CN106098396A - A kind of upright opening carbon compound film for ultracapacitor and preparation method thereof - Google Patents
A kind of upright opening carbon compound film for ultracapacitor and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000001722 carbon compounds Chemical class 0.000 title claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000006260 foam Substances 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000005011 phenolic resin Substances 0.000 claims abstract description 10
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 10
- 239000003990 capacitor Substances 0.000 claims abstract description 8
- 229920001400 block copolymer Polymers 0.000 claims abstract description 7
- 238000001338 self-assembly Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 63
- 229920000642 polymer Polymers 0.000 claims description 50
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 26
- 239000012498 ultrapure water Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- 239000004744 fabric Substances 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 229920002521 macromolecule Polymers 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000693 micelle Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 238000001764 infiltration Methods 0.000 claims description 8
- 230000008595 infiltration Effects 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 230000003068 static effect Effects 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000002596 correlated effect Effects 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 13
- 239000004917 carbon fiber Substances 0.000 abstract description 13
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920000428 triblock copolymer Polymers 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention belongs to technical field of nanometer material preparation, particularly to the preparation method of a kind of vertical mesoporous carbon laminated film for ultracapacitor.This laminated film uses oligomeric water-soluble phenolic resin to be carbon source, block copolymer is template, by precursor solution is repeatedly dripped in the multiple substrate such as nickel foam, carbon fiber, heats volatilization self assembly, after 100 DEG C～150 DEG C of Water Under thermal response 6 48h, and in an inert atmosphere, obtain with the temperature carbonization of 400 DEG C～700 DEG C.Described laminated film is the C film with vertical channel structure, and its vertical channel structure provides high specific surface area, and provides passage for electrolyte ion well into electrode material, and porous carbon promotes the electric conductivity of carbon composite simultaneously.Vertical mesoporous carbon laminated film prepared by the present invention obtains big ratio electric capacity and excellent stability as electrode of super capacitor.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly to the preparation side of a kind of vertical mesoporous carbon laminated film
Method and the application in ultracapacitor field thereof.
Background technology
Along with the exhaustion day by day of the non-renewable mineral energy such as traditional coal, oil, natural gas, and the utilization at them
During produce environmental pollution so that energy and environment become two faced in human kind sustainable development course and mainly ask greatly
Topic.At present, the development and utilization of the renewable and clean energy resource such as new forms of energy such as solar energy, wind energy, heat energy demonstrates good sending out
The exhibition impetus, shows huge potential in terms of large-scale use from now on.But owing to these regenerative resources are supplied
Intermittence, was only stored it can produce when, the stable operation of guarantee energy consumption element；It addition, for clearly
The application of the clean energy such as movable equipment (such as mobile phone, electric automobile etc.), sufficient electric energy storage is also that it is normal
The premise of work.Accordingly, it is capable to storage become renewable and clean energy resource realize application process in one need solve pass
Key problem.
The most widely studied electric energy storage device mainly includes battery and ultracapacitor.Battery has bigger energy
Metric density, can meet the application demand of most of electronic device, but its less cycle charge-discharge number of times and relatively low filling
Discharge rate constrain its application in demand high power density occasion (Science, 1994,264:1115 1118,
Nature,2001,414:359–367).Compared with battery, ultracapacitor has higher cycle life and high charge-discharge speed
Rate, has the characteristic of simple in construction, stable in properties simultaneously, is allowed to supply at high-power energy conversion, portable electronic device, micro-electric current
Good utilization (Science, 2008,321:651 652) has been had on electricity equipment.
In recent years, scientist has put into substantial amounts of energy at the ratio electric capacity increasing material specific surface area and material
(Nanoscale, 2013,5,8,799 8820, Angew Chem Int Ed, 2011,50:1683 1687, ACS
Nano.2012,6(7):6400-6406).The at present research of flexible super capacitor be concentrated mainly on carbon fiber (micrometer fibers and
Nanofiber), CNT, Graphene and their composite construction.As supported based on flexible substrates (such as paper, sponge)
The flexible electrode of CNTs/Graphene coating, flexible electrode based on carbon fiber substrate, paper-like based on CNTs/Graphene
Flexible electrode, flexible electrode based on 3D macrostructure.
