CN108492997B - Silk base flexible electrode material and preparation method thereof - Google Patents

Silk base flexible electrode material and preparation method thereof Download PDF

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Publication number
CN108492997B
CN108492997B CN201810213847.6A CN201810213847A CN108492997B CN 108492997 B CN108492997 B CN 108492997B CN 201810213847 A CN201810213847 A CN 201810213847A CN 108492997 B CN108492997 B CN 108492997B
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silk
electrode material
silk fabric
fabric
flexible electrode
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CN108492997A (en
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李育洲
邢铁玲
卢神州
陈国强
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Suzhou University
Nantong Textile and Silk Industrial Technology Research Institute
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Suzhou University
Nantong Textile and Silk Industrial Technology Research Institute
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • 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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • 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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • 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

Abstract

The present invention relates to a kind of preparation methods of silk base flexible electrode material, and the real silk fabric after degumming is activated in aqueous acetic acid；The real silk fabric after activation is soaked in manganese acetate aqueous solution again；Then potassium permanganate solution is added thereto and obtains the real silk fabric for being deposited with manganese dioxide after washing to neutrality；The real silk fabric for being deposited with manganese dioxide is immersed in the graphene oxide hydrosol and is handled, the real silk fabric for being combined with graphene oxide and manganese dioxide is obtained, the graphene oxide on real silk fabric surface is then reduced to graphene, obtain silk base flexible electrode material.Method provided by the invention overcomes the deficiencies in the prior art, and prepared silk base flexible electrode material had both had ventilative, flexible, the stretchable feature of silk fabric, while still having kept good chemical property in a stretched state.

Description

Silk base flexible electrode material and preparation method thereof
Technical field
The present invention relates to a kind of electrode material technical field more particularly to a kind of silk base flexible electrode material and its preparations Method.
Background technique
Wearable electronic product can be obtained in implantation electronic component in the fabric, makes clothes on the basis of keeping comfort With more electronic information functions.Wearable electronic product successional personal health monitoring device, high-performance gym suit, Flexible display etc. has good application prospect.However, electronic product all needs power supply to provide, therefore have textile institute special Some lightweights, flexibility, the energy conversion of ventilative and stretchable etc. performances or storage equipment necessitate.
As a kind of emerging energy accumulating device, supercapacitor has height ratio capacity, high power density, overlength circulation Service life, high stability and it is environmental-friendly many advantages, such as.It has both the high current fast charging and discharging characteristic and electricity of traditional capacitor The energy storage characteristic in pond has filled up the blank of specific energy and specific power between ordinary capacitor and battery, and electric discharge specific power is than passing The battery of system is nearly ten times high, compensates for the technological gap between current alminium electrolytic condenser and rechargeable battery, while overcoming again The defect of the two.Wherein silk based composites are important one of research direction as electrode of super capacitor.
Carbon material specific surface area height, good conductivity, stable chemical performance.New carbon graphene has very high conductance And great theoretical specific surface area, its dilute special molecular structure of graphite determine its excellent properties, impart graphene and exist The fields such as micro-nano field of electronic devices, sensor application, information science field, catalysis and its energy storage have boundless application Prospect.The high-specific surface area of graphene, high conduction ability and corrosion-resistant determine that it can serve as electrode material for super capacitor.
Processing is carried out to fabric using graphene to be used as in the technology of electrode material for super capacitor, generallys use infusion process Or electrophoretic deposition technique, electrode material is obtained after drying reduction, but this method has some disadvantages, as graphene adsorbs Measure less, electric conductivity cannot significantly improve, and knitted by way of addition crosslinking agent or adhesive to increase graphene Adsorbance on object can seriously affect fabric feeling.
How graphene to be arranged onto fabric using suitable method for sorting, fabric can be used as surpassing after once arranging Grade capacitor flexible electrode material；And the excellent properties of performance fabric how are maximized to prepare supercapacitor flexible electrode Material is that functional textile is applied to electrode material field institute urgent problem to be solved.
