CN114843118B - Electrode composite GO-C@M (OH) with hierarchical pores 2 Preparation method and application - Google Patents

Electrode composite GO-C@M (OH) with hierarchical pores 2 Preparation method and application Download PDF

Info

Publication number
CN114843118B
CN114843118B CN202210468154.8A CN202210468154A CN114843118B CN 114843118 B CN114843118 B CN 114843118B CN 202210468154 A CN202210468154 A CN 202210468154A CN 114843118 B CN114843118 B CN 114843118B
Authority
CN
China
Prior art keywords
sponge
composite material
electrode composite
preparation
electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210468154.8A
Other languages
Chinese (zh)
Other versions
CN114843118A (en
Inventor
刘辉
陈宇晗
方宏宇
李亮
张云飞
吴艳光
蒋灿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Institute of Technology
Original Assignee
Wuhan Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Institute of Technology filed Critical Wuhan Institute of Technology
Priority to CN202210468154.8A priority Critical patent/CN114843118B/en
Publication of CN114843118A publication Critical patent/CN114843118A/en
Application granted granted Critical
Publication of CN114843118B publication Critical patent/CN114843118B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • 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

Abstract

The invention relates to a composite material GO-C@M (OH) with a hierarchical pore electrode 2 The preparation method and the application thereof comprise the following steps: (1) Soaking the porous sponge in a GO solution to obtain a GO modified porous sponge, wherein the mass ratio of the porous sponge to the GO is 1 (0.1-1); (2) Growing microporous MOFs on the GO-modified porous sponge by adopting a hydrothermal reaction, and carbonizing to obtain a GO-C@M material; wherein M is a metal ion in MOFs; (3) Hydrothermal reaction of GO-C@M material and sulfur-containing compound to prepare GO-C@MSO 4 ，GO‑C@MSO 4 Soaking in alkaline solution to obtain electrode composite material GO-C@M (OH) 2 . The material obtained by the invention has a hierarchical pore structure and a large specific surface area, and can effectively prevent the agglomeration of hydroxide nano particles, thereby improving the active point of the electrode material and the electrochemical performance of the composite material.

