CN106158403B - Metal coordination supermolecular grid and two-dimensional carbon composite material, and preparation method and application thereof - Google Patents
Metal coordination supermolecular grid and two-dimensional carbon composite material, and preparation method and application thereof Download PDFInfo
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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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
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Abstract
The invention provides a metal coordination supermolecular grid and two-dimensional carbon composite material, which is formed by compounding a metal coordination supermolecular grid with a supermolecular framework and a two-dimensional carbon material, wherein the metal coordination supermolecular grid and the two-dimensional carbon composite material have huge application potential on a chemical electrode.
Description
Technical Field
The invention relates to the field of composite materials, in particular to preparation and application of a metal coordination supermolecular grid and a two-dimensional carbon composite material.
Background
Metal-organic frameworks, also known as coordination polymers, are a recognized new generation of multifunctional materials. The composite material has the advantages of large specific surface area, designable structure and the like, has potential application value in the aspects of gas adsorption, molecular sieve, electrochemical energy storage and the like, and attracts the attention of a plurality of researchers. Similar to coordination polymers, coordination supramolecular mesh materials have similar porous properties, and due to weak action such as hydrogen bond and van der waals force action connection among supramolecular structural units, the coordination supramolecular mesh materials have better structural flexibility compared with coordination polymers connected with coordination bonds, thereby having wider potential research and application values.
The super capacitor is used as a new generation of energy storage material, has the advantages of high power density, long cycle life, rapid charge and discharge and the like, and is an ideal power supply for electric automobiles, hybrid electric automobiles and high-power tools. Supercapacitors can be divided into two categories according to the energy storage mechanism: electrochemical double-layer capacitors (EDLCs) and faraday pseudocapacitors (faradaic pseudocapacitors). In which an electric double layer capacitor stores energy by reversibly adsorbing charged ions at an electrode/electrolyte interface, and thus has a large power density and excellent cycle life, but generally has a low energy density. The electrode material of the electric double layer capacitor is generally a carbon material, such as activated carbon, carbon nanotubes, graphene and the like, wherein the graphene material is light in weight, large in specific surface area and high in conductivity of the material, and is an ideal electrode material of the supercapacitor, but the specific surface area is reduced due to the fact that an agglomeration phenomenon easily occurs between graphene sheets when the graphene sheets exist independently. The pseudo-capacitance is measured by the electrode materialThe planar, rapid and reversible faradaic redox reaction stores and releases energy, thus significantly increasing energy density, but at the expense of reduced cycle life and rate capability. Even so, its lifetime and power density are far superior to conventional batteries. The common pseudo-capacitance electrode materials are mainly inorganic materials such as variable-valence transition metal oxides, hydroxides and sulfides. The nickel compound has higher theoretical capacitance and chemical stability, is non-toxic, environment-friendly and low in price, and is an ideal electrode material of the super capacitor. Although the material has high theoretical capacitance (for example, the theoretical capacitance of nickel hydroxide under the potential window of 0.5V can still be as high as 2082F g-1) However, the conductivity of the electrolyte is generally poor, and electrolyte ions are difficult to diffuse into the internal region of the bulk material, resulting in the actual capacitance performance being significantly different from the theoretical value.
In order to achieve better charge storage and transfer effects, the internal region of the electrode material can be fully utilized by constructing the electrode material with a porous frame structure. The metal coordination polymer and the metal coordination supermolecule grid are used as ideal porous materials, have the advantage of large specific surface area, and the internal pore channels can be adjusted and designed, so that the metal coordination polymer and the metal coordination supermolecule grid are quite suitable to be used as electrode materials of supercapacitors theoretically.
Disclosure of Invention
The invention provides a metal coordination supermolecular grid and a two-dimensional carbon composite material, which can be connected with different coordination units to form a frame structure similar to a coordination polymer and transfer charges, and meanwhile, an organic coordination unit can also interact with modified graphene to form a conductive grid so as to improve the overall conductivity of the material, so that the material has better structural flexibility, and has greater application potential as an electrode material of a supercapacitor.
The technical scheme of the invention is realized as follows: the metal coordination supermolecular grid and two-dimensional carbon composite material is formed by compounding the metal coordination supermolecular grid and a two-dimensional carbon material.
Further, the metal coordination supermolecular lattice comprises various metal complexes, metal coordination polymers and the like, such as main group metal complexes, transition metal complexes and rare earth metal complexes. Such as nickel-2, 6-pyridinedicarboxylic acid (Ni-pydc) complexes, and the like.
