CN113078002A - Preparation method and application of conductive MOFs/CNTs composite electrode material - Google Patents
Preparation method and application of conductive MOFs/CNTs composite electrode material Download PDFInfo
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Abstract
The invention belongs to the field of preparation of electrode materials, and particularly relates to a preparation method and application of a conductive MOFs/CNTs composite electrode material. The method comprises the following steps: weighing a certain amount of CNTs, placing the CNTs in a sample bottle, adding deionized water, and performing ultrasonic treatment for 6 hours to form a uniform CNTs dispersion liquid. The organic ligand is dissolved in the CNTs dispersion, sonicated for 30 min to allow complete dissolution, and then transferred to a round bottom flask. Dissolving transition metal salt into deionized water, adding ammonia water, mixing uniformly, and transferring to a constant-pressure separating funnel. And finally, dropwise adding the transition metal salt solution into the CNTs dispersion liquid containing the organic ligand while stirring, after the dropwise adding is finished, heating the oil bath to 65 ℃ for reacting for 1.708 h, and after the reaction is finished, carrying out reduced pressure suction filtration, washing and drying to obtain the conductive MOF/CNTs composite electrode material. The conductive MOF/CNTs composite electrode material has a self-supporting porous structure and good conductivity. The preparation method disclosed by the invention is mild in condition and simple to operate, and can effectively prevent the agglomeration of the CNTs and the conductive MOFs crystals.
Description
Technical Field
The invention belongs to the field of preparation of electrode materials, and particularly relates to a preparation method and application of a conductive MOFs/CNTs composite electrode material.
Background
With the increasing demand of people on new generation electronic products such as various portable electronic devices, automatic electric vehicles, roll-up displays and the like, future energy storage devices require high efficiency, low cost, high power density, high energy density and good mechanical flexibility. Supercapacitors (SCs), one of the most promising energy storage technologies, have attracted extensive attention due to their excellent performance in terms of power density, charge/discharge rate and cycling stability. However, the energy density of SCs is currently difficult to meet the increasing energy demand of various consumer electronic devices. It is well known that the energy density E of SCs is determined by the total specific capacitance (C) and the operating voltage (V) of the device. Therefore, to increase the energy density of the single SCs, it is necessary to increase the specific capacitance while increasing the operating voltage. The operating voltage is related to the decomposition voltage of the electrolyte, while the key factor affecting specific capacitance is the electrode material. Therefore, research and development of novel electrode materials with high energy density, high power density, good conductivity and stable structure become research hotspots and problems to be solved urgently for SCs.
Metal organic framework compounds (MOFs) are porous materials with tunable structures and high surface areas. Due to the designed multifunctionality and abundant micropore structures on the molecular level, the method is beneficial to the permeation of electrolyte and ion transmission, and can contribute to double electric layer capacitance and pseudocapacitance simultaneously. However, most MOFs materials have poor conductivity, which severely limits the effective utilization of the built-in redox center, and as the charging and discharging process proceeds, the volume change caused by the faster redox reaction causes the collapse of the MOFs structure, which seriously affects the specific capacitance and the cycle stability thereof. There are two main approaches to solve this problem: 1) developing MOFs materials with good conductivity and stable structure; 2) the composite material is compounded with high-conductivity materials, such as graphene, Carbon Nanotubes (CNTs), conductive polymers and the like, so as to construct a 3D network structure.
The most challenging and potentially rewarding practice is to synthesize MOFs materials with good conductivity. While the high conductivity of conductive MOFs materials results from the high charge density and high charge mobility of the materials. High charge density requires materials containing high concentrations of loosely bound charge carriers (metal ions); high charge mobility requires that the metal atom and the organic ligand form an extended pi-conjugated structure with good spatial and energy overlap between the orbitals with proper symmetry. However, the extended pi-conjugated structure is easy to stack due to pi-pi interaction, so that electrolyte ions cannot reach the interlayer, and charge storage and ion transmission are greatly influenced.
The binary composite material compounded with the carbon material with high conductivity to form high-efficiency synergy is also an effective method for improving the performance of the MOFs-based SCs. Carbon Nanotubes (CNTs) are a carbon material having a 1D tubular structure, and have excellent electrical conductivity due to the presence of long-range delocalized large pi bonds in the structure. More importantly, the microporous structure of the CNTs provides channels and active sites for rapid adsorption and desorption of ions. Therefore, the conductive MOFs and the CNTs are compounded to construct the conductive MOFs/CNTs composite electrode material, the problems of poor conductivity and poor cycle stability of the traditional MOFs material are solved, the problems of easy agglomeration, low specific capacitance and the like of the CNTs are solved, and a reliable way is provided for developing the SCs electrode material with high energy density, high power density and good cycle stability.
Disclosure of Invention
In order to solve the problem, the invention provides a preparation method of a conductive MOFs/CNTs composite electrode material, which is simple to operate and easy to regulate and control. Meanwhile, the application of the conductive MOFs/CNTs composite electrode material in a super capacitor is provided, and the conductive MOFs/CNTs composite electrode material shows good performance.
The specific technical scheme of the invention is as follows:
the preparation method of the conductive MOFs/CNTs composite electrode material comprises the following specific steps:
(1) weighing a certain amount of CNTs, placing the CNTs in a sample bottle, adding deionized water, and performing ultrasonic treatment for 6 hours to form a uniform CNTs dispersion liquid.
(2) The organic ligand is dissolved in the CNTs dispersion, sonicated for 30 min to allow complete dissolution, and then transferred to a round bottom flask.
(3) Dissolving transition metal salt into deionized water, adding ammonia water, mixing uniformly, and transferring to a constant-pressure separating funnel.
(4) And (2) dropwise adding the transition metal salt solution into the CNTs dispersion liquid containing the organic ligand while stirring, after dropwise adding, heating the oil bath to 65 ℃, reacting for 1.708 h, after the reaction is finished, performing vacuum filtration to obtain black powder, washing the obtained powder with distilled water and absolute ethyl alcohol for multiple times respectively, and drying for 12 h to obtain the conductive MOF/CNTs composite electrode material.
In the step (1), the CNTs are single-walled carbon nanotubes (SWCNTs) with the diameter<2 nm and a length of 0.3-5 μm; the concentration of the CNTs dispersion liquid is 0.1-3 mg mL-1。
In the step (1), the CNTs are treated by mixed acid, and the mixed acid comprises the following components: the volume ratio of concentrated sulfuric acid to nitric acid is 3: 1; the concentration of CNTs in the mixed acid is 2.5 mg mL-1(ii) a The treatment method comprises the following steps: ultrasonically treating the mixed solution for 4 h, centrifuging or filtering, washing the mixed solution to be neutral by deionized water, and drying to obtain acidified CNTs; the acidification treatment is intended to open pores or truncate the CNTs at defective locations, allowing the internal microporous structure of the CNTs to be fully utilized.
In the step (2), the organic ligand is 2, 3, 6, 7, 10, 11-hexa-amino triphenyl Hexahydrochloride (HITP), and the concentration is 3.14 mmol L-1The volume of the dispersion was 20 mL.
In the step (3), the transition metal salt is nickel chloride hexahydrate, and the concentration of the transition metal salt solution is 5.55 mmol L-1The volume of the solution was 20 mL, and 1.2 mL of aqueous ammonia was added.
In the step (4), the dropping speed of the two solutions is controlled to be 1-6 s.
In the step (4), the reaction time is 1.708 h, which is the optimal reaction time screened by the preference method of the Wash-leg G, and the conductive MOFs prepared under the reaction time have the best performance.
In the step (4), the drying temperature is 80 ℃.
The preparation method of the monomer conductive MOFs is the same as above, except that CNTs are not added.
The conductive MOFs/CNTs composite material prepared by the invention is used as an electrode material of a super capacitor, and the using method comprises the following steps: uniformly mixing a conductive MOFs/CNTs composite electrode material, a conductive agent and a binder according to a certain mass ratio, coating the mixture on a current collector, drying and pressing the mixture into a film.
The mass ratio of the conductive MOFs/CNTs composite electrode material to the conductive agent to the binder is 8:1: 1; the conductive agent is carbon black; the binder is polyvinylidene fluoride (PVDF); the current collector is foamed nickel.
The conductive MOFs/CNTs composite electrode material is pressed on a current collector to form a film, and the film is dried for 12 hours at the temperature of 80 ℃; the pressure used during film pressing is 10 MPa.
The invention has the beneficial effects that:
(1) the ligand is an organic ligand with an extended pi-conjugated structure, and good space and energy overlap is realized between orbits with proper symmetry, so that high charge mobility of the material is ensured.
(2) The conductive MOFs nanorod is deposited on the surface of the CNTs to form a 3D structure, and the conductive MOFs nanorod is used as a spacer, so that the phenomenon that the CNTs are aggregated due to pi-pi interaction is avoided, the CNTs are also beneficial to preventing the aggregation of the MOF nanorod, more importantly, the high conductivity and hollow structure of the CNTs provide a channel for ion diffusion, and the charge storage is more beneficial.
(3) The preparation method is simple, the self-assembly of MOFs on the surface of CNTs is completed by adopting a bottom-up assembly method, and the structural adjustability of the composite material is realized by changing the dripping speed of the transition metal salt solution and the concentration of the CNTs dispersion liquid, so that the reproducibility of the electrode is strong, and the structure of the electrode is stable.
Drawings
FIG. 1 is an SEM image of a conductive MOF/CNT-0.5 composite electrode material of the present invention;
FIG. 2 shows N at 77K for conductive MOFs and conductive MOF/CNT-0.5 composite electrode materials of the present invention2Adsorption and desorption isotherms;
FIG. 3 is an XRD pattern of the conductive MOFs and conductive MOF/CNT-0.5 composite electrode materials of the present invention;
FIG. 4 is an electrochemical impedance spectrum of the composite electrode material according to examples 1 to 4 of the present invention;
FIG. 5 is a graph of the cycling stability of the conductive MOF/CNT-0.5 composite electrode material of the present invention.
Detailed Description
The technical solution of the present invention is described below with reference to the accompanying drawings and specific embodiments.
Example 1
2, 3, 6, 7, 10, 11-hexaamino triphenyl Hexahydrochloride (HITP) 20 mg (0.0628 mmol) was weighed accurately, 20 mL deionized water was added, sonication was performed for 30 min to completely dissolve it, and then the organic ligand solution was transferred to a 100 mL round bottom flask. 26.4 mg (0.111 mmol) of nickel chloride hexahydrate is accurately weighed into a sample bottle, 20 mL of deionized water is added to be completely dissolved, 1.2 mL of ammonia water is added, the mixture is uniformly mixed and then transferred into a 25 mL constant-pressure separating funnel, the dropping speed is controlled to be 1 drop/2 s, and stirring is carried out while dropping. After the dropwise addition, raising the temperature to 65 ℃ in an oil bath, reacting for 1.708 h, performing centrifugal filtration to obtain black powder, washing the obtained powder with distilled water and absolute ethyl alcohol for multiple times respectively, putting the product into a drying oven, and drying for 12 h, wherein the obtained samples are marked as: MOFs.
Example 2
Weighing 4 mg of acidified CNTs, placing the acidified CNTs in a 25 mL sample bottle, adding 20 mL of deionized water, performing ultrasonic treatment for 6 h to form uniform CNTs dispersion liquid, wherein the concentration of the dispersion liquid is 0.2 mg mL in sequence-1. 20 mg (0.0628 mmol) of 2, 3, 6, 7, 10, 11-hexaamino triphenyl Hexahydrochloride (HITP) was accurately weighed, added to the CNTs dispersion, sonicated for 30 min to completely dissolve, and then the dispersion was transferred to a 100 mL round bottom flask. Accurately weighing 26.4 mg (0.111 mmol) of nickel chloride hexahydrate in a sample bottle, adding 20 mL of deionized water to completely dissolve the nickel chloride hexahydrate, adding 1.2 mL of ammonia water, uniformly mixing, transferring to a 25 mL constant-pressure separating funnel, and controlling the dropping speed to accelerateThe mixture was stirred at a concentration of 1 drop/2 s. After the dropwise addition, raising the temperature to 65 ℃ in an oil bath, reacting for 1.708 h, performing centrifugal filtration to obtain black powder, washing the obtained powder with distilled water and absolute ethyl alcohol for multiple times respectively, putting the product into a drying oven, and drying for 12 h, wherein the obtained samples are marked as: MOF/CNTs-0.2.
Example 3
Weighing 10 mg of acidified CNTs, placing the acidified CNTs in a 25 mL sample bottle, adding 20 mL of deionized water, performing ultrasonic treatment for 6 h to form uniform CNTs dispersion liquid, wherein the concentration of the dispersion liquid is 0.5 mg mL in sequence-1. 20 mg (0.0628 mmol) of 2, 3, 6, 7, 10, 11-hexaamino triphenyl Hexahydrochloride (HITP) was accurately weighed, added to the CNTs dispersion, sonicated for 30 min to completely dissolve, and then the dispersion was transferred to a 100 mL round bottom flask. 26.4 mg (0.111 mmol) of nickel chloride hexahydrate is accurately weighed into a sample bottle, 20 mL of deionized water is added to be completely dissolved, 1.2 mL of ammonia water is added, the mixture is uniformly mixed and then transferred into a 25 mL constant-pressure separating funnel, the dropping speed is controlled to be 1 drop/2 s, and stirring is carried out while dropping. After the dropwise addition, raising the temperature to 65 ℃ in an oil bath, reacting for 1.708 h, performing centrifugal filtration to obtain black powder, washing the obtained powder with distilled water and absolute ethyl alcohol for multiple times respectively, putting the product into a drying oven, and drying for 12 h, wherein the obtained samples are marked as: MOF/CNT-0.5.
Example 4
Weighing 20 mg of acidified CNTs, placing the acidified CNTs in a 25 mL sample bottle, adding 20 mL of deionized water, performing ultrasonic treatment for 6 h to form uniform CNTs dispersion liquid, wherein the concentration of the dispersion liquid is 1.0 mg mL in sequence-1. 20 mg (0.0628 mmol) of 2, 3, 6, 7, 10, 11-hexaamino triphenyl Hexahydrochloride (HITP) was accurately weighed, added to the CNTs dispersion, sonicated for 30 min to completely dissolve, and then the dispersion was transferred to a 100 mL round bottom flask. 26.4 mg (0.111 mmol) of nickel chloride hexahydrate is accurately weighed into a sample bottle, 20 mL of deionized water is added to be completely dissolved, 1.2 mL of ammonia water is added, the mixture is uniformly mixed and then transferred into a 25 mL constant-pressure separating funnel, the dropping speed is controlled to be 1 drop/2 s, and stirring is carried out while dropping. After the dropwise addition, the mixture is heated to 65 ℃ in an oil bath, the reaction is carried out for 1.708 h, black powder can be obtained by centrifugal filtration, and then the obtained powder is respectively treated with distilled water and anhydrous ethylWashing with alcohol for multiple times, putting the product into a drying oven for drying for 12 h, and respectively marking the obtained samples as: MOF/CNT-1.0.
To verify the advantageous effects of the present invention, the inventors conducted tests on the conductive MOF/CNT-0.5 composite electrode material prepared in example 3:
(1) morphology characterization of conductive MOF/CNT-0.5 composite electrode materials
Scanning electron microscope tests (figure 1) were performed on the conductive MOF/CNT-0.5 composite electrode material prepared in example 3, and from SEM pictures of MOF/CNT-0.5 powder, it was found that the protrusions grown uniformly on the bundles of nanotubes successfully completed self-assembly on the surface of CNTs, whereas the presence of particles was rarely observed on thinner bundles, indicating that recombination is difficult to occur on tube diameters with smaller radius of curvature.
(2) Structural characterization of conductive MOFs and conductive MOFs/CNTs-0.5 composite electrode material
The conductive MOFs prepared in example 1 and the conductive MOF/CNT-0.5 composite electrode material prepared in example 3 were subjected to N at 77K2According to the adsorption and desorption isotherm test, as shown in FIG. 2, the average pore diameter of the conductive MOF/CNT-0.5 composite electrode material is 1 nm, and the specific surface area is 753 m2 g−1Much higher than the specific surface area of the conductive MOFs (589 m)2 g−1）。
The conductive MOFs prepared in example 1 and the conductive MOF/CNT-0.5 composite electrode material prepared in example 3 were subjected to X-ray diffraction, as shown in FIG. 3, wherein the conductive MOFs is 2θThe diffraction peaks are obvious at the positions of = 4.7 °, 9.5 °, 12.6 °, 16.5 ° and 27.3 °, and the positions and peak widths of the peaks in the conductive MOF/CNT-0.5 composite electrode material are not obviously changed compared with those of the conductive MOFs material, which indicates that the conductive MOFs are well compounded on CNTs, not just pure mixture.
(3) Electronic conductivity testing of conductive MOF/CNT-0.5 composite electrode materials
The conductive MOF/CNT-0.5 composite electrode material prepared in example 3 is subjected to conductivity test, and the electronic conductivity of the material at normal temperature is up to 10S cm measured by a 4-probe tester-1。
(4) Electrochemical performance test of conductive MOFs/CNTs composite electrode material
Electrochemical performance tests were performed on the conductive MOFs prepared in example 1 and the conductive MOFs/CNTs composite electrode materials prepared in examples 2 to 4, and the AC impedance graphs of all the materials without charge and discharge are shown in FIG. 4, with test voltages of-0.2V to 0.4V and frequencies of 100 kHZ~ 10 mHZ. Of all the materials, the half-circle diameter of the middle frequency region of the MOF/CNT-0.5 electrode is the smallest, representing the charge transfer resistanceR ctThe minimum indicates that the conductivity of the material is the best, and the ion adsorption/desorption process on the surface of the electrode is fast. As can be seen, the MOF/CNT-1.0 material with the highest CNTs loadingR ctNot at a minimum, charge transfer resistanceR ctThe charge transfer resistance is not in direct proportion to the loading amount of the CNTs, and can be laterally reflectedR ctIs more relevant to the structure of the composite material formed by self-assembly of the conductive MOFs and the CNTs. In conclusion, the electrochemical performance of the conductive MOFs material is effectively improved by adding the CNTs.
