CN109192551A - A kind of preparation method of supercapacitor flexible electrode - Google Patents
A kind of preparation method of supercapacitor flexible electrode Download PDFInfo
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- CN109192551A CN109192551A CN201811078402.8A CN201811078402A CN109192551A CN 109192551 A CN109192551 A CN 109192551A CN 201811078402 A CN201811078402 A CN 201811078402A CN 109192551 A CN109192551 A CN 109192551A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 31
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 30
- 239000005539 carbonized material Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 23
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005266 casting Methods 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 21
- 108010010803 Gelatin Proteins 0.000 claims abstract description 16
- 229920000159 gelatin Polymers 0.000 claims abstract description 16
- 239000008273 gelatin Substances 0.000 claims abstract description 16
- 235000019322 gelatine Nutrition 0.000 claims abstract description 16
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000011812 mixed powder Substances 0.000 claims abstract description 16
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 8
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 7
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 230000008961 swelling Effects 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- 239000013049 sediment Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 230000002035 prolonged effect Effects 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 235000010980 cellulose Nutrition 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000002687 intercalation Effects 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 239000003990 capacitor Substances 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- H01G11/84—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
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
-
- 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)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of preparation methods of supercapacitor flexible electrode, belong to novel energy resource material technology field.Microcrystalline cellulose and gelatin are first mixed and are dispersed in water by the present invention; after swelling, vacuum freeze drying, grinding; mixed-powder is made; slowly heating charing under inert gas shielding state by it again, obtains carbonized material, is then dispersed in water carbonized material, zinc acrylate resin and two-dimensional layer barium oxide; again after casting film-forming; with ultraviolet light, with after annealing to get supercapacitor flexible electrode；Wherein, two-dimensional layer barium oxide then is obtained with lithium chloride intercalation by after ammonium metavanadate and oxalic acid solution reaction.
Description
Technical field
The invention discloses a kind of preparation methods of supercapacitor flexible electrode, belong to novel energy resource material technology neck
Domain.
Background technique
Supercapacitor, also referred to as electrochemical capacitor are a kind of important energy storage devices occurred in recent years, it is situated between
Between traditional capacitor and lithium ion battery, key effect is played in terms of combining the two advantage and compares traditional capacitor, is surpassed
The specific energy density of grade capacitor will be several orders of magnitude higher, and have higher capacitance；And compared with battery, super capacitor
The unique charge storage mechanism of device allows to a large amount of charge of storage or transmission in a short period of time, thus can produce more
High power density has the characteristics that the charging time is short, charge efficiency is high, service life cycle is long and substantially without maintenance.
Compared with traditional supercapacitor, emerging flexible super capacitor equally shows good chemical property, and has
The advantages that high power density and good cycling stability, the flexibility on mechanics also extend its application range, set such as wearable
There is potential application in many fields such as standby, biological implant system.The most important part of flexible super capacitor is flexible electrode
The selection of material, researcher have paid many effort in terms of preparing flexible electrode, also achieve good progress.And now
Preparing, there is the flexible electrode of strong mechanical performance and good chemical property still to face many challenges, and metal class electrode is easily by water
It is electrolyte erosion and the flexible design and preparation for focusing on non-metal electrode material that be general, therefore studying.Wherein, carbon
The fast development of nano material makes it have many development potentialities in terms of preparing flexible electrode with excellent mechanical performance, from zero dimension
Carbon nano-particle, one-dimensional carbon nanotube to two-dimensional graphene, various types of other carbon material, which all has, prepares the potential of electrode
Advantage.Since most carbon electrodes are all limited by factors such as specific surface area, pore-size distributions, it is therefore desirable to study novel carbon substrate
Material is to obtain better performance, such as graded porous structure, two-dimensional structure, high-specific surface area, hetero atom modification and high conductance
Rate etc..In view of the factors such as feasibility and easy availability, it is necessary to further explore the carbon-based energy of synthesizing new of high-efficient simple
The method for storing equipment.
