CN109003840A - A kind of preparation method of compound paper base flexible electrode material - Google Patents
A kind of preparation method of compound paper base flexible electrode material Download PDFInfo
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- CN109003840A CN109003840A CN201810903566.3A CN201810903566A CN109003840A CN 109003840 A CN109003840 A CN 109003840A CN 201810903566 A CN201810903566 A CN 201810903566A CN 109003840 A CN109003840 A CN 109003840A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000007772 electrode material Substances 0.000 title claims abstract description 43
- 150000001875 compounds Chemical class 0.000 title abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 51
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 32
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 12
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 12
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 12
- -1 isopropyl alkane Chemical class 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- 229920000128 polypyrrole Polymers 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 32
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000007654 immersion Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 8
- 238000005452 bending Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000219477 Bougainvillea glabra Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000010148 water-pollination Effects 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
- H01G11/84—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
-
- 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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01G11/48—Conductive polymers
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of preparation methods of compound paper base flexible electrode material, and the preparation method includes: 1) to cut filter paper as required；2) filter paper is impregnated with liquor ferri trichloridi and the isopropyl alkane solution containing pyrrole monomer respectively；3) it is dried；4) dry product graphene dispersing solution and ascorbic acid solution stirring are impregnated；5) it is dried.The preparation method is simple, and raw material sources are extensive, cheap, reduces preparation cost, is conducive to subsequent utilization and extention, does not add any adhesive and during the preparation process without any complex operations that need to be heated.Prepared electrode material area specific capacitance is up to 1408mF/cm2, there is superior energy storage potential, can be applied to the assembly of flexible energy storage material, while the electrode material softness folding, it can be using bending fold as arbitrary shape.
Description
Technical field
The invention belongs to Material Fields, are related to a kind of preparation of compound paper base flexible electrode material, more particularly to
A kind of preparation side of redox graphene/polypyrrole/filter paper (rGO/PPy/Filter-paper) composite and flexible electrode material
Method, and the electrode material prepared by this method, the preparation method is simple, and the composite and flexible electrode material performance of preparation is good
It is good, there is the property for generating deformation under external force but not influencing basic structure and functional characteristic.
Background technique
As the whole world is for the sustainable growth of energy demand, people are for supercapacitor and lithium-ion electric in the latest 20 years
The cleaning such as pond and reproducible energy products give great concern.In these storage devices, supercapacitor is because it is high
Power density, low resistance and stable charge-discharge performance are considered as good energy storage device.Electrode of super capacitor exists
It is divided into two classes: electrical double layer capacitor electrodes and pseudocapacitors electrode on the basis of energy storage mechanism.Specifically, electric double layer is electric
Container electrode is based on carbon material, including active carbon, carbon nanotube, graphene etc.；And pseudocapacitors electrode is then mainly by metal
Oxide, hydroxide or conducting polymer are constituted.More and more researchers by conjunction with both the above energy storage mechnism come
Electrode material is prepared to obtain more dominance energy.And now people are to meeting flexible mobile phone, implantable cardiac sensor and flexibility
The concern for the flexible energy storage device that OLED screen power supply needs increases, and therefore, flexible accumulator is prepared on the basis of improving performance
The electrode material of part is still a huge challenge.
Cellulose quantitative filter paper has three-dimensional porous structure as the common consumptive material in process of scientific research, and high-specific surface area is rich
Rich functional group's (hydroxyl) and good hydrophily, therefore be a kind of important mould material, it can be used as building flexible electrical
The substrate of pole material.Yuan etc. is a kind of complete by developing on electro-deposition polyaniline (PANI) to paper base using printing paper as substrate
Solid flexible-paper-base capacitor.PANI fibre diameter after electro-deposition is about 100nm, and is formed on gold plating paper porous
Network.(Longyan Yuan,Xu Xiao,Tianpeng Ding,et al.Paper-based supercapacitors
for self-powered nanosystems[J].Angewandte Communications,2012,20,51:4934-
4938.) ink made of carbon nanotube (CNT) is coated on paper (Kang YJ, Kim B, Chung by Yu Jin Kang etc.