Although make some progress in terms of the synthesis of carbon-based electrode material at present, although Carbon-based supercapacitor is
Through successfully commercialization, but in order to adapt to high integration electronics miniaturization, lightening and flexible needs, existing super electricity
Container there is also a lot of problem, electric charge transmission problem, the ratio electric capacity of material and stability problem, the utilization rate problem of active substance
And the ultra-thin space that there is also raising with flexibility problem of device.Therefore, by electroactive material (electrode material) direct growth
Or directly construct self-supporting high-specific surface area skeleton on collector to become optimization electrode structure, promotion charge transfer efficiency, carry
The effective measures of high active substance utilization rate.
Being inevitable development trend to adapt to this technological development direction develop relevant new technique, the present invention is just
Therefore raw new technique.The present invention provides a kind of upright opening carbon compound film for ultracapacitor and preparation method thereof.
Described carbon compound film has the multilamellar macropore structure being perpendicular to substrate, has high specific surface area and excellent stablizing
Property；Macroporous structure, for improving the efficiency of transmission of ion, increases electric conductivity；Meso-hole structure is used for increasing specific surface area, and raising is deposited
Storage electric capacity.Meanwhile, to have the technology such as preparation technology is simple, low cost, effect are obvious, applied widely excellent for described carbon compound film
Gesture.
Summary of the invention
Technical problem: in view of there is above-mentioned technical problem in prior art, it is an object of the invention to provide a kind of for
Vertical mesoporous carbon laminated film of ultracapacitor and preparation method thereof.The described vertical existing carbon fiber of mesoporous carbon laminated film
The macroporous structure of cloth/nickel foam itself, is also equipped with being perpendicular to the mesopore orbit structure of substrate simultaneously,；Macroporous structure is used for improving
The efficiency of transmission of ion, increases electric conductivity；Meso-hole structure is used for increasing specific surface area, improves storage electric capacity.Described laminated film
Using oligomeric water-soluble phenolic resin is carbon source, and block copolymer is template, by by precursor solution at nickel foam, carbon fiber
Etc. repeatedly dripping, heat volatilization self assembly in multiple substrate, last carbonization obtains；Have that preparation technology is simple, low cost, effect
Substantially, the technical advantage such as applied widely.The technical solution adopted in the present invention is as described below.
Technical scheme: the present invention provides a kind of vertical mesoporous carbon laminated film for ultracapacitor, described carbon is combined
Thin film has the pore passage structure being perpendicular to substrate, and this pore passage structure is multilevel hierarchy, has macropore and meso pore characteristics, the hole of macropore
Footpath is about 30～500 μm, and mesoporous aperture is about 3～7nm；Described carbon film material main component is carbon；Described C film material
Material is supported on nickel foam or carbon cloth surface.
Described carbon compound film be use oligomeric water-soluble phenolic resin be carbon source, block copolymer is template, by will
Precursor solution repeatedly drips in the multiple substrate such as nickel foam, carbon fiber, heats volatilization self assembly, 100～150 DEG C of conditions
Lower hydro-thermal reaction 6～after 48 hours, and in an inert atmosphere, obtain with the temperature carbonization of 400 DEG C～700 DEG C.
Described carbon compound film has macroporous structure and meso-hole structure simultaneously, and macroporous structure is for improving the transmission of ion
Efficiency, increases electric conductivity；Meso-hole structure is used for increasing specific surface area, improves storage electric capacity.Described laminated film be have vertical
The C film of straight pore passage structure, its vertical channel structure provides high specific surface area, and is that electrolyte ion is well into electricity
Pole material provides passage, and porous carbon promotes the electric conductivity of carbon composite simultaneously.
The present invention also provides for the preparation method of the described vertical mesoporous carbon laminated film for ultracapacitor, described preparation
Concretely comprising the following steps of method:
(1) synthesis of performed polymer, i.e. synthesizes phenolic resin performed polymer and the Spherical Carbon strand micelle of low-molecular-weight:
The aqueous solution of phenol, formalin and NaOH is mixed, stirring reaction at 50～90 DEG C, it is thus achieved that low molecule
The phenolic resin prepolymer reaction solution of amount.Then, polyether block copolymer is dissolved in water, and the prepolymer before addition
In reaction solution, after stirring 1～5h.Again by solution dilute, and at 50～90 DEG C further stirring to observing deposition.
Polyether block copolymer described in step (1) is F127, and its molecular characterization is: MW=12600,
PEO106PPO70PEO106。
After step (1) completes, the granular size of the performed polymer that DLS real-time testing formed, step after resolution of precipitate, can be used
Suddenly in (1), the later stage mesoporous formation of rule is played a crucial role by the test effect of the micelle complex granule of performed polymer, and micelle is multiple
Polymer beads is as the construction unit of follow-up mesopore film, if the uneven meeting of micelle complex granule causes thin film uneven,
And micelle is the template in duct in thin film, if micelle is uneven, later stage duct is the most uneven.
