CN108766783A - A kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material - Google Patents
A kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material Download PDFInfo
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- CN108766783A CN108766783A CN201810605092.4A CN201810605092A CN108766783A CN 108766783 A CN108766783 A CN 108766783A CN 201810605092 A CN201810605092 A CN 201810605092A CN 108766783 A CN108766783 A CN 108766783A
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- fiber
- graphene
- electrode material
- graphene oxide
- zinc sulphide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 77
- 239000000835 fiber Substances 0.000 title claims abstract description 44
- 239000007772 electrode material Substances 0.000 title claims abstract description 34
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004744 fabric Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 229910052717 sulfur Chemical group 0.000 claims abstract description 5
- 239000011593 sulfur Chemical group 0.000 claims abstract description 5
- 150000003751 zinc Chemical group 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 20
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 235000005074 zinc chloride Nutrition 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- 229920000742 Cotton Polymers 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- -1 Graphite alkene Chemical class 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 229920004934 Dacron® Polymers 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical class [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of fiber/graphene/zinc sulphide flexible electrode material, include the following steps:A, pretreated fabric is impregnated in graphene oxide suspension and dried, repeated this step and obtain fiber/graphene oxide composite material several times, the graphene oxide suspension is that graphene oxide powder ultrasonic disperse is made in deionized water;B, in-situ reducing is carried out to fiber/graphene oxide composite material and obtains fiber/grapheme material;C, fiber/grapheme material that step B is obtained is immersed in the hydrothermal reaction kettle containing zinc salt and sulfur-bearing precursor solution, heating reaction synthesis obtains fiber/graphene/zinc sulphide flexible electrode material.Material made from the method for the present invention combines the zinc sulphide of the carbon material of good conductivity and specific capacitance height, poorly conductive, gives full play to the two advantage.It is superior with higher area specific capacitance and power characteristic, cycle performance.
Description
Technical field
The present invention relates to a kind of preparation methods of flexible electrode material, more particularly to a kind of fiber/graphene/zinc sulphide
The preparation method of flexible electrode material.
Background technology
Electrochemical capacitor is based on the specific functions such as its high power capacity and high power density, is widely used in hybrid power vapour
The fields such as vehicle, communication, national defence and wearable electronic.Become as current electronic equipment is just showing lightening and flexibility development
Gesture, flexible display screen, distributed sensor, Electronic Paper and wearable multimedia device etc. be portable and wearable electronic day
Benefit enters daily life.But traditional electrochemical capacitor volume is big, weight weight, shape are fixed, and far can not expire
The demand for development of the current flexible electronic devices of foot.Urgent need develops that low with light weight and cost, small, chemical property is excellent
Different and processing performance excellent flexible electrochemical capacitor and its electrode material.
Currently, the research and development of flexible electrochemical capacitor and electrode material have become international hot spot, have a large amount of close both at home and abroad
In the wearing comfort for how improving wearable energy storage device and chemical property etc. research how is improved, but high system
Make cost, poor flexibility, lower durability and environmental factor dependence etc. and limits their real application.Carry green wood
Material, design new construction are the important methods for improving wearable energy storage device performance and improving its environmental suitability.
Textile material is natural wearable material, and there is excellent wearing comfort, selection generality and mechanics to stablize
Property etc..The material and surface nature of textile material have particularity, therefore the conductive materials such as carbon are difficult to be formed on its surface three-dimensional
Continuous conductive network often uses a large amount of crosslinking agent, table to increase the interaction between conductive material and fabric
Activating agent even binder in face enables conductive material preferably to adhere on the fabric, on the one hand the addition of these substances can block up
Hole on plug fabric is unfavorable for the diffusion of electrolyte ion, influences the performance of its chemical property, on the other hand can make material
Building-up process is complicated, difficult, increases cost.
Invention content
In view of the above-mentioned defects in the prior art, the present invention provides a kind of fiber/graphene/zinc sulphide flexible electrode materials
Preparation method, solve textile material surface and be difficult to shaped conductive network, hypodynamic problem is bonded between conductive material and fabric,
The material that can be applied to super capacitor and wearable product is provided.