And conventional Super capacitor flexible electrode is defeated and dispersed there is also being easy to be corroded by water system electrolyte, and in use process
The drawbacks of intermediate ion transmission rate and substance diffusion path cause the chemical property of product not promoted further.Therefore, such as
What improves the shortcomings that conventional Super capacitor flexible electrode, is that it is promoted and application to obtain the promotion of more high combination property
In broader field, meet industrial production demand urgent problem to be solved.
Summary of the invention
The present invention solves the technical problem of: it is easy to be electrolysed by water system for conventional Super capacitor electrode material
Matter corrodes defeated and dispersed, and ion transportation and substance diffusion path cause the chemical property of product can not be into use
The drawbacks of one step is promoted, provides a kind of preparation method of supercapacitor flexible electrode.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of supercapacitor flexible electrode, specific preparation step are as follows:
(1) according to parts by weight, 10~20 parts of microcrystalline celluloses, 3~5 parts of gelatin, 100~150 parts of water, first by crystallite are successively taken
Cellulose and gelatin are poured into water, and swelling is stood after being stirred, then through vacuum freeze drying, grinding obtains mixed-powder；
(2) by mixed-powder under inert gas shielding state, slowly heating charing, cools to room temperature with the furnace, obtains carbonized material；
(3) according to parts by weight, 40~60 parts of carbonized materials, 3~5 parts of zinc acrylate resins, 4~6 parts of two-dimensional layer vanadium oxidations are successively taken
Carbonized material, zinc acrylate resin and two-dimensional layer barium oxide are first dispersed in water by object, 100~200 parts of water, then through casting film-forming
Afterwards, with ultraviolet light, with after annealing to get supercapacitor flexible electrode.
Step (1) described microcrystalline cellulose is the microcrystalline cellulose that levelling off degree of polymerization is 120~150.
Step (2) inert gas is any one in nitrogen, argon gas or helium.
Step (2) the slow heating charing are as follows: be warming up to 800~900 DEG C with 0.6~0.8 DEG C/min rate program.
The preparation process of step (3) the two-dimensional layer barium oxide are as follows: by ammonium metavanadate and water be in mass ratio 1:100
After~1:120 is stirred, 0.1~0.2 times of water quality of oxalic acid solution is added, cooling after heating stirring reaction, centrifugation point
From, collect lower sediment thing, then by gained lower sediment thing and water be in mass ratio 1:10~1:20 mix after, ultrasonic disperse,
Dispersion liquid is obtained, then 0.3~0.5 times of lower sediment amount of substance of lithium chloride is added into dispersion liquid, after being stirred, filters, washes
It washs, it is dry, obtain two-dimensional layer barium oxide.
Step (3) described ultraviolet light are as follows: use wavelength for the ultraviolet light prolonged exposure 30 of 260~280nm~
50min。
Step (3) described annealing are as follows: under the conditions of temperature is 150~160 DEG C, anneal 25~30min.
The beneficial effects of the present invention are:
(1) technical solution of the present invention is by introducing the polyacrylic acid crosslinked network system, in the pore structure of product flexibility electrode
Defect sturcture be passivated, after defect obtains passivation, can be conducive to interiors of products ion transmission and substance diffusion, effectively drop
Low diffusional resistance；In addition, the introducing of polyacrylic acid zinc cross-linked network system, may make flexible electrode film forming more fine and close, is producing
During product storage, the erosion of the water, oxygen in air can be effectively prevented, the storage stability of product is enhanced, and in use process
In, it can effectively prevent water system electrolyte to the erosion of electrode, make product that can remain preferable electricity in the long-term use
Chemical property and mechanical property；
(2) technical solution of the present invention is by using microcrystalline cellulose and gelatin as carbon source, in carbonization process, in carbonized material structure
Effective Doping nitrogen, the presence of nitrogen-atoms can enhance the transmittability of product ion, provide active site, bring hole can
To increase the performance of adsorption charge, the chemical property of product is promoted, in addition, the present invention passes through addition two-dimensional layer vanadium oxidation
Object, two-dimensional layered structure can provide active site, and the channel as ion fast exchange for ion, and barium oxide is certainly
Body charge transfer efficiency with higher, furthermore, the application using lithium chloride by effectively widening its two dimension during the preparation process
The interlamellar spacing of layer structure widens ion exchange channels and charge transmission channel effectively, obtains the chemical property of product
Further promoted.