(2) base treatment and absorption performed polymer:
Substrate is ultrasonically treated, cleans and dried, substrate is immersed in the performed polymer that step (1) prepares also
Fully infiltration, adsorbs performed polymer.
Step (2) described substrate can be carbon cloth, nickel foam or silicon chip.
When using carbon cloth or nickel foam to make substrate, need to take the performed polymer that appropriate step (1) prepares and fully soak
Moistening the carbon cloth or nickel foam handled well, put baking oven 40～80 DEG C of heating 3～10min, this infiltration, heating process repeat 3～5
Secondary adsorb performed polymer.
When using silicon chip as substrate, will be ultrasonically treated, and clean and dried, the silicon chip of ultrasonic mistake is immersed in
Volume ratio is the H of 3:12SO4And H2O2Mixed solution in, soak 10min at normal temperatures, finally clean with ultra-pure water and be dried；
Then silicon chip it is immersed in the performed polymer that step (1) prepares and fully infiltrates, making performed polymer in the abundant self assembly of silicon chip surface.
In step (2), the later stage mesoporous formation of rule is played a crucial role by the process of absorption performed polymer, and thermal evaporation is conducive to
The rule self assembly further of micelle performed polymer composite particles.Without this step, will obtain particle packing thin film rather than
Vertical porous membrane
(3) water-heat process
Substrate after step (2) absorption performed polymer is put in reactor, puts into after adding ultra-pure water static soak
Baking oven, carries out hydro-thermal reaction 6～48h at 100 DEG C～150 DEG C.After it cools down, take out the substrate being loaded with product, fully
After cleaning, put into baking oven℃It is dried, obtains substrate/macromolecule laminated film.
(4) carbonisation
Step (3) is dried the substrate/macromolecule laminated film further carbon in the argon of 400 DEG C～700 DEG C obtained
Change 1～3h to obtain vertical mesoporous carbon laminated film.
In order to test the chemical property of vertical mesoporous carbon laminated film, cyclic voltammetry is used to be surveyed by three-electrode system
The chemical property of examination laminated film.Three electrodes are working electrode (vertical mesoporous carbon laminated film) respectively, to electrode (metal platinum
Sheet) and reference electrode (Ag/AgCl electrode).The Na of 1mol/L2SO4Do electrolyte, and as electrode of super capacitor, survey
Try its ultracapacitor correlated performance.By test, vertical mesoporous carbon laminated film has the chemical property of excellence, especially
It is to have big ratio electric capacity.It addition, vertical mesoporous multilamellar pore passage structure makes this carbon compound film have stable structure spy
Point.In summary, the upright opening carbon compound film prepared by the present invention obtains big ratio electric capacity as electrode of super capacitor
And excellent stability.
Carbon compound film of the present invention, the excellent chemical property having and construction features can be used for surpassing
Level electrode for capacitors.
There is advantages that
1, the upright opening carbon compound film of the present invention has the pore passage structure being perpendicular to substrate, and this pore passage structure is multistage knot
Structure, has macropore and meso pore characteristics, and structural stability is good；
2, the preparation method of carbon compound film of the present invention have that preparation technology is simple, low cost, effect substantially, be suitable for
The technical advantages such as scope is wide；
3, the upright opening carbon compound film of the present invention can be applicable to electrode of super capacitor, and macroporous structure is used for improving ion
Efficiency of transmission, increase electric conductivity；Meso-hole structure is used for increasing specific surface area, improves storage electric capacity.
Accompanying drawing explanation
Fig. 1. in embodiment 1 in performed polymer synthesis micelle that block copolymer is formed and micelle/performed polymer
Grain size test result；
Fig. 2. the SEM figure of carbon cloth/macromolecule laminated film prepared in embodiment 1；
Fig. 3. the SEM figure of upright opening mesoporous carbon fiber cloth/carbon compound film prepared in embodiment 1；
Fig. 4. the SEM figure of nickel foam/macromolecule membrane prepared in embodiment 2；
Fig. 5. the SEM figure of upright opening mesoporous foam nickel carbon laminated film prepared in embodiment 2；
Fig. 6. the SEM figure of silicon chip/macromolecule membrane prepared in embodiment 4；
Fig. 7. the SEM figure of the mesoporous silicon chip/carbon compound film of upright opening prepared in embodiment 4；
Fig. 8. the electrochemical property test of upright opening mesoporous carbon fiber cloth/carbon compound film prepared in embodiment 5；
Fig. 9. the electrochemical property test of upright opening mesoporous foam nickel carbon laminated film prepared in embodiment 6.