Summary of the invention
In order to solve the above technical problems, the object of the present invention is to provide a kind of silk base flexible electrode material and its preparation sides Method, silk base flexible electrode material provided by the invention had both had ventilative, flexible, the stretchable feature of silk fabric, but also with Electric conductivity, while good chemical property is still kept in a stretched state.
On the one hand, the present invention provides a kind of preparation methods of silk base flexible electrode material, are original with real silk fabric Material, comprising the following steps:
(1) it is in mass ratio 1:20, the real silk fabric after degumming is activated -30 minutes 10 minutes in aqueous acetic acid, The mass concentration of aqueous acetic acid is 0.1wt%-1wt%；
(2) it is in mass ratio 1:8-1:20 (preferably 1:10), it is water-soluble that the real silk fabric after activation is soaked in manganese acetate - 10 minutes 1 minute in liquid, the concentration of manganese acetate aqueous solution is 1mmol/L-10mmol/L；Then extra vinegar is removed using pressure roller Sour manganese aqueous solution, the pressure of the pressure roller are 0.1MPa-0.4MPa, obtain the real silk fabric containing manganese acetate；
It (3) is in mass ratio 1:8-1:20 (preferably 1:10) that 1mmol/L- is added in the real silk fabric containing manganese acetate It is aoxidized in the potassium permanganate solution of 10mmol/L, the processing time is that 0.1h-5h obtains being deposited with dioxy after washing to neutrality Change real silk fabric (hereinafter referred to as silk/MnO of manganese2Deposit fabric)；
It (4) is in mass ratio 1:8-1:20 (preferably 1:10) that the real silk fabric for being deposited with manganese dioxide is immersed into 10mg/ 0.5h-5h is handled in the graphene oxide hydrosol of mL-30mg/mL, obtains being combined with the true of graphene oxide and manganese dioxide Silk fabrics (hereinafter referred to as silk/MnO2, graphene oxide fabric), then the graphene oxide on real silk fabric surface is reduced to Graphene obtains silk base flexible electrode material.
Further, in step (1), the preparation method of the real silk fabric after degumming is the following steps are included: silk is knitted At real silk fabric papain degumming -100 minutes 50 minutes at 50 DEG C -80 DEG C, the concentration of papain is 5g/ L-8g/L.Preferably, the concentration of papain is 6g/L.
In step (1), using the silk fiber in acetic acid activation real silk fabric, since silk is acidproof, in acetic acid Under effect, silk fiber can be swollen, and increased the distance between silk fiber in fabric, facilitated itself in next step and manganese The reaction of ion.
Further, after step (1), further include the steps that removing extra aqueous acetic acid using pressure roller, pressure roller Pressure is 0.1MPa-0.4MPa.
In step (2), manganese acetate can play buffer function simultaneously, maintain the balance of reaction system condition.
Further, in step (4), the graphene oxide hydrosol is prepared using hummers method is improved.
Further, in step (4), using chemical reduction method redox graphene.
Further, chemical reduction method the following steps are included: in mass ratio be 1:20-1:50 (preferably 1:50), will tie Conjunction has the real silk fabric of graphene oxide and manganese dioxide to be impregnated in reducing agent aqueous solution, in 85 DEG C -95 DEG C (preferably 90 DEG C) under react 0.5h-5h.
Further, reducing agent is glucose, and the concentration of reducing agent is 0.1mol/L-0.5mol/L.
On the other hand, the present invention is also claimed using silk base flexible electrode material prepared by above-mentioned preparation method Material passes through the manganese dioxide nano particle of coordination key connection, manganese dioxide nano grain including real silk fabric and with real silk fabric Son is connected with graphene by coordinate bond.
The silk base flexible electrode material prepared using the above method, under the current density of 2A/g, specific capacitance value reaches 200F/g-500F/g, air penetrability reach 10000g/m2/24h-20000g/m2/ for 24 hours, in the case where elongation 5%, conductance reaches It arrives: 80S/m-100S/m.
