CN108428567A - A kind of preparation method of graphene-based series connection linear supercapacitor - Google Patents

A kind of preparation method of graphene-based series connection linear supercapacitor Download PDF

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CN108428567A
CN108428567A CN201810204410.6A CN201810204410A CN108428567A CN 108428567 A CN108428567 A CN 108428567A CN 201810204410 A CN201810204410 A CN 201810204410A CN 108428567 A CN108428567 A CN 108428567A
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graphene
series connection
yarn
preparation
based series
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CN108428567B (en
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张坤
张娟
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Donghua University
National Dong Hwa University
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Donghua University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses a kind of preparation methods of graphene-based series connection linear supercapacitor, it is characterized in that, make yarn part conductive using interruption composite conducting active material, to form the yarn of continuous insulation and conducting interval arrangement, coated at insulative yarn colloidal electrolyte can direct-assembling at multiple ultracapacitor Tandem devices.The device volume is small, and output voltage is high, and flexible, and preparation process is simple, easily operated.

Description

A kind of preparation method of graphene-based series connection linear supercapacitor
Technical field
The present invention relates to a kind of preparation methods of graphene-based series connection linear supercapacitor, and in particular to one kind is continuously led The preparation method of electricity-insulation interruption yarn and superelevation output voltage threadiness ultracapacitor, belongs to weaving and electrochemical techniques neck Domain.
Background technology
In recent years, wearable device rapid development, and intelligent skin, health supervision, can the fields exhibition such as drawing-off circuit Reveal wide application prospect, therefore the energy source supplied power for is particularly important.Rechargeable battery is as energy storage device Part, the energy density of Yin Qigao and find broad application, but low power density and poor stable circulation performance are limiting Its development, and it is flexible poor, uses in wearable electronic device and is restricted above.Linear supercapacitor is as a kind of soft Property energy source, it is light, power density is high, have extended cycle life, is small, it is soft knit, however with battery or plate condenser phase Than the low energy density of linear supercapacitor limits it and further applies.
For ultracapacitor, energy density depends primarily on specific capacitance and potential window range, in order to improve its electricity Gesture window can integrate multiple devices in series.There is scholar by the way that the conductive polymer fibers of single-length are spirally wound on elasticity On yarn, a portion coats interior electrode of the gel electrolyte as first ultracapacitor, remainder as conducting wire, A conductive polymer fibers part for one double length is wrapped in outside the interior electrode of first ultracapacitor and is used as external electrode, Remainder is spirally wound on the elastomeric yarn.Equally a part of surface coating of the conducting polymer remainder of the double length Interior electrode of the gel electrolyte as second ultracapacitor, remainder connect two adjacent super capacitors as conducting wire Device.This step is repeated, then elastic gel electrolyte is coated on every section lead surface, you can it is concatenated to obtain multiple ultracapacitors Linear supercapacitor group integration device (CN106592009).
So far, conductive and insulated part is formed directly on an one thread, then is coated electrolyte in insulation position and be made Ultracapacitor, the series connection integrated device of formation is flexible, can knit and method that output voltage is high has not yet to see report, the preparation side Method is easy to operate, at low cost, therefore can be widely applied to linear supercapacitor field.
Invention content
