CN110379641A - A kind of carbon dots/chitosan/manganese dioxide energy storage material and preparation method thereof - Google Patents
A kind of carbon dots/chitosan/manganese dioxide energy storage material and preparation method thereof Download PDFInfo
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- CN110379641A CN110379641A CN201910591266.0A CN201910591266A CN110379641A CN 110379641 A CN110379641 A CN 110379641A CN 201910591266 A CN201910591266 A CN 201910591266A CN 110379641 A CN110379641 A CN 110379641A
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- chitosan
- carbon dots
- manganese dioxide
- energy storage
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 167
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 118
- 238000004146 energy storage Methods 0.000 title claims abstract description 70
- 239000011232 storage material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000004070 electrodeposition Methods 0.000 claims abstract description 54
- 239000006260 foam Substances 0.000 claims abstract description 46
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000002659 electrodeposit Substances 0.000 claims abstract description 26
- 238000000151 deposition Methods 0.000 claims abstract description 15
- 230000008021 deposition Effects 0.000 claims abstract description 14
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 14
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 239000012153 distilled water Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 230000005611 electricity Effects 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 238000003780 insertion Methods 0.000 claims description 6
- 230000037431 insertion Effects 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000005137 deposition process Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 18
- 238000013019 agitation Methods 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000007853 buffer solution Substances 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 230000004936 stimulating effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 238000012956 testing procedure Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of carbon dots/chitosan/manganese dioxide energy storage materials and preparation method thereof.Using carbon dots/chitosan complexes and potassium permanganate solution as electrodeposit liquid, using negative electrode electro-deposition technology on foam nickel electrode electro-deposition carbon dots/chitosan/manganese dioxide deposition layer, obtain the energy storage material to construct directly on foam nickel electrode.The present invention has many advantages, such as controllability and selective, easy to operate, mild condition using electro-deposition techniques, in electrodeposition process, using carbon dots/chitosan/liquor potassic permanganate as electrodeposit liquid, entire electrodeposition process is safely controllable, electro-deposition can obtain carbon dots/chitosan/manganese dioxide energy storage material in nickel foam in a short time.Simultaneously because the effect of carbon dots, improves the specific capacitance of capacitor, there is preferable efficiency for charge-discharge and specific capacitance.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of carbon dots/chitosan/manganese dioxide energy storage material
Preparation method.
Background technique
Electro-deposition techniques can trigger the assembling with the large biological molecule of stimulating responsive, the skill by stimulating electrical signal
Art provides opportunity for the combination of microelectric technique and biotechnology.It is worth noting that, electro-deposition techniques, which are capable of providing, to be had
The method of selectivity and controllability carrys out the assembling of releasing stimulus responsiveness large biological molecule, and in metal electrode or conductive base table
Face forms large biological molecule deposition layer, to construct various new bio electronic devices and functional material.Currently, having pH thorn
The chitosan for swashing responsiveness sol-gel transition performance is a kind of large biological molecule material for being widely used in electro-deposition techniques
Material.In the electrodeposition process of chitosan, when applying certain voltage, electrochemical reaction can occur in electrode surface, so that molten
Chitosan molecule chain deprotonation in liquid near cathode and sol-gel transition occurs, thus in electrode surface electro-deposition shape
At chitosan gel rubber film [Biofabrication, 2010,2 (2): 022002].
Carbon dots are a kind of novel fluorescence carbon nanomaterials, have the spies such as hypotoxicity, good biocompatibility, environmentally protective
Property also has both many advantages, such as fluorescent stability is good, to prepare raw material sources extensive, synthesis technology is simple [Sensors and
Actuators B:Chemical,2017,248:92-100].Carbon dots have unique specific surface area and electric conductivity, it is considered to be
A kind of nano material with excellent electrical.Currently, having some researchs in terms of carbon dots energy storage material.For example,
For Ghosh et al. by carbon dots surface grafting to polyaniline chain, the carbon dots/polyaniline being covalently attached by electro-chemical test discovery is aobvious
Significant higher specific capacitance value [Journal of Materials Chemistry A, 2018,6 (15): 189-197] are shown.
