CN110112004A - A kind of electrode of super capacitor composite material and preparation method - Google Patents
A kind of electrode of super capacitor composite material and preparation method Download PDFInfo
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- CN110112004A CN110112004A CN201910489348.4A CN201910489348A CN110112004A CN 110112004 A CN110112004 A CN 110112004A CN 201910489348 A CN201910489348 A CN 201910489348A CN 110112004 A CN110112004 A CN 110112004A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 239000003990 capacitor Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 95
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 45
- 239000002322 conducting polymer Substances 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 21
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011630 iodine Substances 0.000 claims abstract description 20
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229940006461 iodide ion Drugs 0.000 claims abstract description 13
- 229960000583 acetic acid Drugs 0.000 claims abstract description 11
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- WQBNIORIDCTSRY-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid nickel Chemical compound [Ni].OC(=O)c1cc(cc(c1)C(O)=O)C(O)=O WQBNIORIDCTSRY-UHFFFAOYSA-N 0.000 claims description 58
- 238000001704 evaporation Methods 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 230000008020 evaporation Effects 0.000 claims description 15
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000013110 organic ligand Substances 0.000 claims description 3
- 210000000988 bone and bone Anatomy 0.000 claims 2
- DHOBEDGRIOTEBA-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid;copper Chemical compound [Cu].OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 DHOBEDGRIOTEBA-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 6
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 41
- 239000000047 product Substances 0.000 description 40
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- 239000000843 powder Substances 0.000 description 28
- 235000019441 ethanol Nutrition 0.000 description 27
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 22
- 239000007772 electrode material Substances 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000010586 diagram Methods 0.000 description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 238000000967 suction filtration Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 12
- 239000012467 final product Substances 0.000 description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- 239000013259 porous coordination polymer Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012983 electrochemical energy storage Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- -1 carboxylic acid ion Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01G11/48—Conductive polymers
-
- 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)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
A kind of electrode of super capacitor composite material and preparation method, belongs to energy storage and switch technology field.Electrode composite material provided by the invention is metal organic framework compound and the nano lamellar material that the conducting polymer of in-situ polymerization is combined in the metal organic framework compound hole, and conducting polymer therein is adulterated by iodide ion and chloride ion or by iodide ion and acetate ion twice respectively.Present invention combination metal organic framework compound high-specific surface area, abundant reactivity site and conducting polymer advantage with good conductivity, using metal organic framework compound, conducting polymer, elemental iodine and hydrochloric acid or glacial acetic acid as raw material, conducting polymer monomer is evaporated to by metal organic framework compound using vapor mode, is then adulterated twice.Electrode composite material provided by the invention is used for electrode of super capacitor, has a characteristics such as capacity is big, energy-storage property is good, and stability is strong, and preparation process it is simple, it is at low cost, convenient for batch production.
Description
Technical field
The invention belongs to energy storage and switch technology field, and in particular to a kind of electrode of super capacitor composite material and its system
Preparation Method.
Background technique
Supercapacitor (supercapacitor, SC) is as a kind of new between traditional capacitor and rechargeable battery
Type energy storage device, power density are higher than rechargeable battery, meanwhile, there is efficiency for charge-discharge strong, long service life and environmental-friendly
Many advantages, such as.Although the research and development of electrode material for super capacitor has been achieved with remarkable break-throughs, currently used
The low specific surface area of electrode material and porosity inhibit directly contacting for active component and electrolyte, reduce electronics transfer and
Ion passes the ability of intelligence, is difficult to be promoted so as to cause the energy density and power density of electrode material.
Metal organic framework compound (Metal organoskeleton compounds, MOFs) system by metal ion with
The holey frame structure material that organic ligand is formed by coordination.Compared with traditional porous material, MOFs has
Various structures, porosity height, large specific surface area, hole hold the advantages that controllable, aperture surface area easy functionalization.In recent years, porous
MOFs and derivative are gradually applied to electrochemical energy storage field, such as lithium ion battery, fuel cell and supercapacitor.One
Aspect MOFs is intertwined type cellular structure with abundant, convenient for the transmission of electronics and ion；On the other hand, MOFs belongs to crystalline substance
State material, structure height is orderly, and active site is evenly dispersed, and exposed active site is conducive to participate in conversion process of energy, most
The promotion of SC electrochemical energy storage performance can be effectively realized eventually.Although the SC that MOFs is constructed has good electrochemical energy storage
Can, but MOFs self structure stability influence its energy storage and conversion art practical application.For this purpose, passing through MOFs at present
The composite S C constructed is orderly combined to provide effectively to promote the chemical property of electrode material with other electroactive substances
Approach.