The technical problem to be solved by the present invention is to:Existing ultracapacitor preparation process is complicated, it is flexible it is poor, can not knit, The disadvantages such as volume is big, output voltage is low.
To solve the above-mentioned problems, the technical solution adopted by the present invention is:A kind of linear super capacitor of graphene-based series connection The preparation method of device, which is characterized in that make yarn part conductive using interruption composite conducting active material, it is continuous to be formed The arrangement of insulation and conducting interval yarn, coated at insulative yarn colloidal electrolyte can direct-assembling at multiple super electricity Container Tandem devices.
Preferably, above-mentioned preparation method includes the following steps:
Step 1):Graphene oxide is prepared using Hummers methods, graphene oxide dispersion magnetic agitation obtained is dense It is reduced to gel, is transferred to spare in culture dish;
Step 2):Insulative yarn S-shaped is wound on hollow, rectangular holder, graphene oxide is immersed into the lower end of holder In, it is taken out after 30-60 minutes, the graphene oxide that removal floats on surface is washed with deionized, is put into 30-50 DEG C of baking oven and dries It is dry;It repeats 2-10 times, make graphene oxide fully and is equably attached to insulative yarn surface;
Step 3):Graphene oxide long filament obtained is subjected to local reduction, continuous insulation is made and is arranged with conducting interval The yarn of cloth;
Step 4):Colloidal electrolyte is coated into continuous insulation and the insulation position of the yarn of conducting interval arrangement, stand 12- After 24 hours dry, graphene-based series connection linear supercapacitor is made.
It is highly preferred that the temperature of magnetic agitation is 40 DEG C in the step 1), and it is excessively high, graphene oxide can be caused to be carbonized, Too low then moisture evaporation speed is slow.
It is highly preferred that the material of holder is wire in the step 2), insulation is wound again after the package preservative film of surface Yarn avoids wire surface oxide contaminant yarn;The material of insulative yarn is natural fiber or synthetic fibers.
It is highly preferred that the natural fiber is cotton, wool or silk;Synthetic fibers are terylene, polyamide fibre or acrylic fibers.
It is highly preferred that the wide 3-5mm of holder in the step 2), the tip lengths immersed in electrical conductive activities substance are 1- 2mm.Using superfine and have the wire of certain strength that holder is made so that yarn is reduced with holder contact portion, reduces holder Influence to graphene oxide self assembly, and interruption length of yarn can be reduced, shorten ion transportation range, reduce inefficient length, Improve output voltage density.
It is highly preferred that using laser, direct-reduction process or other method redox graphenes in the step 3).May be used also To use other restoring method, but it should be noted the structure that yarn cannot be destroyed while redox graphene, i.e., yarn is whole Property and partial insulating properties need to be protected.
It is highly preferred that the reducing agent that the direct-reduction process uses is hydrazine hydrate, phenols, dimethylhydrazine or sulfur-bearing chemical combination Object.
It is highly preferred that the reduction method is specially:Insulative yarn is suspended in HI acid and glacial acetic acid, and is sealed place Reason;Beaker, which is put into 40 DEG C of oil bath pan, to react 24-48 hours, is taken out after cooling, is with deionized water and ethyl alcohol washing and drying It can.Using the mixed solution of high-temperature heating HI acid and glacial acetic acid, using steam reduction graphene oxide, graphene obtained/viscous Glue yarn impedance is smaller, and electric conductivity improves.
It is highly preferred that the colloidal electrolyte in the step 4) is potassium hydroxide, sodium chloride, potassium chloride, ammonium chloride, sulfuric acid Any one or a few in ammonium, sodium sulphate, potassium sulfate, ammonium nitrate, sodium nitrate, potassium nitrate, sulfuric acid, phosphoric acid, hydrochloric acid and lithium chlorate Polyvinyl alcohol water solution;Graphene-based series connection linear supercapacitor obtained is through electro-chemical test, specially cyclic voltammetric Method (CV) or crossing current charge and discharge electrical method (GCD);Wherein, sweep speed is 0.005~100V/s in cyclic voltammetry, charge and discharge of flowing over Current density is 0.1~1000mA/cm in method2