H,et al.Fabrication and characterization of flexible and high capacitance
supercapacitors based on MnO2/CNT/papers[J].Synthetic Metals,2010,160(23-24):
2510-2514.), however, the price of CNT and noble metal is higher, preparation method is complex.Therefore, preparation cost, letter are reduced
Change preparation flow, prepares flexible electrode as substrate using cellulose paper and still have great importance.
Summary of the invention
The problem of for current flexible electrode technology of preparing, it is an object of the present invention to provide a kind of reduction
Graphene oxide/polypyrrole/filter paper (rGO/PPy/Filter-paper) composite and flexible electrode material preparation method, the system
Preparation Method includes the following steps:
1) filter paper is cut into required shape as required, such as side length is the square of 4cm.
2) ferric trichloride that molar concentration is 0.1mol/L-0.5mol/L will be immersed by the filter paper cut in step 1)
(FeCl3) 30min is impregnated in aqueous solution, it then takes out the filter paper after above-mentioned immersion after draining in cold compartment of refrigerator (4 DEG C)
The concentration of volume percent for immersing pyrrole monomer is 24 hours in the isopropyl alkane solution of 1%-2%.
3) after then, the taking-up of step 2) products therefrom is drained after deionized water is washed, vacuum is carried out at normal temperature
It is 24 hours dry.
4) dried product exhibited obtained by step 3) is immersed into 1- in the graphene dispersing solution that concentration is 0.16mg/L-2.4mg/L
3h states the ascorbic acid solution for being added that isometric concentration is 0.1-0.2mol/L in mixture then up, stirs 12 hours.
5) it is small to carry out vacuum drying 24 after draining the taking-up of step 4) products therefrom at normal temperature after deionized water is washed
When to get arrive redox graphene/polypyrrole/filter paper (rGO/PPy/Filter-paper) composite and flexible electrode material.
Preferably, ferric trichloride (FeCl described in step 2)3) aqueous solution molar concentration be 0.3mol/L-0.4mol/
L is still more preferably 0.35mol/L.
Preferably, the percent by volume of the solution of pyrrole monomer isopropyl alkane described in step 2) is 1.2%-1.8%, more into one
Step preferably 1.5%.
Preferably, graphene dispersing solution concentration described in step 4) be 0.48mg/L-2.4mg/L, still more preferably for
2.4mg/L.The graphene dispersing solution can be made by general Hummer method.
Preferably, in step 4) ascorbic acid solution concentration be 1.4mol/L-1.6mol/L, still more preferably for
1.5mol/L。
Preferably, preparation method according to the present invention does not add any adhesive and in the synthesis process in preparation process
It is middle without any complex operations that need to be heated.
According to another aspect of the present invention, it is another object of the present invention to provide a kind of redox graphene/
Polypyrrole/filter paper (rGO/PPy/Filter-paper) composite and flexible electrode material, the composite and flexible electrode material is by according to this
The preparation method of invention is prepared.
Beneficial effect
Redox graphene according to the present invention/polypyrrole/quantitative filter paper compound flexible electrode material preparation side
Method is simple, and raw material sources are extensive, cheap, reduces preparation cost, is conducive to subsequent utilization and extention, does not add any adhesive
And during the preparation process without any complex operations that need to be heated.Prepared electrode material area specific capacitance is up to
1408mF/cm2, there is superior energy storage potential, can be applied to the assembly of flexible energy storage material, while the electrode material is soft
Folding, can be using bending fold as arbitrary shape.
Detailed description of the invention
Fig. 1 is the preparation process of the compound paper base flexible electrode material of redox graphene/polypyrrole/filter paper of the invention
Flow chart.
Fig. 2 is the compound paper base flexible electrical of redox graphene/polypyrrole/filter paper prepared according to the embodiment of the present invention 1
The scanning electron microscope (SEM) photograph of pole material.
Fig. 3 is the compound paper base flexible electrical of redox graphene/polypyrrole/filter paper prepared according to the embodiment of the present invention 1
The foldable flexible energy display diagram of pole material.
Fig. 4 is the compound paper base flexible electrical of redox graphene/polypyrrole/filter paper prepared according to the embodiment of the present invention 1
The load-bearing property display diagram of pole material.
Fig. 5 is the compound paper base flexible electrical of redox graphene/polypyrrole/filter paper prepared according to the embodiment of the present invention 1
The cyclic voltammetry curve figure of pole material.
