CN108538614A - A kind of method that the grapheme modified hydrogel of phytate prepares flexible super capacitor electrode - Google Patents
A kind of method that the grapheme modified hydrogel of phytate prepares flexible super capacitor electrode Download PDFInfo
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- CN108538614A CN108538614A CN201810317191.2A CN201810317191A CN108538614A CN 108538614 A CN108538614 A CN 108538614A CN 201810317191 A CN201810317191 A CN 201810317191A CN 108538614 A CN108538614 A CN 108538614A
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- Prior art keywords
- phytate
- super capacitor
- capacitor electrode
- prepares
- flexible super
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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
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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
- H01G11/30—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
- H01G11/84—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 the methods that a kind of grapheme modified hydrogel of phytate prepares flexible super capacitor electrode, first sodium phytate solution is heated to boiling, chloride is slowly added dropwise, obtain phytate solution, it is uniformly mixed with graphene oxide dispersion according to certain volume ratio, obtains graphene hydrogel through one step hydro thermal method, take certain thickness sheet, it is pressed against on collector, obtains flexible super capacitor electrode.The present invention modifies graphene oxide using phytate, prepares highly porous graphene hydrogel, has many advantages, such as safety, low price, environmental protection.The electrode of super capacitor that the present invention obtains has higher mechanical flexibility and chemical property, especially has longer cycle life, is suitable for flexible energy storage electronic field.
Description
Technical field
The present invention relates to the methods that a kind of grapheme modified hydrogel of phytate prepares flexible super capacitor electrode, belong to
Technical field of electronic materials.
Background technology
Ultracapacitor has larger capacity as a kind of novel green energy storage device, than energy or can force density, compared with
Wide operating temperature range and extremely long service life have become the weights such as the energy, resource and the environment for solving that the world is faced
One of the most potential electrochemical energy storage device of big problem.Currently, with the continuous improvement of people's living standards, people couple can
The need of wearing and portable electronic product (such as flexible foldable display, e-book, tablet computer and ultra-thin smart handset)
Ask growing day by day, therefore, there is flexibility, lightweight, low cost and high performance ultracapacitor to be studied as current energy storage for exploitation
The emphasis and hot spot in field.
Can electrode material be one of the key factor that determines performance of the supercapacitor quality and mass produce.And stone
Black alkene is because it is with good electric conductivity, excellent mechanical performance and flexibility, and ultra-thin and slim and graceful quality (density is small) becomes
Prepare the first choice of flexible super capacitor electrode material.But due to π-π interactions and Van der Waals force, pole between graphene sheet layer
It easily forms wadding to gather or stack, so as to cause the decline of chemical property.Therefore, the assembling and regulation and control of graphene are to influence electrochemistry
Performance extremely closes factor.In recent years, most researchers will focus on graphene-based composite material, including graphite
Alkene is compound with polymer, inorganic nano-particle or other carbon materials (activated carbon, carbon nanotube etc.), to expand graphene sheet layer
Spacing prevents the accumulation between graphene nanometer sheet, the diffusion for increasing its specific surface area, promoting electrolyte.However, being worth noting
, the flexility and electric conductivity of the combination electrode material prepared by these methods be but greatly diminished, Wu Faman
Full border production requirement.
Currently, the three-dimensional (3D) that more and more researchers assemble them into complexity using the self assembly performance of graphene is macro
See reticular structure.These with micropore, mesoporous and macropore reticular structure may be implemented big specific surface area, slim and graceful quality and
Quick electrons/ions transmission path.It however, realizing that commercialization still faces some obstacles, need to further reduce the cost, improve
The mechanical flexibility of electrode material, cyclical stability, and searching are safer, renewable, and environmentally friendly nano material is come
Modification regulation and control graphene, makes its performance be fully used.
Phytic acid is mainly derived from legume-seeds, cereal and corn, is nontoxic, environmentally friendly, ABUNDANT NATUREAL RESOURSES and reproducible
Natural organic-compound.Phytic acid is a kind of strong acid, has very strong sequestering power, and there are six electronegative phosphoric acid on cyclohexane
Foundation group can occur chelation with metal ion (such as calcium, magnesium, zinc etc.), can also pass through hydrogen with the surface of graphene sheet layer
Key connection forms reticular structure, while chela altogether can also occur with the oxygen atom in metal ion, phytic acid for the oxygen atom in graphene
Cooperation is used, and phytate can provide many places crosslinking active site, and two or more graphenes are captured with hydrogen bond action by the way that π-is pi-conjugated
Piece forms three-dimensional package assembly.
Invention content
The present invention in view of the deficienciess of the prior art, provide a kind of grapheme modified hydrogel of phytate prepare it is flexible super
The method of grade electrode for capacitors.