And conducting polymer (Conductive polymer, CP) is a kind of important faraday pseudo-capacitance electrode material,
It has been generally acknowledged that during fast charging and discharging, the N-shaped or p-type doping and de- of Rapid reversible will do it in polymer conjugated chain
The redox reaction of doping.Wherein, p-type doping, that is, conjugated polymer chain of conducting polymer loses electronics, and in electrolyte
Anion may build up in polymer chain and realize charge balance；And the n-type doping of conducting polymer refers to polymer chain
The negative electrical charge of middle affluence realizes charge balance by the cation in electrolyte, so that the accumulation of positive ions in electrolyte is polymerizeing
In object chain.By above-mentioned redox reaction, makes polymer charge density with higher and generate the quasi- electricity of very high faraday
Hold, realizes the storage of charge." the Nanostructuration of PEDOT in that Benjamin Le Ouay et al. is delivered
Porous Coordination Polymers for Tunable Porosity and Conductivity " (" match porous
The adjustable port porosity of nano-structured PEDOT in the polymer of position and conductive Journal of Sex Research ") in disclose EDOT be first dissolved in ether
In, it is then evaporated in the hole of Porous coordination polymer (Porous Coordination Polymer, PCP), is recycled
EDOT oxidation polymerization in the hole PCP is formed PEDOT by iodine steam, to realize a kind of Porous coordination polymer (MOFs)/conduction
Polymer composites are constructed and (are detailed in the right column second segments of page 10088).Point out in this article simultaneously: PEDOT is as one
Kind of p-type semiconductor, its fermi level can due to oxidisability analyte presence and change, lead to conductivity surveys variation.
Exactly because this reason, PEDOT are usually used in NO2Chemoresistance detection.It follows that the porous coordination of this article building
With the influence of extraneous oxide isolation, electric conductivity changes very greatly polymer/conducting polymer composite material, special with air-sensitive
Property, suitable for the building of gas sensor, but its conductive stability is poor, can seriously affect the capacitor in electrochemistry cyclic process
Conservation rate is measured, therefore is not suitable as the electrode material of supercapacitor.
Summary of the invention
The purpose of the present invention is to overcome the deficiency in the prior art, provides a kind of electrode of super capacitor composite material and its system
Preparation Method, the composite material are used for electrode of super capacitor, have the characteristics such as capacity is big, energy-storage property is good, and stability is strong, and
Preparation process is simple, it is at low cost, convenient for batch production.
To achieve the above object, the present invention adopts the following technical scheme:
The present invention provides a kind of electrode of super capacitor composite material, which is characterized in that the electrode of super capacitor is multiple
Condensation material is metal organic framework compound and forms three-dimensional after in-situ polymerization in the metal organic framework compound hole
The nano lamellar material that network-like conducting polymer is combined, the conducting polymer respectively by iodide ion and chloride ion or
Person is adulterated twice by iodide ion and acetate ion.
Further, the metal organic framework compound is to be formed by metal ion and organic ligand by coordination
Holey frame structure material.
It is preferred that having carboxyl in the metal organic framework compound, organic match this is because carboxylic-containing acid
Body coordination ability is strong, and the MOFs skeleton structure of synthesis is stablized, and after sloughing smaller ligand, the hole left, which can stablize, is deposited
?.
As a kind of specific embodiment, the metal organic framework compound is trimesic acid nickel or equal benzene front three
Sour copper.
Further, the conducting polymer is PEDOT (polymer of EDOT (3,4-rthylene dioxythiophene monomer)), or
Person PPy (polypyrrole).
The present invention also provides a kind of preparation methods of electrode of super capacitor composite material, which is characterized in that including following
Step:
Step 1: conducting polymer monomer being evaporated to metal organic framework compound, obtains the first product；
Step 2: after the completion of the evaporation of conducting polymer monomer, continue to evaporate elemental iodine to first product, so that the
Oxidation polymerization generation conducting polymer occurs under elemental iodine initiation for conducting polymer monomer in one product, obtains the second product；
Step 3: after the completion of elemental iodine evaporation, continuing to evaporate hydrochloric acid or glacial acetic acid to second product, so that second
Iodide ion in product in conducting polymer is replaced by chloride ion or acetate ion, obtains third product；
Step 4: after the completion of hydrochloric acid or glacial acetic acid evaporation, obtained third product being dried, is so far made
Electrode of super capacitor composite material.
It further, include the preparation step of metal organic framework compound before the step 1.
As a kind of specific embodiment, including the preparation of trimesic acid nickel MOFs before the step 1, specifically
It operates as follows: Nickelous nitrate hexahydrate is completely dissolved in ml ethyl alcohol, then pour into trimesic acid thereto, stirring and dissolving,
The molar ratio of Nickelous nitrate hexahydrate and trimesic acid is 1~2: 3 in mixed solution；It is anti-that the mixed solution is transferred to ml later
It answers in kettle, is reacted 10~24 hours at 100~150 DEG C, suction filtration obtains solid powder, cleans the solid powder, and in 70
It is 8~24 hours dry at~120 DEG C, obtain product trimesic acid nickel MOFs.