Further, the two-dimensional carbon material includes single and multi-layered graphene, carbon nanotube, and the like.
The nickel-2, 6-pyridinedicarboxylic acid (Ni-pydc) complex can be connected with different coordination units to form a frame structure similar to a coordination polymer and transfer charges through the stacking effect of a strong hydrogen bond and pi-pi and lp-pi of a pyridine ring, and meanwhile, the coordination units can also interact with the modified graphene to form a conductive grid so as to improve the overall conductivity of the material. Compared with the common carboxylic acid coordination polymer which is connected with each unit by coordination bonds, the coordination supermolecular framework has better structural flexibility and electrical conductivity, so that the coordination supermolecular framework has larger application potential as an electrode material of a supercapacitor.
Further, the metal coordination supermolecular mesh is connected with the two-dimensional carbon material through a plurality of weak actions (such as hydrogen bonds, halogen bonds, lp-pi, pi-pi stacking, Van der Waals force and the like) to form a composite structure.
The preparation method of the metal coordination supermolecular mesh and two-dimensional carbon composite material is characterized in that the metal coordination supermolecular mesh and the two-dimensional carbon are subjected to chemical reaction (such as solution synthesis, hydrothermal preparation, electrochemical synthesis and the like) or physical composite (such as grinding, heating, pressurizing and the like) to prepare the metal coordination supermolecular mesh and two-dimensional carbon composite material.
According to one of the preparation methods of the metal coordination supermolecular grid and the two-dimensional carbon composite material, the graphene is stripped through an electrochemical method, and meanwhile, the hydro-thermally synthesized Ni-pydc coordination supermolecular framework and the electrochemically stripped graphene are combined in situ, so that the honeycomb-shaped Ni-pydc coordination supermolecular framework-coated graphene composite material is prepared at one time.
Hydrothermally prepared Ni (pydcH) containing two hydrogen ions per unit2Powder deprotonated in the vicinity of the negative electrodeStroke producing moiety [ Ni (pydc)2]2-The electrochemically exfoliated graphene sheets, which are exfoliated from the positive electrode by positive charges (provided by the positively charged groups and the carbonium ion intermediates generated by the graphene sheets during partial oxidation), are attracted to each other by electrostatic interaction. And then, a hydrogen bond, pi-pi stacking and other non-covalent acting forces are tightly combined, so that a nano sheet layer framework structure with a honeycomb structure is reconstructed on the surface of the graphene to form the nano Ni-pydc @ EEG composite material, a layer of honeycomb-shaped nano coordination supermolecule framework is successfully grown on the graphene sheet, and the product is stable in structure and controllable in quality.
As one of preferable modes, the preparation method of the metal coordination supermolecular grid and two-dimensional carbon composite electrode material comprises the following steps:
(1) hydrothermally synthesizing Ni-pydc powder;
(2) adding Ni-pydc powder to Na2SO4Preparing electrolyte in the solution;
(3) and electrochemically stripping graphene in the electrolyte, and separating and synthesizing the obtained graphene composite material coated by the Ni-pydc coordination supermolecular framework.
Preferably, in step (1), the hydrothermal synthesis comprises the following steps:
0.08g of Ni (NO)3)2·6H2Dissolving O and 0.12g of 2, 6-pyridinedicarboxylic acid (pydc) in 15mL of deionized water, and reacting for 6 hours in a hydrothermal reaction kettle at 160 ℃; and then naturally cooling to room temperature, filtering out crystals, washing the crystals with deionized water and DMF (dimethyl formamide) for three times respectively, drying the crystals in an oven at the temperature of 60 ℃, and grinding the crystals to obtain Ni-pydc complex powder.
Preferably, in step (2), 20mg of the Ni-pydc complex powder prepared by the above method is added to 10mL of 0.1MNa2SO4In the solution, the solution is slightly stirred and then is subjected to ultrasonic treatment for 10 minutes to form a suspension solution as an electrolyte.
Preferably, step (3) includes the following steps:
electrochemical stripping and synthesis experiments were performed on an electrophoresis apparatus, the electrolyte was added to a 20mL beaker, a graphite rod was used as the anode, a stainless steel mesh (as the cathode, with a 1cm separation between the two electrodes;applying 5V voltage between the two electrodes, limiting current to 40mA, keeping the solution in a stirring state, turning off the power supply after electrifying for 5-20min, and continuously stirring the solution for 10 min. Then centrifugating and washing with water and ethanol, repeating three times to remove Na2SO4And drying the separated precipitate in a 60 ℃ oven to obtain the graphene composite material coated by the Ni-pydc coordination supermolecular framework.
Through a simple electrochemical method combining electrochemical stripping and electrostatic self-assembly, a hydrothermally synthesized nickel-2, 6-pyridinedicarboxylic acid (Ni-pydc) coordination supermolecular framework and electrochemically stripped graphene are combined while graphene is stripped through the electrochemical method, and the honeycomb-shaped Ni-pydc coordination supermolecular grid-coated graphene composite material (Ni-pydc @ EEG, NiEG for short) is successfully prepared. The material is used as an electrode material of a super capacitor and has high specific capacitance (1282.8F g)-1@1A g-1) While maintaining excellent cycle performance (the initial capacitance of more than 93 percent can be maintained after 3000 charge-discharge cycles), and has higher high-rate charge-discharge capacity than that of a common pseudocapacitance material. The asymmetric solid-state capacitor device formed by combining the composite material and the electrochemical stripping graphene can be 7500W kg-1At a high power density of 14.6Whkg-1Compared with the common carbon material electric double layer super capacitor (the energy density is generally lower than 10Whkg-1) The device has better practical value with the pseudo-capacitance (obviously reduced performance under high power) of metal oxide materials, and the micro device only containing 60mg of electrode materials can directly drive a 2.5W motor.
The metal coordination supermolecular grid and the two-dimensional carbon composite material have great application potential in super capacitor electrodes.
A super capacitor electrode comprises components, 85% of metal coordination supermolecular grids and two-dimensional carbon composite materials, 10% of polyvinylidene fluoride binding agent and 5% of acetylene black in mass ratio.
The preparation method of the super capacitor electrode comprises the steps of dripping ethanol into 85% of metal coordination supermolecular grid, two-dimensional carbon composite material, 10% of polyvinylidene fluoride binder and 5% of acetylene black, and performing ultrasonic stirring to obtain the super capacitor electrode.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows the XRD spectrum of the powder synthesized hydrothermally (top) and the document Ni (pydcH)2Simulated spectrum of crystal (bottom);
FIG. 2 shows Ni (pydcH)2Structural formula of the coordination unit (hydrogen atom omitted);
FIG. 3 is an electron microscope scanning image of a metal coordination supermolecular grid and a two-dimensional carbon composite material, and (b) is an enlarged view;
FIG. 4 is a plot of cyclic voltammetry for a NiEG-5/10/20 electrode;
FIG. 5 is the constant current charge-discharge curve of the NiEG-5/10/20 electrode and the mass specific capacity calculated according to the curve;
FIG. 6 is a cyclic voltammogram of a NiEG-10 electrode at different scan rates.
FIG. 7 is a schematic view of the metal coordinating supramolecular mesh and a two-dimensional carbon composite when used in an electrode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the metal coordination supermolecular grid and the two-dimensional carbon composite material comprises the following steps:
(1) 0.08g of Ni (NO)3)2·6H2O and 0.12g of 2, 6-pyridinedicarboxylic acid (pydc) were dissolved in 15mL of deionized water, placed in a 20mL polytetrafluoroethylene liner, and placed in a hydrothermal reaction kettle to react at 160 ℃ for 6 hours. And then naturally cooling to room temperature, washing the filtered dark green crystal with deionized water and DMF (dimethyl formamide) for three times respectively, drying in an oven at 60 ℃, and grinding to obtain nickel-2, 6-pyridinedicarboxylic acid (Ni-pydc) complex powder for physical property characterization and further synthesis experiments.
(2) 20mg of the Ni-pydc complex powder prepared as described above was taken and 10mL of 0.1M Na was added2SO4In the solution, the solution is slightly stirred and then is subjected to ultrasonic treatment for 10 minutes to form a suspension solution as an electrolyte.
The electrosynthesis experiment was carried out on an electrophoresis apparatus, the complex suspension described above was added to a 20mL beaker, and a natural graphite rod was used as the anode, a stainless steel mesh (375 mesh, 20mm size. times.15 mm) was used as the cathode, and the electrodes were spaced about 1cm apart. The instrument applies 5V voltage between the two electrodes and limits the current to 40mA, meanwhile, the solution keeps a strong stirring state, the power supply is turned off after the solution is electrified for 5 minutes, and the solution is continuously stirred for 10 minutes. Then centrifuged at 6000rpm and washed with water and ethanol, repeated three times to remove Na2SO4And drying the separated grayish green precipitate in a 60 ℃ oven to obtain the Ni-pydc coated EEG composite electrode material (Ni-pydc @ EEG, NiEG for short).