Description

Electrode composite GO-C@M (OH) with hierarchical pores 2 Preparation method and application
Technical Field
The invention relates to the field of composite electrode materials, in particular to a composite electrode material GO-C@M (OH) with hierarchical pores 2 A preparation method and application thereof.
Background
With the continuous consumption of fossil energy, energy crisis and environmental pollution are becoming serious, and clean, efficient and sustainable energy sources capable of replacing fossil energy are being searched for all countries in the world. Super capacitor is a novel energy storage material different from traditional capacitor and accumulator, and has been paid attention to in recent years because of its characteristics of high power density, low use risk, rapid charge and discharge, etc. The electrode material is a key factor for determining the electrochemical performance of the supercapacitor, so that research on electrode materials with higher specific capacitance and electrochemical performance is a current research hotspot of supercapacitors.
Among various electrode materials, transition metal hydroxides have received extensive attention from researchers due to their high specific capacitance and energy density, and are considered as one of candidates for the optimal electrode material for supercapacitors. The transition metal hydroxide is easy to agglomerate during synthesis and preparation, most of the transition metal hydroxide is in a flaky stacking structure, the stacking structure is unfavorable for exposure of active points, meanwhile, the simple metal hydroxide is unfavorable for transmission of electrode electrons due to poor conductivity, and the factors limit the application of the transition metal hydroxide to the electrode material of the supercapacitor.
Disclosure of Invention
The invention aims to overcome the technical defects and provide the electrode composite material GO-C@M (OH) with the hierarchical holes 2 And the preparation method and the application solve the technical problems of easy agglomeration, low active point and poor conductivity of transition metal hydroxide in the prior art.
In order to achieve the technical purpose, the technical scheme of the preparation method of the invention is as follows:
the method comprises the following steps:
(1) Soaking the porous sponge in a GO solution to obtain a GO modified porous sponge, wherein the mass ratio of the porous sponge to the GO is 1 (0.1-1);
(2) Growing microporous MOFs on the GO-modified porous sponge by adopting a hydrothermal reaction to prepare a GO-porous sponge@MOFs composite material, and carbonizing to obtain a GO-C@M material; wherein M is a metal ion in MOFs;
(3) Hydrothermal reaction of GO-C@M material and sulfur-containing compound to prepare GO-C@MSO 4 ，GO-C@MSO 4 Soaking in alkaline solution to obtain electrode composite material GO-C@M (OH) 2 。
Further, the sponge is polyurethane sponge, melamine sponge, polystyrene sponge, polyethylene sponge or polysilicone sponge.
Further, the concentration of the GO solution is 1-10 mg/mL, and the solvent in the GO solution is one or a mixture of more of water, ethanol, methanol and DMF in any proportion.
Further, in the step (2), the raw materials of the MOFs comprise a metal source and an imidazole ligand, wherein the mass ratio of the GO modified porous sponge to the metal source is 1: (1-5): the molar ratio of the imidazole ligand to the metal source is above 5.
Further, in the hydrothermal reaction in the step (2), the concentration of the metal source is 0.05-0.2 g/mL; the metal source includes copper nitrate, zinc nitrate or cobalt nitrate.
Further, the hydrothermal reaction in the step (2) is carried out for 12-24 hours at 50-100 ℃; carbonization is carried out at 500-800 ℃ for 2-5 hours.
Further, in the step (3), the sulfur-containing compound is thioacetamide, and in the hydrothermal reaction, the ratio of GO-C@M to thioacetamide to the solvent is 0.1g (0.1-0.3) g (10-25) mL; the hydrothermal reaction in the step (3) is carried out at 130-150 ℃ for 12-24 h.
Further, the concentration of the alkaline solution in the step (3) is 1-6 mol/L, and the soaking time is 24-48 h.
Electrode composite material GO-C@M (OH) with hierarchical pores prepared by the preparation method 2 。
Electrode composite GO-C@M (OH) with hierarchical pores as above 2 Application in supercapacitors.
Compared with the prior art, the invention has the beneficial effects that:
