CN106449166A - Preparation method of super capacitor based on single-wall carbon nanotube/tungsten oxide nanowire composite film electrodes - Google Patents
Preparation method of super capacitor based on single-wall carbon nanotube/tungsten oxide nanowire composite film electrodes Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003990 capacitor Substances 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000002109 single walled nanotube Substances 0.000 title abstract description 7
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title abstract 3
- 239000002070 nanowire Substances 0.000 claims abstract description 61
- 239000000243 solution Substances 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 238000000967 suction filtration Methods 0.000 claims abstract description 11
- 229920000767 polyaniline Polymers 0.000 claims abstract description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 150000003657 tungsten Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract 2
- 239000006185 dispersion Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical group Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 15
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002114 nanocomposite Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- -1 allyl ester Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- ZRGUXTGDSGGHLR-UHFFFAOYSA-K aluminum;triperchlorate Chemical compound [Al+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZRGUXTGDSGGHLR-UHFFFAOYSA-K 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims 1
- 229910021393 carbon nanotube Inorganic materials 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 16
- 238000002156 mixing Methods 0.000 abstract description 9
- 239000007772 electrode material Substances 0.000 abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 40
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 25
- 239000000463 material Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005452 bending Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
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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
- H01G11/84—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)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
Abstract
The invention relates to a preparation method of a super capacitor based on single-wall carbon nanotube/tungsten oxide nanowire composite film electrodes. The preparation method includes: preparing the anhydrous ethanol precursor solution of tungsten salt and polyvinyl pyrrolidone under air atmosphere, performing reaction at 160-200 DEG C for 10-20 hours, cooling, centrifuging, washing, and dispersing to obtain W18O49 nanowire dispersing liquid; mixing the nanowire dispersing liquid with a single-wall carbon nanotube, performing suction filtration, washing, and drying to obtain the single-wall carbon nanotube/tungsten oxide nanowire composite film electrodes; using the composite film electrode as the cathode, using the single-wall carbon nanotube/polyaniline film as the anode, using an aluminum salt solution as electrolyte, and assembling to obtain the super capacitor. The preparation method has the advantages that compositing of electric double layer electrode materials and pseudocapacitor electrode materials at the micro-nano level is achieved, the prepared super capacitor is excellent in aluminum ion capacitance performance and extremely good in mechanical flexibility, and the application range of the super capacitor is further expanded.
Description
Technical field
The invention belongs to the preparation field of super capacitor film electrode, particularly to a kind of based on SWCN/
The ultracapacitor preparation method of tungsten oxide nano composite film electrode.
Background technology
Ultracapacitor as having the electrochemical energy storing device of application prospect to be widely studied most at present, according to electrochemistry
Energy storage principle is different, and the electrode material of ultracapacitor is divided into double layer electrodes material and fake capacitance electrode material.In general,
The electrical conductivity of double layer electrodes material is high, charge/discharge rates are fast, electrochemical stability is preferable, but capacitance is less.And counterfeit electricity
Hold the capacitive property of electrode material preferably, energy density is high, but have the shortcomings that charge-discharge velocity is relatively low, less stable.Therefore
By above two Material cladding, in conjunction with the advantage of the two, especially select nano material, be current grinding using its cooperative effect
Study carefully focus.
Solution containing monovalent cation being used as electrolyte ultracapacitor at present more, but these ion electrolyte
All there is fatal shortcoming, for example, highly acid hydrogen ion in electrochemical reaction process, to metal oxide-type fake capacitance material
Material corrosivity is strong, and the electrochemical stability often leading to such material is relatively low, and sodium ion or potassium ion are due to ionic radius
Larger, be difficult to be embedded into the inside of fake capacitance electrode material, thus lead to such capacitor capacitance extremely low.In recent years, base
Ultracapacitor in aluminium ion electrolyte is gradually favored by people, and this is primarily due to the relatively low ionic radius of aluminium ion
Lead to solid phase dynamics faster, the ion of high price embeds simultaneously needs more electronics to be neutralized, thus leading to carry at double
High ratio capacitive property.But series of problems is also had in production and application aspect based on aluminum ions ultracapacitor.
First, combination electrode material complicated process of preparation；Second, composite species is single, and micro-nano structure is unfavorable for that aluminium ion embeds,
Thus leading to capacitive property to be affected；3rd, assemble the ultracapacitor bending property difference obtaining it is impossible to meet emerging at present
Wearable device etc. requirement.
Content of the invention
The technical problem to be solved is to provide one kind to be based on SWCN/tungsten oxide nano THIN COMPOSITE
The ultracapacitor preparation method of membrane electrode, the method preparation process is simple, low cost, enable double layer electrodes material (single
Wall carbon nano tube) and fake capacitance electrode material (W18O49Nano wire) structure design on nano-level, make bi-material each
From advantage be not fully exerted, obtain excellent combination property based on aluminum ions ultracapacitor.
The present invention passes through the flexible SWCN/tungsten oxide W of simple efficiently method preparation18O49Nano wire is combined
Membrane electrode, and assemble the aluminium ion ultracapacitor obtaining high-performance high flexibility, there is very high Research Significance and business valency
Value.
A kind of ultracapacitor preparation based on SWCN/tungsten oxide nano composite film electrode of the present invention
Method, including：
(1), under air atmosphere, prepare the absolute ethyl alcohol precursor solution containing tungsten salt and polyvinylpyrrolidone, be transferred to
In water heating kettle, 160～200 DEG C of reaction 10～20h, naturally cool to room temperature, centrifugation, washing, dispersion, obtain W18O49Nano wire
Dispersion liquid；
(2) by the W in step (1)18O49Nanowire dispersion is sufficiently mixed with SWCN, suction filtration, washing, does
Dry, obtain flexible SWCN/W18O49Nano wire composite film electrode；
(3) by the SWCN/W in step (2)18O49Nano wire composite film electrode is received as negative electrode, single wall carbon
As anode, aluminum salt solution, as electrolyte, assembles, obtains based on SWCN/W mitron/polyaniline film18O49Receive
The flexible aluminium ion ultracapacitor of rice noodles composite film electrode.
In precursor solution in described step (1) concentration of tungsten salt be 0.2～1.2mg/ml, polyvinylpyrrolidone dense
Spend for 5～50 μ g/ml.
In described step (1), tungsten salt is tungsten hexachloride.
In the process for preparation of precursor solution in described step (1), ambient humidity is 20～70%.
W in described step (1)18O49The concentration of nanowire dispersion is 1～5mg/ml.
W in described step (1)18O49The solvent of nanowire dispersion is deionized water.
W in described step (2)18O49The mass ratio of nano wire and SWCN is 2:1～5:1.
In described step (3), the concentration of aluminum salt solution is 0.5～1.5mol/L.
Described aluminum salt solution is aluminium chloride, the carbonic allyl ester solution of aluminum sulfate, aluminum nitrate aqueous solution or aluminum perchlorate.
In described step (3), SWCN/polyaniline film is bibliography (ACS Nano, 2010,4,2445)
Prepare.
Beneficial effect
(1) preparation method of the present invention is simple, low cost, suitable large-scale production；
(2) present invention is by directly achieving both answering on nano-level by the method for both dispersion liquid mixing suction filtrations
Close, the nanometer line network with superior structural of formation, provide experiment for opening Novel super capacitor thin-film material further
And theoretical foundation；
(3) flexible SWCN/W that both dispersion liquid mixing, suction filtration are directly obtained by the present invention18O49Nano wire
Composite film electrode not only improves the SWCN deficiency less than electric capacity, also overcomes transition metal oxide simultaneously and follows
The shortcoming that ring stability is poor, power density is little, it is high that what assembling obtained has high electrochemistry based on aluminium ion ultracapacitor
Performance, is widely applied prospect in energy storage device field.
Brief description
Fig. 1 is the W of embodiment 1 preparation18O49The stereoscan photograph of nano wire；
Fig. 2 is the SWCN/W of embodiment 1 preparation18O49The stereoscan photograph of nano wire composite film electrode；
Fig. 3 is the SWCN/W of embodiment 1 preparation18O49Nano wire composite film electrode is molten in the aluminium chloride of 1M
Constant current charge-discharge curve in liquid；
Fig. 4 is the SWCN/W of embodiment 1 preparation18O49Nano wire composite film electrode is molten in the aluminium chloride of 1M
Capacity retention after repeatedly circulating in liquid；
The constant current charge-discharge of the aluminium ion ultracapacitor that Fig. 5 is assembled as electrolyte using the aluminium chloride of 1M for embodiment 1
Curve；
Ratio capacity retention under multiple bending condition for the aluminium ion ultracapacitor that Fig. 6 is assembled by embodiment 1.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
It is in 50% air ambient in humidity, polyvinylpyrrolidone and tungsten hexachloride are respectively put into ethanol solution
Middle stirring, obtains the precursor solution containing 7 μ g/ml polyvinylpyrrolidones and 0.75mg/ml tungsten hexachloride, solution is put
It is placed in water heating kettle, is incubated 18 hours in 180 DEG C, naturally cools to room temperature, add in deionized water after centrifuge washing, obtain