Detailed description of the invention
Elaborating embodiments of the invention below, the present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following example.
Embodiment 1
The preparation of upright opening mesoporous carbon fiber cloth/macromolecule laminated film
(1) synthesis of performed polymer: by the phenol of 0.6g, the formalin (37wt%) of 2.1mL, 15mL 0.1mol/L's
NaOH solution adds in the there-necked flask of 250mL, then stirs 2h at 50 DEG C.Triblock copolymer F127 (the MW=of 0.96g
12600, PEO106PPO70PEO106) be dissolved in 15mL ultra-pure water, and join in phenolic resin performed polymer, at a temperature of 50 DEG C
After stirring 4h, in the ultra-pure water of addition 56mL to above-mentioned solution, continue stir about 10～14h, until stopping during solution turned cloudy
Reaction, takes out and stands dissolving to be precipitated, uses DLS to follow the tracks of the formation (as shown in Figure 1) of performed polymer.
(2) base treatment is with absorption performed polymer: by ultrasonic to carbon cloth acetone, ethanol and ultra-pure water 30min, then use
Ultra-pure water cleans and is dried；Take the performed polymer that appropriate step (1) prepares and fully infiltrate the carbon cloth handled well, put baking oven
80 DEG C of heating 3～10min, this infiltration, heating process repeat to adsorb performed polymer 3～5 times.
(3) water-heat process: above-mentioned absorption performed polymer carbon cloth is put in 25～100mL reactors, add 15～
Baking oven is put into after 75mL ultra-pure water static soak 4h, 100 DEG C of hydro-thermal reactions 6～48h, after it cools down, take out and be loaded with producing
The carbon cloth of thing, after fully cleaning with ultra-pure water, puts into baking oven 30～80 DEG C and is dried, obtain carbon cloth/macromolecule and be combined
Thin film (as shown in Figure 2).
(4) carbonisation: step (3) is dried the carbon cloth/macromolecule membrane obtained at 400 DEG C～the argon of 700 DEG C
In gas, further carbonization 1～3h is to obtain upright opening mesoporous carbon fiber cloth/carbon compound film (as shown in Figure 3).
Embodiment 2
The preparation of upright opening mesoporous foam nickel/macromolecule laminated film
(1) synthesis of performed polymer: by the phenol of 0.6g, the formalin (37wt%) of 2.1mL, 15mL 0.1mol/L's
NaOH solution adds in the there-necked flask of 250mL, then stirs 1h at 60 DEG C.Triblock copolymer F127 (the MW=of 0.96g
12600, PEO106PPO70PEO106) be dissolved in 15mL ultra-pure water, and join in phenolic resin performed polymer, at a temperature of 60 DEG C
After stirring 4h, in the ultra-pure water of addition 56mL to above-mentioned solution, continue stir about 10～14h, until stopping during solution turned cloudy
Reaction, takes out and stands dissolving to be precipitated.
(2) base treatment is with absorption performed polymer: ultrasonic for nickel foam dilute hydrochloric acid 3min ultra-pure water is fully cleaned after bake
Dry；Take the performed polymer that appropriate step (1) prepares and fully infiltrate the nickel foam handled well, put 40 DEG C of baking oven heating 3～
10min, this infiltration, heating process repeat to adsorb performed polymer 1～3 time.
(3) water-heat process: put in 25～100mL reactors by above-mentioned absorption performed polymer nickel foam, adds 15～75mL
Putting into baking oven after ultra-pure water static soak 4h, 100 DEG C～150 DEG C of hydro-thermal reactions 6～48h, after it cools down, taking-up is loaded with
The nickel foam of product, after fully cleaning with ultra-pure water, puts into 40 DEG C of baking oven and is dried, obtain nickel foam/macromolecule laminated film
Preparation (as shown in Figure 4).
(4) carbonisation: step (3) is dried the nickel foam/macromolecule membrane obtained in the argon of 400～550 DEG C
Carbonization 1～3h is to obtain upright opening mesoporous foam nickel carbon laminated film (as shown in Figure 5) further.
Embodiment 3
The preparation of upright opening mesoporous foam nickel/macromolecule laminated film
(1) synthesis of performed polymer: by the phenol of 0.6g, the formalin (37wt%) of 2.1mL, 15mL 0.1mol/L's
NaOH solution adds in the there-necked flask of 250mL, then stirs 0.5h at 90 DEG C.Triblock copolymer F127 (the MW of 0.96g
=12600, PEO106PPO70PEO106) be dissolved in 15mL ultra-pure water, and join in phenolic resin performed polymer, 90 DEG C of temperature
After lower stirring 2h, in the ultra-pure water of addition 56mL to above-mentioned solution, continue stir about 10～14h, until stopping during solution turned cloudy
Only reaction, takes out and stands dissolving to be precipitated,
(2) base treatment is with absorption performed polymer: ultrasonic for nickel foam dilute hydrochloric acid 3min ultra-pure water is fully cleaned after bake
Dry；Take the performed polymer that appropriate step (1) prepares and fully infiltrate the nickel foam handled well, put 40 DEG C of baking oven heating 3～
10min, this infiltration, heating process repeat to adsorb performed polymer 3-5 time.
(3) water-heat process: put in 25～100mL reactors by above-mentioned absorption performed polymer nickel foam, adds 15～75mL
Baking oven is put into after ultra-pure water static soak 4h, 100 DEG C～150 DEG C of hydro-thermal reactions 6h, after it cools down, take out and be loaded with product
Nickel foam, after fully cleaning with ultra-pure water, put into 40 DEG C of baking oven be dried, obtain the preparation of nickel foam/macromolecule laminated film.
(4) carbonisation: step (3) is dried the nickel foam/macromolecule membrane obtained in the argon of 500～700 DEG C
Carbonization 3～5h is to obtain upright opening mesoporous foam nickel carbon laminated film further.
Embodiment 4
The preparation of the mesoporous silicon chip of upright opening/macromolecule laminated film
(1) synthesis of performed polymer: by the phenol of 0.6g, the formalin (37wt%) of 2.1mL, 15mL 0.1mol/L's
NaOH solution adds in the there-necked flask of 250mL, then stirs 0.5h at 50～80 DEG C.The triblock copolymer of 0.96g
F127 (MW=12600, PEO106PPO70PEO106) be dissolved in 15mL ultra-pure water, and join in phenolic resin performed polymer,
After stirring 2h at a temperature of 50～80 DEG C, in the ultra-pure water of addition 56mL to above-mentioned solution, continue stir about 10～14h, until molten
Stopped reaction when liquid becomes cloudy, takes out and stands dissolving to be precipitated.
(2) base treatment is with absorption performed polymer: by ultrasonic to silicon chip ethanol and ultra-pure water 30min, then dry, and afterwards will
The silicon chip of ultrasonic mistake is immersed in 6mL H2SO4, 2mLH2O2(H2SO4: H2O2=3:1) mixed solution in, soak at normal temperatures
10min, finally cleans with ultra-pure water and is dried；Then take 6.60mL prepolymer solution and pour in 50mL reactor, will process
Silicon chip put into solution, be standing and soak for 0.5～3 hour；It is eventually adding 30mL ultra-pure water for dilute solution, and static soak
0.5～4h so that it is in the abundant self assembly of silicon chip surface.
(3) water-heat process: put in 25～100mL reactors by above-mentioned absorption performed polymer silicon chip, adds 15～75mL and surpasses
Baking oven is put into after pure water static soak 4h, 100 DEG C～150 DEG C of hydro-thermal reactions 6h, after it cools down, take out and be loaded with product
Silicon chip, after fully cleaning with ultra-pure water, puts into 40 DEG C of baking oven and is dried, obtain the preparation of silicon chip/macromolecule laminated film (such as Fig. 6
Shown in).
(4) carbonisation: step (3) is dried the nickel foam/macromolecule membrane obtained in the argon of 400～500 DEG C
Carbonization 1～3h is to obtain the mesoporous silicon chip/carbon compound film of upright opening (as shown in Figure 7) further.
Embodiment 5
The electrochemical property test of upright opening mesoporous carbon fiber cloth/carbon compound film
Our use cyclic voltammetry to pass through upright opening mesoporous carbon fiber cloth that three-electrode system testing example 1 prepares/
The chemical property of carbon compound film.Three electrodes are working electrode (vertical mesoporous carbon laminated film) respectively, to electrode (metal platinum
Sheet) and reference electrode (Ag/AgCl electrode).The Na of 1mol/L2SO4 does electrolyte, obtained electrochemistry cyclic voltammetry curve
As shown in Figure 8.