Fig. 6 is the compound paper base flexible electrical of redox graphene/polypyrrole/filter paper prepared according to the embodiment of the present invention 1
The constant current charge-discharge diagram of pole material.
Fig. 7 is the compound paper base flexible electrical of redox graphene/polypyrrole/filter paper prepared according to the embodiment of the present invention 2
The cyclic voltammetry curve figure of pole material.
Fig. 8 is the compound paper base flexible electrical of redox graphene/polypyrrole/filter paper prepared according to the embodiment of the present invention 2
The constant current charge-discharge diagram of pole material.
Fig. 9 is the compound paper base flexible electrical of redox graphene/polypyrrole/filter paper prepared according to the embodiment of the present invention 3
The cyclic voltammetry curve figure of pole material.
Figure 10 is the compound paper base flexible electrical of redox graphene/polypyrrole/filter paper prepared according to the embodiment of the present invention 3
The constant current charge-discharge diagram of pole material.
Figure 11 is that the circulation of the compound paper base flexible electrode material of polypyrrole/filter paper prepared according to the embodiment of the present invention 4 lies prostrate
Pacify curve graph.
Figure 12 is that the constant current of the compound paper base flexible electrode material of polypyrrole/filter paper prepared according to the embodiment of the present invention 4 is filled
Electric discharge figure.
Specific embodiment
Hereinafter, the preferred embodiment of the disclosure is described in detail with reference to the accompanying drawings.Before describing, should
The term that solution uses in the description and the appended claims, and should not be interpreted as limited to general and dictionary meaning, but answer
When the principle for suitably defining term based on the explanation for allowing inventor best, based on the meaning for corresponding to the technology of the present invention level
Justice and concept explain.Therefore, the preferred embodiment of description in this only for illustration purpose, and not refer to the limitation present invention
Range, it is therefore to be understood that, other can be made without departing from the spirit and scope of the invention and equally implement and repair
Change.
Redox graphene/polypyrrole according to the present invention/filter paper composite and flexible electrode material is by conductive material
It is compound to forming on substrate fiber element filter paper, wherein conductive layer is made of polypyrrole and redox graphene.
With flexible electrode prepared by graphene, polypyrrole and quantitative filter paper in preparation method according to the present invention
Material, not only method is simple, but also functional, has the property for not influencing its basic structure and functional characteristic under external force
Matter.
Using quantitative filter paper common in laboratory as substrate in preparation method according to the present invention, in FeCl3As oxidation
Pyrrole monomer elder generation in-situ oxidizing-polymerizing is deposited on filter paper substrate under conditions of agent, then the item in ascorbic acid as reducing agent
Under part, graphene, which is reduced, to be deposited on filter paper substrate existing for polypyrrole.The reality of any complexity is not necessarily in this preparation process
Equipment is tested, adhesive is not added, and during the preparation process without the complex operations of any need heating, whole preparation process is green
Color is pollution-free, easy to operate, concise in technology, is a kind of method for preparing inexpensive flexible electrode material.
There is no particular restriction for used quantitative filter paper in flexible electrode material according to the present invention and preparation method thereof, only
If common filtering quantitative filter paper in laboratory, such as commercial product quantitative filter paper nova NEWSTAR- can be used
202 (Hangzhou Special Paper Industry Co., Ltd.).
Ferric trichloride (FeCl in preparation method according to the present invention3) aqueous solution concentration be 0.1mol/L-
0.5mol/L, further preferably 0.3mol/L-0.4mol/L are still more preferably 0.35mol/L.Work as ferric trichloride
(FeCl3) amount it is very few when, be, for example, less than 0.1mol/L, oxidant content is insufficient, and oxidizable pyrrole polymerization can not be made to become conductive
Polypyrrole；As ferric trichloride (FeCl3) amount it is excessive, be greater than 0.5mol/L, then make the polypyrrole conductivity being polymerized
Decline, reduces the performance of material.
The percentage by volume of the isopropyl alkane solution of pyrrole monomer is 1%-2% in preparation method according to the present invention,
Further preferably 1.2%-1.8% is still more preferably 1.5%.When the percentage by volume of pyrrole monomer is too small, such as
Less than 1%, then the conductive polymer polypyrrole generated is very few；When the percentage by volume of pyrrole monomer is excessive, it is greater than
2%, then oxidant is insufficient, and extra pyrrole monomer can not be made sufficiently to polymerize.