MOFs is used as a metal source, and is grown on the surface and pores of a porous sponge, and is compounded with GO, so that high-dispersity metal nano particles are obtained after high-temperature carbonization, and then the metal nano particles are subjected to hydro-thermal sealing with a sulfur-containing compoundObtaining hydroxide nano particles. The high open cell content of the sponge and the microporous structure of MOFs are benefited, and the resulting GO-C@M (OH) 2 Has a multistage pore structure and a large specific surface area. The preparation method can effectively prevent the agglomeration of hydroxide nano particles, thereby improving the active points of the electrode material. In addition, the addition of graphene oxide can enhance the conductivity of the composite electrode material, thereby improving GO-C@M (OH) 2 Electrochemical properties of the composite material; the invention GO-C/Co (OH) 2 The specific capacity of the electrode can reach 300F/g under the current density of 1A/g.
Drawings
FIG. 1 shows GO-C/Co (OH) in the present invention 2 A TEM image of (a);
FIG. 2 shows GO-C/Co (OH) in the present invention 2 CV diagram of electrode material;
FIG. 3 shows GO-C/Co (OH) in the present invention 2 GCD plot of electrode material.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention has a hierarchical porous electrode composite material GO-C@M (OH) 2 The preparation method of (2) comprises the following steps:
A. adsorbing GO with a porous sponge in a GO solution of 1-10 mg/mL to obtain a GO modified porous sponge, wherein the mass ratio of the sponge to the graphene oxide is 1:0.1-1;
B. the porous sponge @ MOFs composite material is prepared by growing the microporous MOFs on the inner surface and the outer surface of the porous sponge by adopting a hydrothermal reaction method; the mass ratio of the GO modified porous sponge to the cobalt nitrate to the 2-methylimidazole is 1:1 to 5: 4-20; the concentration of the aqueous solution of cobalt nitrate is 0.05-0.2 g/mL; the concentration of the 2-methylimidazole is 0.2-0.8 g/mL; carrying out hydrothermal reaction for 12-24 hours at 50-100 ℃;
C. carbonizing the porous sponge@MOFs composite material at a high temperature under inert gas to obtain a GO-C@M material, and carbonizing at 500-800 ℃ for 2-5 hours;
D. GO-C@MSO is prepared by reacting GO-C@M with thioacetamide through hydrothermal method 4 Wherein the ratio of GO-C@M, thioacetamide and solvent (one or more of water, ethanol, methanol and DMF) is 0.1 g:0.1-0.3 g:10-25 mL; reacting for 12-24 h at 130-150 ℃.
E. GO-c@mso 4 Soaking in 1-6M excessive alkaline solution for 24-48 h to prepare GO-C@M (OH) 2 A composite material.
Preferably, the sponge is polyurethane sponge, melamine sponge, polystyrene sponge, polyethylene sponge, and polysilicone sponge.
Preferably, MOFs are MOF-5, MOF-177, ZIF-5, ZIF-7, ZIF-8, ZIF-11, ZIF-20, ZIF-67, ZIF-68, etc.
Preferably, the metal ion M is Cu 2+ 、Zn 2+ 、Co 2+ Etc.
In the MOFs material, the theoretical molar ratio of the metal source to the imidazole ligand is 1:1, in order to ensure the full reaction of the metal source, excessive imidazole ligand, preferably imidazole ligand with the molar quantity more than 5 times of that of the metal source, is adopted, and the adopted metal source and imidazole ligand are both dissolved in solvents such as water and the like, so that the product is insoluble, and therefore MOFs material with high purity can be obtained; the metal source and the corresponding ligand can be selected according to the specific model of MOFs.
Preferably, the solvent in the GO solution is a mixture of one or more of water, ethanol, methanol and DMF.
Preferably, the alkaline solution is sodium hydroxide or potassium hydroxide solution.
The invention is further illustrated by the following specific examples.
Example 1
(1) Ultrasonic cleaning a melamine sponge block with the concentration of 1cm multiplied by 2cm multiplied by 1cm by using an ethanol solution for 15 minutes, drying at 60 ℃ for 1 hour, then soaking the melamine sponge block in an aqueous solution of 5mg/mL graphene oxide until the melamine sponge block is completely absorbed, drying the sponge at 60 ℃, and preparing a GO-modified porous sponge, wherein the mass ratio of the sponge to the graphene oxide is 1:1;
(2) The GO-modified porous sponge is soaked in an aqueous solution containing 0.1g/mL of cobalt nitrate, extruded for a plurality of times, taken out and dried. Then putting the sponge into a solution containing 0.4g/mL of 2-methylimidazole, carrying out hydrothermal reaction for 24 hours at 100 ℃, taking out and drying the solid after the reaction, then putting the dried sponge into a carbonization furnace, carbonizing for 2 hours at 600 ℃, cooling to room temperature after carbonization, taking out the product, and grinding the product into powder to obtain the GO-C@Co material; wherein, the mass ratio of the GO modified porous sponge to the cobalt nitrate is 1:2, and the mol ratio of the cobalt nitrate to the 2-methylimidazole is 1:5.
(3) 0.1g of thioacetamide and 0.1g of GO-C@Co are weighed and dissolved in 10mL of deionized water, ultrasonic treatment is carried out for 20min, and the mixed solution is put into a 25mL Teflon reaction kettle for reaction for 12h at 150 ℃. Cooling to room temperature, taking out, washing with absolute ethanol, drying, soaking in 1M excessive sodium hydroxide solution for 24 hr, filtering, and drying to obtain black powder (GO-C/Co (OH) 2 A composite material.
