CN109369870B - Nitrogen-doped ultra-stable porous polymer composite material and preparation method thereof - Google Patents
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- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 229920000642 polymer Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007772 electrode material Substances 0.000 claims abstract description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
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- 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
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 11
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 11
- 229940078552 o-xylene Drugs 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
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- 239000003990 capacitor Substances 0.000 abstract description 22
- 239000013259 porous coordination polymer Substances 0.000 description 16
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- 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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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention relates to a nitrogen-doped ultra-stable porous polymer composite material and a preparation method thereof, which comprises the following steps: (1) synthesizing a ligand from melamine and p-aldehyde benzoic acid in an o-xylene solvent, and purifying; (2) adding a ligand and cobalt nitrate hexahydrate into a DMF (dimethyl formamide) and ethanol solvent for reaction, washing after the reaction is finished, and drying at the temperature of 75-85 ℃ to obtain the nitrogen-doped ultra-stable porous polymer composite material. Compared with the prior art, the electrode material prepared by the invention has the characteristics of a double electric layer capacitor and a pseudo capacitor, has good capacitance performance and excellent cycle stability, and is an ideal electrode material of a super capacitor.
Description
Technical Field
The invention belongs to the technical field of electrode materials of super capacitors, and particularly relates to a nitrogen-doped ultra-stable porous polymer composite material and a preparation method thereof.
Background
Electrochemical capacitors are called supercapacitors, which can be divided into two categories. The first type: the double electric layer capacitor stores electric energy through electrostatic adsorption of electrode materials to charges, and the electrochemical performance of the double electric layer capacitor is closely related to the conductivity, specific surface area and pore structure of the electrode materials; the second type: the pseudocapacitance capacitor stores energy through rapid and reversible oxidation-reduction reaction of an electrode material, and the electrochemical performance of the pseudocapacitance capacitor is obviously influenced by the theoretical specific capacitance, the conductivity, the structural morphology and the like of the electrode material. A range of electrochemically active materials have been used as supercapacitor electrode materials, including carbon materials, metal oxides/hydroxides, conductive polymers and composites thereof. The electrochemical properties of MOFs in supercapacitors have been reported in literature to date, including Ni, Zn, Cu, Mn, Fe, Ce and, more recently, Co-MOFs. Among the various MOFs, Co-MOFs are receiving more attention because of their better redox reaction capability. Porous Coordination Polymers (PCPs) are similar to MOFs, have large specific surface areas and adjustable pore diameters, but have the problem of poor conductivity when used as electrode materials.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a nitrogen-doped ultrastable porous polymer (Co-PCPs) supercapacitor electrode material for a supercapacitor and a preparation method thereof. The preparation method is simple and low in cost; the prepared electrode material has good capacitance performance and high stability.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a nitrogen-doped hyperstable porous polymer composite material selects melamine with high N content as an organic ligand raw material, improves the surface wettability of an electrode material, accelerates the ion transmission in electrolyte, can obtain the electrode material with good electrical property, and adopts the following steps:
(1) synthesizing a ligand from melamine and p-aldehyde benzoic acid in an o-xylene solvent, and purifying;
(2) adding a ligand and cobalt nitrate hexahydrate into a DMF (dimethyl formamide) and ethanol solvent to react in a reaction kettle, washing after the reaction is finished, and drying at the temperature of 75-85 ℃ to obtain the nitrogen-doped ultra-stable porous polymer composite material.
In the step (1), the molar ratio of the melamine to the p-aldehyde benzoic acid is 1:2-1: 3. In the step (1), the reaction temperature is controlled to be 150-160 ℃, and the reaction time is 8-10 h. In the step (1), ethanol and water in a volume ratio of 1:1 are used for purification treatment.
In the step (2), the molar ratio of the ligand to the cobalt nitrate hexahydrate is 1:2-1: 3. In the step (2), the volume ratio of DMF to ethanol is 1:2-2: 1.
In the step (2), the reaction time is controlled to be 40-60h, and the reaction temperature is controlled to be 80-160 ℃. And (3) washing treatment by adopting DMF and ethanol in the step (2).
The invention also discloses a Co-PCPs nitrogen-doped ultra-stable porous polymer composite material prepared by the method, which is used as an electrode material for a super capacitor, melamine with high N content is selected as an organic ligand raw material, the surface wettability of the electrode material is improved, the ion transmission in an electrolyte is accelerated, and the material has the characteristics of a double electric layer capacitor and a pseudo capacitor, and has good capacitance performance and excellent cycling stability.
Compared with the prior art, the invention has the following advantages:
(1) the Co-PCPs material prepared by the hydrothermal method is simple in method and low in cost, and the supercapacitor electrode material with stable structure and excellent performance can be obtained only in a short time.
(2) The Co-PCPs material prepared by the invention has excellent electrochemical stability and good capacitance performance, and is an ideal electrode material of a super capacitor.
(3) The invention selects melamine with high nitrogen content as the ligand raw material, improves the surface wettability of the electrode material and is beneficial to the transmission of electrolyte. The distribution of pore sizes in the Porous Coordination Polymer (PCPs) material may also minimize the kinetic barrier to electrolyte access to the active material throughout the battery system.
(4) The Co-PCPs electrode material with excellent electrical property is obtained by optimizing the reaction temperature and time, because the formed polymers are stacked together at low temperature due to the slow nucleation rate, and the products are partially agglomerated at relatively high temperature due to the rapid nucleation to form a compact structure, thereby hindering ion transmission and reducing the electrical property. The optimization of the time is mainly in consideration of the yield and economic efficiency of the electrode material.
Drawings
FIG. 1 is a SEM image of the Co-PCPs electrode material prepared in example 4.
FIG. 2 is a graph showing the adsorption and desorption curves of the Co-PCPs electrode material prepared in example 4.
FIG. 3 is a Nyquist plot of the electrochemical impedance spectrum of the Co-PCPs electrode material prepared in example 4.
FIG. 4 is a cyclic voltammogram of the Co-PCPs electrode material prepared in example 4 at different scan rates.
FIG. 5 is a constant current charge and discharge curve diagram of the Co-PCPs electrode material prepared in example 4 at different current densities.
FIG. 6 is a graph of the cycling stability performance of the Co-PCPs electrode material prepared in example 4.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The organic ligand was first prepared by weighing 0.6306g of melamine and 2.2501g of p-aldehyde benzoic acid in 40ml of o-xylene and reacting at 150 ℃ for 10 h. The white product was filtered off with suction and purified with water and ethanol 1: 1. Dried at 80 ℃ for 8h under vacuum to be used. And then 0.2613g of organic ligand and 0.2910 g of cobalt nitrate hexahydrate are taken and added into a reaction kettle, the solvent is DMF, EtOH 2:1, the mixture reacts for 60 hours at the temperature of 80 ℃, the product is obtained by natural cooling and suction filtration, and the Co-PCPs-80 material is obtained after drying at the temperature of 80 ℃. When the composite material is subjected to electrochemical performance test, the charge transfer resistance (Rct) of the composite material is 0.5737 omega, and the composite material has a lower equivalent series resistance value and excellent diffusion performance. The cyclic voltammetry curve is similar to a rectangle and has a weaker oxidation reduction peak, which shows the rapid charge propagation capacity of the double electric layer capacitor and the pseudocapacitor. Calculated by a charging and discharging curve, when the current density is 1 A.g-1When the composite material is used, the composition shows 336 Fg-1Has excellent electrochemical performance.
Example 2
The organic ligand was first prepared by weighing 0.6306g of melamine and 2.2501g of p-aldehyde benzoic acid in 40ml of o-xylene and reacting at 150 ℃ for 9 h. The white product was filtered off with suction and purified with water and ethanol 1: 1. Dried at 80 ℃ for 8h under vacuum to be used. Then the0.2613g of organic ligand and 0.2910 g of cobalt nitrate hexahydrate are taken and added into a reaction kettle, the solvent is DMF, EtOH 2:1, the materials react for 60 hours at 100 ℃, the products are naturally cooled and filtered, and the products are dried at 80 ℃ to obtain the Co-PCPs-100 material. When the composite material is subjected to electrochemical performance test, the charge transfer resistance (Rct) of the composite material is 0.6319 omega, and the composite material has a lower equivalent series resistance value and excellent diffusion performance. The cyclic voltammetry curve is similar to a rectangle and has a weaker oxidation reduction peak, which shows the rapid charge propagation capacity of the double electric layer capacitor and the pseudocapacitor. Calculated by a charging and discharging curve, when the current density is 1 A.g-1When the composite material shows 360 F.g-1Has excellent electrochemical performance.
Example 3
The organic ligand was first prepared by weighing 0.6306g of melamine and 2.2501g of p-aldehyde benzoic acid in 50ml of o-xylene and reacting at 155 ℃ for 10 h. The white product was filtered off with suction and purified with water and ethanol 1: 1. Dried at 80 ℃ for 8h under vacuum to be used. And then 0.2613g of organic ligand and 0.2910 g of cobalt nitrate hexahydrate are taken and added into a reaction kettle, the solvent is DMF, EtOH 1:1, the mixture reacts for 50 hours at the temperature of 120 ℃, the mixture is naturally cooled and filtered to obtain a product, and the product is dried at the temperature of 80 ℃ to obtain the Co-PCPs-120 material. When the composite material is subjected to electrochemical performance test, the charge transfer resistance (Rct) of the composite material is 0.562 omega, and the composite material has a lower equivalent series resistance value and excellent diffusion performance. The cyclic voltammetry curve is similar to a rectangle and has a weaker oxidation reduction peak, which shows the rapid charge propagation capacity of the double electric layer capacitor and the pseudocapacitor. Calculated by a charging and discharging curve, when the current density is 1 A.g-1When the composite material showed 416 F.g-1Has excellent electrochemical performance.
Example 4
The organic ligand was first prepared by weighing 0.6306g of melamine and 2.2501g of p-aldehyde benzoic acid in 50ml of o-xylene and reacting at 155 ℃ for 10 h. The white product was filtered off with suction and purified with water and ethanol 1: 1. Dried at 80 ℃ for 8h under vacuum to be used. Then 0.2613g of organic ligand and 0.2910 g of cobalt nitrate hexahydrate are added into a reaction kettle, and the solvent is DMF (dimethyl formamide): EtOH ═ 1:1Respectively reacting at 120 ℃ for 50h, naturally cooling, filtering to obtain a product, and drying at 80 ℃ to obtain the Co-PCPs-140 material. When the composite material is subjected to electrochemical performance test, the charge transfer resistance (Rct) of the composite material is 0.621 omega, and the composite material has a lower equivalent series resistance value and excellent diffusion performance. The cyclic voltammetry curve is similar to a rectangle and has a weaker oxidation reduction peak, which shows the rapid charge propagation capacity of the double electric layer capacitor and the pseudocapacitor. Calculated by a charging and discharging curve, when the current density is 1 A.g-1When the composite material showed 512 Fg-1Has excellent electrochemical performance. Specifically, as shown in FIGS. 1 to 6, FIG. 1 is SEM image of the prepared Co-PCPs-140 electrode material. The Co-PCPs-140 form a distinct, loose, porous, spherical structure. This structure allows the electrode material to have more active sites. Fig. 2 is a pore size distribution plot of Co-PCPs-140 electrode materials, with Co-PCPs-140 pore size distribution at 3.8nm and 11.9nm, and a mesoporous (2-50nm) system can provide a reservoir in the electrolyte system, which provides a route for the electrolyte solution to easily reach higher surface area sites, thus exhibiting optimal ion transport capabilities. FIG. 3 is a Nyquist plot of the Electrochemical Impedance Spectroscopy (EIS) of Co-PCPs-140 electrode material in 3M KOH electrolyte solution, the material having a relatively small resistance and being plotted as nearly vertical lines, exhibiting absolutely ideal capacitive behavior. FIG. 4 shows that the Co-PCPs-140 electrode material is 2-100 mV. multidot.s-1The cyclic voltammogram at the scanning rate of (2) has a pair of redox peaks, and the electrode has pseudocapacitance property, which indicates that the electrode material is synergistic effect of an electric double layer and the pseudocapacitance. FIG. 5 shows that the electrode material of Co-PCPs-140 is in the range of 1-10 A.g-1Constant current charge and discharge curve diagram under the current density. There was no significant IR drop at the beginning of the discharge curve, indicating that the internal series resistance of the capacitor was small and the electrical performance was good. FIG. 6 shows the Co-PCPs-140 electrode material at 20A g-1Current density of (c) was measured. After 40000 times of charging and discharging, the capacitance value is kept to 97.4 percent, which shows that the electrode material has excellent cycling stability.
Example 5
The organic ligand was first prepared by weighing 0.6306g of melamine and 2.2501g of p-aldehydeBenzoic acid was reacted in 60ml o-xylene at 160 ℃ for 8 h. The white product was filtered off with suction and purified with water and ethanol 1: 1. Dried at 80 ℃ for 8h under vacuum to be used. And then 0.2613g of organic ligand and 0.2910 g of cobalt nitrate hexahydrate are taken and added into a reaction kettle, the solvent is DMF, EtOH 1:2, the mixture reacts for 40h at the temperature of 120 ℃, the mixture is naturally cooled and filtered to obtain a product, and the product is dried at the temperature of 80 ℃ to obtain the Co-PCPs-160 material. When the composite material is subjected to electrochemical performance test, the charge transfer resistance (Rct) of the composite material is 0.629 omega, and the composite material has a lower equivalent series resistance value and excellent diffusion performance. The cyclic voltammetry curve is similar to a rectangle and has no obvious oxidation reduction peak, which indicates the rapid charge propagation capacity of the double electric layer capacitor. Calculated by a charging and discharging curve, when the current density is 1 A.g-1The composite material showed 274F g-1Has excellent electrochemical performance.
Example 6
A preparation method of a nitrogen-doped hyperstable porous polymer composite material selects melamine with high N content as an organic ligand raw material, improves the surface wettability of an electrode material, accelerates the ion transmission in electrolyte, can obtain the electrode material with good electrical property, and adopts the following steps:
(1) mixing melamine and p-aldehyde benzoic acid according to a molar ratio of 1:2, controlling the temperature at 150 ℃ and the reaction time at 10h, synthesizing a ligand in an o-xylene solvent, and purifying by adopting ethanol and water according to a volume ratio of 1: 1;
(2) mixing a ligand and cobalt nitrate hexahydrate according to a molar ratio of 1:2, adding DMF (dimethyl formamide) and an ethanol solvent with a volume ratio of 1:2, reacting in a reaction kettle, controlling the reaction time to be 40h and the reaction temperature to be 160 ℃, washing by using DMF and ethanol after the reaction is finished, and drying at the temperature of 75 ℃ to obtain the nitrogen-doped ultrastable porous polymer composite material.
Example 7
A preparation method of a nitrogen-doped hyperstable porous polymer composite material selects melamine with high N content as an organic ligand raw material, improves the surface wettability of an electrode material, accelerates the ion transmission in electrolyte, can obtain the electrode material with good electrical property, and adopts the following steps:
(1) mixing melamine and p-aldehyde benzoic acid according to a molar ratio of 1:3, controlling the temperature at 160 ℃, reacting for 8 hours, synthesizing a ligand in an o-xylene solvent, and purifying by adopting ethanol and water according to a volume ratio of 1: 1;
(2) mixing a ligand and cobalt nitrate hexahydrate according to a molar ratio of 1:3, adding DMF (dimethyl formamide) and an ethanol solvent with a volume ratio of 2:1, reacting in a reaction kettle, controlling the reaction time to be 60 hours, controlling the reaction temperature to be 80 ℃, washing by using DMF and ethanol after the reaction is finished, and drying at the temperature of 85 ℃ to obtain the nitrogen-doped ultrastable porous polymer composite material.
The Co-PCPs nitrogen-doped ultra-stable porous polymer composite material prepared by the method is used as an electrode material for a super capacitor, melamine with high N content is selected as an organic ligand raw material, the surface wettability of the electrode material is improved, the ion transmission in an electrolyte is accelerated, and the material has the characteristics of a double electric layer capacitor and a pseudo capacitor, and has good capacitance performance and excellent cycling stability.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (7)
1. A preparation method of a nitrogen-doped ultra-stable porous polymer composite material is characterized by comprising the following steps:
(1) synthesizing a ligand from melamine and p-aldehyde benzoic acid in an o-xylene solvent, and purifying;
(2) adding a ligand and cobalt nitrate hexahydrate into a DMF (dimethyl formamide) and ethanol solvent to react in a reaction kettle, washing after the reaction is finished, and drying at the temperature of 75-85 ℃ to obtain a nitrogen-doped ultra-stable porous polymer composite material;
in the step (1), the molar ratio of melamine to p-aldehyde benzoic acid is 1:2-1: 3;
in the step (2), the molar ratio of the ligand to the cobalt nitrate hexahydrate is 1:2-1: 3.
2. The method as claimed in claim 1, wherein the reaction temperature in step (1) is controlled to be 150-160 ℃ and the reaction time is 8-10 h.
3. The preparation method of the nitrogen-doped ultra-stable porous polymer composite material as claimed in claim 1, wherein the step (1) is performed by purifying ethanol and water in a volume ratio of 1: 1.
4. The method for preparing the nitrogen-doped ultra-stable porous polymer composite material as claimed in claim 1, wherein the volume ratio of DMF and ethanol in the step (2) is 1:2-2: 1.
5. The method for preparing the nitrogen-doped ultra-stable porous polymer composite material as claimed in claim 1, wherein the reaction time in the step (2) is controlled to be 40-60h, and the reaction temperature is controlled to be 80-160 ℃.
6. The method for preparing the nitrogen-doped ultra-stable porous polymer composite material as claimed in claim 1, wherein the washing treatment is performed by using DMF and ethanol in the step (2).
7. The application of the nitrogen-doped ultra-stable porous polymer composite material prepared by the method according to claim 1, which is used as an electrode material for a supercapacitor.
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