CN110098067A - It can ink direct write printing flexible electrode and its preparation method and application - Google Patents
It can ink direct write printing flexible electrode and its preparation method and application Download PDFInfo
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- CN110098067A CN110098067A CN201810085778.5A CN201810085778A CN110098067A CN 110098067 A CN110098067 A CN 110098067A CN 201810085778 A CN201810085778 A CN 201810085778A CN 110098067 A CN110098067 A CN 110098067A
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- 238000007639 printing Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002071 nanotube Substances 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 21
- 239000002322 conducting polymer Substances 0.000 claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000004744 fabric Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 27
- 229920000128 polypyrrole Polymers 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003990 capacitor Substances 0.000 claims description 16
- 229920000767 polyaniline Polymers 0.000 claims description 15
- 239000007772 electrode material Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 238000013019 agitation Methods 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002079 double walled nanotube Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention discloses can ink direct write printing flexible electrode and its preparation method and application, conducting polymer Coaxial Nanotubes and graphene oxide are configured to mixed gel through ultrasonic agitation, then using carbon cloth as substrate, ink direct write goes out the gel device of special construction, it is finally restored under hydrazine hydrate steam atmosphere, the obtained print device with unique morphology.Flexible electrode size adjustable of the invention, density is controllable, has good flexibility and flexible.
Description
Technical field
The present invention relates to flexible electrode material fields, specifically, being related to one kind can be used for ink direct write printing flexible electrical
The preparation and application of pole material.
Background technique
Ink direct write printing technique belongs to increases material manufacturing technology, is a kind of contactless printing shaping technology.In barrel
The ink material of storage is connected with spray head, by piston press, screw extrusion dispatch control system by ink from spray head squeeze out and
It is formed in substrate.Ink direct write printing technique is gradually being answered due to the diversity of simple and efficient operation and material system
For electrochemical energy storage field.
Flexible electrode has good flexibility and flexible, overcomes the influence of conventional Super capacitor rigidity, makees
It for flexible energy storage device, can integrate in portable, flexible and wearable flexible electronic device, be current super capacitor
The hot spot of device research.Ink direct write printing technique is a kind of new tool for making flexible electrode, the electrode ruler of this method production
Very little adjustable, density is controllable, has wide application advantage.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide one kind can be used for inkjet printing flexible electrode, should
Electrode material can be used for preparing flexible super capacitor, have electrode size adjustable, density is controllable, and flexibility is good, energy density
Height, can efficiently ink direct write printing the advantages that.
Technical purpose of the invention is achieved through the following technical solutions:
Can ink direct write printing flexible electrode preparation method, as steps described below carry out:
Step 1, conducting polymer Coaxial Nanotubes composite material and graphene oxide are dispersed in dehydrated alcohol,
Form electrode ink；
Step 2, the printing that electrode ink carries out gel device is prepared using step 1 using carbon cloth as substrate, in water after molding
It closes and is restored under hydrazine steam atmosphere, can be obtained can ink direct write printing flexible electrode.
In the above-mentioned technical solutions, in step 1, conducting polymer Coaxial Nanotubes composite material and graphene oxide
Mass ratio is (1-10): 1, preferably (5-8): 1.
In the above-mentioned technical solutions, in step 1, conducting polymer Coaxial Nanotubes composite material is polypyrrole/polyphenyl
Amine Coaxial Nanotubes composite material generates polypyrrole nanotube with soft template method chemical polymerization, and as template, electrochemistry is heavy
Gather polypyrrole/polyaniline Coaxial Nanotubes composite material of aniline film preparation.
In the above-mentioned technical solutions, in step 1, carried out by the way of mechanical stirring and ultrasonic disperse it is evenly dispersed,
Mechanical stirring is first carried out, churned mechanically speed is 100-200 turns per minute, and the time is 10-30min, then carries out ultrasound point
Dissipate, the ultrasonic disperse time be 1-5h, preferably 2-3 hours.
In the above-mentioned technical solutions, in step 1, the evaporation of solvent absolute ethyl alcohol is carried out after evenly dispersed, until solid
Content reaches 10mg mL-1 or more, obtains electrode ink, and solid content is that conducting polymer Coaxial Nanotubes are multiple in discrete volume
The ratio between the quality sum (mg) of condensation material and graphene oxide and solvent absolute ethyl alcohol volume (ml), preferably 10-20mg mL-
1。
In the above-mentioned technical solutions, in step 2, by electrode ink made of step 1 be added in syringe and with spray
Head connection, syringe is attached on multiaxis positioning system (model Prusa i3), using the mode of Screw Extrusion on carbon cloth
Multilayer printing is carried out, speed selects 1-5mm s-1, next layer is printed again after spontaneously drying after each layer of printing, is terminated
It being restored in hydrazine hydrate atmosphere at 80-90 DEG C afterwards up to the flexible electrode, the recovery time is 1-6 hours, preferably 3-5
Hour.