The present invention is achieved by the following technical programs：
(1) sodium phytate solution is heated to boiling, chloride is slowly added dropwise, mixed solution is then placed into 60-90 DEG C of perseverance
0.5-3.0h is reacted in warm water bath, obtains phytate solution；
(2) according to 10:1-1:1 volume ratio takes the graphene oxide of above-mentioned phytate solution and 0.5-3.0mg/mL point
Dispersion liquid is uniformly mixed, and is ultrasonically treated 20-60min at room temperature, is obtained the mixed solution of phytate and graphene oxide；
(3) above-mentioned mixed solution is placed in 100mL ptfe autoclaves, places 150-180 DEG C of constant temperature in baking oven
12h is reacted, is taken out after cooling, obtains the graphene hydrogel of phytate modification, dialyse 10-24h in deionized water；
(4) it is the above-mentioned graphene hydrogel of 0.5-2.0mm to take thickness, is pressed against on collector at 10-20MPa,
Obtain flexible super capacitor electrode.
Preferably, the chloride described in step (1) is calcium chloride, magnesium chloride, one kind or more in zinc chloride etc.
Kind, obtained phytate is phytic acid calcium, phytic acid magnesium, one or more, the molal weight 0.1-1.0mM in PHYTIC ACID ZINC SALT etc..
Preferably, the collector used in the graphene oxide preparation process described in step (4) include copper sheet,
Nickel sheet, platinized platinum and its alloy and stainless (steel) wire.
The present invention's is significantly a little：(1) the graphene hydrogel of phytate modification has highly porous netted knot
Structure is conducive to the transmission of electrolyte.(2) since the addition of phytate introduces a large amount of phosphonate functional group and metal ion,
Which increase the active site of composite graphite alkene hydrogel and fake capacitance performances, become more preferably electrode material, have
Higher chemical property and mechanical flexibility.(3) micro phytate substantially increases the cyclical stability of Graphene electrodes,
Production cost is reduced, industrialization is conducive to.
Description of the drawings
Fig. 1 is the side that a kind of grapheme modified hydrogel of phytate of the embodiment of the present invention prepares flexible super capacitor electrode
Method flow chart；
Fig. 2 is the SEM figures of the graphene hydrogel of phytic acid magnesium modification provided in an embodiment of the present invention；
Specific implementation mode
A kind of grapheme modified hydrogel of phytate of the present invention is illustrated with reference to the accompanying drawings and embodiments prepares flexibility
The method of electrode of super capacitor.The present invention provides preferred embodiment, but should not be construed as limited to implementation set forth herein
Example.
Fig. 1 is please referred to, the grapheme modified hydrogel of a kind of phytate that the embodiment of the present invention is provided prepares flexible super
The method of electrode for capacitors includes the following steps：
The sodium phytate solution of 30mL 0.4mM is heated to boiling by the first step, and 30mL magnesium chlorides are slowly added dropwise, and will then be mixed
It closes solution and places in 80 DEG C of thermostat water baths and react 1.0h, obtain 0.2mM phytic acid magnesium solutions.
Second step, according to 2:1 volume ratio, by the graphite oxide of 60mL above-mentioned phytate solution and 30mL 2.0mg/mL
Alkene dispersion liquid is uniformly mixed, and is ultrasonically treated 30min at room temperature, is obtained the mixed solution of phytate and graphene oxide.
Third walks, and mixed solution is placed in 100mL ptfe autoclaves, the isothermal reaction in 180 DEG C of baking ovens
12h takes out after cooling, obtains the graphene hydrogel of phytic acid magnesium modification, dialyse 12h in deionized water.It is examined after freeze-drying
The SEM of survey is as shown in Figure 2.
4th step, the graphene hydrogel for taking the phytic acid magnesium that thickness is 1.0mm to modify, is pressed against stainless at 10MPa
On steel mesh, flexible super capacitor electrode is obtained.
The grapheme modified hydrogel of a kind of phytate that example above primarily illustrates the present invention prepares flexible super capacitance
The method of device electrode.Although only the implementation of some of present invention is described, ordinary skill people
Member it is to be appreciated that the present invention can without departing from its spirit with range in the form of many other implement.Therefore, it is shown
Example is considered as illustrative and not restrictive with way of example, is not departing from this hair as defined in appended claims
In the case of bright spirit and scope, the present invention may cover various modification and replacement.The foregoing is merely the preferable of the present invention
Embodiment, all equivalent changes and modifications done according to scope of the present invention patent should all belong to the covering scope of the present invention.