The concentration of graphene dispersing solution is 0.16mg/L-2.4mg/L in preparation method according to the present invention, further
Preferably 0.48mg/L-2.4mg/L is still more preferably 2.4mg/L.When the concentration of graphene dispersing solution is too small, such as
Less than 0.16mg/L, then the redox graphene generated through reduction reaction is very few；When the concentration of graphene dispersing solution is excessive,
It is greater than 2.4mg/L, then be easy to cause graphene sheet layer to reunite.
The concentration of ascorbic acid solution is 0.1mol/L to 0.2mol/L in preparation method according to the present invention, into one
Step is preferably 0.14mol/L-0.16mol/L, is still more preferably 0.15mol/L.When the concentration of ascorbic acid is too low, example
Such as less than 0.1mol/L, then reducing agent is insufficient, and the redox graphene amount of generation is too low；When the concentration of ascorbic acid is excessive
When, it is greater than 0.2mol/L, then the product conductivity decline generated is unfavorable for the performance of product.
Following embodiment is enumerated only as the example of embodiment of the present invention, does not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that modification in the range of without departing from essence and design of the invention each falls within the present invention
Protection scope.Unless stated otherwise, reagent and instrument used in the following embodiment are commercially available product.
Embodiment 1
1) laboratory is often cut into the square that side length is 4cm with quantitative filter paper.
2) ferric trichloride (FeCl will be immersed in by the square filter paper cut in step 1)3) impregnate in aqueous solution
30min, wherein ferric trichloride (FeCl3) aqueous solution molar concentration be 0.35mol/L.It then takes out after draining in refrigerator cold-storage
Filter paper after above-mentioned immersion is sufficiently submerged in the isopropyl alkane of the pyrrole monomer of volume percent content 1.5% in indoor (4 DEG C)
24 hours in solution.
3) it is dried in vacuo at room temperature after being washed with deionized after then, the taking-up of step 2) products therefrom is drained
24 hours.
4) dried product exhibited obtained by step 3) is immersed 15mL concentration is 2 hours in the graphene dispersing solution of 2.4mg/L, so
The ascorbic acid solution that 15mL concentration is 0.15mol/L is added in backward said mixture, stirs 12 hours.
Wherein graphene dispersing solution is made by general Hummer method, and preparation process includes the following steps: 3g first
In the concentrated sulfuric acid that graphite powder and 1.5g sodium nitrate sequentially add 70mL under ice water bath environment, after stirring 15min, it is slowly added to 9g
90min is stirred in potassium permanganate, continuation in ice-water bath, and reaction system is then transferred to reaction stirring 2h in 35 DEG C of water-baths.It is slow
Slow that 150mL deionized water is added, stirring 30mL adjusts the temperature to 90 DEG C, after reacting 20min at 90 DEG C, be added 500mL go from
Sub- water and 15mL hydrogen peroxide (concentration 30%).It stands after removing supernatant liquor, is centrifuged after being neutrality to pH and is ultrasonically treated
30min obtains graphene dispersing solution.
5) it is small that vacuum drying 24 is carried out at room temperature after being washed with deionized after draining the taking-up of step 4) products therefrom
When to get arrive redox graphene/polypyrrole/filter paper composite and flexible electrode material.
Fig. 2 is according to the compound paper base flexible electrode of redox graphene/polypyrrole/quantitative filter paper manufactured in the present embodiment
The scanning electron microscope (SEM) photograph of material, wherein Fig. 2 (a) shows that polypyrrole is deposited on quantitative filter paper surface and is formed by spherical knot
Structure, Fig. 2 (b) show redox graphene/polypyrrole/quantitative filter paper composite and flexible electrode surface structure.From figure
It should be apparent that and, graphene oxide is successfully reduced, and the laminated structure of a large amount of redox graphenes is attached to poly- pyrrole
On the chondritic coughed up, planar substrate below is quantitative filter paper.
