CN115083794B - Graphene @ M (OH) 2 Composite material of/C-N super capacitor and preparation method thereof - Google Patents

Graphene @ M (OH) 2 Composite material of/C-N super capacitor and preparation method thereof Download PDF

Info

Publication number
CN115083794B
CN115083794B CN202210632183.3A CN202210632183A CN115083794B CN 115083794 B CN115083794 B CN 115083794B CN 202210632183 A CN202210632183 A CN 202210632183A CN 115083794 B CN115083794 B CN 115083794B
Authority
CN
China
Prior art keywords
graphene
preparation
solution
water
mso
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
CN202210632183.3A
Other languages
Chinese (zh)
Other versions
CN115083794A (en
Inventor
刘辉
何清
李亮
何应
蒋灿
吴艳光
张云飞
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 CN202210632183.3A priority Critical patent/CN115083794B/en
Publication of CN115083794A publication Critical patent/CN115083794A/en
Application granted granted Critical
Publication of CN115083794B publication Critical patent/CN115083794B/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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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 graphene @ M (OH) 2 The preparation method of the composite material of the/C-N supercapacitor comprises the following steps: (1) Dispersing polystyrene microspheres with carboxylic acid groups in a solvent to obtain PS dispersion, and adding metal salt and imidazole compounds into the PS dispersion to prepare PS/ZIF; (2) carbonizing PS/ZIF to obtain M@C-N material; (3) Carrying out solvothermal reaction on M@C-N material, graphene and sulfur-containing compound to obtain graphene@MSO 4 a/C-N material; (4) Graphene @ MSO 4 Immersing the C-N material in an alkaline solution to obtain graphene @ M (OH) 2 a/C-N supercapacitor composite. The invention can improve the capacitance and stability of the electrode material, and the specific capacitance can reach 295.2-985.4F/g under the current density of 2A/g.