Specific embodiment
According to parts by weight, 10~20 parts of microcrystalline celluloses are successively taken, 3~5 parts of gelatin, 100~150 parts of water first will be micro-
Crystalline cellulose, gelatin and water mixing are poured into beaker, after being stirred 10~20min with glass bar, in standing under room temperature
It is swollen 8~12h, then by after material vacuum freeze-drying in beaker, using liquid nitrogen as abrasive media, carries out freeze grinding, must mix
Powder；Gained mixed-powder is moved into tube furnace, inert gas is passed through into furnace with 80~120mL/min rate, in inertia
Under gas protection status, with the slow temperature programming of 0.6~0.8 DEG C/min rate to 800~900 DEG C, after 4~6h of heat preservation charing,
It cools to room temperature with the furnace, discharges, obtain carbonized material；It is in mass ratio that 1:100~1:120 pours into reaction kettle by ammonium metavanadate and water
In, after being stirred 45~60min with blender with 300~500r/min revolving speed, add water quality 0.1 in reaction kettle~
The oxalic acid solution that 0.2 times of mass fraction is 8~10%, it is then that reaction kettle is closed, it is 200~205 DEG C in temperature, stirring turns
Under the conditions of speed is 400~600r/min, heating stirring reacts 16~18h, to after reaction, cooled to room temperature, then will
Material is transferred in centrifuge in reaction kettle, is centrifugated 10~15min under the conditions of revolving speed is 8000~12000r/min, is collected
Lower sediment thing, then by gained lower sediment thing and deionized water be in mass ratio 1:10~1:20 mix pour into batch mixer,
Under the conditions of supersonic frequency is 55~65kHz, 45~60min of ultrasonic disperse obtains dispersion liquid, then lower layer is added into dispersion liquid and sinks
The lithium chloride that 0.3~0.5 times of starch quality after continuation is stirred 3~5h with 600~800r/min revolving speed, is filtered, must be filtered
Cake, and being washed with deionized filter cake 4~6 times, then the filter cake after washing is transferred in vacuum oven, in temperature be 105~
110 DEG C, under the conditions of pressure is 80~100Pa, it is dried under vacuum to constant weight, discharges, obtains two-dimensional layer barium oxide；In parts by weight
Meter successively takes 40~60 parts of carbonized materials, 3~5 parts of zinc acrylate resins, 4~6 parts of two-dimensional layer barium oxides, 100~200 parts of water, elder generation
Carbonized material, zinc acrylate resin and two-dimensional layer barium oxide are added to the water, with blender with the stirring of 800~1200r/min revolving speed
After dispersing 30~50min, standing and defoaming obtains into film liquid, then will be transferred in casting machine hopper at film liquid, adjusts casting machine scraper knife
Sawing is 0.6~0.8mm, after casting film-forming, after the 30~50min of ultraviolet light prolonged exposure for being 260~280nm with wavelength, and Yu Wen
25~30min of annealing, discharges to get supercapacitor flexible electrode under the conditions of degree is 150~160 DEG C.The microcrystalline cellulose
Element is the microcrystalline cellulose that levelling off degree of polymerization is 120~150.The inert gas is any one in nitrogen, argon gas or helium
Kind.