It is another object of the present invention to provide above schemes to prepare the application in flexible electrode.
It is another object of the present invention to a kind of electrode ink and its preparing the application in flexible electrode.
Electrode ink is dispersed in dehydrated alcohol by conducting polymer Coaxial Nanotubes composite material and graphene oxide
The mass ratio of middle composition, conducting polymer Coaxial Nanotubes composite material and graphene oxide is (1-10): 1, preferably (5-
8): 1.Conducting polymer Coaxial Nanotubes composite material is polypyrrole/polyaniline Coaxial Nanotubes composite material, with soft template
Forensic chemistry polymerization generates polypyrrole nanotube, and as template, polypyrrole/polyaniline of electrochemical deposition polyaniline film preparation
Coaxial Nanotubes composite material.The evaporation of solvent absolute ethyl alcohol is carried out after evenly dispersed, until solid content reaches 10mg mL-1
More than, electrode ink is obtained, solid content is conducting polymer Coaxial Nanotubes composite material and graphite oxide in discrete volume
The ratio between the quality sum (mg) of alkene and solvent absolute ethyl alcohol volume (ml), preferably 10-20mg mL-1.
Application it is another object of the present invention to the flexible electrode of preparation as electrode material for super capacitor.
The prior art is compared, the beneficial effects of the present invention are:
1) using carbon cloth as substrate, multilayer ink direct write prints conducting polymer Coaxial Nanotubes-graphene composite material, leads
Electric polymer and graphene are uniformly mixed, and active material contacts the super capacitor energy density prepared closely with collector
Height, good cycling stability.
2) the electrode material size adjustable prepared, density is controllable, and flexibility is good, has wide application advantage.
Detailed description of the invention
Fig. 1 is the SEM photograph for the electrode material that ink direct write of the invention prints, wherein (a) and (b) is electrode material
SEM photograph；Illustration is the SEM photograph of substrate carbon cloth in b.
Fig. 2 is supercapacitor structures schematic diagram, wherein (a) is solid-state super capacitor assembly structure diagram, (b)
For the digital photograph of the flexible super capacitor under certain pressure.
Fig. 3 is the electrochemical analysis curve graph (1) of flexible super capacitor of the invention, i.e., sweeps the CV under speed in difference
Curve graph.
Fig. 4 is the electrochemical analysis curve graph (2) of flexible super capacitor of the invention, i.e., the different areas swept under speed hold
Measure curve graph.
Fig. 5 is the electrochemical analysis curve graph (3) of flexible super capacitor of the invention, i.e. constant current charge-discharge curve
Figure.
Fig. 6 is the electrochemical analysis curve graph (4) of flexible super capacitor of the invention, i.e., the face under different current densities
Product capacity curve figure.
Fig. 7 is the differently curved degree cyclic voltammetry curve figure (1) of flexible super capacitor of the invention, i.e., different bending angles
Spend lower CV curve graph of the flexible solid-state supercapacitor under the scanning speed of 10mV s-1.
Fig. 8 is the differently curved degree cyclic voltammetry curve figure (2) of flexible super capacitor of the invention, i.e., different bending angles
Area capacity conservation rate curve graph under degree (C0 is raw capacity, and C is actual measurement capacity).
Fig. 9 is that the PPy/PANI- graphene that ink direct write prints on pan paper in the embodiment of the present invention is interdigitated
The photo of microelectrode structure.
Specific embodiment
With reference to the drawings and specific embodiments, the invention will be further described.Graphene oxide uses tradition hummers method
It is prepared.Conducting polymer Coaxial Nanotubes composite material is polypyrrole/polyaniline Coaxial Nanotubes composite material, with soft mode
The polymerization of plate forensic chemistry generates polypyrrole nanotube, and as template, polypyrrole prepared by electrochemical deposition polyaniline film/poly-
Aniline Coaxial Nanotubes composite material, in the preparation with reference to a kind of Chinese invention patent " polypyrrole/polyaniline double-walled nanotubes electricity
The preparation method and application of pole ", application No. is 2017106426035, the applying date is on July 31st, 2017, first by methyl orange
Powder is evenly dispersed in water, and chlorination iron powder is added and stirs to get red suspension, and pyrroles is added thereto, is continuing
Reaction obtains polypyrrole nanotube under liquid phase under conditions of stirring；Polypyrrole nanotube washing and drying will be obtained under liquid phase again
The polypyrrole film being made of polypyrrole nanotube is obtained afterwards as working electrode, and Ag/AgCl electrode is as reference electrode, Pt electrode
As auxiliary electrode, electrolyte is the mixed aqueous solution of aniline and sulfuric acid, carries out electrochemical deposition outside polypyrrole nanotube
Form polyaniline-coated layer, i.e. polypyrrole/polyaniline Coaxial Nanotubes composite material.