Description

Graphene @ M (OH) 2 Composite material of/C-N super capacitor and preparation method thereof
Technical Field
The invention belongs to the field of electrode materials, and particularly relates to graphene@M (OH) 2 A composite material of a/C-N super capacitor and a preparation method thereof.
Background
Among the electrochemical energy storage technologies, the super capacitor is considered to be a very promising energy storage device due to the advantages of rapid energy storage, high power output, long cycle life, environmental friendliness and the like, and has a wide application prospect. However, it is critical to design and prepare suitable electrode materials to improve the energy storage performance of the supercapacitor.
The hydroxide is focused by researchers due to the characteristics of high theoretical capacity and low cost, but the application of the hydroxide to the super capacitor is limited by the defects of easy agglomeration, low conductivity, poor cycling stability and the like.
The conductivity of the electrode material can be effectively improved by introducing conductive substances (carbon nanotubes, polypyrrole and polyaniline) onto the hydroxide, thereby improving the electrochemical activity. Electrode materials with larger porosity can be prepared by taking Metal Organic Frameworks (MOFs) as templates, and the MOFs serve as sacrificial templates and provide metal ions for the materials in the preparation process. Meanwhile, the material prepared by taking MOFs as a template can inherit some characteristics of MOFs such as a higher specific surface area, a unique pore structure and the like, so that the MOFs can be utilized to prepare the supercapacitor material with better electrochemical performance, but the electrochemical performance of the electrode material prepared by taking single MOFs as the template is improved only in a limited way, and at present, the electrode material is only in a theoretical view, and no scheme for reference is available in practical application.
Disclosure of Invention
The invention aims to overcome the technical defects and provide the graphene@M (OH) 2 The composite material of the/C-N super capacitor and the preparation method thereof solve the technical problem of poor electrochemical performance caused by easy agglomeration of 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) Dispersing polystyrene microspheres with carboxylic acid groups in a solvent to obtain PS dispersion, and adding metal salt and imidazole compounds into the PS dispersion to prepare PS/ZIF; the mass ratio of the polystyrene microsphere to the metal salt to the imidazole compound is 1: (4-8): (4-8);
(2) Carbonizing PS/ZIF to obtain M@C-N material;
(3) Carrying out solvothermal reaction on M@C-N material, graphene and sulfur-containing compound to obtain graphene@MSO 4 a/C-N material; wherein the mass ratio of M@C-N material, graphene and sulfur-containing compoundIs 1: (0.25-0.5): (0.5-2);
(4) Graphene @ MSO 4 Immersing the C-N material in an alkaline solution to obtain graphene @ M (OH) 2 a/C-N supercapacitor composite.
Further, the polystyrene microsphere with carboxylic acid groups in the step (1) is prepared by emulsion polymerization of styrene, acrylic acid and an initiator in water; the mass ratio of the styrene to the acrylic acid to the initiator is 6: (0.1-1): (0.01-0.2).
Further, the initiator is potassium persulfate or ammonium persulfate; the temperature of emulsion polymerization is 60-80 ℃ and the polymerization time is 3-10 h.
Further, in the step (1), the solvent is a mixture of ethanol and water, and the mass volume ratio of the polystyrene microspheres to the ethanol to the water is 1g: (8-12) mL: (180-220) mL.
Further, in the step (1), the metal salt is one or two of cobalt nitrate and zinc nitrate; the imidazole compound is 2-methylimidazole, 2-ethylimidazole or benzimidazole.
Further, in the step (2), the carbonization is carried out at 500-900 ℃ for 1-4 hours.
Further, in step (3), the sulfur-containing compound is thioacetamide; the solvothermal reaction is carried out at 170-190 ℃ for 22-26 h.
Further, in the step (3), M@C-N material and a sulfur-containing compound are added into a graphene solution for solvothermal reaction, the concentration of the graphene solution is 1.5-3 mg/mL, and the solvent of the graphene solution is absolute ethyl alcohol or a mixture of absolute ethyl alcohol and water.
Further, in the step (4), graphene @ MSO 4 The material/C-N is soaked in alkaline solution with the concentration of 1-6M for 1-2 days.