Embodiment 6
The electrochemical property test of upright opening mesoporous foam nickel carbon laminated film
Our use cyclic voltammetry to pass through upright opening mesoporous carbon fiber cloth that three-electrode system testing example 2 prepares/
The chemical property of carbon compound film.Three electrodes are working electrode (vertical mesoporous carbon laminated film) respectively, to electrode (metal platinum
Sheet) and reference electrode (Ag/AgCl electrode).The Na of 1mol/L2SO4Doing electrolyte, obtained electrochemistry cyclic voltammetry curve is such as
Shown in Fig. 9.
Claims (8)
1. the vertical mesoporous carbon laminated film for ultracapacitor, it is characterised in that described carbon compound film has vertical
Straight in the pore passage structure of substrate, this pore passage structure is multilevel hierarchy, has macroporous structure and meso-hole structure feature simultaneously, macropore
Aperture is about 30-500 μm, and mesoporous aperture is about 3-7nm；Described thin-film material main component is carbon.
2. the preparation method of a vertical mesoporous carbon laminated film as claimed in claim 1, it is characterised in that described method bag
Include following steps:
(1) synthesis of performed polymer, i.e. synthesizes phenolic resin performed polymer and the Spherical Carbon strand micelle of low-molecular-weight:
The aqueous solution of phenol, formalin and NaOH is mixed, stirring reaction 0.5-2h at 50-90 DEG C, it is thus achieved that low point
The prepolymer reaction solution of son amount；Then, polyether block copolymer is dissolved in water, and the prepolymer reaction before addition is molten
In liquid, stirring 2～4h after, add water by solution dilute, and at 50-90 DEG C further stirring to observing deposition；
(2) base treatment and absorption performed polymer:
Substrate is ultrasonically treated, cleans and dried, substrate is immersed in the performed polymer that step (1) prepares the most fully
Infiltration, adsorbs performed polymer；
(3) water-heat process:
Substrate after step (2) absorption performed polymer is put in reactor, after adding ultra-pure water static soak, puts into baking oven,
Hydro-thermal reaction 6-48h is carried out at 100 DEG C-150 DEG C；After it cools down, take out the substrate being loaded with product, after fully cleaning, put
Enter 30-80 DEG C of baking oven to be dried, obtain substrate/macromolecule laminated film；
(4) carbonisation:
Step (3) is dried the substrate/macromolecule laminated film obtained at carbonization 1-further in the argon of 400～700 DEG C
5h is to obtain vertical mesoporous carbon laminated film.
Method the most according to claim 2, it is characterised in that: step (2) described substrate is carbon cloth, nickel foam or silicon
Sheet.
Method the most according to claim 4, it is characterised in that: when using carbon cloth or nickel foam to make substrate, need to take
The performed polymer that appropriate step (1) prepares fully infiltrates the carbon cloth or nickel foam handled well, puts the heating of 40-80 DEG C of baking oven
3～10min, this infiltration, heating process repeat to adsorb performed polymer 1-5 time.
Method the most according to claim 4, it is characterised in that: when using silicon chip as substrate, will be ultrasonically treated,
Clean and dried, the silicon chip of ultrasonic mistake is immersed in the H that volume ratio is 3:12SO4And H2O2Mixed solution in, at normal temperatures
Soak 10min, finally clean with ultra-pure water and be dried；Then silicon chip is immersed in the performed polymer that step (1) prepares and abundant
Infiltration, makes performed polymer in the abundant self assembly of silicon chip surface.
Method the most according to claim 2, it is characterised in that: test the chemical property of vertical mesoporous carbon laminated film
Time, use the cyclic voltammetry chemical property by three-electrode system test compound thin film.
Method the most according to claim 6, it is characterised in that: three electrodes are the vertical mesoporous carbon as working electrode respectively
Laminated film, as the metal platinized platinum to electrode and the Ag/AgCl electrode as reference electrode, the Na of 1mol/L2SO4It is electrolysed
Matter, and as electrode of super capacitor, test its ultracapacitor correlated performance.
8. the application in electrochemical field of a upright opening carbon compound film as claimed in claim 1, it is characterised in that should
Carbon compound film can be applicable to electrode of super capacitor.
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