Technical solution of the present invention is as follows:A kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material, including
Following steps:
A, pretreated fabric is impregnated in graphene oxide suspension and dried, repeated this step and obtain several times
To fiber/graphene oxide composite material, the graphene oxide suspension is by graphene oxide powder ultrasonic disperse in deionization
It is made in water;
B, in-situ reducing is carried out to fiber/graphene oxide composite material and obtains fiber/grapheme material;
C, that fiber/grapheme material that step B is obtained is immersed in the hydro-thermal containing zinc salt and sulfur-bearing precursor solution is anti-
It answers in kettle, heating reaction synthesis obtains fiber/graphene/zinc sulphide flexible electrode material.
Further, dip time is in a concentration of 0.5-3mg/mL of the graphene oxide suspension, the step A
Drying temperature is 40-70 DEG C in 20-60min, the step A, drying time 2-3h.
Preferably, the number of repetition of the step A is 5-40 times.
Further, it is that fiber/graphene oxide composite material is immersed NaBH that the step B, which carries out in-situ reducing,4In solution
Restore and dry after being cleaned with deionized water, or by fiber/graphene oxide composite material under inert gas protection into
Row heating reduction.
Preferably, the NaBH4Solution concentration is 0.1-1mol/L, the immersion NaBH4The time of solution is 4-12h, institute
It is 90-120 DEG C to state the drying temperature dried after deionized water cleaning, drying time 1-3h.
Preferably, 150-350 DEG C of the heating temperature of the heating reduction, heating time 0.5-5h, the inert gas
He or N2。
Further, the pretreated fabric is to pre-process fabric using aqueous slkali, then
It is cleaned up, is dried with deionized water.
Preferably, the aqueous slkali is sodium hydroxide solution or sodium bicarbonate solution, a concentration of 0.5- of the aqueous slkali
2mol/L, the pretreatment temperature be 90-120 DEG C, pretreatment time 1-3h, in the pretreatment drying temperature be 80 DEG C-
130 DEG C, drying time 1-3h.
Further, the zinc salt and sulfur-bearing precursor solution be zinc chloride and thiocarbamide, zinc sulfate and thiocarbamide, zinc chloride and
Carbon disulfide either zinc acetate and thioacetamide.
Preferably, the heating temperature that reaction is heated in the step C is 100 DEG C -180 DEG C, reaction time 4h-20h.
The advantages of technical solution provided by the present invention, is:
1, the present invention, which is combined using layer assembly with hydro-thermal method, is prepared for a kind of novel three-dimensional grown based on textile fabric
Graphene/zinc sulphide super capacitance electrode material.The material high, poorly conductive sulphur by the carbon material of good conductivity and specific capacitance
Change zinc to combine, gives full play to the two advantage.
2, material prepared by the present invention can be as the electrode material of ultracapacitor, the material use flexible textile fiber
Between the porous structure structure that has promote the diffusion of electrolyte ion, while also giving full play to the high-ratio surface of graphene and height is led
Electrical property is effectively increased the contact interface of zinc sulphide/graphene, and effective dispersed sulfur zinc carries for its fake capacitance redox reaction
For more reactivity points, the advantage of the capacitance of zinc sulphide is played, and ensures quick transmission of the electronics in electrode material, from
And obtain high specific capacitance, high power density and high-energy density.
3, electrode material lightweight obtained, softness have higher area specific capacitance and power characteristic, cycle performance excellent
More, synthesis is simple, and cost is relatively low, and durability is good, it is made to play making for bigger in wearable electronic product energy storage etc.
With value.
Specific implementation mode
With reference to embodiment, the invention will be further described, but not as a limitation of the invention.
Oxygen in each embodiment of the preparation method of fiber/graphene/zinc sulphide flexible electrode material of the present invention
Graphite alkene powder is prepared by the following method:Graphene oxide is prepared using improved Hummers synthetic methods.It will
1.5g powdered graphites are added to be mixed by what 98% concentrated sulfuric acids of 10mL, 1.25g potassium thiosulfates and 1.25g phosphorus pentoxides formed
It closes in object, 4.5h is stirred under the conditions of 80 DEG C.Then obtained product is cleaned with deionized water, in 50 in vacuum drying chamber
It is dried under the conditions of DEG C.Product after drying is added in 98% concentrated sulfuric acids of 60mL, is slowly added into 7.5g permanganic acid again later
Potassium, temperature is maintained at 20 DEG C hereinafter, then adding the deionized water of 125mL in the adition process of potassium permanganate.After 2h again
The hydrogen peroxide of 200mL deionized waters and 10mL a concentration of 30% is added, solution becomes glassy yellow after 10min.It is bright what is obtained
The solution of yellow is centrifuged, and is then cleaned, is removed with diluted hydrochloric acid solution (concentrated hydrochloric acid/deionized water volume ratio is 1/10)
Then metal ion and sulfate ion are cleaned with deionized water to weakly acidic pH again, finally in 50 DEG C of bakings in vacuum drying chamber
It is dry to obtain graphene oxide.