Further, the operation of the step 1 to 4 carries out in closed environment.
Further, the step 2 and 3 it is combinable at a step carry out, i.e., after conducting polymer monomer evaporation after the completion of, after
Continuous evaporation elemental iodine and hydrochloric acid or elemental iodine and glacial acetic acid are to first product, so that conducting polymer list in the first product
Oxidation polymerization occurs under elemental iodine initiation and generates conducting polymer for body, and the iodide ion in conducting polymer by chloride ion or
Person's acetate ion replaces.
Further, metal organic framework compound and the molar ratio of conducting polymer monomer are 10: 1 in the step 1
~1: 5.
Further, evaporating temperature is 20 DEG C~30 DEG C in the step 1, and evaporation time is 3 hours~12 hours.
Further, the molar ratio of conducting polymer monomer and elemental iodine is 1: 10~2: 1 in the step 2.
Further, evaporating temperature is 60 DEG C~120 DEG C in the step 2, and evaporation time is 5 hours~12 hours.
Further, hydrochloric acid is concentrated hydrochloric acid in the step 3, and concentration range is 10~12mol/L.
Further, the mass ratio of conducting polymer monomer and concentrated hydrochloric acid is 1: 5~1: 20 in the step 3.
Further, the mass ratio of conducting polymer monomer and glacial acetic acid is 1: 5~2: 1 in the step 3.
Further, evaporating temperature is 60 DEG C~120 DEG C in the step 3, and evaporation time is 3 hours~12 hours.
Further, drying temperature is 60 DEG C~80 DEG C in the step 4, and drying time is 8 hours~12 hours.
Design of the invention is specific as follows:
It is found that it can be reversible by the specific surface area and raising faraday that increase electrode material according to supercapacitor principle
The probability of reaction improves the performance of supercapacitor, and the present invention selects metal organic framework compound (MOFs) and conducting polymer
Object (CP) constructs composite material, the former also provides higher specific surface area, Hou Zheke while providing surface-active site
Improve electric conductivity and specific capacity.But since the complex stabilities that iodine oxidation conducting polymer monomer polymerization generates are very poor, in sky
It can not be stabilized in gas,
For this purpose, the application propose it is a kind of elemental iodine by the hole MOFs monomer oxidation polymerize webbed CP on the basis of
Further using concentrated hydrochloric acid perhaps glacial acetic acid carry out gas phase doping by iodide ion and chloride ion or iodide ion and acetate from
Sub- front and back is adulterated twice, so that chloride ion or acetate ion replace in iodide ion insertion PEDOT conducting polymer, so not
The stability of CP only can be improved, but also can make Multilayer Network shape CP in concentrated hydrochloric acid gaseous environment, deposit slabbing.MOFs
Internal sheet CP can support MOFs to become the more stable sheet of structure, so that the electric conductivity of electrode composite material increases
By force, specific capacity improves, and the flaky nanometer structure generated staggeredly interconnects, and has stronger mechanical stability, can recycle
Electrode material is not easily disconnected from the process, keeps material structure stability, and there is good capacity to keep for cyclical stability enhancing
Rate.MOFs/CP electrode composite material provided by the invention can adjust according to actual needs elemental iodine oxidizing temperature and time and
Doped hydrochloride temperature and time, to control the pattern, ingredient and chemical property of product.
Compared with prior art, the invention has the benefit that
(1) super capacitor material provided by the invention has multi-stage nano laminated structure, large specific surface area and has
Reactivity site abundant shows good electrochemical energy storage performance, while having good electric conductivity and stronger leading
Electrical stability, be conducive to electrode material specific capacitance promotion and good capacity retention ratio, and nanometer sheet in composite material
Shape structure staggeredly interconnects, and has stronger mechanical stability, and electrode material is not easily disconnected from cyclic process, guarantees that structure is steady
It is fixed, it is also beneficial to good capacity retention ratio.
(2) MOFs/CP electrode composite material preparation process provided by the invention is simple, and raw material is cheap, and device dependence is low,
Exploitation suitable for industrialization large-scale production application.
Detailed description of the invention
Fig. 1 is the experimental provision schematic diagram of electrode material for super capacitor prepared by the embodiment of the present invention 1.
Fig. 2 is the IR figure of electrode material for super capacitor prepared by the embodiment of the present invention 1.
Fig. 3 is electrode material for super capacitor prepared by the embodiment of the present invention 1 and the SEM of pure trimesic acid nickel MOFs
Comparison diagram；Wherein figure (a) be it is not compound before microscopic appearance figure, figure (b) be it is compound after microscopic appearance figure.