The compound that Zhou et al. is doped by carbon dots and using the polypyrrole of iron coordination, is designed as the activity of supercapacitor
Electrode material, effectively improve its chemical property [Journal ofSolid State Electrochemistry, 2018,22
(8):2515–2529].The studies above shows that carbon dots have unique chemical property, has in energy storage material field huge
Application potential.
With the development of social economy and the rapid growth of population, traditional fossil energy is rapidly depleted, and people are to clear
While clean energy urgent need, the development of different types of energy storage material and energy storage device is also promoted.Manganese dioxide
It is a kind of semiconductor material, by the microstructure observing to manganese dioxide, it is found that it is very suitable to do energy storage material
[Nanotechnology,2019,30(23):1-7].Yin et al. prepares polystyrene by a step hydrothermal oxidization polymerization
Sodium sulfonate/manganese dioxide composites, the electrode material as supercapacitor, specific capacitance are shown when current density is 1A/g
The high capacitance [Ionics, 2019,25 (2): 685-695] of 365.5F/g out.
Using the energy storage characteristic of electro-deposition techniques and the carbon dots unique chemical property and manganese dioxide of chitosan,
Constructing carbon dots/chitosan/manganese dioxide energy storage material will be before energy and material and supercapacitor field has good application
Scape.However, having no related about using electro-deposition techniques building carbon dots/chitosan/manganese dioxide energy storage material method at present
Document and patent report.
Summary of the invention
Present invention aims at the energy storage characteristics using carbon dots unique chemical property and manganese dioxide, using electro-deposition
One step of technology constructs carbon dots/chitosan/manganese dioxide energy storage material.This method has preparation condition mild, easy to operate, controllable
Property good, environmentally protective, favorable repeatability the advantages that, gained energy storage material will have good in energy and material and supercapacitor field
Good application value.
In order to achieve the above objectives, as follows using technical solution:
A kind of carbon dots/chitosan/manganese dioxide energy storage material, with carbon dots/chitosan complexes and potassium permanganate solution
As electrodeposit liquid, electro-deposition carbon dots/chitosan/manganese dioxide electro-deposition on foam nickel electrode using negative electrode electro-deposition technology
Layer, so that building obtains a kind of carbon dots/chitosan/manganese dioxide energy storage material directly on foam nickel electrode.
The preparation method of above-mentioned carbon dots/chitosan/manganese dioxide energy storage material, comprising the following steps:
1) carbon dots/chitosan complexes preparation: chitosan solid powder is added in distilled water, stirring and dissolving is simultaneously added
Vinegar acid for adjusting pH value 5.3~5.7 obtains the chitosan solution that mass concentration is 2~3g/mL after being completely dissolved；Gained chitosan
30~50mL of solution is placed in 800~1000W micro-wave oven, takes out within microwave treatment 5~10 minutes, 30~50mL of distilled water is added,
Continue to obtain carbon dots/chitosan solution in stirring 10~12 hours；With 8000~10000 revs/min centrifugal treating 10~20 minutes,
Supernatant liquid is separated, carbon dots/chitosan complexes are obtained；
2) preparation of electrodeposit liquid: by the potassium permanganate solution of 0.1M~0.5M and gained carbon dots/chitosan complexes
It is mixed and mixes, obtain electrodeposit liquid；
3) electro-deposition techniques construct carbon dots/chitosan/manganese dioxide energy storage material: using foam nickel electrode as cathode, with platinum
Plate electrode is anode, applies 1.7~2.4V of constant voltage using high-precision programmable DC power supply and carries out electro-deposition, when electro-deposition
Between be 4~8 minutes；Cathode material is taken out, is deposited with carbon dots/chitosan/manganese dioxide deposition layer on cathode material at this time, is steamed
Distilled water is rinsed, and carbon dots/chitosan/manganese dioxide energy storage material is obtained after natural drying.
According to the above scheme, the volume ratio of potassium permanganate solution and the carbon dots/chitosan complexes is 1 in step 2:
(1.5-4)。
According to the above scheme, foam nickel electrode described in step 3 is 4~5 centimetres long, wide 1~2 centimetre of rectangle.
According to the above scheme, platinum plate electrode described in step 3 uses hydrochloric acid, acetone, distilled water flushing 3~5 using front surface respectively
It is secondary, then ultrasonic treatment is carried out 5~10 minutes with distilled water.