GO-C/Co (OH) prepared in example 1 2 Mixing the powder of the composite material, acetylene black and polytetrafluoroethylene PTFE in a mass ratio of 8:1:1, manually pressing the mixture into a test tube, then putting the test tube into a steel mesh, and pressing the steel mesh under 6M pressure to form GO-C/Co (OH) 2 An electrode sheet; GO-C/Co (OH) 2 The composite material-steel mesh electrode plate is used as an electrode of the super capacitor.
The electrochemical performance test adopts a Kerst electrochemical workstation, and a cyclic voltammetry test (CV), a constant current charge discharge test (GCD), an alternating current impedance spectroscopy test (EIS) and a cyclic stability test are carried out on the material. The electrolyte was 3mol/L KOH and a three-electrode system was used at room temperature for the test, wherein an electrode sheet made of a composite material was used as a working electrode, a platinum wire was used as a counter electrode, and a silver electrode was used as a reference electrode.
The discharge time of the composite material under different current densities can be obtained in GCD according to the formula:
Cs＝(I*Δt)/(m*ΔV) (1)
the specific capacitance can be calculated. Wherein Cs represents the specific capacitance (F/g) of the electrode material; i represents a discharge current (A); Δt represents the discharge time(s), m represents the mass (g) of the active material in the electrode; deltaV represents the voltage range of the test system.
FIG. 1 is GO-C/Co (OH) 2 TEM image of composite material, from which Co (OH) with particle size of 20-30nm can be seen 2 The particles were uniformly dispersed on GO-C, indicating GO-C/Co (OH) 2 The composite material can effectively prevent Co (OH) 2 Agglomeration of particles is a problem.
FIG. 2 is GO-C/Co (OH) 2 The CV curve of the electrode material shows obvious oxidation-reduction peak, which shows that the electrode is mainly composed of Faraday pseudocapacitance and the electrode material is subjected to oxidation-reduction reaction in electrochemical reaction. These peaks are due to Co (OH) on the electrode surface 2 The particles are caused by redox chemistry occurring during the electrochemical process.
FIG. 3 is GO-C/Co (OH) 2 The GCD diagram of the electrode material shows that the constant current charge-discharge curve is highly symmetrical, which illustrates GO-C/Co (OH) 2 The composite material has good conductivity and coulombic efficiency. Calculation of GO-C/Co (OH) by equation (1) 2 The specific capacity of the electrode at a current density of 1A/g is 300F/g, and the electrode has higher capacitance performance compared with the traditional carbon material and MOFs material.
Example 2
(1) Ultrasonically cleaning a polyurethane sponge block with the concentration of 1cm multiplied by 2cm multiplied by 1cm by using an ethanol solution for 15 minutes, drying at 60 ℃ for 1 hour, then soaking the polyurethane sponge block in 2mg/mL of the ethanol solution of graphene oxide until the polyurethane sponge block is completely absorbed, drying the sponge at 60 ℃, and preparing a GO-modified porous sponge with the mass ratio of the sponge to the graphene oxide of 1:0.2;
(2) The GO-modified porous sponge is soaked in an aqueous solution containing 0.05g/mL zinc nitrate, extruded for a plurality of times, taken out and dried. Then putting the sponge into a solution containing 0.2g/mL of 2-methylimidazole, carrying out hydrothermal reaction at 80 ℃ for 12 hours, taking out and drying the solid after the reaction, then putting the dried sponge into a carbonization furnace for carbonization at 800 ℃ for 2 hours, cooling to room temperature after carbonization, taking out the product, and grinding the product into powder to obtain the GO-C@Zn material; wherein, the mass ratio of the GO modified porous sponge to the zinc nitrate is 1:1, and the mol ratio of the zinc nitrate to the 2-methylimidazole is 1:6.
(3) 0.1g of thioacetamide and 0.2g of GO-C@Zn are weighed and dissolved in 12mL of deionized water, ultrasonic treatment is carried out for 20min, and the mixed solution is put into a Teflon reaction kettle for reaction at 130 ℃ for 24h. Cooling to room temperature, taking out, washing with absolute ethanol, drying, soaking in 2M excessive sodium hydroxide solution for 26 hr, filtering, and drying to obtain black powder (GO-C/Zn (OH) 2 The specific capacity of the composite material, as an electrode, was 291F/g at a current density of 1A/g.
Example 3
(1) Ultrasonically cleaning a polystyrene sponge block with the volume of 1cm multiplied by 2cm multiplied by 1cm by using an ethanol solution for 15 minutes, drying at 60 ℃ for 1 hour, then soaking the polystyrene sponge block in a solution of 4mg/mL graphene oxide (a mixed solution of methanol and DMF according to the volume ratio of 1:5) until the polystyrene sponge block is completely absorbed, drying the sponge at 60 ℃, wherein the mass ratio of the sponge to the graphene oxide is 1:0.4, and preparing the GO modified porous sponge;