Fig. 4 is the charge-discharge performance test chart of electrode material for super capacitor prepared by the embodiment of the present invention 1.
Fig. 5 is the cyclic voltammogram of electrode material for super capacitor prepared by the embodiment of the present invention 1.
Fig. 6 is the knot of the EIS test of electrode material for super capacitor prepared by the embodiment of the present invention 1 and pure MOFs material
Fruit comparison diagram.
Specific embodiment
In order to enable one of ordinary skill in the art can more understand the present invention program and principle, with reference to the accompanying drawing and have
Body embodiment is described in detail.The contents of the present invention are not limited to any specific embodiment, and also not representing is most preferred embodiment,
General substitution well-known to those skilled in the art is also encompassed within the scope of the invention.
Comparative example:
(1) preparation of trimesic acid nickel:
It prepares trimesic acid nickel MOFs: first 1.27g Nickelous nitrate hexahydrate being completely dissolved in 50ml ethyl alcohol, it is then past
Wherein pour into 0.513g trimesic acid, stirring and dissolving.Obtained solution is transferred in 100ml reaction kettle later, it is anti-at 150 DEG C
It answers 24 hours, suction filtration obtains solid powder and utilizes alcohol washes solid powder three times, is dried in vacuo 12 hours at 80 DEG C, obtains product
Trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.15g to be placed in diameter 50mm, aperture 0.22um
Filter paper on, and put and be placed in eminence, laboratory uses following Fig. 1 of schematic diagram of device, and 1ml EDOT is taken to be placed under it
It is square, it is fumigated 12 hours at 30 DEG C of room temperature；0.3g I is placed on the position of EDOT2, high-temperature oxydation 10 hours at 80 DEG C；Will
The product arrived is dried in vacuo 12 hours at 80 DEG C, and obtained product is done electro-chemical test.
Comparative example 1 only uses iodine oxidation preparation MOFs/CP compound, the stability of obtained MOFs/CP compound
It is very poor, it can especially be reflected in air by the color change of composite material, and can also be seen by chemical property variation
Out.MOFs/CP composite material is placed in air in comparative example, and the color of composite material can be become again originally by initial black
The dark green of MOFs, and according to CV test result, after composite material places 3~5 hours in air, in the electric current of 1A/g
Specific capacity drops to 500F/g by 800F/g under density, and capacitor specific capacity can reduce half；It then proceedes to place 5 hours, ratio
Capacity is only left 200F/g, finally substantially close to the capacity of MOFs itself.
Embodiment 1:
The present embodiment provides a kind of preparation methods of electrode of super capacitor composite material, specifically includes the following steps:
(1) preparation of trimesic acid nickel:
First 1.27g Nickelous nitrate hexahydrate is completely dissolved in 50ml ethyl alcohol, then pours into the equal benzene three of 0.513g thereto
Formic acid, stirring and dissolving；Obtained solution is transferred in 100ml reaction kettle later, is reacted 24 hours at 150 DEG C, suction filtration is consolidated
Body powder three times, is dried in vacuo 12 hours at 80 DEG C using alcohol washes solid powder, obtains product trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.15g to be placed in diameter 50mm, aperture 0.22um
Filter paper on, and put and be placed in eminence, laboratory uses following Fig. 1 of schematic diagram of device, and 1ml EDOT is taken to be placed under it
It is square, it is fumigated 12 hours at 30 DEG C of room temperature；0.3g I is placed on the position of EDOT2With 1ml glacial acetic acid；High-temperature oxydation 10 at 80 DEG C
Hour；Obtained product is dried in vacuo 12 hours at 80 DEG C, obtained product is done into electro-chemical test.
Fig. 2 is the IR analysis of the present embodiment composite material as a result, it will be seen that peak near 1640cm-1 therein
Represent PEDOT and adulterate later characteristic peak, and its 1616, at 1385 near peak represent matching for MOFs carboxylic acid ion
Body mode, it can thus be appreciated that MOFs and PEDOT compound success.
Electrode material for super capacitor prepared by the present invention possesses stronger mechanical stability, Fig. 3 compared to MOFs material
Show the microscopic appearance of pure MOFs and iodine, chlorine secondary doping, from Fig. 3, we can significantly see, not with conducting polymer
MOFs before object is compound is flower-shaped form, and it is compound after material there is the sheet MOFs of stacking and PEDOT to be staggeredly superimposed
Together, mechanical support intensity becomes stronger.Meanwhile it can be seen that from the GCD test result that Fig. 4 is provided, MOFs/CP composite wood
Material has even more still maintained certain capacity in 2.5A/g under high current density, and pure MOFs material is in the electricity of 2A/g or more
It is just dissolved in electrolyte under current density.