Graphene @ M (OH) prepared by the preparation method 2 a/C-N supercapacitor composite.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares graphene@M (OH) by taking PS and ZIFs as templates 2 Composite material of a C-N super capacitor, the composite materialThe method takes ZIFs as a template to provide a metal source and prepares nano M (OH) in the carbonization process 2 Can solve the defects that the graphene is not easy to be uniformly dispersed in the graphene and easy to agglomerate, which is beneficial to improving M (OH) 2 Electrochemical activity of the electrode material. The introduction of PS can improve M (OH) 2 The pore volume of the composite electrode material increases the porosity, thereby increasing the specific surface area; in addition, the introduction of the graphene can enhance the conductivity of the composite material so as to improve the electron migration rate of the electrode material, thereby improving the capacitance of the electrode material, and the specific capacitance of the electrode material serving as an electrode under the current density of 2A/g can reach 295.2-985.4F/g.
Drawings
FIG. 1 is graphene @ Co (OH) 2 SEM image of/C-N-33%;
FIG. 2 is Co (OH) in the present invention 2 C-N, graphene @ Co (OH) 2 C-N-25%, graphene @ Co (OH) 2 C-N-33% and graphene @ Co (OH) 2 CV diagram of/C-N-50%;
FIG. 3 is Co (OH) in the present invention 2 C-N, graphene @ Co (OH) 2 C-N-25%, graphene @ Co (OH) 2 C-N-33% and graphene @ Co (OH) 2 GCD diagram of/C-N-50%.
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 provides a method for preparing a graphene@M (OH) 2/C-N supercapacitor composite material by taking PS and ZIFs as templates. Firstly, copolymerizing styrene and acrylic acid to prepare polystyrene microsphere with carboxylic acid group, growing ZIFs around PS by coordination of carboxylic acid and metal ion, preparing M/C-N material with pore structure by high temperature carbonization, and generating graphene@MSO by the generated M/C-N material and graphene and thioacetamide under solvothermal reaction 4 C-N composite material, finally graphene @ MSO 4 Preparation of stones by soaking the C-N material in an alkaline solutionGraphene @ M (OH) 2 /C-N。
The invention comprises the following steps:
A. the polystyrene microsphere containing carboxyl group is prepared by emulsion polymerization of monomers such as styrene, acrylic acid and the like and an initiator in water. The mass ratio of the styrene to the acrylic acid to the initiator is 6: (0.1-1): (0.01-0.2), the reaction time is 3-10 h, and the temperature is 60-80 ℃;
B. the polystyrene microsphere is dispersed in an alcohol solution, and metal salt and imidazole compound are added so that the microporous ZIFs grow around the polystyrene microsphere to prepare the PS/ZIF. The mass ratio of the polystyrene microsphere to the metal salt to the imidazole compound is 1: (4-8): (4-8); wherein the molar excess of the imidazole compound relative to the metal salt (theoretical molar ratio is 1:1) ensures the metal salt to react completely; the mass volume ratio among the polystyrene microsphere, the ethanol and the water is 1g: (8-12) mL: (180-220) mL;
C. carbonizing PS/ZIF under a certain temperature and inert gas to prepare M@C-N material with porous structure, wherein the carbonization temperature is 500-900 ℃ and the carbonization time is 1-4 h; wherein M is a metal ion in a metal salt;
D. preparation of graphene @ MSO by reacting M@C-N with graphene and thioacetamide by solvothermal method 4 C-N material. The mass ratio of M@C-N to graphene to thioacetamide is 1: (0.25-0.5): (0.5-2); the reaction is to keep the temperature between 170 and 190 ℃ for 22 to 26 hours;
E. by combining graphene @ MSO 4 Soaking the/C-N material in an excessive alkaline solution for a certain time to prepare graphene@M (OH) 2 The concentration of the alkaline solution of the material/C-N is 1-6M, and the soaking time is 1-2 days.
Preferably, the initiator is potassium persulfate, ammonium persulfate, or the like.
Preferably, the ZIFs imidazole ligand is 2-methylimidazole, 2-ethylimidazole, benzimidazole and the like, and the metal salt is cobalt nitrate, zinc nitrate and mixtures thereof.
Preferably, the alkaline solution is potassium hydroxide or sodium hydroxide solution.
The invention is further illustrated by the following specific examples.
Example 1
(1) Preparation of carboxyl-containing polystyrene microspheres (PS)
10g of styrene, 0.5g of acrylic acid and 100mL of water were mechanically stirred in a 250mL three-necked flask and flushed with Ar protection, and the solution was a milky turbid liquid. After stirring the reaction solution for 30 minutes, heating was started to 70℃and then 10mL of an aqueous solution containing 0.25g of APS was added dropwise. After about 1h of reaction, polymerization is initiated, the system is white solution, after the reaction is continued for 6h, the reaction is naturally cooled to room temperature, white powder is obtained by centrifugal separation, and PS is obtained by drying under reduced pressure at 40 ℃.
(2) Preparation of PS/ZIF-67
1g of PS and 10mL of absolute ethanol were added to a beaker, and the mixture was subjected to ultrasonic dispersion for 10 minutes to prepare a PS ethanol dispersion. The PS ethanol dispersion was poured into 200mL of water and the dispersion was continued by sonication for 10 min. Then 4.8g (16 mmol) Co (NO) 2 ) 2 ·6H 2 O was added to the reaction solution, and the solution was pink. After stirring thoroughly for 1h, 10mL of water containing 4.25g (52 mmol) of 2-methylimidazole was added dropwise, the solution turned purple immediately, stirring was continued for 1h, centrifugal separation, washing with absolute ethanol, and oven drying at 60 ℃ to obtain 3.2 g purple solid ps@zif-67.