Graphene in the present invention can also use other electrical conductive activities substances, such as conducting polymer composite, metal material Material or carbon-based material, polyacetylene can be selected in conducting polymer composite, polyaniline, poly- give a tongue-lashing are coughed up, polythiophene, polyparaphenylene's acetylene or gather To benzene.
Compared with prior art, the beneficial effects of the present invention are:
1, preparation method is quick and easy, easy to spread;
2, prepare continuous conduction-insulation gap yarn it is high, flexible as electrode material output voltage, can directly into Row braiding;
3, thus yarn is excellent as ultracapacitor chemical property made of electrode material, it is contemplated that in wearable field It is with a wide range of applications.
Description of the drawings
Fig. 1 is that (current density is for the comparison diagram of unit piece and the charge and discharge time of four Tandem devices in embodiment 1 0.1mA/cm2)。
Specific implementation mode
In order to make the present invention more obvious and understandable, it is hereby described in detail below with preferred embodiment.
Embodiment 1
A kind of preparation method of superelevation output voltage threadiness ultracapacitor, includes the following steps:
Prepare gel:Graphene oxide is prepared using Hummers methods, mass fraction obtained is aoxidized for 1~5mg/mL Graphene dispersing solution magnetic agitation at 40 DEG C, is concentrated into gel, is transferred to spare in 60mm culture dishes.
Self assembly:Viscose yarn S-shaped is wound on homemade hollow, rectangular holder, the wide 5mm of holder, concentration is immersed in lower end Graphene oxide in 2mm, taken out after 30 minutes, be put into 40 DEG C of baking ovens and dry after deionized water washing.It is repeated 4 times, makes oxygen Graphite alkene is abundant and is equably attached to viscose yarn surface.
Reduction:Yarn obtained is suspended in the 300mL beakers of 2mLHI acid and 5mL glacial acetic acid, and is sealed place Reason.Beaker, which is put into 40 DEG C of oil bath pans, to react 24 hours, takes out after cooling, with deionized water and ethyl alcohol washing and drying, thus makes At continuous insulation-conducting interval yarn.
Ultracapacitor assembling test:Colloid electrolysis is coated in the insulation position of continuous insulation-conducting interval yarn of preparation Liquid is made superelevation output voltage threadiness ultracapacitor and is tested after standing is dried for 12-24 hours, test result such as Fig. 1 It is shown.
As shown in Figure 1, as ultracapacitor serial number increases, assembly device overall output voltage increases, says therewith The serial connected super capacitor globality that bright this method is obtained is good, can reach output HIGH voltage by increasing serial number Purpose.
Embodiment 2
A kind of preparation method of superelevation output voltage threadiness ultracapacitor, includes the following steps:
It prepares:Graphene oxide is prepared using Hummers methods, by the graphene oxide that mass fraction obtained is 2mg/ml Dispersion liquid is transferred to spare in 60mm culture dishes.Long filament is made by wet spinning process in graphene oxide dispersion, by letter The dry drying of (40~60 DEG C) of single low temperature, obtains continuous pure zirconia graphene long filament.
Reduction:Graphene oxide long filament obtained is restored with local laser, continuous conduction-insulation gap stone is thus made Black alkene yarn.
Ultracapacitor assembling test:Colloid electrolysis is coated in the insulation position of continuous conduction-insulation gap yarn of preparation Liquid is made superelevation output voltage threadiness ultracapacitor and is tested after standing is dried for 12-24 hours.
Test result is same as Example 1, as concatenated supercapacitors increase, assembly device overall output electricity Pressure increases therewith.