According to the above scheme, by below the cathode and anode insertion electrodeposit liquid liquid level 1~2 in step 3 electrodeposition process
Centimetre, adjusting distance between two electrodes is 1~2 centimetre.
Technical principle of the invention is that carbon dots/chitosan/titanium dioxide is prepared on foam nickel electrode using electro-deposition techniques
Carbon dots/chitosan complexes first mix as electro-deposition using certain proportion by manganese energy storage material with liquor potassic permanganate
Liquid, then carry out negative electrode electro-deposition on foam nickel electrode and construct carbon dots/chitosan/manganese dioxide energy storage material.Chitosan has
Good biocompatibility, biodegradability, it is from a wealth of sources and cheap the advantages that, also have unique pH stimuli responsive
Property sol-gel transition performance.Using the pH stimulating responsive sol-gel transition performance of chitosan, in electrodeposition process
Electrochemical cathode reaction can create certain pH gradient in nickel foam cathode surface, to can carry out on foam nickel electrode
Carbon dots/chitosan co-deposition；Potassium permanganate is a kind of oxidant simultaneously, it can carry out reduction reaction in cathode to generate
Manganese dioxide, these newly-generated manganese dioxide can be co-deposited together with carbon dots and chitosan and be formed on foam nickel electrode surface
Carbon dots/chitosan/manganese dioxide energy storage is prepared in carbon dots/chitosan/manganese dioxide deposition layer on foam nickel electrode
Material.
The beneficial effects of the present invention are:
1) present invention constructs carbon dots/chitosan/manganese dioxide energy storage material, this method preparation process using electro-deposition techniques
Convenient, the features such as condition is mild safely, environmentally protective, easy to operate, easily controllable, instrument and equipment is simple, at low cost and advantage.
2) carbon dots/chitosan/manganese dioxide energy storage material that the present invention constructs first prepares carbon dots/chitosan with microwave method
Compound, then electro-deposition is carried out as electrodeposit liquid using the mixed solution of itself and potassium permanganate.Carbon dots have hypotoxicity, and carbon dots
These good characteristics with unique chemical property, therefore carbon dots are all advantageous to its answering in energy storage material field
With.
3) for the present invention using in electrodeposition process, potassium permanganate is a kind of oxidant, can be restored in cathode
To generate manganese dioxide, these manganese dioxide generated can be co-deposited in nickel foam electricity together with carbon dots and chitosan for reaction
Pole surface forms carbon dots/chitosan/manganese dioxide energy storage material, because the method is simple, operation is convenient.
4) present invention constructs carbon dots/chitosan/manganese dioxide energy storage material, the electro-deposition utilized using electro-deposition techniques
Technology has many advantages, such as controllability and selective, easy to operate, mild condition, in electrodeposition process, with carbon dots/chitosan/
Liquor potassic permanganate is electrodeposit liquid, and entire electrodeposition process is safely controllable, and it is heavy to power in a short time in nickel foam
Product obtains carbon dots/chitosan/manganese dioxide energy storage material.
5) carbon dots/chitosan/manganese dioxide energy storage material constructed by the present invention improves electricity due to the effect of carbon dots
The specific capacitance of container has preferable efficiency for charge-discharge and specific capacitance.
Detailed description of the invention
Fig. 1: 1 gained carbon dots of embodiment/chitosan/manganese dioxide energy storage material；
Fig. 2: 1 gained carbon dots of embodiment/chitosan/manganese dioxide energy storage material constant current charge-discharge curve；
Fig. 3: 1 gained carbon dots of embodiment/chitosan/manganese dioxide energy storage material specific capacitance with cycle-index variation
Figure.
Specific embodiment
Following embodiment further illustrates technical solution of the present invention, but must limit not as to the scope of the present invention.