(3) Preparation of Co/C-N
3g of PS@ZIF-67 is placed in a tube furnace, the temperature is raised from room temperature to 600 ℃ at a heating rate of 5 ℃/min under the protection of Ar, the temperature is kept for 2 hours, and then the temperature is reduced to the room temperature, so that 1.72g of black Co@C-N powder is obtained.
(4) Graphene @ Co (OH) 2 Preparation of/C-N
Accurately weighing 0.09g of Co@C-N and 0.08g of thioacetamide in a hydrothermal reaction kettle, adding 10mL of graphene ethanol solution and 5mL of water (the total volume of the graphene ethanol solution and the water is 15mL, the concentration of the obtained graphene solution is 2mg/mL, preparing electrode materials with different graphene relative to Co@C-N according to the change of graphene content of the water and the graphene ethanol solution in proportion), carrying out ultrasonic treatment and stirring for 5min, placing the materials into an oven for reaction for 24h at 180 ℃, cooling and filtering after the reaction, and drying at 60 ℃ under reduced pressure to obtain graphene@CoSO 4 C-N. Graphene @ CoSO 4 soaking/C-N in 3M potassium hydroxide solution for 24 hr, filtering, and drying at 60deg.C under reduced pressureObtaining graphene @ Co (OH) 2 The amount of graphene is 33% relative to the mass of Co@C-N, so that the product is recorded as graphene@Co (OH) 2 /C-N-33％。
Example 2
For convenience of comparison, changing the ratio of graphene ethanol solution to water, and respectively preparing graphene@Co (OH) with different graphene contents 2 a/C-N composite. Such as Co (OH) 2 C-N, graphene @ Co (OH) 2 C-N-25%, graphene @ Co (OH) 2 C-N-33% and graphene @ Co (OH) 2 The content of the graphene is 0 percent, 25 percent, 33 percent and 50 percent of the mass of Co@C-N.
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.
In GCD we can get the discharge time of the composite material at different current densities 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 shows graphene @ Co (OH) 2 SEM image of/C-N-33%, co (OH) having an average diameter of 30-40nm is evident from the image 2 The nano-sheets are uniformly dispersed on the graphene sheet layer without any accumulation and aggregation, and the structure is active substance Co (OH) 2 More electrolyte contact area is provided, so that rapid diffusion of ions is realized, and more conductive channels are provided by the presence of graphene.
FIG. 2 shows Co (OH) 2 C-N, graphene @ Co (OH) 2 C-N-25%, graphene @ Co(OH) 2 C-N-33% and graphene @ Co (OH) 2 CV diagram of C-N-50%, from which it can be seen that CV curves of four materials exhibit distinct redox peaks, rather than an approximately rectangular shape, and Co (OH) 2 C-N and graphene @ Co (OH) 2 The CV curves of/C-N-25% overlap, which indicates that the four material electrodes are mainly composed of Faraday pseudocapacitance, and that the electrode materials must undergo Faraday reaction in electrochemical reaction. These peaks are caused by redox chemistry of the metal ions on the electrode surface during the electrochemical process.
FIG. 3 is a GCD graph of four materials, from which it can be seen that the constant current charge-discharge curves are highly symmetric, illustrating graphene @ Co (OH) 2 the/C-N composite material has good electric conductivity. Co (OH) was calculated by equation (1) 2 C-N, graphene @ Co (OH) 2 C-N-25%, graphene @ Co (OH) 2 C-N-33% and graphene @ Co (OH) 2 The specific capacities of the electrodes/C-N-50% at a current density of 2A/g were 161, 616.1, 985.4 and 295.2F/g, respectively. The result shows that the addition amount of the graphene has a great influence on the material of the electrode, and the better the specific capacitance performance of the composite electrode material is along with the increase of the content of the graphene, mainly because the graphene can increase the conductivity of the material so as to enhance the specific capacitance. However, when the graphene content reaches 50%, the specific capacitance of the composite electrode material is reduced, and the active substance Co (OH) is mainly caused by the too high graphene content 2 Resulting in a decrease in specific capacitance performance thereof. Thus, graphene @ Co (OH) 2 The graphene content in the/C-N material is preferably 25-50% of the mass of the Co@C-N; more preferably, the specific capacitance is between 25 and 33%, and the specific capacitance is the best.
Example 3
(1) Preparation of carboxyl-containing polystyrene microspheres (PS)
10g of styrene, 0.2g of acrylic acid and 100mL of water were mechanically stirred in a 250mL three-necked flask and flushed with Ar protection, and the solution was a milky turbid liquid. After the reaction mixture was stirred for 30 minutes, heating was started to 60℃and then 10mL of an aqueous solution containing 0.02g of APS was added dropwise. After about 1h of reaction, polymerization is initiated, the system is white solution, after the reaction is continued for 8h, the reaction is naturally cooled to room temperature, white powder is obtained by centrifugal separation, and PS is obtained by drying under reduced pressure at 40 ℃.
(2) Preparation of PS/ZIF
1g of PS and 10mL of absolute ethanol were added to a beaker, and the mixture was subjected to ultrasonic dispersion for 10 minutes to prepare a PS ethanol dispersion. The PS ethanol dispersion was poured into 200mL of water and the dispersion was continued by sonication for 10 min. Then 6g (21 mmol) Co (NO) 2 ) 2 ·6H 2 O was added to the reaction solution, and the solution was pink. After stirring thoroughly for 1h, 10mL of water containing 8g (68 mmol) of benzimidazole was added dropwise, the solution turned purple immediately, stirring was continued for 1h, centrifugal separation, washing with absolute ethanol, and oven drying at 60℃to obtain a purple solid PS@ZIF-7-Co.
(3) Preparation of Co/C-N
And (3) placing PS@ZIF-7-Co in a tube furnace, heating from room temperature to 700 ℃ at a heating rate of 5 ℃/min under Ar protection, preserving heat for 1.5 hours, and cooling to room temperature to obtain black Co@C-N powder.
(4) Graphene @ Co (OH) 2 Preparation of/C-N
Accurately weighing 0.09g of Co@C-N and 0.05g of thioacetamide in a hydrothermal reaction kettle, adding 10mL of 3mg/mL graphene ethanol solution and 5mL of water, carrying out ultrasonic treatment and stirring for 5min, placing into an oven to react at 170 ℃ for 25h, cooling and filtering after the reaction is finished, and drying at 60 ℃ under reduced pressure to obtain graphene@CoSO 4 C-N. Graphene @ CoSO 4 soaking/C-N in 5M potassium hydroxide solution for 24 hr, filtering, and drying at 60deg.C under reduced pressure to obtain graphene @ Co (OH) 2 A/C-N composite electrode material having a specific capacitance of 937.2F/g at a current density of 2A/g.
Example 4
(1) Preparation of carboxyl-containing polystyrene microspheres (PS)
10g of styrene, 1.5g of acrylic acid and 100mL of water were mechanically stirred in a 250mL three-necked flask and flushed with Ar protection, and the solution was a milky turbid liquid. After stirring the reaction solution for 30 minutes, heating was started to 80℃and then 10mL of an aqueous solution containing 0.3g of potassium persulfate was added dropwise. After about 1 to h, polymerization is initiated, the system is white solution, after the reaction is continued for 4 hours, the system is naturally cooled to room temperature, white powder is obtained by centrifugal separation, and PS is obtained by drying under reduced pressure at 40 ℃.
(2) Preparation of PS/ZIF
1g of PS and 10mL of absolute ethanol were added to a beaker, and the mixture was subjected to ultrasonic dispersion for 10 minutes to prepare a PS ethanol dispersion. The PS ethanol dispersion was poured into 200mL of water and the dispersion was continued by sonication for 10 min. Then 8g (27 mmol) Zn (NO) 2 ) 2 ·6H 2 O was added to the reaction solution, and the solution was pink. After stirring thoroughly for 1h, 10mL of water containing 6g (62 mmol) of 2-methylimidazole was added dropwise, the solution turned purple immediately, stirring was continued for 1h, centrifugal separation was continued, washing with absolute ethanol, and oven drying at 60 ℃ was carried out to obtain a purple solid ps@zif-8.
(3) Preparation of Zn/C-N
And (3) placing the PS@ZIF-8 into a tube furnace, heating from room temperature to 800 ℃ at a heating rate of 5 ℃/min under the protection of Ar, preserving heat for 1h, and then cooling to room temperature to obtain black Zn@C-N powder.
(4) Graphene @ Zn (OH) 2 Preparation of/C-N
Accurately weighing 0.09g of Zn@C-N and 0.15g of thioacetamide in a hydrothermal reaction kettle, adding 10mL of 3mg/mL graphene ethanol solution and 5mL of water, carrying out ultrasonic treatment and stirring for 5min, placing into an oven to react at 190 ℃ for 23h, cooling and filtering after the reaction is finished, and drying at 60 ℃ under reduced pressure to obtain graphene@ZnSO 4 C-N. Graphene @ ZnSO 4 soaking/C-N in 2M sodium hydroxide solution for 36h, filtering, and drying at 60deg.C under reduced pressure to obtain graphene @ Zn (OH) 2 A/C-N composite electrode material having a specific capacitance of 929.6F/g at a current density of 2A/g.
The invention prepares the electrode material graphene@M (OH) of the supercapacitor by taking polystyrene microspheres (PS) and ZIFs as templates 2 Firstly preparing polystyrene microsphere with carboxylic acid group, growing ZIFs around PS by coordination of carboxylic acid and metal ion, preparing M/C-N material with pore structure by high temperature carbonization, and then performing solvothermal reaction of M/C-N with graphene and thioacetamide to generate graphene@MSO 4 C-N material, finally graphene @ MSO 4 the/C-N material is converted into graphene @ M (OH) under alkaline conditions 2 C-N. M (OH) in the composite material 2 Uniformly dispersed on graphene sheets, the structure can provide specific surface area and hasIs beneficial to promoting ion diffusion, thereby effectively improving 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 (4)

1. Graphene @ M (OH) 2 The preparation method of the/C-N supercapacitor composite material is characterized by comprising the following steps of:
(1) Dispersing polystyrene microspheres with carboxylic acid groups in a solvent to obtain PS dispersion, and adding metal salt and imidazole compounds into the PS dispersion to prepare PS/ZIF; the mass ratio of the polystyrene microsphere to the metal salt to the imidazole compound is 1: (4-8): (4-8);
(2) Carbonizing PS/ZIF to obtain M@C-N material;
(3) Carrying out solvothermal reaction on M@C-N material, graphene and sulfur-containing compound to obtain graphene@MSO 4 a/C-N material; wherein the mass ratio of M@C-N material, graphene and sulfur-containing compound is 1: (0.25-0.5): (0.5-2);
(4) Graphene @ MSO 4 Immersing the C-N material in an alkaline solution to obtain graphene @ M (OH) 2 a/C-N supercapacitor composite;
the polystyrene microsphere with carboxylic acid groups in the step (1) is prepared by emulsion polymerization of styrene, acrylic acid and an initiator in water; the mass ratio of the styrene to the acrylic acid to the initiator is 6: (0.1-1): (0.01-0.2);
the initiator is potassium persulfate or ammonium persulfate; the temperature of emulsion polymerization is 60-80 ℃ and the polymerization time is 3-10 h;
in the step (1), the solvent is a mixture of ethanol and water, and the mass volume ratio among the polystyrene microspheres, the ethanol and the water is 1g: (8-12) mL: (180-220) mL;
in the step (1), the metal salt is one or two of cobalt nitrate and zinc nitrate; the imidazole compound is 2-methylimidazole, 2-ethylimidazole or benzimidazole;
in the step (3), the sulfur-containing compound is thioacetamide; the solvothermal reaction is carried out by preserving heat at 170-190 ℃ and 22-26 h;
in the step (3), M@C-N material and sulfur-containing compound are added into graphene solution for solvothermal reaction, the concentration of the graphene solution is 1.5-3 mg/mL, and the solvent of the graphene solution is absolute ethyl alcohol or a mixture of absolute ethyl alcohol and water.
2. The graphene @ M (OH) according to claim 1 2 The preparation method of the/C-N supercapacitor composite material is characterized in that in the step (2), the carbonization is carried out at 500-900 ℃ for 1-4 h.
3. The graphene @ M (OH) according to claim 1 2 The preparation method of the/C-N supercapacitor composite material is characterized in that in the step (4), graphene@MSO 4 The material/C-N is soaked in alkaline solution with the concentration of 1-6M for 1-2 days.
4. The process according to any one of claims 1 to 3, wherein the graphene @ M (OH) 2 a/C-N supercapacitor composite.
CN202210632183.3A 2022-04-29 2022-04-29 Graphene @ M (OH) 2 Composite material of/C-N super capacitor and preparation method thereof Active CN115083794B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210632183.3A CN115083794B (en) 2022-04-29 2022-04-29 Graphene @ M (OH) 2 Composite material of/C-N super capacitor and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210632183.3A CN115083794B (en) 2022-04-29 2022-04-29 Graphene @ M (OH) 2 Composite material of/C-N super capacitor and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115083794A CN115083794A (en) 2022-09-20
CN115083794B true CN115083794B (en) 2024-03-26

Family

ID=83249980

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210632183.3A Active CN115083794B (en) 2022-04-29 2022-04-29 Graphene @ M (OH) 2 Composite material of/C-N super capacitor and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115083794B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015184815A1 (en) * 2014-06-04 2015-12-10 福州大学 Flocculent-polyaniline-coated graphene composite material, method for preparation thereof, and use thereof
CN105938761A (en) * 2016-03-21 2016-09-14 浙江大学 Magnesium-cobalt oxide/graphene composite material used as supercapacitor electrode material and preparation method thereof
WO2016169034A1 (en) * 2015-04-23 2016-10-27 中国科学院福建物质结构研究所 Porous conductive graphene/carbon nanohorn composite material, preparation method and use thereof
CN108766785A (en) * 2018-07-02 2018-11-06 桂林电子科技大学 A kind of graphene-polypyrrole-cobalt nickel bimetal hydroxide composite material and its preparation method and application
CN110867327A (en) * 2019-11-27 2020-03-06 华北电力大学 Multi-level secondary pore carbon aerogel material, supercapacitor electrode material and preparation method
CN113415831A (en) * 2021-05-08 2021-09-21 湖南大学 A kind of Ni (OH)2Preparation method of/graphene composite material and preparation method of supercapacitor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015184815A1 (en) * 2014-06-04 2015-12-10 福州大学 Flocculent-polyaniline-coated graphene composite material, method for preparation thereof, and use thereof
WO2016169034A1 (en) * 2015-04-23 2016-10-27 中国科学院福建物质结构研究所 Porous conductive graphene/carbon nanohorn composite material, preparation method and use thereof
CN105938761A (en) * 2016-03-21 2016-09-14 浙江大学 Magnesium-cobalt oxide/graphene composite material used as supercapacitor electrode material and preparation method thereof
CN108766785A (en) * 2018-07-02 2018-11-06 桂林电子科技大学 A kind of graphene-polypyrrole-cobalt nickel bimetal hydroxide composite material and its preparation method and application
CN110867327A (en) * 2019-11-27 2020-03-06 华北电力大学 Multi-level secondary pore carbon aerogel material, supercapacitor electrode material and preparation method
CN113415831A (en) * 2021-05-08 2021-09-21 湖南大学 A kind of Ni (OH)2Preparation method of/graphene composite material and preparation method of supercapacitor

Also Published As

Publication number Publication date
CN115083794A (en) 2022-09-20

Similar Documents

Publication Publication Date Title
Wang et al. Effect of activated carbon surface functional groups on nano-lead electrodeposition and hydrogen evolution and its applications in lead-carbon batteries
CN102522218B (en) Nano nickel oxide/graphene composite electrode material as well as preparation method and application thereof
CN105253871B (en) Ultracapacitor nitrogenous carbon material and preparation method thereof, electrode material for super capacitor
CN102923698A (en) Preparation method for three-dimensional porous graphene for supercapacitor
CN109767924B (en) LDH-based supercapacitor composite electrode material, and preparation method and application thereof
CN113629249B (en) Preparation method of MXene-based supported platinum catalyst applied to lithium-sulfur battery anode
CN113517143B (en) Composite electrode material and preparation method and application thereof
CN111883366A (en) Polypyrrole nanosphere @ titanium carbide composite material and preparation method and application thereof
CN104157858A (en) Hierarchical porous ferroferric oxide / graphene nano wire and preparation method and application thereof
CN110697795B (en) Cobalt-based binary metal sulfide and preparation method and application thereof
CN104167298A (en) Graphene-protein derived carbon supercapcaitor material and preparation method thereof
CN110310838B (en) Hollow nano cage composite material and preparation method and application thereof
Mahieddine et al. Core-shell structured hierarchical Ni nanowires and NiS/Co3S4 microflowers arrays as a high-performance supercapacitor electrode
CN111063549B (en) Two-dimensional MOFs nanosheet-derived full-electrode material for hybrid capacitor
CN114843118B (en) Electrode composite GO-C@M (OH) with hierarchical pores 2 Preparation method and application
CN115083794B (en) Graphene @ M (OH) 2 Composite material of/C-N super capacitor and preparation method thereof
CN114560508B (en) Composite catalyst for super capacitor and preparation method and application thereof
CN115763096A (en) Ni-MOF based on urotropine and preparation method and application thereof
CN114758898A (en) C/N-NiCoFeMn LDH composite electrode material and preparation method thereof
CN115224291A (en) Hollow spherical Fe and N co-doped porous carbon-based catalyst and preparation method and application thereof
CN110808170B (en) High-energy super capacitor with porous carbon nitride interlayer material configuration and preparation method thereof
CN112420401B (en) Bismuth oxide/manganese oxide composite supercapacitor and preparation method thereof
CN114446671A (en) Preparation method of MOF-5/PPy/GO nano material and application thereof in aspect of super capacitor
CN115083798A (en) Multistage nanosheet array NiCo 2 O 4 Preparation method of/rGO/NF and application of/rGO/NF as electrode
CN110323080B (en) Preparation method of water system super capacitor

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
GR01 Patent grant