According to parts by weight, 20 parts of microcrystalline celluloses, 5 parts of gelatin, 150 parts of water, first by microcrystalline cellulose, gelatin are successively taken
It is poured into beaker with water mixing, after being stirred 20min with glass bar, is swollen 12h in standing under room temperature, then will be in beaker
After material vacuum freeze-drying, using liquid nitrogen as abrasive media, freeze grinding is carried out, mixed-powder is obtained；Gained mixed-powder is moved
Enter in tube furnace, inert gas is passed through into furnace with 120mL/min rate, under inert gas shielding state, with 0.8 DEG C/min
The slow temperature programming of rate after heat preservation charing 6h, cools to room temperature with the furnace, discharges, obtain carbonized material to 900 DEG C；By ammonium metavanadate
In mass ratio it is that 1:120 is poured into reaction kettle with water, after being stirred 60min with blender with 500r/min revolving speed, adds
In reaction kettle 0.2 times of water quality of mass fraction be 10% oxalic acid solution, it is then that reaction kettle is closed, in temperature be 205 DEG C,
Under the conditions of speed of agitator is 600r/min, heating stirring reacts 18h, to after reaction, cooled to room temperature, then will reaction
Material is transferred in centrifuge in kettle, is centrifugated 15min under the conditions of revolving speed is 12000r/min, is collected lower sediment thing, then
By gained lower sediment thing and deionized water be in mass ratio 1:20 mix pour into batch mixer, in supersonic frequency be 65kHz item
Under part, ultrasonic disperse 60min obtains dispersion liquid, then 0.5 times of lower sediment amount of substance of lithium chloride is added into dispersion liquid, continues
After being stirred 5h with 800r/min revolving speed, filters, obtain filter cake, and be washed with deionized filter cake 6 times, then by the filter after washing
Cake is transferred in vacuum oven, is 110 DEG C in temperature, under the conditions of pressure is 100Pa, is dried under vacuum to constant weight, discharges, obtain two-dimentional
Stratiform barium oxide；According to parts by weight, 60 parts of carbonized materials are successively taken, 5 parts of zinc acrylate resins, 6 parts of two-dimensional layer barium oxides,
Carbonized material, zinc acrylate resin and two-dimensional layer barium oxide are first added to the water by 200 parts of water, with blender with 1200r/min revolving speed
After being dispersed with stirring 50min, standing and defoaming obtains into film liquid, then will be transferred in casting machine hopper at film liquid, adjusts casting machine scraper knife
Saw is 0.8mm, after casting film-forming, with wavelength be 280nm ultraviolet light prolonged exposure 50min after, under the conditions of temperature is 160 DEG C
Anneal 30min, discharges to get supercapacitor flexible electrode.The microcrystalline cellulose is the crystallite that levelling off degree of polymerization is 150
Cellulose.The inert gas is nitrogen.
According to parts by weight, 20 parts of microcrystalline celluloses are successively taken, microcrystalline cellulose and water are first mixed and poured by 150 parts of water
In beaker, after being stirred 20min with glass bar, it is swollen 12h in standing under room temperature, then material vacuum in beaker is freezed
After drying, using liquid nitrogen as abrasive media, freeze grinding is carried out, mixed-powder is obtained；Gained mixed-powder is moved into tube furnace, with
120mL/min rate is passed through inert gas into furnace, under inert gas shielding state, with the slow program of 0.8 DEG C/min rate
900 DEG C are warming up to, after heat preservation carbonizes 6h, cools to room temperature with the furnace, discharges, obtains carbonized material；In mass ratio by ammonium metavanadate and water
It is poured into reaction kettle for 1:120, after being stirred 60min with blender with 500r/min revolving speed, adds water quality in reaction kettle
The oxalic acid solution that the mass fraction of 0.2 times of amount is 10%, it is then that reaction kettle is closed, it is 205 DEG C in temperature, speed of agitator is
Under the conditions of 600r/min, heating stirring reacts 18h, to after reaction, cooled to room temperature, then material in reaction kettle is turned
Enter in centrifuge, be centrifugated 15min under the conditions of revolving speed is 12000r/min, collect lower sediment thing, then by gained lower layer
Sediment and deionized water are that 1:20 mixing is poured into batch mixer in mass ratio, under the conditions of supersonic frequency is 65kHz, ultrasound point