Carbon dots/chitosan/manganese dioxide energy storage material preparation method of the present invention is as follows:
1) carbon dots/chitosan complexes preparation: 2~6g chitosan solid powder is taken, is added in beaker, and inject
100~200mL distilled water carries out magnetic agitation about 24~72 hours, in speed drop of the process of stirring to drip each second 1~2
The acetum of 0.1M~0.5M is added to adjust pH, so that solution final pH is 5.3~5.7, chitosan obtains matter after being completely dissolved
Measure the solution that concentration is 2~3g/mL.Then, the configured chitosan solution of 30~50mL is taken, 800~1000W microwave is placed in
In furnace, 30~50mL distilled water is added in microwave treatment 5~after ten minutes take out product, is carried out magnetic agitation 10~12 hours.
Finally, carbon dots/the chitosan solution being sufficiently stirred is carried out centrifugal treating 10 with 8000~10000 revs/min of centrifugal speed
~20 minutes, supernatant liquid was taken after the completion, that is, carbon dots/chitosan complexes are prepared；
2) preparation of electrodeposit liquid: potassium permanganate 3.16~15.8g of solid is weighed, the distilled water of 100~200mL is added to
In, it stirs 15~30 minutes, obtains the liquor potassic permanganate of 0.1M~0.5M.2~4mL liquor potassic permanganate and 6~8mL is taken to walk
Carbon dots/chitosan complexes of rapid 1) preparation use magnetic agitation 10~20 minutes, are uniformly mixed, as electrodeposit liquid；
3) preparation of electrode material: foam nickel electrode cutting is grown into 4~5 centimetres, the rectangle that width is 1~2 centimetre is standby
With；Hydrochloric acid, acetone, distilled water flushing 3~5 times are used into platinum plate electrode surface respectively, then carries out ultrasonic treatment 5~10 with distilled water
Minute, it is spare；
4) electro-deposition techniques construct carbon dots/chitosan/manganese dioxide energy storage material: being yin with the nickel foam in step 3)
Pole, using platinized platinum as anode, by 1~2 centimetre below cathode and anode insertion electrodeposit liquid liquid level, adjusting distance between two electrodes is
1~2 centimetre, 1.7~2.4V of constant voltage is applied using high-precision programmable DC power supply and carries out electro-deposition, electrodeposition time is
4~8 minutes.Cathode nickel foam is taken out after the completion of electro-deposition, is deposited with carbon dots/chitosan/manganese dioxide in nickel foam at this time
Deposition layer carefully rinses the electrodeposit liquid of surface adhesion with distilled water, is prepared on foam nickel electrode after spontaneously drying
To carbon dots/chitosan/manganese dioxide energy storage material.It is again working electrode with this carbon dots/chitosan/manganese dioxide energy storage material,
Using three-electrode system, electrochemistry cyclic voltammetric, AC impedance and constant current charge-discharge test are carried out using electrochemical workstation, surveyed
Try the specific capacitance of capacitor, internal resistance, the performances such as coulombic efficiency.
Embodiment 1
1) carbon dots/chitosan complexes preparation: 2g chitosan solid powder is taken, is added in beaker, and inject 100mL
Distilled water carries out magnetic agitation about 72 hours, and the acetum tune of 0.1M is added dropwise with the speed dripped each second 1 in the process of stirring
PH is saved, so that solution final pH is 5.3, chitosan obtains the solution that mass concentration is 2g/mL after being completely dissolved.Then, it takes
The configured chitosan solution of 50mL, is placed in 800W micro-wave oven, and microwave treatment after five minutes takes out product, and 50mL is added
Distilled water carries out magnetic agitation 10 hours.Finally, by the carbon dots/chitosan solution being sufficiently stirred with 8000 revs/min of centrifugation
Speed carries out centrifugal treating 10 minutes, takes supernatant liquid after the completion, that is, carbon dots/chitosan complexes are prepared；
2) preparation of electrodeposit liquid: weighing potassium permanganate solid 3.16g, be added in the distilled water of 100mL, stirs 15 points
Clock obtains the liquor potassic permanganate of 0.1M.Carbon dots/the chitosan complexes for taking 2mL liquor potassic permanganate and 8mL step 1) to prepare
Using magnetic agitation 10 minutes, it is uniformly mixed, as electrodeposit liquid；
3) preparation of electrode material: foam nickel electrode cutting is grown into 4 centimetres, the rectangle that width is 1 centimetre is spare；It will
Hydrochloric acid, acetone, distilled water flushing 3 times are used in platinum plate electrode surface respectively, then carry out ultrasonic treatment 5 minutes with distilled water, spare；