Electrode material for super capacitor prepared by the present invention has carried out secondary doping after I2 doping, from the test of Fig. 5
As a result it can be seen that, the specific capacity of electrode material for super capacitor prepared by the present invention is 356F/g when current density is 1A/g,
It is 200F/g when 1.5A/g, is 156.25F/g when 2A/g；Simple MOFs specific capacity only has 241F/g at 1A/g, works as electric current
When density is added to 2A/g or more, then its capacity is reduced to rapidly 0, illustrates that MOFs has been dissolved in electrolyte.As it can be seen that utilizing dense salt
After the secondary gas phase doping of acid, specific capacity is become stable.
In addition, by the EIS map analysis result shown in Fig. 6 it is found that electrode material prepared by the present invention, compared to simple
MOFs material, electrochemical contact impedance and reaction impedance will be much smaller, and the last present invention after circulation 1000 times, protect by capacity
Holdup is 70% or so, and the capacity retention ratio of pure MOFs only has 40%.
Embodiment 2:
(1) preparation of trimesic acid nickel:
First 1.27g Nickelous nitrate hexahydrate is completely dissolved in 50ml ethyl alcohol, then pours into the equal benzene three of 0.513g thereto
Formic acid, stirring and dissolving；Obtained solution is transferred in 100ml reaction kettle later, is reacted 24 hours at 150 DEG C, suction filtration is consolidated
Body powder three times, is dried in vacuo 12 hours at 80 DEG C using alcohol washes solid powder, obtains product trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.15g to be placed in diameter 50mm, aperture 0.22um
Filter paper on, and put and be placed in eminence, the following Fig. 1 of schematic diagram takes 1ml EDOT to be arranged below, and fumigates at 30 DEG C of room temperature
12 hours；0.3g I is placed on the position of EDOT2, high-temperature oxydation 10 hours at 100 DEG C；Then in I2It disposes the position of storing
The concentrated hydrochloric acid 1ml for putting 12mol/L is adulterated 10 hours at 80 DEG C；It will be dried in vacuo 12 hours at 80 DEG C of product obtained；Preparation
Obtain final product.
Embodiment 3:
(1) preparation of trimesic acid nickel:
First 1g Nickelous nitrate hexahydrate is completely dissolved in 50ml ethyl alcohol, then pours into 0.3g trimesic acid thereto,
Stirring and dissolving；Obtained solution is transferred in 100ml reaction kettle later, is reacted 12 hours at 150 DEG C, suction filtration obtains solid powder benefit
Three times with alcohol washes solid powder, it is dried in vacuo 12 hours at 80 DEG C, obtains product trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.15g to be placed in diameter 50mm, aperture 0.22um
Filter paper on, and put and be placed in eminence, the following Fig. 1 of schematic diagram takes 0.5ml EDOT to be arranged below, and smokes at 20 DEG C of room temperature
It steams 10 hours；0.3g I is placed on the position of EDOT2, high-temperature oxydation 8 hours at 90 DEG C；Then in I2It disposes the position of storing
The concentrated hydrochloric acid 0.5ml for putting 12mol/L is adulterated 10 hours at 70 DEG C；It will be dried in vacuo 10 hours at 80 DEG C of product obtained；System
It is standby to obtain final product.
Embodiment 4:
(1) preparation of trimesic acid nickel:
First 2g Nickelous nitrate hexahydrate is completely dissolved in 60ml ethyl alcohol, then pours into 0.78g trimesic acid thereto,
Stirring and dissolving；Obtained solution is transferred in 100ml reaction kettle later, is reacted 18 hours at 120 DEG C, suction filtration obtains solid powder benefit
Three times with alcohol washes solid powder, it is dried in vacuo 12 hours at 80 DEG C, obtains product trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.2g to be placed in diameter 50mm, aperture 0.22um's
It on filter paper, and is put and is placed in eminence, the following Fig. 1 of schematic diagram takes 0.8ml EDOT to be arranged below, and fumigates at 25 DEG C of room temperature
3 hours；0.3g I is placed on the position of EDOT2, high-temperature oxydation 6 hours at 100 DEG C；Then in I2The position disposition of storing is put
The concentrated hydrochloric acid 0.5ml of 12mol/L is adulterated 12 hours at 70 DEG C；It will be dried in vacuo 9 hours at 80 DEG C of product obtained；Preparation
Obtain final product.