Embodiment 1:
120mg PPy/PANI CANTs is put into mortar, powder is ground into, is subsequently poured into beaker, and be added
10mL dehydrated alcohol stirs 10min, re-ultrasonic dispersion 3h, is uniformly mixed it.Taking concentration is 6mg mL-1GO anhydrous second
Alcohol dispersion 2mL is added in above-mentioned suspension, ultrasonic 5h.Said mixture is evaporated to 10mg mL in an oven-1, it is made
Electrode ink.Manufactured electrode ink is added in the syringe of a 1mL, the spray head of the syringe and 340 μ L of internal diameter connect
It connects.Syringe is attached on multiaxis positioning system (model Prusa i3), using the mode of Screw Extrusion with 3mm on carbon cloth
s-1Speed carry out multilayer printing.Each layer printing after print next layer again after spontaneously drying, after at 90 DEG C
6h is restored in hydrazine hydrate atmosphere.It is collector and electrode by the PPy/PANI CANTs composite material printed on carbon cloth, upper
Face coats one layer of commercially available PVA/H2SO4Gel electrolyte is assembled into sandwich type supercapacitor.
By Fig. 1 (a) it can be seen that conductive polymer nanometer pipe is evenly distributed in graphene, mutually between overlapped nanotube
There are many holes, form the structure of stephanoporate interpenetrating.The illustration of Fig. 1 (b) is the SEM figure of carbon cloth, it can be seen that carbon cloth is by carbon
Fibrage forms, and fiber surface is smooth, and Fig. 1 (b) is it can be seen that the material cladding that the carbon cloth surfaces after printing are printed, the two
It combines closely.Such structure provides guarantee for the flexibility and self-supporting of electrode.Constant current charge-discharge survey is carried out to it
Examination, when current density is 1mAcm-2When, area capacity is 297mF cm-2.When current density increases to 10mA cm-2When, capacity subtracts
It is small to arrive 216mF cm-2。
Further progress performance test, as shown in the picture, assemble formation capacitor show excellent cyclic voltammetric and
Charge-discharge performance, under the conditions of different scanning speed, area capacity is 200 or more；Under different current densities, area capacity exists
220 or more.The capacitor that assembling is formed keeps good bending property, and differently curved angle influences less, CV curve
Excellent performance is shown, and maintains 90% or more area capacity.
Embodiment 2:
120mg PPy/PANI CANTs is put into mortar, powder is ground into, is subsequently poured into beaker, and be added
10mL dehydrated alcohol stirs 10min, re-ultrasonic dispersion 3h, is uniformly mixed it.Taking concentration is 6mg mL-1GO anhydrous second
Alcohol dispersion 2mL is added in above-mentioned suspension, ultrasonic 5h.Said mixture is evaporated to 10mg mL in an oven-1, it is made
Electrode ink.The ink is printed upon on pan paper by above-mentioned standard, obtains flexible electrode.Fig. 9 is that ink is straight on pan paper
Write the interdigitated microelectrode structure of PPy/PANI- graphene of printing.The ink still can be printed efficiently on pan paper, table
The bright electrode material practicability is extensive, high-efficient simple.
Embodiment 3:
120mg PPy/PANI CANTs is put into mortar, powder is ground into, is subsequently poured into beaker, and be added
10mL dehydrated alcohol stirs 10min, re-ultrasonic dispersion 2h, is uniformly mixed it.Taking concentration is 6mg mL-1GO anhydrous second
Alcohol dispersion 2mL is added in above-mentioned suspension, ultrasonic 3h.Said mixture is evaporated to 10mg mL in an oven-1, it is made
Electrode ink.The ink is printed upon on carbon cloth by above-mentioned standard, obtains flexible electrode.
Constant current charge-discharge test is carried out to it, when current density is 1mA cm-2When, area capacity is 216mF cm-2,
Relative to embodiment 1, since the ultrasonic disperse time is reduced in this example, conducting polymer is low with the mixability of graphene oxide,
Prepared electrode capacity is obviously reduced.