4) electro-deposition techniques construct carbon dots/chitosan/manganese dioxide energy storage material: being yin with the nickel foam in step 3)
Pole, using platinized platinum as anode, by 1 centimetre below cathode and anode insertion electrodeposit liquid liquid level, adjusting distance between two electrodes is 1 li
Rice applies constant voltage 1.7V using high-precision programmable DC power supply and carries out electro-deposition, and electrodeposition time is 4 minutes.Electricity is heavy
Cathode nickel foam is taken out after the completion of product, carbon dots/chitosan/manganese dioxide deposition layer is deposited in nickel foam at this time, with steaming
Distilled water carefully rinses the deposition liquid of surface contamination, and carbon dots/chitosan/manganese dioxide energy storage material is obtained after spontaneously drying and is surveyed
It is 0.113g that amount, which is deposited with carbon dots/chitosan/manganese dioxide nickel foam quality,.Electricity is carried out using CHI electrochemical workstation
Chemical constant current charge-discharge test；Taking carbon dots/chitosan/manganese bioxide electrode material constructed in step 4) is working electrode,
It is that using Ag/AgCl electrode as reference electrode, using the metabisulfite solution of 0.1M as buffer solution, perseverance is done to electrode with platinum electrode
Charge-discharge test is flowed, setting cathode voltage, anode voltage are 0.001V, and initial polarity is set as anode, to utilize electrochemistry
Work station carries out constant current charge-discharge test to carbon dots/chitosan/manganese dioxide energy storage material.CHI electrochemical workstation is used again
500 above-mentioned constant current charge-discharge experiments are carried out continuously, its specific capacitance stability is tested.
Fig. 1 is carbon dots/chitosan/manganese dioxide energy storage material that the electro-deposition on foam nickel electrode of the present embodiment 1 obtains
(foam nickel electrode (left side) of electro-deposition is not carried out, electro-deposition carbon dots/chitosan/manganese dioxide energy storage material on foam nickel electrode
(right side)).From Fig. 1 it can be found that after carrying out electro-deposition in carbon dots/chitosan/potassium permanganate electrodeposit liquid, foam nickel electrode table
Face forms one layer of fairly obvious deposition layer.
Fig. 2 be carbon dots/chitosan/manganese dioxide energy storage material constant current charge-discharge curve constructed by the present embodiment 1 (a:
Compare the constant current charge-discharge curve of manganese dioxide energy storage material, b: carbon dots/chitosan/manganese dioxide energy storage material constant current charge and discharge
Electric curve).Specific testing procedure is: doing electrochemical time-measuring electric potential analysis test using CHI electrochemical workstation, takes electro-deposition
The foam nickel electrode (control manganese dioxide energy storage material) of manganese dioxide sedimentary is used as working electrode, is to electricity with platinum electrode
, using 0.1M sodium sulphate as buffer solution, constant current charge-discharge test, setting cathode electricity are done using Ag/AgCl electrode as reference electrode in pole
Pressure, anode voltage are 0.001V, measure to obtain curve a using electrochemical workstation；Take constructed carbon dots/shell poly-
Sugar/manganese dioxide energy storage material be working electrode, with platinum electrode be to electrode, using Ag/AgCl electrode as reference electrode, with
0.1M sodium sulphate is buffer solution, does constant current charge-discharge test, and setting cathode voltage, anode voltage are 0.001V, utilize electricity
Chem workstation measures to obtain curve b.From Fig. 2 it can be found that two electrodes all show linear voltage-time curve
With the charge flash-over characteristic of high degree of symmetry；Compared with compareing manganese dioxide energy storage material, carbon dots/chitosan/manganese dioxide energy storage
The discharge time of material is longer.In addition, by calculating it can be found that carbon dots/chitosan/manganese dioxide energy storage material specific capacitance
It is 375F/g when current density is 1A/g, and the value for compareing manganese dioxide energy storage material is 230F/g, this illustrates the present invention
Constructed carbon dots/chitosan/manganese dioxide energy storage material has preferable efficiency for charge-discharge and a specific capacitance, therefore the carbon dots/
Chitosan/manganese dioxide energy storage material has application prospect in energy and material and supercapacitor field.