Embodiment 5:
(1) preparation of trimesic acid nickel:
First 2g Nickelous nitrate hexahydrate is completely dissolved in 60ml ethyl alcohol, then pours into 0.78g trimesic acid thereto,
Stirring and dissolving；Obtained solution is transferred in 100ml reaction kettle later, is reacted 6 hours at 120 DEG C, suction filtration obtains solid powder benefit
Three times with alcohol washes solid powder, it is dried in vacuo 12 hours at 80 DEG C, obtains product trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.2g to be placed in diameter 50mm, aperture 0.22um's
It on filter paper, and is put and is placed in eminence, the following Fig. 1 of schematic diagram takes 0.8ml EDOT to be arranged below, and fumigates at 30 DEG C of room temperature
6 hours；0.2g I is placed on the position of EDOT2, high-temperature oxydation 12 hours at 80 DEG C；Then in I2The position disposition of storing is put
The concentrated hydrochloric acid 0.5ml of 12mol/L is adulterated 4 hours at 120 DEG C；It will be dried in vacuo 10 hours at 60 DEG C of product obtained；Preparation
Obtain final product.
Embodiment 6:
(1) preparation of trimesic acid nickel:
First 1.5g Nickelous nitrate hexahydrate is completely dissolved in 60ml ethyl alcohol, then pours into the equal benzene front three of 0.78g thereto
Acid, stirring and dissolving；Obtained solution is transferred in 100ml reaction kettle later, is reacted 6 hours at 150 DEG C, suction filtration obtains solid powder
Three times using alcohol washes solid powder, it is dried in vacuo 12 hours at 80 DEG C, obtains product trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.2g to be placed in diameter 50mm, aperture 0.22um's
It on filter paper, and is put and is placed in eminence, the following Fig. 1 of schematic diagram takes 0.8ml EDOT to be arranged below, and fumigates at 20 DEG C of room temperature
8 hours；0.25g I is placed on the position of EDOT2, high-temperature oxydation 6 hours at 120 DEG C；Then in I2The position disposition of storing is put
The concentrated hydrochloric acid 0.5ml of 12mol/L is adulterated 9 hours at 80 DEG C；It will be dried in vacuo 10 hours at 70 DEG C of product obtained；Preparation
Obtain final product.
Embodiment 7:
(1) preparation of trimesic acid nickel:
First 1.27g Nickelous nitrate hexahydrate is completely dissolved in 50ml ethyl alcohol, then pours into the equal benzene three of 0.513g thereto
Formic acid, stirring and dissolving；Obtained solution is transferred in 100ml reaction kettle later, is reacted 24 hours at 150 DEG C, suction filtration is consolidated
Body powder three times, is dried in vacuo 12 hours at 80 DEG C using alcohol washes solid powder, obtains product trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.15g to be placed in diameter 50mm, aperture 0.22um
Filter paper on, and put and be placed in eminence, the following Fig. 1 of schematic diagram takes 1ml EDOT to be arranged below, and fumigates at 30 DEG C of room temperature
12 hours；0.3g I is placed on the position of EDOT2, high-temperature oxydation 10 hours at 60 DEG C；Then in I2The position disposition of storing is put
The concentrated hydrochloric acid 1ml of 12mol/L is adulterated 10 hours at 80 DEG C；It will be dried in vacuo 12 hours at 80 DEG C of product obtained；It is prepared into
To final product.
Embodiment 8:
(1) preparation of trimesic acid nickel:
First 1.27g Nickelous nitrate hexahydrate is completely dissolved in 50ml ethyl alcohol, then pours into the equal benzene three of 0.513g thereto
Formic acid, stirring and dissolving；Obtained solution is transferred in 100ml reaction kettle later, is reacted 24 hours at 150 DEG C, suction filtration is consolidated
Body powder three times, is dried in vacuo 12 hours at 80 DEG C using alcohol washes solid powder, obtains product trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.15g to be placed in diameter 50mm, aperture 0.22um
Filter paper on, and put and be placed in eminence, the following Fig. 1 of schematic diagram takes 1ml EDOT to be arranged below, and fumigates at 30 DEG C of room temperature
12 hours；0.3g I is placed on the position of EDOT2, high-temperature oxydation 10 hours at 120 DEG C；Then in I2It disposes the position of storing
The concentrated hydrochloric acid 1ml for putting 12mol/L is adulterated 10 hours at 80 DEG C；It will be dried in vacuo 12 hours at 80 DEG C of product obtained；Preparation
Obtain final product.
Embodiment 9:
(1) preparation of trimesic acid nickel:
First 1.27g Nickelous nitrate hexahydrate is completely dissolved in 50ml ethyl alcohol, then pours into the equal benzene three of 0.513g thereto
Formic acid, stirring and dissolving；Obtained solution is transferred in 100ml reaction kettle later, is reacted 24 hours at 150 DEG C, suction filtration is consolidated
Body powder three times, is dried in vacuo 12 hours at 80 DEG C using alcohol washes solid powder, obtains product trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.15g to be placed in diameter 50mm, aperture 0.22um
Filter paper on, and put and be placed in eminence, the following Fig. 1 of schematic diagram takes 1ml EDOT to be arranged below, and fumigates at 30 DEG C of room temperature
12 hours；0.3g I is placed on the position of EDOT2, high-temperature oxydation 10 hours at 100 DEG C；Then it is disposed in the position that I2 is put
The concentrated hydrochloric acid 1ml for putting 12mol/L is adulterated 10 hours at 60 DEG C；It will be dried in vacuo 12 hours at 80 DEG C of product obtained；Preparation
Obtain final product.