Content is recorded technological parameter and is adjusted according to the present invention, and the preparation of electrode ink and flexible electrode can be achieved,
And show the performance almost the same with embodiment.Illustrative description has been done to the present invention above, it should explanation, not
In the case where being detached from core of the invention, any simple deformation, modification or other skilled in the art can not be spent
The equivalent replacement of creative work each falls within protection scope of the present invention.
Claims (10)
1. can ink direct write printing flexible electrode preparation method, which is characterized in that as steps described below carry out:
Step 1, conducting polymer Coaxial Nanotubes composite material and graphene oxide are dispersed in dehydrated alcohol, are formed
Electrode ink；The mass ratio of conducting polymer Coaxial Nanotubes composite material and graphene oxide is (1-10): 1, conducting polymer
Object Coaxial Nanotubes composite material is polypyrrole/polyaniline Coaxial Nanotubes composite material；Carry out after evenly dispersed solvent without
The evaporation of water-ethanol, until solid content reaches 10mg mL-1 or more；
Step 2, the printing that electrode ink carries out gel device is prepared using step 1 using carbon cloth as substrate, in hydrazine hydrate after molding
It is restored under steam atmosphere, can be obtained can ink direct write printing flexible electrode.
2. it is according to claim 1 can ink direct write printing flexible electrode preparation method, which is characterized in that in step 1
In, the mass ratio of conducting polymer Coaxial Nanotubes composite material and graphene oxide is (5-8): 1.
3. it is according to claim 1 can ink direct write printing flexible electrode preparation method, which is characterized in that in step 1
In, it is carried out by the way of mechanical stirring and ultrasonic disperse evenly dispersed, first carries out mechanical stirring, churned mechanically speed is every
100-200 turns of minute, the time is 10-30min, then carries out ultrasonic disperse, and the ultrasonic disperse time is 1-5h, and preferably 2-3 is small
When.
4. it is according to claim 1 can ink direct write printing flexible electrode preparation method, which is characterized in that in step 1
In, the evaporation of solvent absolute ethyl alcohol is carried out after evenly dispersed, until solid content reaches 10-20mg mL-1.
5. it is according to claim 1 can ink direct write printing flexible electrode preparation method, which is characterized in that in step 2
In, electrode ink made of step 1 is added in syringe and is connect with spray head, syringe is attached to multiaxis positioning system
On, multilayer printing is carried out on carbon cloth using the mode of Screw Extrusion, after restored in hydrazine hydrate atmosphere at 80-90 DEG C
Up to the flexible electrode, the recovery time is 1-6 hours, preferably 3-5 hours.
6. it is according to claim 1 can ink direct write printing flexible electrode preparation method, which is characterized in that in step 2
In, print speed is 1-5mm s-1, next layer is printed again after spontaneously drying after each layer of printing.
7. the preparation method as described in one of claim 1-6 is preparing the application in flexible electrode.
8. flexible electrode prepared by the preparation method as described in one of claim 1-6 is as electrode material for super capacitor
Using.
9. electrode ink is preparing the application in flexible electrode, which is characterized in that electrode ink is by conducting polymer co-axial nano
Pipe composite material and graphene oxide, which are dispersed in dehydrated alcohol, to be formed, conducting polymer Coaxial Nanotubes composite material and
The mass ratio of graphene oxide is (1-10): 1；Conducting polymer Coaxial Nanotubes composite material is that polypyrrole/polyaniline is coaxial
Nanometer tube composite materials；The evaporation of solvent absolute ethyl alcohol is carried out after evenly dispersed, until solid content reach 10mg mL-1 with
On, obtain electrode ink.
10. electrode ink according to claim 9 is preparing the application in flexible electrode, which is characterized in that conducting polymer
The mass ratio of object Coaxial Nanotubes composite material and graphene oxide is (5-8): 1；The anhydrous second of solvent is carried out after evenly dispersed
The evaporation of alcohol, until solid content reaches 10-20mg mL-1.
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| CN112509820A (en) * | 2019-09-16 | 2021-03-16 | 天津大学 | 3D printing self-repairing flexible supercapacitor taking ionic gel electrolyte as substrate |
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| CN114479354A (en) * | 2022-01-24 | 2022-05-13 | 东莞市维斯德新材料技术有限公司 | Preparation method of porous carbon fiber/epoxy resin composite material |
| CN114479354B (en) * | 2022-01-24 | 2024-01-05 | 东莞市维斯德新材料技术有限公司 | Preparation method of porous carbon fiber/epoxy resin composite material |
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