(2) The GO-modified porous sponge is soaked in an aqueous solution containing 0.15g/mL zinc nitrate, extruded for a plurality of times, taken out and dried. Then putting the sponge into a solution containing 0.5g/mL of 2-methylimidazole, carrying out hydrothermal reaction at 70 ℃ for 16 hours, taking out and drying the solid after the reaction, then putting the dried sponge into a carbonization furnace, carbonizing at 700 ℃ for 2.5 hours, cooling to room temperature after carbonization, taking out the product, and grinding the product into powder to obtain the GO-C@Zn material; wherein, the mass ratio of the GO modified porous sponge to the zinc nitrate is 1:5, the mole ratio of zinc nitrate to 2-methylimidazole is 1:5.
(3) 0.1g of thioacetamide and 0.3g of GO-C@Zn are weighed and dissolved in 25mL of deionized water together, ultrasonic treatment is carried out for 20min, and the mixed solution is put into a Teflon reaction kettle for reaction for 14h at 140 ℃. Cooling to room temperature, taking out, washing with absolute ethanol, drying, soaking in 5M excessive sodium hydroxide solution for 30 hr, filtering, and drying to obtain black powder (GO-C/Zn (OH) 2 The specific capacity of the composite, as electrode, at a current density of 1A/g was 289F/g.
Example 4
(1) Ultrasonically cleaning a 1cm multiplied by 2cm multiplied by 1cm polyorganosiloxane sponge block with ethanol solution for 15 minutes, drying at 60 ℃ for 1 hour, then soaking the sponge block in 8mg/mL graphene oxide solution (a mixed solution of water and ethanol according to a volume ratio of 1:1) until the sponge block is completely absorbed, drying the sponge at 60 ℃ and obtaining a GO modified porous sponge, wherein the mass ratio of the sponge to the graphene oxide is 1:0.8;
(2) The GO-modified porous sponge is soaked in an aqueous solution containing 0.2g/mL of copper nitrate, extruded for a plurality of times, taken out and dried. Then putting the sponge into a solution containing 0.8g/mL of 2-methylimidazole, carrying out hydrothermal reaction for 20 hours at 50 ℃, taking out and drying the solid after the reaction, then putting the dried sponge into a carbonization furnace for carbonization for 3 hours at 500 ℃, cooling to room temperature after carbonization, taking out the product, and grinding the product into powder to obtain the GO-C@Cu material; wherein, the mass ratio of the GO modified porous sponge to the copper nitrate is 1: the molar ratio of the copper nitrate to the 2-methylimidazole is 1:5.
(3) 0.1g of thioacetamide and 0.2g of GO-C@Cu are weighed and dissolved in 20mL of deionized water, ultrasonic treatment is carried out for 20min, and the mixed solution is put into a Teflon reaction kettle for reaction for 16h at 135 ℃. Cooling to room temperature, taking out, washing with absolute ethanol, drying, soaking in 4M excessive sodium hydroxide solution for 28 hr, filtering, and drying to obtain black powder (GO-C/Cu (OH) 2 The specific capacity of the composite, as electrode, was 279F/g at a current density of 1A/g.
Comparative example 1
The sponge was replaced with a polyurethane plastic block of the same size, with the other conditions being the same as in example 2.
The specific capacity of the obtained material under the current density of 1A/g is 30F/g, so that the porous material of the sponge is adopted, the growth area of MOFs is effectively increased, the specific surface area and active site of the obtained final material are increased, and the electrochemical performance of the material is improved.
The invention takes sponges such as melamine, polyurethane and the like as substrates, takes metal organic framework compounds (MOFs) as metal ion sources and is compounded with Graphene (GO), and successfully prepares GO-C@M (OH) 2 A composite material. By utilizing the characteristic of high porosity of the sponge, MOFs are grown on the outer surface and pores of the sponge, the specific surface area of the composite material is increased, the composite material benefits from the high porosity of the sponge, and the obtained composite material has a multi-stage pore structure and a large specific surface area, and meanwhile, the method is characterized in thatThe method effectively prevents the agglomeration of hydroxide nano particles, thereby improving the active point of the electrode material. In addition, the addition of graphene can enhance the conductivity of the composite electrode material, thereby improving GO-C@M (OH) 2 Electrochemical properties of the composite material. Thus, the GO-C@M (OH) obtained according to the invention 2 The composite material has a unique hierarchical pore structure and shows excellent electrochemical performance.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.