Embodiment 10:
(1) preparation of trimesic acid nickel:
First 1.27g Nickelous nitrate hexahydrate is completely dissolved in 50ml ethyl alcohol, then pours into the equal benzene three of 0.513g thereto
Formic acid, stirring and dissolving；Obtained solution is transferred in 100ml reaction kettle later, is reacted 24 hours at 150 DEG C, suction filtration is consolidated
Body powder three times, is dried in vacuo 12 hours at 80 DEG C using alcohol washes solid powder, obtains product trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.15g to be placed in diameter 50mm, aperture 0.22um
Filter paper on, and put and be placed in eminence, the following Fig. 1 of schematic diagram takes 1ml EDOT to be arranged below, and fumigates at 30 DEG C of room temperature
12 hours；0.3g I is placed on the position of EDOT2, high-temperature oxydation 10 hours at 100 DEG C；Then it is disposed in the position that I2 is put
The concentrated hydrochloric acid 1ml for putting 12mol/L is adulterated 10 hours at 80 DEG C；It will be dried in vacuo 12 hours at 80 DEG C of product obtained；Preparation
Obtain final product.
Embodiment 11:
(1) preparation of trimesic acid nickel:
First 1.27g Nickelous nitrate hexahydrate is completely dissolved in 50ml ethyl alcohol, then pours into the equal benzene three of 0.513g thereto
Formic acid, stirring and dissolving；Obtained solution is transferred in 100ml reaction kettle later, is reacted 24 hours at 150 DEG C, suction filtration is consolidated
Body powder three times, is dried in vacuo 12 hours at 80 DEG C using alcohol washes solid powder, obtains product trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.15g to be placed in diameter 50mm, aperture 0.22um
Filter paper on, and put and be placed in eminence, the following Fig. 1 of schematic diagram takes 1ml EDOT to be arranged below, and fumigates at 30 DEG C of room temperature
3 hours；0.3g I is placed on the position of EDOT2, high-temperature oxydation 10 hours at 100 DEG C；Then it is disposed in the position that I2 is put
The concentrated hydrochloric acid 1ml for putting 12mol/L is adulterated 10 hours at 80 DEG C；It will be dried in vacuo 12 hours at 80 DEG C of product obtained；Preparation
Obtain final product.
Embodiment 12:
(1) preparation of trimesic acid nickel:
First 1.27g Nickelous nitrate hexahydrate is completely dissolved in 50ml ethyl alcohol, then pours into the equal benzene three of 0.513g thereto
Formic acid, stirring and dissolving；Obtained solution is transferred in 100ml reaction kettle later, is reacted 24 hours at 150 DEG C, suction filtration is consolidated
Body powder three times, is dried in vacuo 12 hours at 80 DEG C using alcohol washes solid powder, obtains product trimesic acid nickel MOFs；
(2) trimesic acid nickel/MOFs preparation:
In closed container, the trimesic acid nickel MOFs that will be obtained takes 0.15g to be placed in diameter 50mm, aperture 0.22um
Filter paper on, and put and be placed in eminence, the following Fig. 1 of schematic diagram takes 1ml EDOT to be arranged below, and fumigates at 30 DEG C of room temperature
6 hours；0.3g I is placed on the position of EDOT2, high-temperature oxydation 10 hours at 100 DEG C；Then it is disposed in the position that I2 is put
The concentrated hydrochloric acid 1ml for putting 12mol/L is adulterated 10 hours at 80 DEG C；It will be dried in vacuo 12 hours at 80 DEG C of product obtained；Preparation
Obtain final product.
Position on the position of EDOT on the position of EDOT on the position of EDOT on the position of EDOT in EDOT
On on the position of EDOT more than the embodiment of the present invention is elaborated in conjunction with attached drawing, but the present invention does not limit to
In above-mentioned specific embodiment, above-mentioned specific embodiment is only schematical, rather than restrictive, this field it is general
Under the inspiration of the present invention, not departing from the case where present inventive concept and claimed range can be with by logical technical staff
Many variations is made, these belong to protection of the invention.