60min is dissipated, dispersion liquid is obtained, then 0.5 times of lower sediment amount of substance of lithium chloride is added into dispersion liquid, continues to turn with 800r/min
After speed is stirred 5h, filters, obtain filter cake, and be washed with deionized filter cake 6 times, then the filter cake after washing is transferred to vacuum and is done
In dry case, it is 110 DEG C in temperature, under the conditions of pressure is 100Pa, is dried under vacuum to constant weight, discharges, obtain the oxidation of two-dimensional layer vanadium
Object；According to parts by weight, 60 parts of carbonized materials are successively taken, 5 parts of zinc acrylate resins, 6 parts of two-dimensional layer barium oxides, 200 parts of water first will
Carbonized material, zinc acrylate resin and two-dimensional layer barium oxide are added to the water, and are dispersed with stirring with blender with 1200r/min revolving speed
After 50min, standing and defoaming obtains into film liquid, then will be transferred in casting machine hopper at film liquid, adjusts casting machine scraper knife saw and is
0.8mm, after casting film-forming, with wavelength be 280nm ultraviolet light prolonged exposure 50min after, anneal under the conditions of being 160 DEG C in temperature
30min discharges to get supercapacitor flexible electrode.The microcrystalline cellulose is the microcrystalline cellulose that levelling off degree of polymerization is 150
Element.The inert gas is nitrogen.
According to parts by weight, 20 parts of microcrystalline celluloses, 5 parts of gelatin, 150 parts of water, first by microcrystalline cellulose, gelatin are successively taken
It is poured into beaker with water mixing, after being stirred 20min with glass bar, is swollen 12h in standing under room temperature, then will be in beaker
After material vacuum freeze-drying, using liquid nitrogen as abrasive media, freeze grinding is carried out, mixed-powder is obtained；Gained mixed-powder is moved
Enter in tube furnace, inert gas is passed through into furnace with 120mL/min rate, under inert gas shielding state, with 0.8 DEG C/min
The slow temperature programming of rate after heat preservation charing 6h, cools to room temperature with the furnace, discharges, obtain carbonized material to 900 DEG C；By ammonium metavanadate
In mass ratio it is that 1:120 is poured into reaction kettle with water, after being stirred 60min with blender with 500r/min revolving speed, adds
In reaction kettle 0.2 times of water quality of mass fraction be 10% oxalic acid solution, it is then that reaction kettle is closed, in temperature be 205 DEG C,
Under the conditions of speed of agitator is 600r/min, heating stirring reacts 18h, to after reaction, cooled to room temperature, then will reaction
Material is transferred in centrifuge in kettle, is centrifugated 15min under the conditions of revolving speed is 12000r/min, is collected lower sediment thing, then
By gained lower sediment thing and deionized water be in mass ratio 1:20 mix pour into batch mixer, in supersonic frequency be 65kHz item
Under part, ultrasonic disperse 60min obtains dispersion liquid, then 0.5 times of lower sediment amount of substance of lithium chloride is added into dispersion liquid, continues
After being stirred 5h with 800r/min revolving speed, filters, obtain filter cake, and be washed with deionized filter cake 6 times, then by the filter after washing
Cake is transferred in vacuum oven, is 110 DEG C in temperature, under the conditions of pressure is 100Pa, is dried under vacuum to constant weight, discharges, obtain two-dimentional
Stratiform barium oxide；According to parts by weight, 60 parts of carbonized materials are successively taken, 6 parts of two-dimensional layer barium oxides, 200 parts of water first will
Carbonized material and two-dimensional layer barium oxide are added to the water, and after being dispersed with stirring 50min with blender with 1200r/min revolving speed, stand
Deaeration obtains into film liquid, then will be transferred in casting machine hopper at film liquid, and adjusting casting machine scraper knife saw is 0.8mm, casting film-forming
Afterwards, with wavelength be 280nm ultraviolet light prolonged exposure 50min after, anneal 30min under the conditions of being 160 DEG C in temperature, discharging, i.e.,
Obtain supercapacitor flexible electrode.The microcrystalline cellulose is the microcrystalline cellulose that levelling off degree of polymerization is 150.The indifferent gas
Body is nitrogen.
According to parts by weight, 20 parts of microcrystalline celluloses, 5 parts of gelatin, 150 parts of water, first by microcrystalline cellulose, gelatin are successively taken
It is poured into beaker with water mixing, after being stirred 20min with glass bar, is swollen 12h in standing under room temperature, then will be in beaker
After material vacuum freeze-drying, using liquid nitrogen as abrasive media, freeze grinding is carried out, mixed-powder is obtained；Gained mixed-powder is moved
Enter in tube furnace, inert gas is passed through into furnace with 120mL/min rate, under inert gas shielding state, with 0.8 DEG C/min
The slow temperature programming of rate after heat preservation charing 6h, cools to room temperature with the furnace, discharges, obtain carbonized material to 900 DEG C；In parts by weight
Meter, successively takes 60 parts of carbonized materials, 5 parts of zinc acrylate resins, carbonized material, zinc acrylate resin are first added to the water, use blender by 200 parts of water
After being dispersed with stirring 50min with 1200r/min revolving speed, standing and defoaming obtains into film liquid, then will be transferred in casting machine hopper at film liquid,
Adjusting casting machine scraper knife saw is 0.8mm, after casting film-forming, with wavelength be 280nm ultraviolet light prolonged exposure 50min after, in
Temperature is annealed 30min under the conditions of being 160 DEG C, is discharged to get supercapacitor flexible electrode.The microcrystalline cellulose is the limit
The microcrystalline cellulose that the degree of polymerization is 150.The inert gas is nitrogen.
According to parts by weight, 20 parts of microcrystalline celluloses, 5 parts of gelatin, 150 parts of water, first by microcrystalline cellulose, gelatin are successively taken
It is poured into beaker with water mixing, after being stirred 20min with glass bar, is swollen 12h in standing under room temperature, then will be in beaker
After material vacuum freeze-drying, using liquid nitrogen as abrasive media, freeze grinding is carried out, mixed-powder is obtained；Gained mixed-powder is moved
Enter in tube furnace, inert gas is passed through into furnace with 120mL/min rate, under inert gas shielding state, with 0.8 DEG C/min
The slow temperature programming of rate after heat preservation charing 6h, cools to room temperature with the furnace, discharges, obtain carbonized material to 900 DEG C；In parts by weight
Meter, successively takes 60 parts of carbonized materials, 5 parts of zinc acrylate resins, 6 parts of vanadic anhydrides, 200 parts of water, first by carbonized material, zinc acrylate resin and five
V 2 O is added to the water, and after being dispersed with stirring 50min with blender with 1200r/min revolving speed, standing and defoaming obtains into film liquid, then
It will be transferred at film liquid in casting machine hopper, adjusting casting machine scraper knife saw is 0.8mm, is 280nm's with wavelength after casting film-forming
After ultraviolet light prolonged exposure 50min, anneal 30min under the conditions of being 160 DEG C in temperature, and discharging is to get supercapacitor flexibility
Electrode.The microcrystalline cellulose is the microcrystalline cellulose that levelling off degree of polymerization is 150.The inert gas is nitrogen.
Comparative example: the supercapacitor flexible electrode of Wuxi new material Co., Ltd production.
Example 1 to 5 resulting supercapacitor flexible electrical of example and comparative example product is subjected to performance detection, it is specific to examine
Survey method is as follows:
0.5~0V is set by potential window, sample itself weight is 12mg, surface area 0.5cm2, obtained different voltages
Current-voltage under sweep speed, with the increase of sweep speed, the area that figure surrounds is bigger, and the different scanning rates following figure
Shape is all approximate rectangular, illustrates the electrode that it is electric double layer capacitance working mechanism, and stability is good.