Example 2
The procedure was the same as in example 1, except that the energization time in step 2 was 10 minutes.
Example 3
The procedure was the same as in example 1, except that the energization time in step 2 was 20 minutes.
The hydrothermally synthesized green complex powder (NiEG) was characterized by X-ray powder diffraction, as shown in figure 1.
The molecular structure is shown in figure 2, wherein one nickel atom is cross-chelated by four carboxyl groups of two 2, 6-pyridinedioic acids (two of which also retain hydrogen atoms) to form a Ni (pydcH)2Structural units, and the nickel and the nitrogen atom on the pyridine ring have coordination force. Non-covalent interactions between building blocks by hydrogen bonding and stacking with C ═ O … πAre connected with each other by force, and have stronger binding force. The binding energy of the C ═ O … π stacking is calculated by theory to be-24.3 kcal mol-1About 102kJmol-1The binding has approached the level of chemical bonds. And then, under the action of hydrogen bonds, coordination units can infinitely extend along the horizontal direction to form a stable two-dimensional supramolecular structure as shown in fig. 3-4 (a). Therefore, the stability of the complex is far higher than that of a common complex, and the product crystal or the ground powder has higher stability in an alkaline aqueous solution and still has no obvious change after being soaked in a 0.5M LiOH aqueous solution for 15 days. In addition, channels in which free water between the coordination compound lamella in the two-dimensional extension structure is located are connected through weak hydrogen bond action, so that the pore channel has good flexibility and is beneficial to ion diffusion in the channels.
The scanning electron microscope image of the prepared product is shown in fig. 3.
Example 4
Preparation and assembly of supercapacitor electrodes
Before the experiment, a plurality of pieces of foamed nickel with the sizes of 15mm multiplied by 10mm and 25mm multiplied by 20mm are respectively subjected to ultrasonic treatment in acetone, ethanol and deionized water for 20 minutes, and the foamed nickel is cleaned, aired and respectively weighed for later use. The electrode material slurry is prepared by mixing 85% of active electrode material, 10% of polyvinylidene fluoride (PVDF) binder and 5% of acetylene black by mass with ethanol and then fully and ultrasonically stirring for 10 minutes, for a three-electrode test system, the total mass of the used solid is slightly larger than 2mg, the amount of the ethanol is 2-3 drops, the slurry is uniformly coated on a 15mm x 10mm foam nickel substrate, the three-electrode test system is placed in a 60 ℃ oven for overnight, the mass is weighed again to subtract the mass of the previous blank foam nickel substrate, and the mass of the load-bearing active electrode material is calculated and used for calculating the specific capacitance later.
For a two-electrode test system, the Ni-pydc @ EEG composite material and a separate EEG material are assembled into an asymmetric solid-state supercapacitor microdevice. Wherein the Electrochemically Exfoliated Graphene (EEG) was prepared using the same instrument and the same method as described above, except that it was not in Na2SO4The Ni-pydc complex is added to the solution. Adding 10mg of Ni-pydc @ EEG into the adjuvant slurry according to the above ratio, and uniformly coating the adjuvant slurry on the surface of the substrate with the size of 25mm × 20mmOn a foamed nickel substrate, 50mg EEG was proportioned to prepare a slurry for the same counter electrode and applied to a foamed nickel substrate of the same dimensions. The two electrodes are separated by solid electrolyte (PVA-NaOH), wherein the PVA film is formed by adding 1g of PVA and 0.5g of NaOH into 10mL of water, heating to 90 ℃, stirring for 30 minutes to form transparent glue solution, uniformly pouring the transparent glue solution between the two electrodes for condensation, and lightly pressing until the distance between the two pieces of foamed nickel is about 2 mm. And finally, sealing the outer layer of the device by adopting a polytetrafluoroethylene raw material tape, and standing for 1 day to obtain the device for testing.