Fig. 3 is carbon dots/chitosan/manganese dioxide energy storage material specific capacitance constructed by the present embodiment 1 with circulation time
Several variations.Specific testing procedure is: doing electrochemical time-measuring electric potential analysis test using CHI electrochemical workstation, takes constructed
Carbon dots/chitosan/manganese dioxide energy storage material be working electrode, be to electrode with platinum electrode, be ginseng with Ag/AgCl electrode
Than electrode, using 0.1M sodium sulphate as buffer solution, constant current charge-discharge test is done, setting cathode voltage, anode voltage are
0.001V loop test 500 times, is tested to obtain Fig. 3 using electrochemical operation.It can be found that carbon dots/chitosan/titanium dioxide
Manganese energy storage material shows good cyclical stability, can still keep its initial capacitance substantially after circulation 500 times,
This illustrates that carbon dots/chitosan/manganese dioxide energy storage material is with good stability.
Embodiment 2
1) carbon dots/chitosan complexes preparation: 6g chitosan solid powder is taken, is added in beaker, and inject 200mL
Distilled water carries out magnetic agitation about 24 hours, and the acetum tune of 0.5M is added dropwise with the speed dripped each second 2 in the process of stirring
PH is saved, so that solution final pH is 5.7, chitosan obtains the solution that mass concentration is 3g/mL after being completely dissolved.Then, it takes
The configured chitosan solution of 30mL, is placed in 1000W micro-wave oven, and microwave treatment after five minutes takes out product, and 30mL is added
Distilled water carries out magnetic agitation 12 hours.Finally, carbon dots/the chitosan solution being sufficiently stirred be put into being with centrifugal speed
It is centrifuged 20 minutes in 8000 revs/min of supercentrifuge, takes supernatant liquid after the completion, that is, carbon dots/chitosan is prepared
Compound；
2) preparation of electrodeposit liquid: weighing potassium permanganate solid 15.8g, be added in the distilled water of 100mL, stirs 30 points
Clock obtains the liquor potassic permanganate of 0.5M.Carbon dots/the chitosan complexes for taking 4mL liquor potassic permanganate and 6mL step 1) to prepare
Using magnetic agitation 20 minutes, it is uniformly mixed, as electrodeposit liquid；
3) preparation of electrode material: foam nickel electrode cutting is grown into 5 centimetres, width is 2 centimetres of rectangle, and measures bubble
The initial mass of foam nickel is 0.121g, spare；Hydrochloric acid, acetone, distilled water flushing 5 times are used into platinum plate electrode surface respectively, then is used
Distilled water carries out ultrasonic treatment 10 minutes, spare；
4) electro-deposition techniques construct carbon dots/chitosan/manganese dioxide energy storage material: using platinized platinum as anode, in step 3)
Nickel foam be cathode, by cathode and anode insertion electrodeposit liquid liquid level below 2 centimetres, adjust two electrodes between distance be 2 lis
Rice applies constant voltage 2.4V using high-precision programmable DC power supply and carries out electro-deposition, and electrodeposition time is 8 minutes.Electricity is heavy
Cathode nickel foam is taken out after the completion of product, carbon dots/chitosan/manganese dioxide deposition layer is deposited in nickel foam at this time, with steaming
Distilled water carefully rinses the deposition liquid of surface contamination, and carbon dots/chitosan/manganese dioxide electrode is obtained after spontaneously drying and is measured to sink
It is 0.123g that product, which has carbon dots/chitosan/manganese dioxide nickel foam quality,.Electrochemistry is carried out using CHI electrochemical workstation
Constant current charge-discharge test；Taking carbon dots/chitosan/manganese bioxide electrode material constructed in step 4) is working electrode, with platinum
Silk electrode is that electrode using Ag/AgCl electrode as reference electrode, using the metabisulfite solution of 0.1M as buffer solution, is done constant current and filled
Discharge test, setting cathode voltage, anode voltage are 0.002V, and initial polarity is set as anode, to utilize electrochemical operation
It stands and constant current charge-discharge test is carried out to carbon dots/chitosan/manganese dioxide supercapacitor.Connected again using CHI electrochemical workstation
It is continuous to carry out 500 above-mentioned constant current charge-discharge experiments, test its specific capacitance stability.
