CN109369870A - A kind of overstable porous polymer composite material and preparation method of N doping - Google Patents
A kind of overstable porous polymer composite material and preparation method of N doping Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000003990 capacitor Substances 0.000 claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 13
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 claims abstract description 12
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims abstract description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 239000013259 porous coordination polymer Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 abstract description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000013110 organic ligand Substances 0.000 description 15
- 230000005540 biological transmission Effects 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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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
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- 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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- Microelectronics & Electronic Packaging (AREA)
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Abstract
The present invention relates to a kind of overstable porous polymer composite material and preparation methods of N doping, using following steps: (1) by melamine and terephthalaldehydic acid in ortho-xylene solvent synthetic ligands, and carry out purification process；(2) ligand and cabaltous nitrate hexahydrate are added in DMF and alcohol solvent and are reacted, carry out carrying out washing treatment after reaction, in 75-85 DEG C of at a temperature of drying, obtain the overstable porous polymer composite material of N doping.Compared with prior art, the present invention is prepared electrode material while the characteristic with double layer capacitor and fake capacitance capacitor have good capacitive property and excellent cyclical stability, are ideal electrode material for super capacitor.
Description
Technical field
The invention belongs to electrode material for super capacitor technical fields, overstable porous poly- more particularly, to a kind of N doping
Compound composite material and preparation method thereof.
Background technique
Electrochemical capacitor is referred to as supercapacitor, and supercapacitor can be divided into two classes.The first kind: electric double layer capacitance
Device, it is that electric energy is stored by Electrostatic Absorption of the electrode material to charge, conductivity, the ratio of chemical property and electrode material
Surface area is closely related with pore structure；Second class: fake capacitance capacitor, fake capacitance capacitor is quickly can by electrode material
Inverse redox reaction carrys out energy storage, and the theoretical specific capacitance of electrode material, electric conductivity, structure and morphology etc. can significantly affect
The chemical property of fake capacitance capacitor.A series of electroactive substance has been used as electrode material for super capacitor, packet
Include carbon material, metal oxide/metal hydroxides, conducting polymer and their composite material.There is document report at present
The electrochemical properties of MOFs in road supercapacitor, including Ni, Zn, Cu, Mn, Fe, Ce and nearest Co-MOFs.Various
In MOFs, Co-MOFs is got more attention because of its better redox reaction ability.Porous coordination polymer (PCPs)
Similar MOF, large specific surface area and aperture is adjustable, but the problem of poorly conductive is all suffered from when as electrode material.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of supercapacitors to use
The overstable porous polymer of N doping (Co-PCPs) ultra-capacitor electrode material and preparation method thereof.Preparation method of the invention
Simply, at low cost；Electrode material obtained has good capacitive property and high stability.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of the overstable porous polymer composite material of N doping, selects the melamine of high leaded wastewater to make
For organic ligand raw material, the surface wettability of electrode material is improved, accelerates the transmission of electrolyte intermediate ion, can obtain has well
The electrode material of electrical property, using following steps:
(1) by melamine and terephthalaldehydic acid in ortho-xylene solvent synthetic ligands, and carry out purification process；
(2) ligand and cabaltous nitrate hexahydrate are added in DMF and alcohol solvent and are reacted in a kettle, reaction terminates
After carry out carrying out washing treatment, 75-85 DEG C at a temperature of it is dry, obtain the overstable porous polymer composite material of N doping.
Melamine and terephthalaldehydic acid molar ratio are 1:2-1:3 in step (1).Reaction temperature is controlled in step (1)
It is 150-160 DEG C, reaction time 8-10h.Volume ratio is used to carry out purification process for the second alcohol and water of 1:1 in step (1).
Ligand and cabaltous nitrate hexahydrate molar ratio are 1:2-1:3 in step (2).The volume ratio of DMF and ethyl alcohol in step (2)
For 1:2-2:1.
The control reaction time is 40-60h in step (2), and reaction temperature is 80-160 DEG C.DMF and second are used in step (2)
Alcohol carries out carrying out washing treatment.
The invention also discloses the overstable porous polymer composite woods of Co-PCPs N doping prepared by the above method
Material selects the melamine of high leaded wastewater as organic ligand raw material, improves electrode material as electrode for super capacitor material
The surface wettability of material, accelerates the transmission of electrolyte intermediate ion, and material has double layer capacitor and fake capacitance capacitor simultaneously
Characteristic has good capacitive property and excellent cyclical stability.
Compared with prior art, the invention has the following advantages that
(1) present invention is simple using the Co-PCPs MATERIALS METHODS of hydro-thermal method preparation, and cost is relatively low, it is only necessary to when shorter
Between the electrode material for super capacitor that can obtain stable structure, have excellent performance.
(2) Co-PCPs material prepared by the present invention has excellent electrochemical stability and good capacitive property, is super
The ideal electrode material of grade capacitor.
(3) present invention selects the melamine of high nitrogen quantity as ligand stock, improves the surface wettability of electrode material,
Be conducive to the transmission of electrolyte.Multiple aperture distribution in Porous coordination polymer (PCPs) material is it is also possible that entire battery system
The dynamics that electrolyte in system reaches active material hinders to minimize.
(4) present invention obtains the Co-PCPs electrode material with excellent electrical properties by optimization reaction temperature and time,
This is because the polymer of formation is packed together at low temperature since nucleation rate is slower, and at relatively high temperature, by
In fast nucleation, part reunion is had occurred in product, forms more close structure, hinders ion transmission, reduces its electricity
Performance.The yield and economic benefit of electrode material are then mainly in view of for the optimization of time.
Detailed description of the invention
Fig. 1 is the scanning electron microscope SEM figure of the Co-PCPs electrode material prepared in embodiment 4.
Fig. 2 is the adsorption desorption curve graph of the Co-PCPs electrode material prepared in embodiment 4.
Fig. 3 is the nyquist diagram of the electrochemical impedance spectroscopy of the Co-PCPs electrode material prepared in embodiment 4.
Fig. 4 is the cyclic voltammogram of the Co-PCPs electrode material for preparing under different scanning rates in embodiment 4.
Fig. 5 is the constant current charge-discharge curve of the Co-PCPs electrode material for preparing under different current densities in embodiment 4
Figure.
Fig. 6 is the stable circulation performance curve graph of the Co-PCPs electrode material prepared in embodiment 4.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
Organic ligand is prepared first, weighs 0.6306g melamine and 2.2501g terephthalaldehydic acid in 40ml neighbour two
10h is reacted at 150 DEG C in toluene.Suction filtration obtains white product, and is purified with water and ethyl alcohol 1:1.It is dried in vacuo 8h at 80 DEG C,
With to be used.Then 0.2613g organic ligand and 0.2910 cabaltous nitrate hexahydrate is taken to be added in reaction kettle, solvent DMF:EtOH
=2:1 filters to obtain product after natural cooling after reaction 60h at 80 DEG C respectively, Co-PCPs-80 material is obtained after 80 DEG C of dryings
Material.Electrochemical property test is carried out to it, the charge transfer resistance (Rct) of the composite material is 0.5737 Ω, and is had lower
Equivalent series impedance and excellent diffusion.Cyclic voltammetry curve is in class rectangle, has weaker redox peaks, shows
The rapid electric charge transmission capacity of both electric double layer capacitance and fake capacitance.It can be calculated by charging and discharging curve, work as current density
For 1Ag-1When, which goes out 336Fg-1Specific capacitance value, have excellent chemical property.
Embodiment 2
Organic ligand is prepared first, weighs 0.6306g melamine and 2.2501g terephthalaldehydic acid in 40ml neighbour two
9h is reacted at 150 DEG C in toluene.Suction filtration obtains white product, and is purified with water and ethyl alcohol 1:1.It is dried in vacuo 8h at 80 DEG C,
With to be used.Then 0.2613g organic ligand and 0.2910 cabaltous nitrate hexahydrate is taken to be added in reaction kettle, solvent DMF:EtOH
=2:1 filters to obtain product after natural cooling after reaction 60h at 100 DEG C respectively, Co-PCPs-100 is obtained after 80 DEG C of dryings
Material.Carry out electrochemical property test to it, the charge transfer resistance (Rct) of the composite material is 0.6319 Ω, and have compared with
Low equivalent series impedance and excellent diffusion.Cyclic voltammetry curve is in class rectangle, there is weaker redox peaks, table
The rapid electric charge transmission capacity of both electric double layer capacitance and fake capacitance is illustrated.It can be calculated by charging and discharging curve, when electric current is close
Degree is 1Ag-1When, which goes out 360Fg-1Specific capacitance value, have excellent chemical property.
Embodiment 3
Organic ligand is prepared first, weighs 0.6306g melamine and 2.2501g terephthalaldehydic acid in 50ml neighbour two
10h is reacted at 155 DEG C in toluene.Suction filtration obtains white product, and is purified with water and ethyl alcohol 1:1.It is dried in vacuo 8h at 80 DEG C,
With to be used.Then 0.2613g organic ligand and 0.2910 cabaltous nitrate hexahydrate is taken to be added in reaction kettle, solvent DMF:EtOH
=1:1 filters to obtain product after natural cooling after reaction 50h at 120 DEG C respectively, Co-PCPs-120 is obtained after 80 DEG C of dryings
Material.Carry out electrochemical property test to it, the charge transfer resistance (Rct) of the composite material is 0.562 Ω, and have compared with
Low equivalent series impedance and excellent diffusion.Cyclic voltammetry curve is in class rectangle, there is weaker redox peaks, table
The rapid electric charge transmission capacity of both electric double layer capacitance and fake capacitance is illustrated.It can be calculated by charging and discharging curve, when electric current is close
Degree is 1Ag-1When, which goes out 416Fg-1Specific capacitance value, have excellent chemical property.
Embodiment 4
Organic ligand is prepared first, weighs 0.6306g melamine and 2.2501g terephthalaldehydic acid in 50ml neighbour two
10h is reacted at 155 DEG C in toluene.Suction filtration obtains white product, and is purified with water and ethyl alcohol 1:1.It is dried in vacuo 8h at 80 DEG C,
With to be used.Then 0.2613g organic ligand and 0.2910 cabaltous nitrate hexahydrate is taken to be added in reaction kettle, solvent DMF:EtOH
=1:1 filters to obtain product after natural cooling after reaction 50h at 120 DEG C respectively, Co-PCPs-140 is obtained after 80 DEG C of dryings
Material.Carry out electrochemical property test to it, the charge transfer resistance (Rct) of the composite material is 0.621 Ω, and have compared with
Low equivalent series impedance and excellent diffusion.Cyclic voltammetry curve is in class rectangle, there is weaker redox peaks, table
The rapid electric charge transmission capacity of both electric double layer capacitance and fake capacitance is illustrated.It can be calculated by charging and discharging curve, when electric current is close
Degree is 1Ag-1When, which goes out 512Fg-1Specific capacitance value, have excellent chemical property.Specifically such as
Shown in Fig. 1-Fig. 6, Fig. 1 is the Scanning Electron microscope SEM figure for the Co-PCPs-140 electrode material being prepared. Co-PCPs-
140 form apparent loose porous ball shape structure.This structure makes electrode material have more active sites.Fig. 2 is
The graph of pore diameter distribution of Co-PCPs-140 electrode material, Co-PCPs-140 pore-size distribution is in 3.8nm and 11.9nm, mesoporous (2-
50nm) system can provide repository in electrolyte system, this provides for electrolyte solution and is accessible to high surface area
The route in site, therefore show optimal ion transport capability.Fig. 3 is that Co-PCPs-140 electrode material is electrolysed in 3M KOH
The nyquist diagram of electrochemical impedance spectroscopy (EIS) in matter solution, the resistance of the material is smaller and curve is almost vertical
Line shows the capacitance behavior of absolute ideal.Fig. 4 is Co-PCPs-140 electrode material in 2-100mVs-1Sweep speed under
Cyclic voltammogram have a pair of of redox peaks, electrode has fake capacitance property, shows that the electrode material is electric double layer and fake capacitance
Synergistic effect.Fig. 5 is Co-PCPs-140 electrode material in 1-10Ag-1Current density under constant current charge-discharge curve graph.It puts
Electric curve is started without apparent IR drop, shows that the series resistors inside of the capacitor is smaller, electrical property is preferable.Fig. 6 is Co-
PCPs-140 electrode material is in 20Ag-1Current density under the cycle performance curve graph that measures.By 40000 charge and discharges
Electricity, capacitance retain 97.4%, show that electrode material has excellent cyclical stability.
Embodiment 5
Organic ligand is prepared first, weighs 0.6306g melamine and 2.2501g terephthalaldehydic acid in 60ml neighbour two
8h is reacted at 160 DEG C in toluene.Suction filtration obtains white product, and is purified with water and ethyl alcohol 1:1.It is dried in vacuo 8h at 80 DEG C,
With to be used.Then 0.2613g organic ligand and 0.2910 cabaltous nitrate hexahydrate is taken to be added in reaction kettle, solvent DMF:EtOH
=1:2 filters to obtain product after reacting 40h natural cooling at 120 DEG C respectively, and Co-PCPs-160 material is obtained after 80 DEG C of dryings
Material.Electrochemical property test is carried out to it, the charge transfer resistance (Rct) of the composite material is 0.629 Ω, and is had lower
Equivalent series impedance and excellent diffusion.Cyclic voltammetry curve is shown in class rectangle without obvious redox peaks
The rapid electric charge transmission capacity of electric double layer capacitance.It can be calculated by charging and discharging curve, when current density is 1Ag-1When, this is multiple
Condensation material shows 274Fg-1Specific capacitance value, have excellent chemical property.
Embodiment 6
A kind of preparation method of the overstable porous polymer composite material of N doping, selects the melamine of high leaded wastewater to make
For organic ligand raw material, the surface wettability of electrode material is improved, accelerates the transmission of electrolyte intermediate ion, can obtain has well
The electrode material of electrical property, using following steps:
It (1) is in molar ratio that 1:2 is mixed by melamine and terephthalaldehydic acid, controlled at 150 DEG C, the reaction time
For 10h, the synthetic ligands in ortho-xylene solvent, and volume ratio is used to carry out purification process for the second alcohol and water of 1:1；
(2) in molar ratio it is that 1:2 is mixed by ligand and cabaltous nitrate hexahydrate, DMF and ethyl alcohol that volume ratio is 1:2 is added
It is reacted in a kettle in solvent, the control reaction time is 40h, and reaction temperature is 160 DEG C, uses DMF after reaction
Carrying out washing treatment is carried out with ethyl alcohol, in 75 DEG C of at a temperature of drying, obtains the overstable porous polymer composite material of N doping.
Embodiment 7
A kind of preparation method of the overstable porous polymer composite material of N doping, selects the melamine of high leaded wastewater to make
For organic ligand raw material, the surface wettability of electrode material is improved, accelerates the transmission of electrolyte intermediate ion, can obtain has well
The electrode material of electrical property, using following steps:
It (1) is in molar ratio that 1:3 is mixed by melamine and terephthalaldehydic acid, controlled at 160 DEG C, the reaction time
For 8h, the synthetic ligands in ortho-xylene solvent, and volume ratio is used to carry out purification process for the second alcohol and water of 1:1；
(2) in molar ratio it is that 1:3 is mixed by ligand and cabaltous nitrate hexahydrate, DMF and ethyl alcohol that volume ratio is 2:1 is added
Reacted in a kettle in solvent, the control reaction time is 60h, and reaction temperature is 80 DEG C, after reaction using DMF and
Ethyl alcohol carries out carrying out washing treatment, in 85 DEG C of at a temperature of drying, obtains the overstable porous polymer composite material of N doping.
The overstable porous polymer composite material of Co-PCPs N doping being prepared using this method, as super electricity
Container electrode material selects the melamine of high leaded wastewater as organic ligand raw material, improves the moistened surface of electrode material
Property, accelerate the transmission of electrolyte intermediate ion, material has the characteristic of double layer capacitor and fake capacitance capacitor simultaneously, has good
Capacitive property and excellent cyclical stability.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (9)
1. a kind of preparation method of the overstable porous polymer composite material of N doping, which is characterized in that this method is using following
Step:
(1) by melamine and terephthalaldehydic acid in ortho-xylene solvent synthetic ligands, and carry out purification process；
(2) ligand and cabaltous nitrate hexahydrate are added in DMF and alcohol solvent and are reacted in reaction kettle, after reaction into
Row carrying out washing treatment obtains the overstable porous polymer composite material of N doping in 75-85 DEG C of at a temperature of drying.
2. a kind of preparation method of the overstable porous polymer composite material of N doping according to claim 1, feature
It is, the molar ratio of melamine and terephthalaldehydic acid is 1:2-1:3 in step (1).
3. a kind of preparation method of the overstable porous polymer composite material of N doping according to claim 1, feature
It is, control reaction temperature is 150-160 DEG C in step (1), reaction time 8-10h.
4. a kind of preparation method of the overstable porous polymer composite material of N doping according to claim 1, feature
It is, volume ratio is used to carry out purification process for the second alcohol and water of 1:1 in step (1).
5. a kind of preparation method of the overstable porous polymer composite material of N doping according to claim 1, feature
It is, ligand and cabaltous nitrate hexahydrate molar ratio are 1:2-1:3 in step (2).
6. a kind of preparation method of the overstable porous polymer composite material of N doping according to claim 1, feature
It is, the volume ratio of DMF and ethyl alcohol is 1:2-2:1 in step (2).
7. a kind of preparation method of the overstable porous polymer composite material of N doping according to claim 1, feature
It is, the control reaction time is 40-60h in step (2), and reaction temperature is 80-160 DEG C.
8. a kind of preparation method of the overstable porous polymer composite material of N doping according to claim 1, feature
It is, carrying out washing treatment is carried out using DMF and ethyl alcohol in step (2).
9. the overstable porous polymer composite material of the Co-PCPs N doping that the method as described in claim 1 is prepared is made
For electrode for super capacitor material.
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Cited By (4)
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| CN109880032A (en) * | 2019-01-16 | 2019-06-14 | 大连理工大学 | Rich nitrogen micropore organic polymer containing functional group and preparation method thereof |
| CN112876632A (en) * | 2021-01-18 | 2021-06-01 | 杭州师范大学 | Synthetic method of nitrogen-rich Schiff base polymer |
| CN114890841A (en) * | 2022-03-24 | 2022-08-12 | 武汉绿农瑞益生物科技有限公司 | Long-acting microbial compound fertilizer and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880032A (en) * | 2019-01-16 | 2019-06-14 | 大连理工大学 | Rich nitrogen micropore organic polymer containing functional group and preparation method thereof |
| CN112876632A (en) * | 2021-01-18 | 2021-06-01 | 杭州师范大学 | Synthetic method of nitrogen-rich Schiff base polymer |
| CN114890841A (en) * | 2022-03-24 | 2022-08-12 | 武汉绿农瑞益生物科技有限公司 | Long-acting microbial compound fertilizer and preparation method thereof |
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