method of graphene phenolic-resin based composite fibre film, it is characterised in that including as follows
Step:
(1)Using biomass active Carbon fibe as skeleton, lotion bead is template, and water is added together with the graphene oxide hydrosol
With the in the mixed solvent formation suspension of organic solvent composition, the mass ratio of graphene oxide and biomass active Carbon fibe is 1:
0.1~20, the mass ratio of graphene oxide and lotion bead is 1:0.5~5, the volume ratio of water and organic solvent for 1: 0.5~
10, the mass ratio of biomass active Carbon fibe, the quality sum of lotion bead and graphene oxide and mixed solvent is:1.6-
26:50~500;
(2)The graphene oxide hydrosol, lotion bead and activated carbon from activated sludge fibrous suspension deposit compound, answered
Close flexible membrane;
(3)By step(2)Middle gained composite and flexible film be coated with vacuumized in graphite fixture or inert atmosphere under, through 500-1000
DEG C hot-pressing processing 0.1-15h obtains 3D macropore blister composite membranes;
(4)By step(3)In prepared 3D macropore blister composite membranes be coated with prepreg phenolic resin, take out at room temperature true
Sky, through 150~180 DEG C of hot pressing 30-120min;And further dipping, activation in lye, it is compound to obtain graphene phenolic-resin base
Tunica fibrosa.
2. a kind of preparation method of electrode for capacitors graphene phenolic-resin based composite fibre film as described in requiring 1, it is special
Sign is the step(1)Middle organic solvent for absolute ethyl alcohol, acetone, 1-methyl-2-pyrrolidinone, N,N-dimethylformamide,
One kind in DMAC N,N' dimethyl acetamide.
3. a kind of preparation method of electrode for capacitors graphene phenolic-resin based composite fibre film as described in requiring 1, it is special
Sign is the step(1)Middle activated carbon from activated sludge fiber includes preparing using one kind in poplar wadding, catkin, cattail, kapok
Biomass active Carbon fibe.
4. a kind of preparation method of electrode for capacitors graphene phenolic-resin based composite fibre film as described in requiring 1, it is special
Sign is the step(1)The middle graphene oxide hydrosol, graphite oxide is ultrasonically treated in deionized water, ultrasonic time
For 10-120min, ultrasonic power 100-800W, the graphene oxide hydrosol of 0.1-10mg/ml is obtained.
5. a kind of preparation method of electrode for capacitors graphene phenolic-resin based composite fibre film as described in requiring 1, it is special
Sign is the step(1)Middle lotion bead is polymethyl methacrylate emulsus bead or polystyrene emulsus bead.
6. a kind of preparation method of electrode for capacitors graphene phenolic-resin based composite fibre film as described in requiring 1, it is special
Sign is the step(2)The graphene oxide hydrosol, lotion bead and activated carbon from activated sludge fibrous suspension are sunk
Product is compound, the spraying of deposition Combined Mining, coating, press filtration or vacuum filtration here.
7. a kind of preparation method of electrode for capacitors graphene phenolic-resin based composite fibre film as described in requiring 1, it is special
Sign is the step(3)Middle inert atmosphere is argon gas, nitrogen, helium or ammonia.
8. a kind of preparation method of electrode for capacitors graphene phenolic-resin based composite fibre film as described in requiring 1, it is special
Sign is the step(4)Graphene is 0.5~10 with phenolic resin mass ratio:100.
9. a kind of preparation method of electrode for capacitors graphene phenolic-resin based composite fibre film as described in requiring 1, it is special
Sign is the step(4)The mass ratio of film and alkali in being impregnated in lye is 1: 0.5~6, dip time 6-12h.
10. a kind of preparation method of electrode for capacitors graphene phenolic-resin based composite fibre film as described in requiring 1, it is special
Sign is the step(4)Activation temperature is 500-900 DEG C, soak time 0.5-6h.
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