Embodiment 1
Graphene oxide powder is add to deionized water, the graphite oxide of a concentration of 1.5mg/L is made in ultrasonic 60min
Alkene suspension.Cotton fabric handles 2h with the sodium hydroxide solution of 1mol/L in 100 DEG C, is then cleaned up with deionized water, in
2h is dried in 110 DEG C of drying boxes.Pretreated cotton fabric is impregnated into the graphene oxide suspension prepared, in room temperature
After lower stirring 30min, dry 2h, repeated impregnations-drying course 20 times are placed in 50 DEG C of vacuum drying ovens.By cotton/graphite oxide
Alkene compound fabric is immersed in the NaBH of a concentration of 0.5mol/L4In solution, in room temperature condition stir 12h, then take out spend from
Sub- water cleans 3 times, and 2h is dried in 100 DEG C, and reduction obtains cotton/graphene composite material.
It is 1 ︰ 1 that cotton/graphene composite material, which is immersed in containing zinc chloride and thiourea solution (Xin ︰ sulphur molar ratios) water
In thermal response kettle, 160 DEG C of reaction 6h, synthesis obtains fiber/graphene/zinc sulphide electrode material, and 80 DEG C of bakings are carried out to the material
Dry 2h, it is 206 Ω/sq to measure sheet resistance, and when sweep speed is 2m V/s, specific capacitance has good up to 530F/g
Flex capability.
Embodiment 2
Graphene oxide powder is add to deionized water, the graphene oxide of a concentration of 2mg/L is made in ultrasonic 30min
Suspension.Cotton fabric handles 3h with the sodium bicarbonate solution of 0.5mol/L in 90 DEG C, is then cleaned up with deionized water, in
2.5h is dried in 100 DEG C of drying boxes.Pretreated cotton fabric is impregnated into the graphene oxide suspension prepared, in room
After the lower stirring 20min of temperature, dry 3h, repeated impregnations-drying course 30 times are placed in 50 DEG C of vacuum drying ovens.By cotton/oxidation stone
Black alkene compound fabric is immersed in the NaBH of a concentration of 0.1mol/L4In solution, 12h is stirred in room temperature condition, then takes out and spends
Ionized water cleans 3 times, and 2h is dried in 100 DEG C, and reduction obtains cotton/graphene composite material.
Cotton/graphene composite material is immersed in the ethylene glycol solution (Xin ︰ sulphur mole containing zinc chloride and carbon disulfide
Than for 1 ︰ 1) hydrothermal reaction kettle in, 130 DEG C of reaction 8h, synthesis obtains fiber/graphene/zinc sulphide electrode material, to the material
Material carries out 80 DEG C of drying 2h, and it is 183 Ω/sq to measure sheet resistance, and when sweep speed is 2mV/s, specific capacitance has up to 565F/g
There is good flex capability.
Embodiment 3
Graphene oxide powder is add to deionized water, the graphite oxide of a concentration of 2.5mg/L is made in ultrasonic 60min
Alkene suspension.Cotton fabric handles 1h with the sodium hydroxide solution of 1mol/L in 110 DEG C, is then cleaned up with deionized water, in
3h is dried in 90 DEG C of drying boxes.Pretreated cotton fabric is impregnated into the graphene oxide suspension prepared, in room temperature
After lower stirring 40min, dry 2.5h, repeated impregnations-drying course 20 times are placed in 40 DEG C of vacuum drying ovens.By cotton/oxidation stone
Black alkene compound fabric is placed in high temperature process furnances, and heating rate is 2 DEG C/min, in 250 DEG C, N2It is anti-by high temperature under atmospheric condition
3h, reduction is answered to obtain cotton/graphene composite material.