The results of the cycling stability test of the conductive MOF/CNT-0.5 composite electrode material prepared in example 3 are shown in FIG. 5 at 4A g−1After 10000 times of charge and discharge under the condition, the capacity retention rate of the conductive MOF/CNT-0.5 is 83.5 percent, and the coulombic efficiency is 100 percent. The higher capacity retention rate of the MOF/CNT-0.5 material shows that the CNTs are added to play a certain supporting role on the structure of conductive MOFs in the charging and discharging processes.
The above description is only for the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention.
Claims (12)
1. The preparation method of the conductive MOFs/CNTs composite electrode material is characterized by comprising the following steps of:
(1) weighing a certain amount of CNTs, placing the CNTs in a sample bottle, adding deionized water, and performing ultrasonic treatment for 6 hours to form a uniform CNTs dispersion liquid;
(2) dissolving an organic ligand into the CNTs dispersion liquid, carrying out ultrasonic treatment for 30 min to completely dissolve the organic ligand, and then transferring the organic ligand into a round-bottom flask;
(3) dissolving transition metal salt into deionized water, adding ammonia water, uniformly mixing, and transferring to a constant-pressure separating funnel;
(4) and (2) dropwise adding the transition metal salt solution into the CNTs dispersion liquid containing the organic ligand while stirring, after dropwise adding, heating the oil bath to 65 ℃, reacting for 1.708 h, after the reaction is finished, performing vacuum filtration to obtain black powder, washing the obtained powder with distilled water and absolute ethyl alcohol for multiple times respectively, and drying for 12 h to obtain the conductive MOF/CNTs composite electrode material.
2. The method for preparing conductive MOFs/CNTs composite electrode material according to claim 1, wherein in step (1), the CNTs are single-walled carbon nanotubes (SWCNTs) with diameter<2 nm and a length of 0.3-5 μm; the concentration of the CNTs dispersion liquid is 0.1-3 mg mL-1。
3. The preparation method of the conductive MOFs/CNTs composite electrode material according to claim 1, wherein in the step (1), the concentration of the CNTs dispersion liquid is 0.1-3 mg mL-1。
4. The method for preparing the conductive MOFs/CNTs composite electrode material according to claim 1, wherein in the step (1), the CNTs are treated by mixed acid, and the mixed acid comprises: the volume ratio of concentrated sulfuric acid to nitric acid is 3: 1; the concentration of CNTs in the mixed acid is 2.5 mg mL-1(ii) a The treatment method comprises the following steps: and (3) carrying out ultrasonic treatment on the mixed solution for 4 h, centrifuging or carrying out suction filtration, washing the mixed solution to be neutral by using deionized water, and drying the washed solution to obtain the acidified CNTs.
5. The method for preparing conductive MOFs/CNTs composite electrode material according to claim 1, wherein in step (2), the organic ligand is 2, 3, 6, 7, 10, 11-hexa-amino triphenyl Hexahydrochloride (HITP), and the concentration is 3.14 mmol L-1The volume of the dispersion was 20 mL.
6. The method for preparing the conductive MOFs/CNTs composite electrode material according to claim 1, wherein in the step (3), the transition metal salt is nickel chloride hexahydrate, and the concentration of the transition metal salt solution is 5.55 mmol L-1The volume of the solution was 20 mL, and 1.2 mL of aqueous ammonia was added.
7. The method for preparing the conductive MOFs/CNTs composite electrode material according to claim 1, wherein in the step (4), the dropping speed of the two solutions is controlled to be 1 s-6 s.
8. The method for preparing conductive MOFs/CNTs composite electrode material according to claim 1, wherein in step (4), the reaction time is 1.708 h, which is the best reaction time screened by the Wash-Raept method, and the conductive MOFs prepared under the reaction time has the best performance.
9. The method for preparing conductive MOFs/CNTs composite electrode material according to claim 1, wherein in step (4), the drying temperature is 80 ℃.
10. The conductive MOFs/CNTs composite electrode material prepared by the preparation method of any one of claims 1-9 is applied to a super capacitor electrode.
11. The use according to claim 10, wherein the mass ratio of the conductive MOFs/CNTs composite electrode material to the conductive agent to the binder is 8:1: 1; the conductive agent is carbon black; the binder is polyvinylidene fluoride (PVDF); the current collector is foamed nickel.
12. The use according to claim 10, characterized in that the conductive MOFs/CNTs composite electrode material is pressed to a film on a current collector and dried at 80 ℃ for 12 h; the pressure used during film pressing is 10 MPa.
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