Supercapacitor performance testing
Electrochemical performance tests of the super capacitor are all carried out at an AutoLab PGSTAT-302N electrochemical workstation, supporting software is NOVA 1.7, and electrode configurations are respectively three electrodes/double electrodes. The experiment of the three-electrode system was carried out in an electrochemical cell with the sample-coated nickel foam as the working electrode, a platinum sheet (15 mm. times.10 mm) as the counter electrode and an Ag/AgCl electrode filled with saturated KCl solution as the reference electrode. The three electrodes are distributed according to a regular triangle, wherein the working electrode and the counter electrode are arranged in parallel at a distance of 1 cm. The experiment was started after soaking the electrode in 0.5M LiOH solution and standing for 5 minutes. And the two-electrode system directly connects the two poles of the asymmetric solid-state capacitor device with a working electrode clamp and a counter electrode clamp for testing, wherein one pole coated with Ni-pydc @ EEG material is used as a working electrode, and the other pole coated with EEG is used as a counter electrode. The electrochemical performance test comprises cyclic voltammetry analysis, constant current charging and discharging, alternating current impedance and cyclic life test.
In the three-electrode system, different scanning speeds (1 to 50mV s) are respectively selected for cyclic voltammetry analysis and constant current charging and discharging of electrode materials-1) And current density (1 to 20A g)-1) The potential window of nickel-based pseudocapacitors is commonly used and analyzed in the potential range of 0.2 to 0.6V (vs. ag/AgCl). 50mV s per electrode run at 50 times-1After the rapid cyclic voltammetry scanning, the material is formally tested after being activated, and the specific capacitance is uniformly calculated according to the discharge time measured by a constant-current charge-discharge method. The cycle life test adopts a constant current charge-discharge method (the specific current is 5A g)-1) Repeatedly charging and discharging, and performing thousands of cycles according to the set lowest and highest potentialsAnd then, taking a discharge curve of each cycle to respectively calculate specific capacitance, and then comparing the specific capacitance with the initial specific capacitance to calculate the percentage of capacitance numerical value loss so as to evaluate the service life condition.
In a two-electrode system, when the assembled asymmetric capacitor device is tested, the working mode of the instrument is switched to two electrodes, then a NiEG electrode is used as an anode, an EEG electrode is used as a cathode for testing, and different voltage ranges (1.1-1.5V) and current densities (1-10A g) are selected for cyclic voltammetry analysis and constant current charging and discharging-1). The specific capacitance is calculated according to a discharge curve in constant-current charge and discharge, and the mass is calculated according to the total mass of the active substances of the two poles. The cycle life test adopts a constant current charge-discharge method (the specific current is 5A g)-1) The charge and discharge cycle was carried out in the range of 0 to 1.5V. The alternating current impedance test is carried out in the range of 0.1-100000Hz, and the amplitude of the sine wave is 5 mV.
Electrochemical performance test of Ni-pydc @ EEG composite electrode
The electrochemical test of the composite electrode is carried out in a three-electrode mode of an electrochemical workstation, and 0.5MLiOH solution is adopted as electrolyte. In order to investigate the influence of the Ni-pydc @ EEG composite material formulation on the electrochemical performance of the electrode, first, the ratio of Ni-pydc to EEG in the composite material was intensively studied. Since the addition amount of Ni-pydc powder before electrochemical synthesis was a fixed value, the EEG production increased with increasing energization time.[29]Therefore, NiEG composite electrode materials with different proportions are obtained by controlling the electrifying time to be 5 minutes, 10 minutes and 20 minutes respectively in the electrochemical synthesis step, and then electrodes prepared by the same method are respectively marked as NiEG-5/10/20. Firstly, NiEG-5/10/20 electrodes with different proportions are respectively subjected to a comparison test of cyclic voltammetry (sweep rate of 5mv/s) and constant current charge and discharge (specific current of 5A/g) in a potential range of 0.2 to 0.6V (vs. Ag/AgCl). The results of the tests are shown in fig. 4 and 5. The results show that among the three materials with different Ni-pydc: EEG ratios, the NiEG-10 material prepared with the power-on time of 10 minutes in the electrochemical synthesis step has the best electrochemical performance. Firstly, the specific capacity of the NiEG-10 electrode calculated by a discharge curve of a 5A/g constant-current charge and discharge test is 835.8F/g, which is much higher than that of the other two electrodes. In addition, by observing the redox peak of cyclic voltammogram andthe charge and discharge platform of the constant-current charge and discharge curve can find that the oxidation reduction peak of the NiEG-5 electrode with less graphene content is obviously shifted, the difference value of the charge and discharge platform is large, and the material has large internal impedance and is difficult to effectively transfer charges. Therefore, the Ni-pydc material in the NiEG-5 electrode can not fully exert the electrochemical performance, and the electrochemical capacity is low. In contrast, the NiEG-20 electrode with high graphene content has good electrochemical performance, but the NiEG-10 electrode contains less Ni-pydc materials and more graphene, so that a relatively obvious electric double layer capacitance characteristic is shown from a test curve, an oxidation reduction peak and a charge-discharge platform are not obvious, and the proportion of the Ni-pydc materials serving as main contributors of composite material capacitance is low, so that the overall capacitance performance is lower than that of the NiEG-10 electrode.