Claims (9)

1. Electrode composite material GO-C@M (OH) with hierarchical pores 2 The preparation method of (2) is characterized by comprising the following steps:
(1) Soaking the porous sponge in a GO solution to obtain a GO modified porous sponge, wherein the mass ratio of the porous sponge to the GO is 1 (0.1-1);
(2) Growing microporous MOFs on the GO-modified porous sponge by adopting a hydrothermal reaction to prepare a GO-porous sponge@MOFs composite material, and carbonizing to obtain a GO-C@M material; wherein M is a metal ion in MOFs;
(3) Hydrothermal reaction of GO-C@M material and sulfur-containing compound to prepare GO-C@MSO 4 ，GO-C@MSO 4 Soaking in alkaline solution to obtain electrode composite material GO-C@M (OH) 2 ；
The sponge is polyurethane sponge, melamine sponge, polystyrene sponge, polyethylene sponge or polysilicone sponge.
2. The electrode composite material with hierarchical pores GO-C@M (OH) as claimed in claim 1 2 The preparation method is characterized in that the concentration of the GO solution is 1-10 mg/mL, and the solvent in the GO solution is one or a mixture of more of water, ethanol, methanol and DMF in any proportion.
3. According to claim1 GO-C@M (OH) with hierarchical pore electrode composite material 2 The preparation method of the catalyst is characterized in that in the step (2), the raw materials of MOFs comprise a metal source and an imidazole ligand, wherein the mass ratio of the GO modified porous sponge to the metal source is 1: (1-5): the molar ratio of the imidazole ligand to the metal source is above 5.
4. The electrode composite material with hierarchical pores GO-C@M (OH) of claim 3 2 The preparation method of (2) is characterized in that in the hydrothermal reaction of the step (2), the concentration of the metal source is 0.05-0.2 g/mL; the metal source includes copper nitrate, zinc nitrate or cobalt nitrate.
5. The electrode composite material with hierarchical pores GO-C@M (OH) as claimed in claim 1 2 The preparation method of (2) is characterized in that the hydrothermal reaction in the step (2) is carried out at 50-100 ℃ for 12-24 hours; carbonization is carried out at 500-800 ℃ for 2-5 hours.
6. The electrode composite material with hierarchical pores GO-C@M (OH) as claimed in claim 1 2 The preparation method of (2) is characterized in that in the step (3), the sulfur-containing compound is thioacetamide, and in the hydrothermal reaction, the ratio of GO-C@M, thioacetamide and solvent is 0.1g (0.1-0.3) g (10-25) mL; the hydrothermal reaction in the step (3) is carried out at 130-150 ℃ for 12-24 h.
7. The electrode composite material with hierarchical pores GO-C@M (OH) as claimed in claim 1 2 The preparation method is characterized in that the concentration of the alkaline solution in the step (3) is 1-6 mol/L, and the soaking time is 24-48 h.
8. Electrode composite material GO-C@M (OH) with hierarchical pores prepared by the method of any one of claims 1-7 2 。
9. The electrode composite material with hierarchical pores GO-C@M (OH) as claimed in claim 8 2 In super capacitorIs used in the field of applications.
CN202210468154.8A 2022-04-29 2022-04-29 Electrode composite GO-C@M (OH) with hierarchical pores 2 Preparation method and application Active CN114843118B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210468154.8A CN114843118B (en) 2022-04-29 2022-04-29 Electrode composite GO-C@M (OH) with hierarchical pores 2 Preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210468154.8A CN114843118B (en) 2022-04-29 2022-04-29 Electrode composite GO-C@M (OH) with hierarchical pores 2 Preparation method and application