Fig. 3 is according to the compound paper base flexible electrode material of redox graphene/polypyrrole/filter paper manufactured in the present embodiment
Foldable flexible energy display diagram.As shown in figure 3, Fig. 3 (a) illustrates the foldability of flexible electrode material, Fig. 3 (b)
The flexible of flexible electrode material is illustrated, Fig. 3 (c) illustrates the paper helicopter folded with flexible electrode material, Fig. 3 (d) exhibition
The paper flower folded with flexible electrode material is shown.As can be seen from Figure 3 according to redox graphene manufactured in the present embodiment/poly-
The compound paper base flexible electrode material of pyrroles/filter paper has good flexibility and bendable folding endurance.
Fig. 4 is according to the compound paper base flexible electrode material of redox graphene/polypyrrole/filter paper manufactured in the present embodiment
Load-bearing property display diagram.As shown in figure 4, Fig. 4 illustrates the load-bearing capacity of flexible-paper-base electrode material.In unsupported premise
Under, the square paper base flexible electrode of a piece of 4*4cm can withstand up to the weight of 180g.
Embodiment 2
1) laboratory is often cut into the square that side length is 4cm with quantitative filter paper.
2) ferric trichloride (FeCl will be immersed in by the square filter paper cut in step 1)3) impregnate in aqueous solution
30min, wherein ferric trichloride (FeCl3) aqueous solution molar concentration be 0.35mol/L.It then takes out after draining in refrigerator cold-storage
Filter paper after above-mentioned immersion is sufficiently submerged in the isopropyl alkane of the pyrrole monomer of volume percent content 1.5% in indoor (4 DEG C)
24 hours in solution.
3) it is dried in vacuo at room temperature after being washed with deionized after then, the taking-up of step 2) products therefrom is drained
24 hours.
4) dried product exhibited obtained by step 3) is immersed in the graphene dispersing solution that 15mL concentration is 0.48mg/L 2 hours,
The ascorbic acid solution that 15mL concentration is 0.15mol/L is added in backward said mixture, stirs 12 hours.
5) it is small that vacuum drying 24 is carried out at room temperature after being washed with deionized after draining the taking-up of step 4) products therefrom
When to get arrive redox graphene/polypyrrole/filter paper composite and flexible electrode material.
Embodiment 3
1) laboratory is often cut into the square that side length is 4cm with quantitative filter paper.
2) ferric trichloride (FeCl will be immersed in by the square filter paper cut in step 1)3) impregnate in aqueous solution
30min, wherein ferric trichloride (FeCl3) aqueous solution molar concentration be 0.35mol/L.It then takes out after draining in refrigerator cold-storage
Filter paper after above-mentioned immersion is sufficiently submerged in the isopropyl alkane of the pyrrole monomer of volume percent content 1.5% in indoor (4 DEG C)
24 hours in solution.
3) it is dried in vacuo at room temperature after being washed with deionized after then, the taking-up of step 2) products therefrom is drained
24 hours.
4) dried product exhibited obtained by step 3) is immersed in the graphene dispersing solution that 15mL concentration is 0.16mg/L 2 hours,
The ascorbic acid solution that 15mL concentration is 0.15mol/L is added in backward said mixture, stirs 12 hours.
5) it is small that vacuum drying 24 is carried out at room temperature after being washed with deionized after draining the taking-up of step 4) products therefrom
When to get arrive redox graphene/polypyrrole/filter paper composite and flexible electrode material.
Embodiment 4
1) laboratory is often cut into the square that side length is 4cm with quantitative filter paper.
2) ferric trichloride (FeCl will be immersed in by the square filter paper cut in step 1)3) impregnate in aqueous solution
30min, wherein ferric trichloride (FeCl3) aqueous solution molar concentration be 0.35mol/L.It then takes out after draining in refrigerator cold-storage
Filter paper after above-mentioned immersion is sufficiently submerged in the isopropyl alkane of the pyrrole monomer of volume percent content 1.5% in indoor (4 DEG C)
24 hours in solution.
3) it is dried in vacuo at room temperature after being washed with deionized after then, the taking-up of step 2) products therefrom is drained
24 hours, polypyrrole/filter paper composite and flexible electrode material was both obtained.