Claims (8)
1. a kind of method that the grapheme modified hydrogel of phytate prepares flexible super capacitor electrode, which is characterized in that the system
Preparation Method includes following operating procedure：
(1) sodium phytate solution is heated to boiling, chloride is slowly added dropwise, mixed solution is then placed into 60-90 DEG C of thermostatted water
0.5-3.0h is reacted in bath, obtains phytate solution；
(2) according to certain volume ratio, above-mentioned phytate solution is taken to be uniformly mixed with graphene oxide dispersion, it is ultrasonic at room temperature
20-60min is handled, the mixed solution of phytate and graphene oxide is obtained；
(3) above-mentioned mixed solution is placed in 100mL ptfe autoclaves, isothermal reaction 12h in baking oven is placed, after cooling
It takes out, obtains the graphene hydrogel of phytate modification, dialyse 10-24h in deionized water；
(4) certain thickness above-mentioned graphene hydrogel is taken, is pressed against on collector at 10-20MPa, obtains flexible super
Electrode for capacitors.
2. the grapheme modified hydrogel of a kind of phytate according to claim 1 prepares the side of flexible super capacitor electrode
Method, which is characterized in that chloride described in step 1 is calcium chloride, magnesium chloride, one or more in zinc chloride etc., is obtained
Phytate is phytic acid calcium, phytic acid magnesium, one or more in PHYTIC ACID ZINC SALT etc..
3. the grapheme modified hydrogel of a kind of phytate according to claim 1 prepares the side of flexible super capacitor electrode
Method, which is characterized in that the phytate solution molal weight described in step 1 is 0.1-1.0mM.
4. the grapheme modified hydrogel of a kind of phytate according to claim 1 prepares the side of flexible super capacitor electrode
Method, which is characterized in that the volume ratio described in step 2 is 10:1-1:1.
5. the grapheme modified hydrogel of a kind of phytate according to claim 1 prepares the side of flexible super capacitor electrode
Method, which is characterized in that the graphene oxide described in step 2 is obtained by improved Hummers methods, and oxidant is the concentrated sulfuric acid, height
One or more, the ultimate density 0.5-3.0mg/mL of potassium manganate, potassium ferrate, sodium nitrate, hydrogen peroxide.
6. the grapheme modified hydrogel of a kind of phytate according to claim 1 prepares the side of flexible super capacitor electrode
Method, which is characterized in that the oven temperature described in step 3 is 150-180 DEG C.
7. the grapheme modified hydrogel of a kind of phytate according to claim 1 prepares the side of flexible super capacitor electrode
Method, which is characterized in that the thickness of the selection electrode material described in step 4 is 0.5-2.0mm.
8. the grapheme modified hydrogel of a kind of phytate according to claim 1 prepares the side of flexible super capacitor electrode
Method, which is characterized in that the collector described in step 4 includes copper sheet, nickel sheet, platinized platinum and its alloy and stainless (steel) wire.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810317191.2A CN108538614A (en) | 2018-04-10 | 2018-04-10 | A kind of method that the grapheme modified hydrogel of phytate prepares flexible super capacitor electrode |
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| CN201810317191.2A CN108538614A (en) | 2018-04-10 | 2018-04-10 | A kind of method that the grapheme modified hydrogel of phytate prepares flexible super capacitor electrode |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678142A (en) * | 2018-12-24 | 2019-04-26 | 华中科技大学 | A kind of function dough porous graphene and preparation method thereof |
| CN111517297A (en) * | 2020-04-02 | 2020-08-11 | 太原理工大学 | Preparation method and application of heterostructure/graphene composite material |
| CN112495344A (en) * | 2020-10-22 | 2021-03-16 | 南京工业大学 | Copper ion adsorbent and preparation method and adsorption method thereof |
| CN112934003A (en) * | 2021-01-27 | 2021-06-11 | 天津大学 | Super-hydrophilic graphene oxide composite membrane and preparation and application thereof |
-
2018
- 2018-04-10 CN CN201810317191.2A patent/CN108538614A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678142A (en) * | 2018-12-24 | 2019-04-26 | 华中科技大学 | A kind of function dough porous graphene and preparation method thereof |
| CN109678142B (en) * | 2018-12-24 | 2021-01-19 | 华中科技大学 | Functionalized porous graphene and preparation method thereof |
| CN111517297A (en) * | 2020-04-02 | 2020-08-11 | 太原理工大学 | Preparation method and application of heterostructure/graphene composite material |
| CN111517297B (en) * | 2020-04-02 | 2023-03-24 | 太原理工大学 | Preparation method and application of heterostructure/graphene composite material |
| CN112495344A (en) * | 2020-10-22 | 2021-03-16 | 南京工业大学 | Copper ion adsorbent and preparation method and adsorption method thereof |
| CN112934003A (en) * | 2021-01-27 | 2021-06-11 | 天津大学 | Super-hydrophilic graphene oxide composite membrane and preparation and application thereof |
| CN112934003B (en) * | 2021-01-27 | 2022-10-14 | 天津大学 | Super-hydrophilic graphene oxide composite membrane and preparation and application thereof |
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