Claims (9)
1. a kind of electrode of super capacitor composite material, which is characterized in that the electrode of super capacitor composite material is metal
Organic framework compounds and the conduction for forming three-dimensional network shape after in-situ polymerization in the metal organic framework compound hole
The nano lamellar material that polymer is combined, the conducting polymer respectively by iodide ion and chloride ion or by iodide ion and
Acetate ion is adulterated twice.
2. a kind of electrode of super capacitor composite material according to claim 1, which is characterized in that the organic bone of metal
Frame compound is the holey frame structure material formed by metal ion and organic ligand by coordination.
3. a kind of electrode of super capacitor composite material according to claim 1, which is characterized in that the organic bone of metal
Frame compound is trimesic acid nickel or trimesic acid copper；The conducting polymer is PEDOT or PPy.
4. a kind of preparation method of electrode of super capacitor composite material, which comprises the following steps:
Step 1: conducting polymer monomer being evaporated to metal organic framework compound, obtains the first product；
Step 2: after the completion of the evaporation of conducting polymer monomer, continuing to evaporate elemental iodine to first product, so that first produces
Oxidation polymerization generation conducting polymer occurs under elemental iodine initiation for conducting polymer monomer in object, obtains the second product；
Step 3: after the completion of elemental iodine evaporation, continuing to evaporate hydrochloric acid or glacial acetic acid to second product, so that the second product
Iodide ion in middle conducting polymer is replaced by chloride ion or acetate ion, obtains third product；
Step 4: after the completion of hydrochloric acid or glacial acetic acid evaporation, obtained third product being dried, is so far made super
Electrode for capacitors composite material.
5. preparation method according to claim 1, which is characterized in that the step 2 and step 3 are merged into step progress,
I.e. after the completion of the evaporation of conducting polymer monomer, continue to evaporate elemental iodine and hydrochloric acid or elemental iodine and glacial acetic acid to described first
Product, so that oxidation polymerization generation conducting polymer occurs under elemental iodine initiation for conducting polymer monomer in the first product, and
And the iodide ion in conducting polymer is replaced by chloride ion or acetate ion.
6. preparation method according to claim 1, which is characterized in that in the step 1 metal organic framework compound with
The mass ratio of conducting polymer monomer is 10: 1~1: 5；Evaporating temperature is 20 DEG C~30 DEG C in the step 1, evaporation time 3
Hour~12 hours.
7. preparation method according to claim 1, which is characterized in that conducting polymer monomer and iodine list in the step 2
The mass ratio of matter is 1: 10~2: 1；Evaporating temperature is 60 DEG C~120 DEG C in the step 2, and evaporation time is 3 hours~12 small
When.
8. preparation method according to claim 1, which is characterized in that hydrochloric acid is concentrated hydrochloric acid, concentration range in the step 3
For 10~12mol/L；The mass ratio of the conducting polymer monomer and concentrated hydrochloric acid is 1: 5~1: 20；Conducting polymer monomer with
The mass ratio of glacial acetic acid is 1: 5~2: 1；Evaporating temperature is 60 DEG C~120 DEG C in the step 3, and evaporation time is 3 hours~12
Hour.
9. preparation method according to claim 1, which is characterized in that drying temperature is 60 DEG C~80 DEG C in the step 4,
Drying time is 8 hours~12 hours.
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| US20210065997A1 (en) * | 2020-06-11 | 2021-03-04 | University Of Electronic Science And Technology Of China | MOFs composite electrode material for supercapacitors, preparation method thereof, and working electrode |
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| CN108335919A (en) * | 2018-02-12 | 2018-07-27 | 华中科技大学 | A kind of metal organic frame/conducting polymer composite material, it is prepared and application |
| CN109192531A (en) * | 2018-09-26 | 2019-01-11 | 辽宁大学 | The composite material and preparation method and application of hollow core-shell structural conductive polymer and metal organic framework |
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| CN109192531A (en) * | 2018-09-26 | 2019-01-11 | 辽宁大学 | The composite material and preparation method and application of hollow core-shell structural conductive polymer and metal organic framework |
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| US20210065997A1 (en) * | 2020-06-11 | 2021-03-04 | University Of Electronic Science And Technology Of China | MOFs composite electrode material for supercapacitors, preparation method thereof, and working electrode |
| US11694855B2 (en) * | 2020-06-11 | 2023-07-04 | University Of Electronic Science And Technology Of China | MOFs composite electrode material for supercapacitors, preparation method thereof, and working electrode |
| CN112382759A (en) * | 2020-10-17 | 2021-02-19 | 东莞东阳光科研发有限公司 | Preparation method of nitrogen-doped porous carbon-coated silicon composite nanofiber |
| CN112382759B (en) * | 2020-10-17 | 2022-04-29 | 东莞东阳光科研发有限公司 | Preparation method of nitrogen-doped porous carbon-coated silicon composite nanofiber |
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