3mg/ml W18O49Nanowire dispersion.By the suspension containing 15mg SWCN and the above-mentioned W of 15ml18O49Nano wire divides
Dispersion liquid mixing, suction filtration, washing are dried to obtain SWCN/W18O49Nano wire flexible composite film electrode.By answering of obtaining
Close film as negative electrode, SWCN/polyaniline film as anode, 1mol/L aluminum chloride aqueous solution as electrolyte,
Assembling obtains aluminium ion ultracapacitor.Fig. 1 is the W of preparation18O49The stereoscan photograph of nano wire is it can be seen that W18O49Nanometer
Line has higher draw ratio, a diameter of 5nm～25nm.Fig. 2 is the SWCN/W of preparation18O49Nano wire THIN COMPOSITE
The stereoscan photograph of membrane electrode is it can be seen that CNT and W18O49Nano wire is intertwined to form network, and has multi-stage porous
Hole structure is it is ensured that good ion transmits and electro transfer.Fig. 3 is in 1mol/L liquor alumini chloridi, the single wall carbon of preparation
Nanotube/W18O49The constant current charge-discharge diagram of nano wire composite film electrode is it can be seen that composite film electrode has high area
Ratio electric capacity and have good discharge and recharge invertibity.Fig. 4 is the cyclical stability figure of composite film electrode it can be seen that combination electrode
There is high cyclical stability, Fig. 5 is the constant current of the aluminium ion ultracapacitor assembling as electrolyte using the aluminium chloride of 1M
Charging and discharging curve, it can be seen that prepared aluminium ion ultracapacitor has longer discharge time, illustrates that its higher energy is close
Degree.Fig. 6 ratio capacity retention under multiple bending condition by the aluminium ion ultracapacitor that assembled, illustrates that this aluminium ion surpasses
Level capacitor has high mechanical flexibility.
Embodiment 2
It is in 20% air ambient in humidity, polyvinylpyrrolidone and tungsten hexachloride are respectively put into ethanol solution
Middle stirring, obtains the precursor solution containing 7 μ g/ml polyvinylpyrrolidones and 0.2mg/ml tungsten hexachloride, solution is put
It is placed in water heating kettle, is incubated 18 hours in 160 DEG C, naturally cools to room temperature, add in deionized water after centrifuge washing, obtain
3mg/ml W18O49Nanowire dispersion.By the suspension containing 15mg SWCN and the above-mentioned W of 15ml18O49Nano wire divides
Dispersion liquid mixing, suction filtration, washing are dried to obtain SWCN/W18O49Nano wire flexible composite film electrode.By answering of obtaining
Close film as negative electrode, SWCN/polyaniline film as anode, 1mol/L aluminum nitrate aqueous solution as electrolyte,
Assembling obtains aluminium ion ultracapacitor.Amount due to tungsten hexachloride in precursor solution significantly reduces, and and polyvinyl pyrrole
Alkanone mass ratio substantially reduces, and temperature retention time has reduced the W so that obtaining in addition18O49Nano wire is compared with embodiment 1
Average diameter substantially reduces；But due to SWCN suspension connection function so that obtain SWCN/
W18O49Nano wire composite film electrode still has good film forming, but slightly reduces than electric capacity, assembles the aluminium ion obtaining super
Capacitor power density is also declined slightly.
Embodiment 3
It is in 20% air ambient in humidity, polyvinylpyrrolidone and tungsten hexachloride are respectively put into ethanol solution
Middle stirring, obtains the precursor solution containing 5 μ g/ml polyvinylpyrrolidones and 1.2mg/ml tungsten hexachloride, solution is put
It is placed in water heating kettle, is incubated 18 hours in 180 DEG C, naturally cools to room temperature, add in deionized water after centrifuge washing, obtain
5mg/ml W18O49Nanowire dispersion.By the suspension containing 10mg SWCN and the above-mentioned W of 10ml18O49Nano wire divides
Dispersion liquid mixing, suction filtration, washing are dried to obtain SWCN/W18O49Nano wire flexible composite film electrode.By answering of obtaining
Close film as negative electrode, as anode, 0.5mol/L aluminum nitrate aqueous solution is as electrolysis for SWCN/polyaniline film
Liquid, assembling obtains aluminium ion ultracapacitor.Amount due to tungsten hexachloride in precursor solution increased, and with polyethylene pyrrole
Pyrrolidone mass ratio improves, the W obtaining18O49Nano wire average diameter compared with embodiment 1 slightly increases, and draw ratio is obvious
Reduce, thus the nanometer line network resulting in is flexible declining, the electricity in multiple BENDING PROCESS of aluminium ion ultracapacitor
Hold conservation rate to decline；Due to W in mixed liquor18O49Nano wire is improved a lot with SWCN mass ratio, reduces film
Whole conductivity, simultaneously because W18O49Nanowire diameter slightly increases, draw ratio reduces, and leads to active material specific surface area
Reduce, so that it slightly reduces than electric capacity and embodiment 1, simultaneously because the reduction of concentration of electrolyte, aluminium ion super capacitor
Device power density is also declined slightly.