Cotton/graphene composite material is immersed in containing PEG-400 (0.1%), zinc acetate and thioacetyl amine aqueous solution
In the hydrothermal reaction kettle of (zinc ︰ sulphur molar ratios are 1 ︰ 1), 140 DEG C of reaction 4h, synthesis obtains fiber/graphene/vulcanization zinc electrode material
Material carries out 80 DEG C of drying 2h to the material, and it is 172 Ω/sq to measure sheet resistance, and when sweep speed is 2mV/s, specific capacitance is reachable
590F/g, and there is good flex capability.
Embodiment 4
Graphene oxide powder is add to deionized water, the graphene oxide of a concentration of 3mg/L is made in ultrasonic 30min
Suspension.Dacron handles 1.5h with the sodium bicarbonate solution of 2mol/L in 120 DEG C, is then cleaned up with deionized water,
3h is dried in 80 DEG C of drying boxes.Pretreated dacron is impregnated into the graphene oxide suspension prepared, in
After stirring 50min at room temperature, dry 2.5h, repeated impregnations-drying course 40 times are placed in 60 DEG C of vacuum drying ovens.Terylene is knitted
Object/graphene oxide compound fabric is immersed in the NaBH of a concentration of 1mol/L4In solution, 12h is stirred in room temperature condition, is then taken
Go out and cleaned 3 times with deionized water, 2h is dried in 100 DEG C, reduction obtains dacron/graphene composite material.
Dacron/graphene composite material is immersed in the ethylene glycol solution (Xin ︰ sulphur containing zinc chloride and carbon disulfide
Molar ratio be 1 ︰ 1) hydrothermal reaction kettle in, 100 DEG C reaction 20h, synthesis obtain fiber/graphene/zinc sulphide electrode material, it is right
The material carries out 80 DEG C of drying 2h, and it is 358 Ω/sq to measure sheet resistance, when sweep speed is 2mV/s, specific capacitance up to 462F/g,
And there is good flex capability.
Embodiment 5
Graphene oxide powder is add to deionized water, the graphite oxide of a concentration of 0.5mg/L is made in ultrasonic 30min
Alkene suspension.The sodium hydroxide solution of cotton/wash blended fabric 1.5mol/L handles 2.5h in 120 DEG C, then uses deionized water
It cleans up, 1.5h is dried in 130 DEG C of drying boxes.Pretreated cotton/wash blended fabric is impregnated into the oxidation prepared
In graphene suspension, after stirring 60min at room temperature, dry 2h, repeated impregnations-drying course are placed in 70 DEG C of vacuum drying ovens
10 times.The NaBH that cotton/wash blended fabric/graphene oxide compound fabric is immersed in a concentration of 0.5mol/L4In solution, in room
Warm condition stirs 12h, then takes out and clean 3 times with deionized water, and 2h are dried in 100 DEG C, restore obtain cotton/wash blended fabric/
Graphene composite material.
Cotton/wash blended fabric/graphene composite material is immersed in containing zinc chloride and thiourea solution (Xin ︰ sulphur molar ratios
For 1 ︰ 1) hydrothermal reaction kettle in, 110 DEG C reaction 15h, synthesis obtain fiber/graphene/zinc sulphide electrode material, to the material
80 DEG C of drying 2h are carried out, it is 265 Ω/sq to measure sheet resistance, and when sweep speed is 2mV/s, specific capacitance has up to 492F/g
Good flex capability.
Embodiment 6
Graphene oxide powder is add to deionized water, the graphene oxide of a concentration of 1mg/L is made in ultrasonic 30min
Suspension.Nylon fabric handles 3h with the sodium hydroxide solution of 0.5mol/L in 100 DEG C, is then cleaned up with deionized water,
1h is dried in 120 DEG C of drying boxes.Pretreated nylon fabric is impregnated into the graphene oxide suspension prepared, in
After stirring 30min at room temperature, dry 3h, repeated impregnations-drying course 5 times are placed in 40 DEG C of vacuum drying ovens.By nylon fabric/oxygen
Graphite alkene compound fabric is placed in high temperature process furnances, and heating rate is 2 DEG C/min, passes through height under 350 DEG C, He atmospheric conditions
Temperature reaction 0.5h, reduction obtain nylon fabric/graphene composite material.