Preparation method principle of the present invention is as follows: the real silk fabric after degumming first adsorbs acetic acid, sends out fibroin albumen therein Biology reason swelling post activation.There is relatively large gap between fibroin albumen after activation, then reacted with manganese acetate, it is more Manganese element be transferred to the surface and inside of real silk fabric, oxidant potassium permanganate solution is then added, potassium permanganate is in situ Manganese ion is aoxidized, manganese dioxide (MnO is formed2) nano particle, the nano-manganese dioxide particle and fibroin albumen pass through coordinate bond Connection has very strong binding force.The oxidation of the vacancy coordination and addition of other manganese ion on nano-manganese dioxide particle Carboxyl, hydroxyl coordination on graphene combine, so that graphene oxide be made to be firmly bound to very by nano-manganese dioxide particle On the fibroin albumen of silk fabrics, to prepare silk base flexible electrode material.
According to the above aspect of the present invention, the present invention has at least the following advantages:
By novel simple coating process, the graphene oxide that improved hummers method is prepared connects the present invention Branch arrives silk/MnO as made from in-situ chemical sedimentation2Deposit fabric surface, thus in nanometer MnO2The real silk fabric of modification Sample surfaces form one layer of graphene oxide film, MnO2Nano particle theoretical specific capacity with higher, is knitted so that being integrated to Graphene oxide in the hole of object keeps the porosity of electrode, so as to cause superior quality load density.Then, stone will be aoxidized Black alkene is reduced into graphene, to prepare a kind of equalization electrodes material with compared with high specific capacitance value.This programme provides soft The preparation method of property electrode is simple and novel, environmentally protective, safe and efficient.The electrode material can be used for supercapacitor, conductive film Etc. in electricity product.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention, And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is the cyclic voltammetry curve of silk base flexible electrode prepared by present example 1；
Fig. 2 is the constant current charge-discharge curve of silk base flexible electrode prepared by present example 1, current density 2A/g.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below Example is not intended to limit the scope of the invention for illustrating the present invention.
Embodiment 1
A kind of silk base flexible electrode material and preparation method thereof for supercapacitor is present embodiments provided, specifically Steps are as follows:
Silk: being weaved the real silk fabric to be formed papain degumming by the degumming of silk fabric, and papain is dense Spending is 6g/L, temperature 70 C, usually time 60 minutes.
Silk/MnO2The preparation of deposit fabric: 0.8wt% vinegar is added with the mass ratio of 1:20 in the real silk fabric after degumming It is activated 15 minutes in acid solution, the real silk fabric after activation is removed into extra acetum through pressure roller, the pressure of pressure roller is 0.2MPa；5mmol/L acetic acid manganese solution is configured, the real silk fabric after activation is immersed in acetic acid manganese solution with mass ratio 1:10 Reason 5 minutes；Then extra manganese acetate aqueous solution is removed using pressure roller, the pressure of the pressure roller is 0.2MPa, obtains and contains manganese acetate Real silk fabric；8mmol/L liquor potassic permanganate is configured, is in mass ratio 1:10, the real silk fabric containing manganese acetate is added high Aoxidized in mangaic acid aqueous solutions of potassium, the processing time be 2h, by after reaction real silk fabric take out washing to neutrality to get silk/ MnO2Deposit fabric.
Using natural flake graphite as raw material, graphene oxide is prepared using hummers method is improved, first centrifugation is primary, It is washed again through washing, alcohol, centrifugation is primary each time after washing, and dialysis obtains the graphene oxide hydrosol after 6 days, what when dialysis used Bag filter diameter is 44mm, molecular cut off 14000Da, and solution that dialysis obtains is added deionized water to be configured to concentration to be The graphene oxide hydrosol of 25mg/mL.
By silk/MnO2Deposit fabric is cut into 20cm × 30cm size, immerses above-mentioned steps with the mass ratio of 1:10 and obtains To the graphene oxide hydrosol in handle 3 hours, obtain silk/MnO2, graphene oxide fabric.