Embodiment 4
It is in 70% air ambient in humidity, polyvinylpyrrolidone and tungsten hexachloride are respectively put into ethanol solution
Middle stirring, obtains the precursor solution containing 50 μ g/ml polyvinylpyrrolidones and 1.2mg/ml tungsten hexachloride, solution is put
It is placed in water heating kettle, is incubated 18 hours in 160 DEG C, naturally cools to room temperature, add in deionized water after centrifuge washing, obtain
5mg/ml W18O49Nanowire dispersion.By the suspension containing 10mg SWCN and the above-mentioned W of 10ml18O49Nano wire divides
Dispersion liquid mixing, suction filtration, washing are dried to obtain SWCN/W18O49Nano wire flexible composite film electrode.By answering of obtaining
Close film as negative electrode, as anode, 0.5mol/L aluminum sulfate aqueous solution is as electrolysis for SWCN/polyaniline film
Liquid, assembling obtains aluminium ion ultracapacitor.Due in precursor solution tungsten hexachloride amount showed increased so as to get W18O49
Nano wire average diameter compared with embodiment 1 increased, simultaneously because the raising of polyvinylpyrrolidone amount, causes
W18O49Nanowire surface has wrapped up excessive macromolecule, is unfavorable for electric transmission；Due to W in mixed liquor18O49Nano wire and single wall
Carbon nanotube mass ratio increases so that SWCN compound quantity is less, and composite film electrode electric conductivity declines, electronics
Transmission is obstructed, and causes SWCN/W18O49Nano wire laminated film capacitive character is poor, aluminium ion ultracapacitor power
Density is also declined slightly.
Embodiment 5
It is in 50% air ambient in humidity, polyvinylpyrrolidone and tungsten hexachloride are respectively put into ethanol solution
Middle stirring, obtains the precursor solution containing 5 μ g/ml polyvinylpyrrolidones and 0.75mg/ml tungsten hexachloride, solution is put
It is placed in water heating kettle, is incubated 10 hours in 160 DEG C, naturally cools to room temperature, add in deionized water after centrifuge washing, obtain
5mg/ml W18O49Nanowire dispersion.By the suspension containing 25mg SWCN and the above-mentioned W of 10ml18O49Nano wire divides
Dispersion liquid mixing, suction filtration, washing are dried to obtain SWCN/W18O49Nano wire flexible composite film electrode.By answering of obtaining
Close film as negative electrode, as anode, the propene carbonate of 1.5mol/L aluminum perchlorate is molten for SWCN/polyaniline film
Liquid obtains aluminium ion ultracapacitor as electrolyte, assembling.In precursor solution, the minimizing of polyvinylpyrrolidone amount makes
The one-dimensional growth of nano wire is obstructed, therefore the W obtaining18O49Nano wire average diameter compared with embodiment 1 slightly improves, and also leads
The mechanical stability causing aluminium ion ultracapacitor declines；Due to W in mixed liquor18O49Nano wire and the matter of SWCN
Amount reduces than, and it is slightly below embodiment 1 than electric capacity, and aluminium ion ultracapacitor power density is also declined slightly.
Embodiment 6
It is in 70% air ambient in humidity, polyvinylpyrrolidone and tungsten hexachloride are respectively put into ethanol solution
Middle stirring, obtains the precursor solution containing 50 μ g/ml polyvinylpyrrolidones and 0.2mg/ml tungsten hexachloride, solution is put
It is placed in water heating kettle, is incubated 20 hours in 200 DEG C, naturally cools to room temperature, add in deionized water after centrifuge washing, obtain
5mg/ml W18O49Nanowire dispersion.By the suspension containing 25mg SWCN and the above-mentioned W of 10ml18O49Nano wire divides
Dispersion liquid mixing, suction filtration, washing are dried to obtain SWCN/W18O49Nano wire flexible composite film electrode.By answering of obtaining
Close film as negative electrode, SWCN/polyaniline film as anode, 1mol/L aluminum chloride aqueous solution as electrolyte,
Assembling obtains aluminium ion ultracapacitor.Although precursor solution has fraction to hydrolyze, due to leading as structure under high humility
To effect polyvinylpyrrolidone amount improve so as to get W18O49Nano wire average diameter phase compared with embodiment 1
Seemingly, but nanowire surface has more polymeric PTC materials, electric transmission is obstructed, thus leading to SWCN/W18O49Nano wire
The ratio electric capacity of flexible composite film electrode is less than embodiment 1, and aluminium ion ultracapacitor power density is also declined slightly.