EXPERIMENTAL EXAMPLE 1: electrochemical property test
Using the hydrochloric acid of 1mol/L as electrolyte, platinized platinum is to electrode, and silver/silver chloride electrode is reference electrode, is used
Standard three electrode system in electro-chemical test measures following for the flexible electrode material being prepared in embodiment 1,2,3,4 respectively
Ring C-V characteristic.Fig. 5,7,9,11 are respectively the cyclic voltammetric for the flexible electrode material being prepared according to embodiment 1,2,3,4
Characteristic curve, as shown in Fig. 5,7,9,11, in the scanning process of forward and reverse, Cyclic voltamogram curve has good
Symmetry, it can be seen that flexible electrode material prepared in accordance with the present invention has good invertibity.
EXPERIMENTAL EXAMPLE 2: electrochemical property test
According to the hydrochloric acid using 1mol/L as electrolyte, platinized platinum is to electrode, and silver/silver chloride electrode is reference electrode,
Using Conventional electrochemical test in standard three electrode system measure the flexible electrode being prepared in embodiment 1,2,3,4 respectively
The constant current charge-discharge characteristic of material.Fig. 6,8,10,12 are respectively the perseverance for the flexible electrode being prepared according to embodiment 1,2,3,4
Flow charge-discharge characteristic curve.By calculating, the flexible electrode area specific capacity being prepared according to embodiment 1 reaches
1408mF/cm2, the flexible electrode area specific capacity being prepared according to embodiment 2 reached 848mF/cm2, according to embodiment 3
The flexible electrode area specific capacity being prepared has reached 523mF/cm2, the flexible electrode area that is prepared according to embodiment 4
Specific capacity has reached 411mF/cm2, it can be seen that the flexible electrode that the present invention is prepared area specific capacity with higher, and
Embodiment 1 is the most preferably condition of preparation.And in the case where being not added with redox graphene in example 4, electrode area
Specific capacity is much smaller than electrode area specific capacity of the invention.
Claims (9)
1. a kind of redox graphene/polypyrrole/filter paper composite and flexible electrode material preparation method, the preparation method packet
Include following steps:
1) filter paper is cut into required shape as required；
2) ferric trichloride (FeCl that molar concentration is 0.1mol/L-0.5mol/L will be immersed by the filter paper cut in step 1)3)
30min is impregnated in aqueous solution, then takes out and the filter paper after above-mentioned immersion is immersed into pyrroles in cold compartment of refrigerator (4 DEG C) after draining
The concentration of volume percent of monomer is 24 hours in the isopropyl alkane solution of 1%-2%；
3) it after then, the taking-up of step 2) products therefrom is drained after deionized water is washed, is dried in vacuo at normal temperature
24 hours；
4) dried product exhibited obtained by step 3) is immersed into 1-3h in the graphene dispersing solution that concentration is 0.16mg/L-2.4mg/L, so
The ascorbic acid solution that isometric concentration is 0.1-0.2mol/L is added in backward said mixture, stirs 12 hours；
5) vacuum drying 24 hours is carried out at normal temperature after deionized water is washed after draining the taking-up of step 4) products therefrom, i.e.,
Obtain redox graphene/polypyrrole/filter paper (rGO/PPy/Filter-paper) composite and flexible electrode material.
2. preparation method according to claim 1, which is characterized in that ferric trichloride (FeCl described in step 2)3) aqueous solution
Molar concentration be 0.3mol/L-0.4mol/L.
3. preparation method according to claim 1, which is characterized in that ferric trichloride (FeCl described in step 2)3) aqueous solution
Molar concentration be 0.35mol/L.
4. preparation method according to claim 1, which is characterized in that the solution of pyrrole monomer isopropyl alkane described in step 2)
Percent by volume is 1.2%-1.8%.
5. preparation method according to claim 1, which is characterized in that the solution of pyrrole monomer isopropyl alkane described in step 2)
Percent by volume is 1.5%.
6. preparation method according to claim 1, which is characterized in that graphene dispersing solution concentration described in step 4) is
0.48mg/L-2.4mg/L is still more preferably 2.4mg/L.
7. preparation method according to claim 1, which is characterized in that the concentration of ascorbic acid solution is in step 4)
1.4mol/L-1.6mol/L is still more preferably 1.5mol/L.
8. preparation method according to claim 1, which is characterized in that the preparation method is not added in the synthesis process appoints
What adhesive and during the preparation process without any complex operations that need to be heated.
9. a kind of redox graphene/polypyrrole/filter paper composite and flexible electrode material, the composite and flexible electrode material is by basis
Preparation method described in any one of claim 1 to 8 is prepared.
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