Embodiment 3
1) carbon dots/chitosan complexes preparation: 6g chitosan solid powder is taken, is added in beaker, and inject 200mL
Distilled water carries out magnetic agitation about 72 hours, and the acetum tune of 0.2M is added dropwise with the speed dripped each second 1 in the process of stirring
PH is saved, so that solution final pH is 5.5, chitosan obtains the solution that mass concentration is 3g/mL after being completely dissolved.Then, it takes
The configured chitosan solution of 50mL, is placed in 1000W micro-wave oven, and microwave treatment took out product after 8 minutes, and 30mL is added
Distilled water carries out magnetic agitation 12 hours.Finally, carbon dots/the chitosan solution being sufficiently stirred be put into being with centrifugal speed
It is centrifuged 10 minutes in 10000 revs/min of supercentrifuge, takes supernatant liquid after the completion, that is, carbon dots/chitosan is prepared
Compound；
2) preparation of electrodeposit liquid: weighing potassium permanganate solid 3.16, be added in the distilled water of 100mL, stirs 30 points
Clock obtains the liquor potassic permanganate of 0.1M.Carbon dots/the chitosan complexes for taking 2mL liquor potassic permanganate and 8mL step 1) to prepare
Using magnetic agitation 20 minutes, it is uniformly mixed, as electrodeposit liquid；
3) preparation of electrode material: foam nickel electrode cutting is grown into 4 centimetres, width is 1 centimetre of rectangle, and measures bubble
The initial mass of foam nickel is 0.101g, spare；Hydrochloric acid, acetone, distilled water flushing 3 times are used into platinum plate electrode surface respectively, then is used
Distilled water carries out ultrasonic treatment 6 minutes, spare；
4) electro-deposition techniques construct carbon dots/chitosan/manganese dioxide energy storage material: using platinized platinum as anode, in step 3)
Nickel foam be cathode, by cathode and anode insertion electrodeposit liquid liquid level below 2 centimetres, adjust two electrodes between distance be 1 li
Rice applies constant voltage 2.0V using high-precision programmable DC power supply and carries out electro-deposition, and electrodeposition time is 8 minutes.Electricity is heavy
Cathode nickel foam is taken out after the completion of product, carbon dots/chitosan/manganese dioxide deposition layer is deposited in nickel foam at this time, with steaming
Distilled water carefully rinses the deposition liquid of surface contamination, and carbon dots/chitosan/manganese dioxide electrode is obtained after spontaneously drying and is measured to sink
It is 0.103g that product, which has carbon dots/chitosan/manganese dioxide nickel foam quality,.Electrochemistry is carried out using CHI electrochemical workstation
Constant current charge-discharge test；Taking carbon dots/chitosan/manganese bioxide electrode material constructed in step 4) is working electrode, with platinum
Silk electrode is that electrode using Ag/AgCl electrode as reference electrode, using the metabisulfite solution of 0.1M as buffer solution, is done constant current and filled
Discharge test, setting cathode voltage, anode voltage are 0.002V, and initial polarity is set as anode, to utilize electrochemical operation
It stands and constant current charge-discharge test is carried out to carbon dots/chitosan/manganese dioxide supercapacitor.Connected again using CHI electrochemical workstation
It is continuous to carry out 500 above-mentioned constant current charge-discharge experiments, test its specific capacitance stability.
It should be noted that those skilled in the art should understand that, technical solution of the present invention can be carried out
Modification or equivalent replacement should all cover without departing from the objective and range of technical solution of the present invention in right of the invention
In claimed range.
Claims (6)
1. a kind of carbon dots/chitosan/manganese dioxide energy storage material, it is characterised in that with carbon dots/chitosan complexes and permanganic acid
Aqueous solutions of potassium mixing is used as electrodeposit liquid, prepares carbon dots/chitosan/dioxy on foam nickel electrode using negative electrode electro-deposition technology
Change manganese deposition layer, to directly obtain carbon dots/chitosan/manganese dioxide energy storage material on foam nickel electrode.