Claims (9)
1. a kind of ultracapacitor preparation method based on SWCN/tungsten oxide nano composite film electrode, including：
(1) under air atmosphere, the absolute ethyl alcohol precursor solution containing tungsten salt and polyvinylpyrrolidone for the preparation, 160～200 DEG C
Reaction 10～20h, cooling, centrifugation, washing, dispersion, obtain tungsten oxide W18O49Nanowire dispersion；
(2) by the W in step (1)18O49Nanowire dispersion is mixed with SWCN, suction filtration, washing, is dried, obtains list
Wall carbon nano tube/W18O49Nano wire composite film electrode；
(3) by the SWCN/W in step (2)18O49Nano wire composite film electrode as negative electrode, SWCN/
As anode, aluminum salt solution, as electrolyte, assembles, obtains based on SWCN/W polyaniline film18O49Nano wire is multiple
Close the ultracapacitor of membrane electrode.
2. according to claim 1 a kind of super based on SWCN/tungsten oxide nano composite film electrode
Method of preparing capacitor it is characterised in that in precursor solution in described step (1) tungsten salt concentration be 0.2～1.2mg/ml,
The concentration of polyvinylpyrrolidone is 5～50 μ g/ml.
3. according to claim 2 a kind of super based on SWCN/tungsten oxide nano composite film electrode
Method of preparing capacitor is it is characterised in that described tungsten salt is tungsten hexachloride.
4. according to claim 1 a kind of super based on SWCN/tungsten oxide nano composite film electrode
Method of preparing capacitor it is characterised in that in the process for preparation of precursor solution in described step (1) ambient humidity be 20～
70%.
5. according to claim 1 a kind of super based on SWCN/tungsten oxide nano composite film electrode
Method of preparing capacitor is it is characterised in that W in described step (1)18O49The concentration of nanowire dispersion is 1～5mg/ml.
6. according to claim 1 a kind of super based on SWCN/tungsten oxide nano composite film electrode
Method of preparing capacitor is it is characterised in that W in described step (1)18O49The solvent of nanowire dispersion is deionized water.
7. according to claim 1 a kind of super based on SWCN/tungsten oxide nano composite film electrode
Method of preparing capacitor is it is characterised in that W in described step (2)18O49The mass ratio of nano wire and SWCN is 2:1
～5:1.
8. according to claim 1 a kind of super based on SWCN/tungsten oxide nano composite film electrode
Method of preparing capacitor it is characterised in that in described step (3) aluminum salt solution concentration be 0.5～1.5mol/L.
9. according to claim 8 a kind of super based on SWCN/tungsten oxide nano composite film electrode
Method of preparing capacitor is it is characterised in that described aluminum salt solution is aluminium chloride, aluminum sulfate, aluminum nitrate aqueous solution or aluminum perchlorate
Carbonic allyl ester solution.
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| CN106847544B (en) * | 2017-03-10 | 2019-05-03 | 东华大学 | A kind of preparation method of high specific capacitance flexible super capacitor negative electrode material |
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| CN110967887A (en) * | 2018-09-30 | 2020-04-07 | 马亮 | Electrochromic film and preparation method thereof |
| CN109467128A (en) * | 2018-12-18 | 2019-03-15 | 吉林大学 | A kind of preparation method and applications of sea urchin shape tungstic acid electrode material |
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| CN110433869A (en) * | 2019-07-29 | 2019-11-12 | 华南理工大学 | A kind of Polyaniline-modified defect state W18O49Composite material and preparation method and application |
| CN112588286A (en) * | 2020-12-11 | 2021-04-02 | 江苏大学 | Preparation method and application of carbon nanotube modified molybdenum-doped tungsten oxide catalyst |
| CN112701268A (en) * | 2021-01-30 | 2021-04-23 | 江西理工大学 | Flexible integrated carbon-coated tungsten oxide/carbon nanotube film composite electrode and preparation method thereof |
| CN114130385A (en) * | 2021-11-12 | 2022-03-04 | 上海纳米技术及应用国家工程研究中心有限公司 | One-dimensional p-n heterojunction material with near-infrared photoelectric response and preparation method thereof |
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| CN115346803A (en) * | 2022-08-03 | 2022-11-15 | 昆明理工大学 | W 18 O 49 Carbon paper composite electrode material and preparation method thereof |
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