Nylon fabric/graphene composite material is immersed in the ethylene glycol solution (Xin ︰ sulphur containing zinc chloride and carbon disulfide
Molar ratio be 1 ︰ 1) hydrothermal reaction kettle in, 120 DEG C reaction 10h, synthesis obtain fiber/graphene/zinc sulphide electrode material, it is right
The material carries out 80 DEG C of drying 2h, and it is 416 Ω/sq to measure sheet resistance, when sweep speed is 2mV/s, specific capacitance up to 403F/g,
And there is good flex capability.
Embodiment 7
Graphene oxide powder is add to deionized water, the graphene oxide of a concentration of 1mg/L is made in ultrasonic 30min
Suspension.Non-woven fabrics handles 3h with the sodium hydroxide solution of 0.5mol/L in 100 DEG C, is then cleaned up with deionized water, in
1h is dried in 120 DEG C of drying boxes.Pretreated non-woven fabrics is impregnated into the graphene oxide suspension prepared, in room temperature
After lower stirring 30min, dry 3h, repeated impregnations-drying course 5 times are placed in 40 DEG C of vacuum drying ovens.By non-woven fabrics/graphite oxide
Alkene compound fabric is placed in high temperature process furnances, and heating rate is 2 DEG C/min, passes through pyroreaction under 150 DEG C, He atmospheric conditions
5h, reduction obtain non-woven fabrics/graphene composite material.
It is 1 ︰ 1 that non-woven fabrics/graphene composite material, which is immersed in containing zinc chloride and thiourea solution (Xin ︰ sulphur molar ratios)
In hydrothermal reaction kettle, 130 DEG C of reaction 12h, synthesis obtains fiber/graphene/zinc sulphide electrode material, and 80 DEG C are carried out to the material
2h is dried, it is 440 Ω/sq to measure sheet resistance, and when sweep speed is 2mV/s, specific capacitance has good soft up to 389F/g
Property performance.
Claims (10)
1. a kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material, which is characterized in that include the following steps:
A, pretreated fabric is impregnated in graphene oxide suspension and dried, repeated this step and obtain fibre several times
Dimension/graphene oxide composite material, the graphene oxide suspension be by graphene oxide powder ultrasonic disperse in deionized water
It is made;
B, in-situ reducing is carried out to fiber/graphene oxide composite material and obtains fiber/grapheme material;
C, fiber/grapheme material that step B is obtained is immersed in the hydrothermal reaction kettle containing zinc salt and sulfur-bearing precursor solution
In, heating reaction synthesis obtains fiber/graphene/zinc sulphide flexible electrode material.
2. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 1, which is characterized in that
Dip time is 20-60min, the step in a concentration of 0.5-3mg/mL of the graphene oxide suspension, the step A
Drying temperature is 40-70 DEG C in A, drying time 2-3h.
3. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 1, which is characterized in that
The number of repetition of the step A is 5-40 times.
4. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 1, which is characterized in that
It is that fiber/graphene oxide composite material is immersed NaBH that the step B, which carries out in-situ reducing,4It is restored in solution and uses deionization
It is dried after water cleaning, or fiber/graphene oxide composite material is subjected to heating reduction under inert gas protection.
5. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 4, which is characterized in that
The NaBH4Solution concentration is 0.1-1mol/L, the immersion NaBH4The time of solution is 4-12h, the deionized water cleaning
The drying temperature dried afterwards is 90-120 DEG C, drying time 1-3h.
6. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 4, which is characterized in that
150-350 DEG C of the heating temperature of the heating reduction, heating time 0.5-5h, the inert gas He or N2。
7. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 1, which is characterized in that
The pretreated fabric is to pre-process fabric using aqueous slkali, is then cleaned with deionized water dry
Only, it dries.
8. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 7, which is characterized in that
The aqueous slkali is sodium hydroxide solution or sodium bicarbonate solution, a concentration of 0.5-2mol/L of the aqueous slkali, the pre- place
It is 90-120 DEG C, pretreatment time 1-3h to manage temperature, and drying temperature is 80 DEG C -130 DEG C in the pretreatment, and drying time is
1-3h。
9. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 1, which is characterized in that
The zinc salt and sulfur-bearing precursor solution are zinc chloride and thiocarbamide, zinc sulfate and thiocarbamide, zinc chloride and carbon disulfide either vinegar
Sour zinc and thioacetamide.
10. the preparation method of fiber/graphene/zinc sulphide flexible electrode material according to claim 1, feature exist
In the heating temperature for heating reaction in the step C is 100 DEG C -180 DEG C, reaction time 4h-20h.
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