Claims (10)

1. a kind of preparation method of graphene-based series connection linear supercapacitor, which is characterized in that lived using interruption composite conducting Property material and keep yarn part conductive, to form the yarn of continuous insulation and conducting interval arrangement, applied at insulative yarn Upper colloidal electrolyte can direct-assembling at multiple ultracapacitor Tandem devices.
2. the preparation method of graphene-based series connection linear supercapacitor as described in claim 1, which is characterized in that including with Lower step:
Step 1):Graphene oxide is prepared using Hummers methods, graphene oxide dispersion magnetic agitation obtained is concentrated into Gel is transferred to spare in culture dish;
Step 2):Insulative yarn S-shaped is wound on hollow, rectangular holder, the lower end of holder is immersed in graphene oxide, 30- It takes out after sixty minutes, the graphene oxide that removal floats on surface is washed with deionized, is put into 30-50 DEG C of baking oven and dries;Weight It is 2-10 times multiple, make graphene oxide fully and is equably attached to insulative yarn surface;
Step 3):Graphene oxide long filament obtained is subjected to local reduction, continuous insulation and conducting interval arrangement is made Yarn;
Step 4):Colloidal electrolyte is coated into continuous insulation and the insulation position of the yarn of conducting interval arrangement, it is small to stand 12-24 When dry after, graphene-based series connection linear supercapacitor is made.
3. the preparation method of graphene-based series connection linear supercapacitor as claimed in claim 2, which is characterized in that the step It is rapid 1) in magnetic agitation temperature be 40 DEG C.
4. the preparation method of graphene-based series connection linear supercapacitor as claimed in claim 2, which is characterized in that the step It is rapid 2) in holder material be wire, surface package preservative film after wind insulative yarn again;The material of insulative yarn is day Right fiber or synthetic fibers.
5. the preparation method of graphene-based series connection linear supercapacitor as claimed in claim 4, which is characterized in that the day Right fiber is cotton, wool or silk;Synthetic fibers are terylene, polyamide fibre or acrylic fibers.
6. the preparation method of graphene-based series connection linear supercapacitor as claimed in claim 2, which is characterized in that the step It is rapid 2) in the wide 3-5mm of holder, immerse electrical conductive activities substance in tip lengths be 1-2mm.
7. the preparation method of graphene-based series connection linear supercapacitor as claimed in claim 2, which is characterized in that the step It is rapid 3) middle using laser, direct-reduction process or other method redox graphenes.
8. the preparation method of graphene-based series connection linear supercapacitor as claimed in claim 7, which is characterized in that described straight The reducing agent that reduction method uses is connect as hydrazine hydrate, phenols, dimethylhydrazine or sulfur-containing compound.
9. the preparation method of graphene-based series connection linear supercapacitor as claimed in claim 7, which is characterized in that described to go back Former method is specially:Insulative yarn is suspended in HI acid and glacial acetic acid, and carries out encapsulation process;Beaker is put into 40 DEG C of oil bath pan Middle reaction 24-48 hours is taken out after cooling, with deionized water and ethyl alcohol washing and drying.
10. the preparation method of graphene-based series connection linear supercapacitor as claimed in claim 2, which is characterized in that described Colloidal electrolyte in step 4) is potassium hydroxide, sodium chloride, potassium chloride, ammonium chloride, ammonium sulfate, sodium sulphate, potassium sulfate, nitric acid The polyvinyl alcohol water solution of any one or a few in ammonium, sodium nitrate, potassium nitrate, sulfuric acid, phosphoric acid, hydrochloric acid and lithium chlorate;It is made Graphene-based series connection linear supercapacitor through electro-chemical test, specially cyclic voltammetry or crossing current charge and discharge electrical method;Wherein, Sweep speed is 0.005~100V/s in cyclic voltammetry, and current density is 0.1~1000mA/cm in the charge and discharge electrical method that flows over2
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103594251A (en) * 2013-11-10 2014-02-19 浙江大学 Graphene fiber super capacitor preparing method
CN104916453A (en) * 2015-04-17 2015-09-16 浙江大学 Coaxial graphene fiber supercapacitor and manufacturing method thereof
CN105428090A (en) * 2015-12-13 2016-03-23 复旦大学 Fibrous super capacitor possessing high output voltage and manufacturing method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103594251A (en) * 2013-11-10 2014-02-19 浙江大学 Graphene fiber super capacitor preparing method
CN104916453A (en) * 2015-04-17 2015-09-16 浙江大学 Coaxial graphene fiber supercapacitor and manufacturing method thereof
CN105428090A (en) * 2015-12-13 2016-03-23 复旦大学 Fibrous super capacitor possessing high output voltage and manufacturing method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUAN LIANG,ET AL.: ""Series of in-fiber graphene supercapacitors for flexible wearable devices"", 《J. MATER. CHEM. A》 *

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