Silk/the MnO that will be obtained2, graphene oxide fabric use electronation, reducing agent is glucose, and concentration is 0.3mol/L.Silk/MnO that needs are restored2, graphene oxide fabric reducing agent solution is impregnated in the mass ratio of 1:50 In, 90 DEG C of reduction 3h to get arrive silk base flexible electrode material.
Obtained silk base flexible electrode material is cut into 2cm × 2cm size, carries out electricity in RST electrochemical workstation Test chemical, test method include cyclic voltammetry, constant current charge-discharge test and ac impedance measurement.Wherein, electrolyte is The KCl solution of 1M, auxiliary electrode are Pt electrode, and reference electrode is Ag/AgCl electrode, and working electrode is the silkworm of above method preparation Silk base flexible electrode carries out electro-chemical test using three-electrode system.Test result is shown in Fig. 1-2.The silk base flexible electrode material Material is under the current density of 2A/g, and specific capacitance value reaches 320F/g, and air penetrability reaches 18000g/m2/ for 24 hours, the feelings of elongation 5% Under condition, conductance reaches 85S/m.
Embodiment 2
A kind of silk base flexible electrode material and preparation method thereof for supercapacitor is present embodiments provided, specifically Steps are as follows:
Silk: being weaved the real silk fabric to be formed papain degumming by the degumming of silk fabric, and papain is dense Spending is 5g/L, temperature 60 C, usually time 90 minutes.
Silk/MnO2The preparation of deposit fabric: 1wt% acetic acid is added with the mass ratio of 1:10 in the real silk fabric after degumming It is activated 10 minutes in solution, the real silk fabric after activation is removed into extra acetum through pressure roller, the pressure of pressure roller is 0.25MPa；4mmol/L acetic acid manganese solution is configured, the real silk fabric after activation is immersed in acetic acid manganese solution with mass ratio 1:10 Processing 6 minutes；Then extra manganese acetate aqueous solution is removed using pressure roller, the pressure of the pressure roller is 0.25MPa, obtains and contains acetic acid The real silk fabric of manganese；4mmol/L liquor potassic permanganate is configured, is in mass ratio 1:10, the real silk fabric containing manganese acetate is added Aoxidized in potassium permanganate solution, the processing time be 5h, by after reaction real silk fabric take out washing to neutrality to get silk/ MnO2Deposit fabric.
Using natural flake graphite as raw material, graphene oxide is prepared using hummers method is improved, first centrifugation is primary, It is washed again through washing, alcohol, centrifugation is primary each time after washing, and dialysis obtains the graphene oxide hydrosol after 5 days, what when dialysis used Bag filter diameter is 44mm, molecular cut off 14000Da, and solution that dialysis obtains is added deionized water to be configured to concentration to be The graphene oxide hydrosol of 21mg/mL.
By silk/MnO2Deposit fabric is cut into 15cm × 30cm size, immerses above-mentioned steps with the mass ratio of 1:20 and obtains To the graphene oxide hydrosol in handle 4 hours, obtain silk/MnO2, graphene oxide fabric.
Silk/the MnO that will be obtained2, graphene oxide fabric use electronation, reducing agent is glucose, and concentration is 0.5mol/L.Silk/MnO that needs are restored2, graphene oxide fabric reducing agent solution is impregnated in the mass ratio of 1:40 In, 80 DEG C of reductase 12 .5h to get arrive silk base flexible electrode material.
Obtained silk base flexible electrode material is cut into 2cm × 2cm size, carries out electricity according to the method for embodiment 1 Test chemical.For the silk base flexible electrode material under the current density of 2A/g, specific capacitance value reaches 280F/g, and air penetrability reaches 15000g/m2/ for 24 hours, in the case where elongation 5%, conductance reaches 90S/m.
Embodiment 3
A kind of silk base flexible electrode material and preparation method thereof for supercapacitor is present embodiments provided, specifically Steps are as follows:
Silk: being weaved the real silk fabric to be formed papain degumming by the degumming of silk fabric, and papain is dense Spending is 7g/L, 85 DEG C of temperature, usually time 40 minutes.