Specific testing result is as shown in table 1:
The 1 specific testing result of supercapacitor flexible electrode of table
| Detection project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example |
| Current density/mA/cm2 | 0.007 | 0.005 | 0.001 | -0.005 | -0.002 | -0.015 |
| Area specific capacitance/mF/cm2 | 245 | 231 | 227 | 223 | 176 | 85 |
By 1 testing result of table it is found that the supercapacitor of technical solution of the present invention preparation has excellent electrification with flexible electrode
Learn performance and can keep electrochemistry stability the characteristics of, in the development of novel energy resource material technology industry have it is wide before
Scape.
Claims (7)
1. a kind of preparation method of supercapacitor flexible electrode, it is characterised in that specific preparation step are as follows:
(1) according to parts by weight, 10~20 parts of microcrystalline celluloses, 3~5 parts of gelatin, 100~150 parts of water, first by crystallite are successively taken
Cellulose and gelatin are poured into water, and swelling is stood after being stirred, then through vacuum freeze drying, grinding obtains mixed-powder；
(2) by mixed-powder under inert gas shielding state, slowly heating charing, cools to room temperature with the furnace, obtains carbonized material；
(3) according to parts by weight, 40~60 parts of carbonized materials, 3~5 parts of zinc acrylate resins, 4~6 parts of two-dimensional layer vanadium oxidations are successively taken
Carbonized material, zinc acrylate resin and two-dimensional layer barium oxide are first dispersed in water by object, 100~200 parts of water, then through casting film-forming
Afterwards, with ultraviolet light, with after annealing to get supercapacitor flexible electrode.
2. a kind of preparation method of supercapacitor flexible electrode according to claim 1, it is characterised in that step (1)
The microcrystalline cellulose is the microcrystalline cellulose that levelling off degree of polymerization is 120~150.
3. a kind of preparation method of supercapacitor flexible electrode according to claim 1, it is characterised in that step (2)
The inert gas is any one in nitrogen, argon gas or helium.
4. a kind of preparation method of supercapacitor flexible electrode according to claim 1, it is characterised in that step (2)
The slow heating charing are as follows: be warming up to 800~900 DEG C with 0.6~0.8 DEG C/min rate program.
5. a kind of preparation method of supercapacitor flexible electrode according to claim 1, it is characterised in that step (3)
The preparation process of the two-dimensional layer barium oxide are as follows: by ammonium metavanadate and water be in mass ratio that 1:100~1:120 is stirred
Afterwards, 0.1~0.2 times of water quality of oxalic acid solution is added, cooling after heating stirring reaction, lower sediment is collected in centrifuge separation
Object, then by gained lower sediment thing and water be in mass ratio after 1:10~1:20 is mixed, ultrasonic disperse obtains dispersion liquid, then to point
0.3~0.5 times of lower sediment amount of substance of lithium chloride is added in dispersion liquid, after being stirred, filters, washs, it is dry, obtain two-dimensional layer
Shape barium oxide.
6. a kind of preparation method of supercapacitor flexible electrode according to claim 1, it is characterised in that step (3)
The ultraviolet light are as follows: use wavelength for 30~50min of ultraviolet light prolonged exposure of 260~280nm.
7. a kind of preparation method of supercapacitor flexible electrode according to claim 1, it is characterised in that step (3)
The annealing are as follows: under the conditions of temperature is 150~160 DEG C, anneal 25~30min.
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| CN104743540A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method for nitrogen-doped carbon material |
| CN107134373A (en) * | 2017-04-25 | 2017-09-05 | 武汉大学 | A kind of carbon aerogels/metal oxide composite and preparation method and application |
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| CN104743540A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method for nitrogen-doped carbon material |
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