2. carbon dots/chitosan/manganese dioxide energy storage material preparation method described in claim 1, it is characterised in that including following
Step:
1) carbon dots/chitosan complexes preparation: chitosan solid powder is added in distilled water, simultaneously acetic acid is added in stirring and dissolving
PH value 5.3~5.7 is adjusted, the chitosan solution that mass concentration is 2~3g/mL is obtained after being completely dissolved；Gained chitosan solution
30~50mL is placed in 800~1000W micro-wave oven, takes out within microwave treatment 5~10 minutes, 30~50mL of distilled water is added, continue
Stirring obtains carbon dots/chitosan solution in 10~12 hours；With 8000~10000 revs/min centrifugal treating 10~20 minutes, separation
Supernatant liquid obtains carbon dots/chitosan complexes；
2) preparation of electrodeposit liquid: the potassium permanganate solution of 0.1M~0.5M is mixed with gained carbon dots/chitosan complexes
It stirs and evenly mixs, obtains electrodeposit liquid；
3) electro-deposition techniques construct carbon dots/chitosan/manganese dioxide energy storage material: using foam nickel electrode as cathode, with platinized platinum electricity
Extremely anode applies 1.7~2.4V of constant voltage using high-precision programmable DC power supply and carries out electro-deposition, and electrodeposition time is
4~8 minutes；Cathode material is taken out, is deposited with carbon dots/chitosan/manganese dioxide deposition layer, distilled water on cathode material at this time
It rinses, carbon dots/chitosan/manganese dioxide energy storage material is obtained after natural drying.
3. the preparation method of carbon dots/chitosan/manganese dioxide energy storage material as claimed in claim 2, it is characterised in that in step 2
The volume ratio of potassium permanganate solution and the carbon dots/chitosan complexes is 1:(1.5-4).
4. the preparation method of carbon dots/chitosan/manganese dioxide energy storage material as claimed in claim 2, it is characterised in that step 3 institute
Foam nickel electrode is stated as 4~5 centimetres of length, wide 1~2 centimetre of rectangle.
5. the preparation method of carbon dots/chitosan/manganese dioxide energy storage material as claimed in claim 2, it is characterised in that step 3 institute
It states platinum plate electrode and uses hydrochloric acid, acetone, distilled water flushing 3~5 times respectively using front surface, then carry out ultrasonic treatment 5 with distilled water
~10 minutes.
6. the preparation method of carbon dots/chitosan/manganese dioxide energy storage material as claimed in claim 2, it is characterised in that step 3 electricity
By 1~2 centimetre below the cathode and anode insertion electrodeposit liquid liquid level in deposition process, adjusting distance between two electrodes is 1
~2 centimetres.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709058A (en) * | 2012-07-01 | 2012-10-03 | 吉林大学 | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors |
| US20150069295A1 (en) * | 2013-09-09 | 2015-03-12 | National University Of Singapore | Hydrogel nanocomposite |
| CN105778906A (en) * | 2016-04-15 | 2016-07-20 | 哈尔滨工业大学 | Method for synthesizing metallic element in-situ doped fluorescence carbon dots deriving from chitosan biomass |
| CN108735525A (en) * | 2018-08-14 | 2018-11-02 | 武汉科技大学 | A kind of graphene/carbon point/manganese dioxide composite material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709058A (en) * | 2012-07-01 | 2012-10-03 | 吉林大学 | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors |
| US20150069295A1 (en) * | 2013-09-09 | 2015-03-12 | National University Of Singapore | Hydrogel nanocomposite |
| CN105778906A (en) * | 2016-04-15 | 2016-07-20 | 哈尔滨工业大学 | Method for synthesizing metallic element in-situ doped fluorescence carbon dots deriving from chitosan biomass |
| CN108735525A (en) * | 2018-08-14 | 2018-11-02 | 武汉科技大学 | A kind of graphene/carbon point/manganese dioxide composite material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111912890A (en) * | 2020-06-24 | 2020-11-10 | 西安理工大学 | Preparation method of carbon quantum dot/nano-silver modified foamed nickel electrode |
| CN111912890B (en) * | 2020-06-24 | 2022-08-12 | 西安理工大学 | Preparation method of carbon quantum dot/nano-silver modified foamed nickel electrode |
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