Silk/MnO2The preparation of deposit fabric: 0.5wt% vinegar is added with the mass ratio of 1:15 in the real silk fabric after degumming It is activated 30 minutes in acid solution, the real silk fabric after activation is removed into extra acetum through pressure roller, the pressure of pressure roller is 0.16MPa；6mmol/L acetic acid manganese solution is configured, the real silk fabric after activation is immersed in acetic acid manganese solution with mass ratio 1:10 Processing 7 minutes；Then extra manganese acetate aqueous solution is removed using pressure roller, the pressure of the pressure roller is 0.3MPa, obtains and contains acetic acid The real silk fabric of manganese；6mmol/L liquor potassic permanganate is configured, is in mass ratio 1:10, the real silk fabric containing manganese acetate is added Aoxidized in potassium permanganate solution, the processing time be 3h, by after reaction real silk fabric take out washing to neutrality to get silk/ MnO2Deposit fabric.
Using natural flake graphite as raw material, graphene oxide is prepared using hummers method is improved, first centrifugation is primary, It is washed again through washing, alcohol, centrifugation is primary each time after washing, and dialysis obtains the graphene oxide hydrosol after 7 days, what when dialysis used Bag filter diameter is 44mm, molecular cut off 14000Da, and solution that dialysis obtains is added deionized water to be configured to concentration to be The graphene oxide hydrosol of 24mg/mL.
By silk/MnO2Deposit fabric is cut into 20cm × 20cm size, immerses above-mentioned steps with the mass ratio of 1:12 and obtains To the graphene oxide hydrosol in handle 2.5 hours, obtain silk/MnO2, graphene oxide fabric.
Silk/the MnO that will be obtained2, graphene oxide fabric use electronation, reducing agent is glucose, and concentration is 0.25mol/L.Silk/MnO that needs are restored2, graphene oxide fabric reducing agent solution is impregnated in the mass ratio of 1:35 In, 65 DEG C of reduction 4h to get arrive silk base flexible electrode material.
Obtained silk base flexible electrode material is cut into 2cm × 2cm size, carries out electricity according to the method for embodiment 1 Test chemical.For the silk base flexible electrode material under the current density of 2A/g, specific capacitance value reaches 350F/g, and air penetrability reaches 14000g/m2/ for 24 hours, in the case where elongation 5%, conductance reaches 85S/m.
Embodiment 4
A kind of silk base flexible electrode material and preparation method thereof for supercapacitor is present embodiments provided, specifically Steps are as follows:
Silk: being weaved the real silk fabric to be formed papain degumming by the degumming of silk fabric, and papain is dense Spending is 6.5g/L, 65 DEG C of temperature, usually time 80 minutes.
Silk/MnO2The preparation of deposit fabric: 0.7wt% vinegar is added with the mass ratio of 1:14 in the real silk fabric after degumming It is activated 18 minutes in acid solution, the real silk fabric after activation is removed into extra acetum through pressure roller, the pressure of pressure roller is 0.2MPa；7mmol/L acetic acid manganese solution is configured, the real silk fabric after activation is immersed in acetic acid manganese solution with mass ratio 1:15 Reason 7 minutes；Then extra manganese acetate aqueous solution is removed using pressure roller, the pressure of the pressure roller is 0.35MPa, obtains and contains manganese acetate Real silk fabric；7mmol/L liquor potassic permanganate is configured, is in mass ratio 1:10, the real silk fabric containing manganese acetate is added high It aoxidizes, handles 1.5 hours in mangaic acid aqueous solutions of potassium, the real silk fabric after reaction is taken out into washing to neutrality to get silk/MnO2 Deposit fabric.
Using natural flake graphite as raw material, graphene oxide is prepared using hummers method is improved, first centrifugation is primary, It is washed again through washing, alcohol, centrifugation is primary each time after washing, and dialysis obtains the graphene oxide hydrosol after 6 days, what when dialysis used Bag filter diameter is 44mm, molecular cut off 14000Da, and solution that dialysis obtains is added deionized water to be configured to concentration to be The graphene oxide hydrosol of 26mg/mL.
By silk/MnO2Deposit fabric is cut into 15cm × 35cm size, immerses above-mentioned steps with the mass ratio of 1:13 and obtains To the graphene oxide hydrosol in handle 5 hours, obtain silk/MnO2, graphene oxide fabric.
Silk/the MnO that will be obtained2, graphene oxide fabric use electronation, reducing agent is glucose, and concentration is 0.45mol/L.Silk/MnO that needs are restored2, graphene oxide fabric reducing agent solution is impregnated in the mass ratio of 1:30 In, 75 DEG C of reduction 3.5h to get arrive silk base flexible electrode material.
Obtained silk base flexible electrode material is cut into 2cm × 2cm size, carries out electricity according to the method for embodiment 1 Test chemical.For the silk base flexible electrode material under the current density of 2A/g, specific capacitance value reaches 431F/g, and air penetrability reaches 17000g/m2/ for 24 hours, in the case where elongation 5%, conductance reaches 95S/m.
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and Modification, these improvements and modifications also should be regarded as protection scope of the present invention.

Claims (7)

1. a kind of preparation method of silk base flexible electrode material, using real silk fabric as raw material, which is characterized in that including following step It is rapid:
(1) it is in mass ratio 1:20, the real silk fabric after degumming is activated in aqueous acetic acid, the matter of the aqueous acetic acid Amount concentration is 0.1wt%-1wt%；
(2) it is in mass ratio 1:8-1:20, the real silk fabric after activation is soaked in manganese acetate aqueous solution -10 minutes 1 minute, The concentration of the manganese acetate aqueous solution is 1mmol/L-10mmol/L；Then extra manganese acetate aqueous solution, institute are removed using pressure roller The pressure for stating pressure roller is 0.1MPa-0.4MPa, obtains the real silk fabric containing manganese acetate；
(3) in mass ratio it is 1:8-1:20, the real silk fabric containing manganese acetate is added to the potassium permanganate of 1mmol/L-10mmol/L It is aoxidized in aqueous solution, the processing time is that 0.1h-5h obtains the real silk fabric for being deposited with manganese dioxide after washing to neutrality；
(4) in mass ratio it is 1:8-1:20, the real silk fabric for being deposited with manganese dioxide is immersed 10mg/mL-30mg/mL's It is handled in the graphene oxide hydrosol, obtains the real silk fabric for being combined with graphene oxide and manganese dioxide, then knit silk The graphene oxide on object surface is reduced to graphene, obtains the silk base flexible electrode material.
2. the preparation method of silk base flexible electrode material according to claim 1, which is characterized in that in step (1), The preparation method of real silk fabric after the degumming is the following steps are included: the real silk fabric papain that silk is made into is existed Degumming is carried out at 50 DEG C -80 DEG C, the concentration of the papain is 5g/L-8g/L.
3. the preparation method of silk base flexible electrode material according to claim 1, it is characterised in that: step (1) it Afterwards, further include the steps that removing extra aqueous acetic acid using pressure roller, the pressure of the pressure roller is 0.1MPa-0.4MPa.
4. the preparation method of silk base flexible electrode material according to claim 1, it is characterised in that: in step (4), Using chemical reduction method redox graphene.
5. the preparation method of silk base flexible electrode material according to claim 4, which is characterized in that the electronation Method is the following steps are included: be in mass ratio 1:20-1:50, the real silk fabric that will be combined with graphene oxide and manganese dioxide impregnates In reducing agent aqueous solution, 0.5h-5h is reacted at 85 DEG C -95 DEG C.
6. the preparation method of silk base flexible electrode material according to claim 5, it is characterised in that: the reducing agent is Glucose, the concentration of the reducing agent are 0.1mol/L-0.5mol/L.
7. silk base flexible electrode material prepared by a kind of preparation method of any of claims 1-6, including it is true Silk fabrics and the manganese dioxide nano particle being keyed with the real silk fabric by coordination, the manganese dioxide nano particle Graphene is connected with by coordinate bond.
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