Publications (2)

Publication Number Publication Date
CN114843118A CN114843118A (en) 2022-08-02
CN114843118B true CN114843118B (en) 2024-04-09

Family

ID=82568729

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210468154.8A Active CN114843118B (en) 2022-04-29 2022-04-29 Electrode composite GO-C@M (OH) with hierarchical pores 2 Preparation method and application

Country Status (1)

Country Link
CN (1) CN114843118B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115846374B (en) * 2022-12-28 2023-05-30 杭州楠大环保科技有限公司 Method for preparing carbon source for wastewater treatment by utilizing kitchen waste

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105914058A (en) * 2016-06-20 2016-08-31 黑龙江科技大学 Composite electrode material and preparation method thereof
CN106229163A (en) * 2016-08-05 2016-12-14 上海应用技术学院 A kind of Graphene coupling flower ball-shaped Ni Mn bimetallic oxide three-dimensional hierarchical structure electrode material and preparation method thereof
CN108074751A (en) * 2017-12-08 2018-05-25 中北大学 A kind of flexible 3 D porous carbon materials and its preparation method and application
CN109686580A (en) * 2019-01-07 2019-04-26 湖北文理学院 A kind of ultra-thin Ni of 3D structure (OH)2Nanometer sheet/Ni nanoparticle@rGO combination electrode material preparation method and application
CN110164709A (en) * 2019-05-20 2019-08-23 常熟理工学院 A kind of preparation method of fiber/graphene/carbon quantum dot/cobalt sulfide nickel flexible electrode material
WO2022000070A1 (en) * 2020-06-30 2022-01-06 Atlas Power Generation Inc. Energy storage devices, components and materials thereof, and methods therefor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105914058A (en) * 2016-06-20 2016-08-31 黑龙江科技大学 Composite electrode material and preparation method thereof
CN106229163A (en) * 2016-08-05 2016-12-14 上海应用技术学院 A kind of Graphene coupling flower ball-shaped Ni Mn bimetallic oxide three-dimensional hierarchical structure electrode material and preparation method thereof
CN108074751A (en) * 2017-12-08 2018-05-25 中北大学 A kind of flexible 3 D porous carbon materials and its preparation method and application
CN109686580A (en) * 2019-01-07 2019-04-26 湖北文理学院 A kind of ultra-thin Ni of 3D structure (OH)2Nanometer sheet/Ni nanoparticle@rGO combination electrode material preparation method and application
CN110164709A (en) * 2019-05-20 2019-08-23 常熟理工学院 A kind of preparation method of fiber/graphene/carbon quantum dot/cobalt sulfide nickel flexible electrode material
WO2022000070A1 (en) * 2020-06-30 2022-01-06 Atlas Power Generation Inc. Energy storage devices, components and materials thereof, and methods therefor

Also Published As

Publication number Publication date
CN114843118A (en) 2022-08-02

Similar Documents

Publication Publication Date Title
CN108922790B (en) Preparation method and application of composite material
CN105529192A (en) Preparing method of copper quantum dot/activated carbon composite material applied to super capacitor
CN113517143B (en) Composite electrode material and preparation method and application thereof
CN113299486B (en) Selenium nickel cobalt/carbon composite material and preparation method and application thereof
WO2022021641A1 (en) Battery negative electrode material and preparation method therefor
CN110697795B (en) Cobalt-based binary metal sulfide and preparation method and application thereof
AU2020101283A4 (en) Method for Manufacturing Straw-Based Activated Carbon Electrode Material for Super Capacitor with Energy Storage Efficiency Enhanced Through Acid Mine Drainage
CN105719846B (en) A kind of preparation method of cobalt sulfide/carbon composite and products thereof and application
CN113675010A (en) Method for preparing Ce-Ni-MOF-based supercapacitor electrode material by electrodeposition method
Lu et al. Preparation of metal sulfide electrode materials derived based on metal organic framework and application of supercapacitors
CN114843118B (en) Electrode composite GO-C@M (OH) with hierarchical pores 2 Preparation method and application
Meghanathan et al. Metal-organic framework-derived Nickle Tellurideporous structured composites electrode materials for asymmetric supercapacitor application
CN115036516A (en) Cobalt and nitrogen co-doped hollow tubular porous carbon composite material and preparation method and application thereof
CN108484415B (en) Preparation method of cadmium metal organic complex, product and derivative thereof
CN110415993B (en) Preparation method and application of Mn-Co-S/Co-MOF nano material
CN109087820B (en) Graphene composite electrode material prepared in situ by ultrasonic chemical method
CN112279308A (en) Method for preparing high-energy-storage nickel-cobalt hydroxide electrode material in large batch
CN112216528A (en) Method for preparing electrode plate of high-voltage water-system supercapacitor by hydrothermal method
CN115763096A (en) Ni-MOF based on urotropine and preparation method and application thereof
CN110182781A (en) A kind of preparation method of supercapacitor three-dimensional framework charcoal nanometer sheet
CN115360363A (en) Porous carbon nanosheet domain-limited transition metal electrocatalyst prepared from chitosan and method
CN115547697A (en) Zinc-cobalt double-metal hydroxide electrode material with ultrahigh specific capacity and preparation method thereof
CN110797206B (en) Co-Mn-S composite material and preparation method and application thereof
CN111847526B (en) High-capacity super capacitor
CN111341567B (en) 3D poplar catkin derived carbon-supported NiCo-LDH nanosheet supercapacitor and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant