CN111591981B - Preparation method of low-layer gauze-shaped nitrogen-doped graphene - Google Patents

Preparation method of low-layer gauze-shaped nitrogen-doped graphene Download PDF

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CN111591981B
CN111591981B CN202010318601.2A CN202010318601A CN111591981B CN 111591981 B CN111591981 B CN 111591981B CN 202010318601 A CN202010318601 A CN 202010318601A CN 111591981 B CN111591981 B CN 111591981B
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高波
付海洋
刘状
阚家文
李魁
孙悦
尹俊太
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Northeastern University China
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Abstract

The invention belongs to the field of material preparation, and provides a preparation method of low-layer gauze-shaped nitrogen-doped graphene. The method comprises the steps of dispersing a solution obtained after oxidation reaction in an ethanol solvent by using an ethanol intercalation technology, adding a proper amount of diethanolamine after ultrasonic treatment, placing the mixture in a reaction kettle, heating, filtering, and drying to obtain the nitrogen-doped graphene. Secondly, the nitrogen-containing graphene is placed in a vacuum tube and embedded in a microwave oven for a certain time, microwave energy is converted into heat through pi electron movement in the graphite hybrid structure, and oxygen-containing functional groups in the precursor are decomposed into CO 2 And H 2 And O gas, wherein the pressure generated by the gas exceeds the Van der Waals force between the sheet layers, and at the moment, the nitrogen-doped graphene sheet layers are peeled off, so that 1-4 layers of the porous nitrogen-containing graphene powder material are obtained. The nitrogen-containing graphene prepared by the method is simple in whole preparation process and low in raw material cost, has a porous and interconnected three-dimensional structure, is large in specific surface area and good in conductivity, and can promote the rapid diffusion of electrolyte ions and improve the specific capacity after being used for a super capacitor.

Description

Preparation method of low-layer gauze-shaped nitrogen-doped graphene
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a preparation method and application of low-layer gauze nitrogen-doped graphene ethanol intercalation microwave embedding.
Background
When fossil energy is continuously exhausted, as the population base is large and the demand is increasing, the development of new energy sources such as biomass energy, wind energy, ocean energy, nuclear energy, solar energy and the like is urgent. With the increasing emphasis on environmental problems in China, environmental protection technology is widely accepted. The state advocates low carbon and environmental protection, but the development of energy storage devices with excellent performance is very important, and the energy storage devices can be applied to solar energy storage plates, super capacitors, lithium ion batteries, fuel cells and new energy automobiles. The ideal electrode material for a supercapacitor should have three properties: the high specific capacitance is used for improving the energy density, and the excellent rate performance is used for maintaining high power output and good reversibility to meet the charge-discharge cycle life. How to obtain high-quality graphene with high yield is crucial to future development and application.
The super capacitor is a high-efficiency energy storage source with potential development, and attracts wide attention in the field of energy storage due to excellent electrochemical performance of the super capacitor. The super capacitor device mainly comprises a working electrode, a collector electrode, electrolyte, a diaphragm and a packaging material. The electrode material is the most important component affecting the performance of the supercapacitor. Future development of carbon-based materials will be mainly focused on high-power graphite-based negative electrodes and non-graphite-based high-capacity carbon negative electrodes. The material has larger theoretical capacity, but the problems of long production period, easy agglomeration of samples and difficult preparation of low-layer graphene easily occur in the using process, so the development of the material is restricted. The research on the performance of the graphene can be widely applied, and the required porous graphene can be prepared in a reliable, low-cost and high-quality mode. A series of studies have been conducted by academia on how to improve the process conditions for the performance of graphene materials.
Graphene has great potential for development in electrochemical supercapacitors due to its extremely high thermal and electrical conductivity, excellent mechanical strength and large specific surface area. In recent years, Graphene (Graphene) is found to be sp from carbon atoms 2 The hybrid tracks form a hexagonal honeycomb lattice two-dimensional carbon nanomaterial. The material has the advantages of high hardness, good toughness, large specific surface area and good energy storage performance. But also has the disadvantage that agglomerated graphene sheets are formed due to strong pi-pi interactions and do not provide sufficient channels for electrolyte ion conduction, resulting in slowing of capacitor activity and rate capability. In order to solve the problem, various functions of graphene need to be modified to form the three-dimensional nitrogen-doped graphene aerogel, and the porous and interconnected three-dimensional structures have a large specific surfaceAnd the area can promote the rapid diffusion of electrolyte ions. But the implementation steps need to be improved and perfected, and the process for researching a small amount of products which are simple and feasible in reaction conditions and can be synthesized is researched. The nitrogen-doped carbon material is prepared by matching nitrogen atoms to lattices in carbon, and the research on the doped porous graphene material with excellent performance is crucial to the development of a super capacitor and can also be applied to energy storage batteries of new energy vehicles.
At present, a plurality of preparation methods for graphene materials exist at home and abroad, but different preparation methods and preparation conditions have great influence on the structural performance of graphene. The main methods for preparing graphene currently include microwave solvothermal method, Chemical Vapor Deposition (CVD), solid-phase microwave irradiation method, heat treatment method, and the like. Although the CVD method can prepare graphene with large specific surface area, the process is complex, the preparation cost is high, the period is long, and the transfer difficulty of the graphene generated on the surface of the substrate is large. And (3) directly carrying out microwave heating on the precursor of the graphite by a solid-phase microwave radiation method, and stripping the precursor of the graphite into single-layer or multi-layer graphene. The stripping effect is affected by long stripping time and high oxygen content in the precursor. The ethanol intercalation microwave embedding method for preparing the low-layer porous nitrogen-doped graphene has low cost and environmental protection, the product can stably exist in water or an organic solvent without subsequent substrate transfer, and a feasible preparation method is provided for development and industrial application of obtaining a small amount of low-layer thin gauze-shaped nitrogen-doped graphene material.
The ethanol intercalation microwave intercalation method is studied by adjusting the bond in the carbon-carbon planar graphene structure. And the replacement of carbon in the graphene lattice by heteroatoms can prevent the re-stacking of graphene sheets and enhance the electrochemical performance of the faraday reaction. The incorporation of heteroatoms can also alter the electronic structure and density. The capacitance limit of the quantum nano carbon is overcome on the Fermi level, and finally the specific capacitance is increased. Compared with the traditional industrial method, the method has the advantages of low production cost, simple principle, strong operation feasibility, capability of preparing low-layer nitrogen-containing graphene by energy production and the like, and has wide industrial application prospect. At present, research work on the aspects of microstructure, performance change and the like of materials is relatively little carried out by the method, most researches on graphene modification are in an exploratory state, and researches on practical application aspects are relatively slow.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing low-layer gauze-shaped nitrogen-doped graphene by embedding ethanol intercalation microwaves, so as to obtain a porous nitrogen-doped graphene material with high specific capacity, and the porous nitrogen-doped graphene material is applied to a super capacitor.
The specific technical scheme of the invention is as follows:
a preparation method of low-layer gauze-shaped nitrogen-doped graphene comprises the following steps:
(1) preparing nitrogen-doped graphene:
mixing the crystalline flake graphite with a mixed solution of concentrated sulfuric acid and concentrated nitric acid according to the proportion of 1:110 g/ml; and stirring at 45 ℃; then, adding potassium permanganate and graphite in a mass ratio of 6:1, continuously stirring, heating to 60 ℃, reacting for 7 hours, and then continuously heating to 90 ℃ to react for 40 min; then naturally cooling the reacted solution to room temperature; mixing the cooled solution and an ethanol intercalation solvent according to a volume ratio of 22: 1-1.5, carrying out ultrasonic treatment, adding Diethanolamine (DEA) into the mixture, carrying out nitrogen doping on the mixture according to a volume ratio of 1-5: 100, putting the solution into a high-pressure reaction kettle, heating at the temperature of 190-;
(2) synthesis of microwave-embedded porous low-layer nitrogen-containing graphene:
and (2) putting the nitrogen-containing graphene obtained in the step (1) into a vacuum tube, embedding the nitrogen-containing graphene into a microwave oven, wherein the microwave power is 700-800W, and the reaction time is 2-5min, so as to obtain the porous nitrogen-containing graphene powder.
Wherein, the graphite is a commercial graphite powder product with the specification of 325 meshes.
The solution H 2 SO 4 The mass concentration is 98%, the mass concentration of nitric acid is 65%, the content of potassium permanganate is more than 99.5%, the content of Diethanolamine (DEA) is more than or equal to 99.0%, and the mass fraction of ethanol is 99.7%.
Further, the concentrated sulfuric acid and the concentrated nitric acid used are mixed in a volume ratio of 10: 1.
The cooled solution and the ethanol intercalation solvent are in a volume ratio of 22:1.
The volume ratio of diethanol amine (DEA) to the solution after intercalation is about 1-2: 100.
The application of the gauze-shaped porous nitrogen-doped graphene with the low layer prepared by the method in manufacturing the button type super capacitor comprises the following steps:
(1) preparing an electrode slice: weighing the nitrogen-containing graphene serving as an active substance, acetylene black serving as a conductive agent and polytetrafluoroethylene serving as a binder according to the weight ratio of 78:12:10 (wt%), adding a proper amount of deionized water, and mixing into a slurry. The slurry was uniformly applied to 10mm phi foamed nickel (weighed). Drying at 120 deg.C for 1h under vacuum, tabletting, and weighing.
(2) Assembling the button capacitor: in a vacuum glove box, a lower shell, a current collector (foamed nickel)/positive electrode, a diaphragm, a negative electrode/current collector (foamed nickel), a gasket, a spring, a proper amount of 3mol/L KOH electrolyte and an upper shell are assembled into a button type super capacitor in sequence, and 50kg/cm is used 2 The pressure of the sealing cap seals the supercapacitor.
The invention has the beneficial effects that:
in the prior art, the defects of high cost, long production period, sample stacking and poor conductivity caused by introduction of more impurities occur in the processes of a microwave solvothermal method, a Chemical Vapor Deposition (CVD) method, a solid-phase microwave radiation method, a heat treatment method and the like.
In the prior art, doped graphene obtained by a redox method only can obviously attenuate the surface porous capacity and cannot fully ensure the conductivity of the graphene. In the invention, the microwave energy is used for converting the movement of pi electrons in the graphite hybrid structure into heat energy, and oxygen-containing functional groups and doped substances in the precursor are rapidly decomposed into CO 2 And H 2 And (4) O gas. When the pressure generated by the gas exceeds the Van der Waals force between the sheet layers, the nitrogen-containing graphene sheet layers are peeled off to obtain 1-4 layers of porous nitrogen-doped graphene. And the abundant redox active sites of the porous nitrogen-doped structure provide effective paths for ion diffusion and electron transmission. The sample prepared by the microwave embedding method shortens the reaction time and has more obvious porosity. The low-layer nitrogen-doped graphene shows more excellent performance than pure graphene, is in a disordered, transparent and folded gauze shape, and shows higher specific capacitance and good cycle life. Through the research on the reaction conditions of the intercalation microwave intercalation method, a method for preparing high-performance graphene simply, conveniently and quickly with low energy consumption is developed, and nitrogen-containing graphene is prepared from ethanol and then subjected to microwave intercalation to perform avalanche-like deoxidation reaction under the action of microwaves. The method solves the problems that the prepared graphene layers have high influence on conductivity and zero band gap influence on ion passing rate, increases the interlayer spacing of the graphene sheets, and prepares the low-layer porous high-quality nitrogen-doped graphene film with large specific surface area. The porosity can improve the material transportation rate and effectively open the energy band gap of the graphene, and the nitrogen-containing porous graphene is applied to the electrode of the supercapacitor, can improve the ion transportation rate, has excellent electrochemical performance and stability, and makes a certain contribution to a new generation of energy storage devices.
The whole preparation process flow is simple, the material cost is low, the operation is easy, the prepared nitrogen-containing graphene has a porous and interconnected three-dimensional structure, the specific surface area is large, 1-4 layers of films and good conductivity, and after the nitrogen-containing graphene is used for a super capacitor, the rapid diffusion of electrolyte ions can be promoted, the specific capacity is greatly improved, and the stability is improved.
Drawings
Fig. 1 is a diagram of an assembly of the button capacitor according to example 1.
FIG. 2 is a FE-SEM scanning electron microscope morphology image of material comparison. (a) Nitrogen-doped graphene which is not intercalated with ethanol; (b) non-nitrogen doped graphene; (c) and (3) carrying out ethanol intercalation nitrogen-doped graphene.
Detailed Description
Example 1
The preparation method of the low-layer gauze-shaped nitrogen-doped graphene of the embodiment is carried out according to the following steps:
(1) preparing nitrogen-doped graphene:
2.0g of flake graphite was mixed with 220ml of concentrated sulfuric acid and concentrated nitric acid at a volume ratio of 10:1, and stirred at 45 ℃ for 30 min. And then adding 12.0g of potassium permanganate and graphite in a mass ratio of 6:1, continuously stirring for 40min, heating to 60 ℃, reacting for 7h, and then continuously heating to 90 ℃ for reacting for 40 min. Then the reacted solution was naturally cooled to room temperature. Mixing the cooled solution and an ethanol intercalation solvent according to a volume ratio of 22:1 for reaction, carrying out ultrasonic treatment for 20 minutes, then adding Diethanolamine (DEA) into the mixture to carry out nitrogen doping with the volume ratio of 1:100, putting the solution into a reaction kettle, heating for 12 hours at 200 ℃, finally carrying out suction filtration on the solution, washing with deionized water, repeatedly carrying out suction filtration until the pH value is 7, and carrying out freeze drying to obtain nitrogen-containing graphene;
(2) synthesis of microwave-embedded porous low-layer nitrogen-containing graphene:
and (2) putting the nitrogen-containing graphene (NG) obtained in the step (1) in a vacuum tube, wherein the microwave power used in a microwave oven is 750W, and the reaction time is 3min, so as to obtain the porous nitrogen-containing graphene powder.
Wherein, the graphite is a commercial graphite powder product with the specification of 325 meshes.
The solution H 2 SO 4 The mass concentration is 98%, the mass concentration of nitric acid is 65%, the content of potassium permanganate is more than 99.5%, the content of Diethanolamine (DEA) is more than or equal to 99.0%, and the mass fraction of ethanol is 99.7%.
The gauze-like porous nitrogen-doped graphene finally obtained after the step (2) has good electron and ion mobility, and can be applied to preparation of capacitor electrode materials. As shown in fig. 2, FE-SEM electron micrographs analyze the microstructure of graphene. Fig. a shows that the nitrogen-doped graphene intercalated by ethanol is seriously agglomerated, and fig. b shows that the nitrogen-doped graphene is delaminated without separation and the layers are stacked. And the graph c shows that the ethanol intercalated nitrogen-doped graphene sheet layers are in a gauze shape, the distance between the sheet layers is increased, and the layering effect of the surface area expanded sheet layers is very good. Moreover, after nitrogen incorporation, the same morphology as non-nitrogen-doped graphene was observed, indicating that the surface microstructure was preserved before and after doping.
The application of the gauze-shaped nitrogen-doped porous graphene in the embodiment is to manufacture a button-type supercapacitor, and the method specifically comprises the following steps, wherein a button-type capacitor assembly object diagram is shown in fig. 1:
(1) preparing an electrode plate: weighing the nitrogen-containing graphene serving as an active substance, acetylene black serving as a conductive agent and polytetrafluoroethylene serving as a binder according to the weight ratio of 78:12:10 (wt%), adding a proper amount of deionized water, and mixing into a slurry. The slurry was applied uniformly (weighed) to 10mm phi nickel foam. Drying at 120 deg.C for 1 hr, tabletting, and weighing.
(2) Assembling the button capacitor: in a vacuum glove box, a lower shell, a current collector (foamed nickel)/positive electrode, a diaphragm, a negative electrode/current collector (foamed nickel), a gasket, a spring, a proper amount of 3mol/L KOH electrolyte and an upper shell are assembled into a button type super capacitor according to the sequence, and 50kg/cm of the current collector/positive electrode, the diaphragm, the negative electrode/current collector (foamed nickel), the gasket, the spring, the proper amount of KOH electrolyte and the upper shell are assembled into the button type super capacitor 2 The pressure of the sealing cap seals the supercapacitor.
Example 2
(1) Preparing nitrogen-doped graphene:
2.0g of flake graphite was mixed with 220ml of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 10:1, and stirred at 45 ℃ for 30 min. And then adding 12.0g of potassium permanganate and graphite in a mass ratio of 6:1, continuously stirring for 40min, heating to 60 ℃, reacting for 7h, and then continuously heating to 90 ℃ for reacting for 40 min. Then the reacted solution was naturally cooled to room temperature. Mixing the cooled solution and an ethanol intercalation solvent according to a volume ratio of 22:1.5, reacting, performing ultrasonic treatment for 30 minutes, adding Diethanolamine (DEA) into the mixed solution to perform nitrogen doping according to a volume ratio of 2:100, feeding the solution into a reaction kettle, heating at 190 ℃ for 10 hours, performing suction filtration on the solution, washing with deionized water, performing suction filtration repeatedly until the pH value is 7, and performing freeze drying to obtain nitrogen-containing graphene;
(2) synthesis of microwave-embedded porous low-layer nitrogen-containing graphene:
and (2) placing the nitrogen-containing graphene (NG) obtained in the step (1) in a vacuum tube, wherein the microwave power used in a microwave oven is 800W, and the reaction time is 2min, so as to obtain the porous nitrogen-containing graphene powder.
Wherein, the graphite is a commercial graphite powder product with the specification of 325 meshes.
The solution H 2 SO 4 The mass concentration is 98%, the mass concentration of nitric acid is 65%, the content of potassium permanganate is more than 99.5%, the content of Diethanolamine (DEA) is more than or equal to 99.0%, and the mass fraction of ethanol is 99.7%.
The gauze-like porous nitrogen-doped graphene finally obtained after the step (2) has good electron and ion mobility, and can be applied to preparation of lithium ion battery electrode materials.
The application of the gauze-shaped nitrogen-doped porous graphene in the embodiment is to manufacture a button type lithium ion battery, and the method specifically comprises the following steps:
(1) preparing an electrode slice: preparing an electrode by using a slurry coating method, dissolving active material nitrogen-doped graphene, acetonitrile black and binder PVDF in NMP according to the mass ratio of 8:1:1, stirring for about 30min to prepare slurry, and carefully and flatly and uniformly coating the electrode material slurry on a carrier fluid copper foil by using a blade. Then processing the mixture for 8 hours in a vacuum drying box at the temperature of 80 ℃, drying and pressing the dried mixture into an electrode slice.
(2) Assembling a button cell: in a vacuum glove box, a battery case is utilized, a metal lithium sheet is used as a positive electrode, a positive electrode shell, an electrode plate, a diaphragm, a spring piece, a lithium sheet, a gasket, a proper amount of electrolyte solution and a negative electrode shell are assembled into a button battery according to the sequence, and the battery is sealed by using a manual sealing machine.

Claims (5)

1. A preparation method of low-layer gauze-shaped nitrogen-doped graphene is characterized by comprising the following steps:
(1) preparing nitrogen-doped graphene:
mixing the crystalline flake graphite with a mixed solution of concentrated sulfuric acid and concentrated nitric acid according to the proportion of 1:110 g/ml; and stirring at 45 ℃; then, adding potassium permanganate and graphite in a mass ratio of 6:1, continuously stirring, heating to 60 ℃, reacting for 7 hours, and then continuously heating to 90 ℃ to react for 40 min; then naturally cooling the reacted solution to room temperature; mixing the cooled solution and an ethanol intercalation solvent according to a volume ratio of 22: 1-1.5 for reaction, performing ultrasonic treatment, adding diethanolamine and the intercalated solution according to a volume ratio of 1-5: 100 for nitrogen doping, putting the solution into a high-pressure reaction kettle, heating at the temperature of 190-220 ℃, heating for 8-12h, finally performing suction filtration on the solution, washing with deionized water, repeatedly performing suction filtration until the pH value is =7, and performing freeze drying to obtain nitrogen-containing graphene;
(2) synthesis of microwave-embedded porous low-layer nitrogen-containing graphene:
putting the nitrogen-containing graphene obtained in the step (1) into a vacuum tube, embedding the nitrogen-containing graphene into a microwave oven, wherein the microwave power is 700-800W, and the reaction time is 2-5min, so as to obtain porous nitrogen-containing graphene powder;
mixing concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of 10: 1;
the volume ratio of the diethanol amine to the intercalated solution is 1-2: 100.
2. The method for preparing the low-layer veil-like nitrogen-doped graphene according to claim 1, wherein the cooled solution and the ethanol intercalation solvent are in a volume ratio of 22:1.
3. The method for preparing the low-layer veil-like nitrogen-doped graphene according to claim 1, wherein the graphite is a commercially available 325-mesh graphite powder product.
4. The method for preparing the low-layer veil-like nitrogen-doped graphene according to claim 1, wherein the solution H is 2 SO 4 The mass concentration is 98%, the mass concentration of nitric acid is 65%, the content of potassium permanganate is more than 99.5%, the content of diethanolamine is more than or equal to 99.0%, and the mass fraction of ethanol is 99.7%.
5. The application of the tissue-like nitrogen-doped graphene with the low layer prepared by the method of any one of claims 1 to 4, which is used for manufacturing a button type super capacitor, comprises the following steps:
(1) preparing an electrode plate: weighing active substance nitrogen-containing graphene, conductive agent acetylene black and binder polytetrafluoroethylene according to the mass ratio of 78:12:10, adding a proper amount of deionized water, and mixing into slurry; uniformly coating the slurry on foam nickel with phi =10 mm; drying at 120 deg.C for 1 hr, tabletting, and weighing;
(2) assembling the button capacitor: in a vacuum glove box, a lower shell, a current collector/positive electrode, a diaphragm, a negative electrode/current collector, a gasket, a spring, a proper amount of 3mol/L KOH electrolyte and an upper shell are assembled into a button type super capacitor according to the sequence, and 50kg/cm is used for the super capacitor 2 The pressure of (2) seals the supercapacitor.
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