In order to further explore the electrochemical performance of the NiEG-10 electrode which shows the best performance, cyclic voltammetry tests and constant current charge and discharge tests under different multiplying powers are carried out on the NiEG-10 electrode. Wherein the cyclic voltammetry test is performed at different scanning speeds (1 to 50mV/s) and at a scanning potential in the range of 0.2 to 0.6V (vs. Ag/AgCl). The cyclic voltammogram obtained by the test is shown in FIG. 6, the cyclic voltammogram of the NiEG electrode shows a typical redox peak, and a pair of obvious redox peaks are arranged near 0.35V/0.45V, corresponding to Ni2+/Ni3+Reversible redox reaction of (2). Moreover, the symmetry of the redox peaks is good, which indicates that the reversibility of the reaction is good. In addition, as the scanning rate is increased, the current density is also increased, which shows that the cyclic voltammetry response speed of the electrode is high and the multiplying power performance is good. The phenomenon that the peak position of the oxidation peak shifts to the positive potential direction and the peak position of the reduction peak shifts to the negative potential direction is caused by the increase of the diffusion resistance in the electrode. In addition, the curve shape of the cyclic voltammetry gradually transits to a parallelogram, which shows that the proportion of the electric double layer capacitance of the material to the total capacitance is increased under the condition of larger scanning speed.
In order to more visually display the structure of the metal coordinating supermolecular lattice and two-dimensional carbon composite material when used in an electrode, the structure shown in fig. 7 is a schematic diagram.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. The metal coordination supermolecular grid and two-dimensional carbon composite material is characterized in that: is compounded by metal coordination supermolecular grids and a two-dimensional carbon material; the two-dimensional carbon material comprises single-layer graphene and multi-layer graphene;
the metal coordination supermolecule grid comprises a metal complex and a metal coordination polymer;
the metal complex is a main group metal complex or a transition metal complex;
the metal coordination supermolecular grid is connected with the two-dimensional carbon through weak action, and the whole structure is a compound;
the preparation method of the metal coordination supermolecule grid and two-dimensional carbon composite material comprises the following steps: the metal coordination supermolecular grid and the two-dimensional carbon are subjected to chemical reaction or physical compounding to obtain the metal coordination supermolecular grid; specifically, the graphene composite material coated by the Ni-pydc coordination supermolecular framework in the honeycomb shape is prepared by in-situ combination of the Ni-pydc coordination supermolecular framework synthesized by a hydro-thermal method and the graphene stripped by electrochemistry while stripping the graphene by an electrochemistry method.
2. The metal-coordinated supramolecular lattice and two-dimensional carbon composite as claimed in claim 1, wherein: the specific preparation method of the honeycomb-shaped Ni-pydc coordination supermolecular frame-coated graphene composite material comprises the following steps:
(1) hydrothermally synthesizing Ni-pydc powder;
(2) adding Ni-pydc powder to Na2SO4Preparing electrolyte in the solution;
(3) and electrochemically stripping graphene in the electrolyte, and separating and synthesizing the obtained Ni-pydc coordination supermolecular frame-coated graphene composite material.
3. Use of the metal-coordinated supramolecular mesh and the two-dimensional carbon composite material according to any one of claims 1 to 2 in supercapacitor electrodes.
4. A supercapacitor electrode, characterized by: the paint consists of the following components in percentage by mass: 85% of the metal coordinating supramolecular mesh of claim 1 with two-dimensional carbon composite, 10% polyvinylidene fluoride binder, and 5% acetylene black; the metal coordination supermolecular grid and two-dimensional carbon composite material is specifically prepared by in-situ combining a hydrothermally synthesized Ni-pydc coordination supermolecular framework and electrochemically stripped graphene while stripping graphene by an electrochemical method to obtain the honeycomb-shaped Ni-pydc coordination supermolecular framework-coated graphene composite material.
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