CN106517157B - Preparation method and application of nitrogen-doped carbon nanofiber/graphene aerogel - Google Patents
Preparation method and application of nitrogen-doped carbon nanofiber/graphene aerogel Download PDFInfo
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Abstract
The invention discloses a preparation method and application of nitrogen-doped carbon nanofiber/graphene aerogel; mixing nano-cellulose, graphene oxide and an amino compound, and preparing composite hydrogel by using a hydrothermal method; and then carrying out freeze drying and high-temperature carbonization treatment to obtain the nitrogen-doped carbon nanofiber/graphene aerogel. The advantages are that: 1) the nano-cellulose has higher specific surface area; 2) carrying out self-assembly on graphene oxide and nanocellulose by adopting a hydrothermal method to form porous hydrogel; 3) the nano-cellulose is converted into carbon nano-fiber through freeze drying and carbonization treatment, the carbon nano-fiber has excellent conductivity and stability, and compared with other carbon nano-tube materials, the carbon nano-fiber has low cost and wider application prospect, and 4) the prepared aerogel has excellent electrochemical performance, the specific capacitance can reach 289F/g, the capacitance retention rate can reach 90% after 5000 charge-discharge cycles, and the carbon nano-fiber can be used as a super capacitor electrode material.
Description
Technical Field
The invention relates to a composite aerogel and a preparation method thereof, in particular to a preparation method of a nitrogen-doped carbon nanofiber/graphene aerogel, and belongs to the technical field of nano materials and electrochemistry.
Background
Aerogel, also called xerogel, is a nano material with a multi-branch nano porous three-dimensional network structure with low density, high specific surface area and high porosity. The emergence of carbon material aerogels is the most representative aerogel material in the research of aerogel materials, so that the possession range of the aerogel materials is wider.
In recent years, a super capacitor has attracted much attention because it has advantages of higher energy density than a conventional capacitor and higher power density than a secondary battery, and has a long cycle life, superior low-temperature performance, high stability, and little environmental pollution. The super capacitor has wide application prospect, such as portable instrument equipment, a data memory storage system, an electric automobile power supply, an emergency backup power supply and the like, and particularly on an electric automobile, the super capacitor is combined with a battery to respectively provide high power and high energy, so that the size of the power supply is reduced, and the service life of the battery is prolonged. At present, supercapacitors are the key research targets in all countries of the world, and developed countries such as russia, the united states and the united kingdom invest a great deal of funds for researching high-performance supercapacitors. Meanwhile, the research and development of the super capacitor in China are rapidly developing and show certain market prospects.
The key to the performance of the supercapacitor lies in the composition and structure of the electrode material. Graphene is one of the most widely studied carbon materials, and has a honeycomb hexagonal planar structure formed by arranging single-layer carbon atoms, so that the graphene has excellent physicochemical properties. The graphene aerogel is an aerogel taking graphene as a framework unit, has the characteristics of graphene and aerogel, has a unique three-dimensional network structure, and also has the advantages of high conductivity, large specific surface area, high porosity, good thermal conductivity and the like, so that the graphene aerogel has a great prospect in the application of a super capacitor.
In order to further improve the capacitance performance of graphene, studies are currently conducted to compound graphene with materials such as multi-walled carbon nanotubes, single-walled carbon nanotubes, activated carbon and the like to prepare a composite gas electrode material. For example, Zhixin Tai (Journal of Power Sources, 2012, 199, 373-378) and the like are prepared into a flexible and curved carbon nano-cellulose/graphene composite electrode material by an electrostatic spinning method, and the capacitance of the flexible and curved carbon nano-cellulose/graphene composite electrode material can reach 197F/g. Compared with pure carbon nano-cellulose, the capacitance is improved by 24 percent. Ting-Ting Lin (electrochemical Acta, 2015, 178 th period, 517-524 th page) and other people utilize urea as a nitrogen source, and graphene oxide and carbon nanotubes as raw materials to prepare the nitrogen-doped graphene/carbon nanotube composite aerogel, and the capacitance of the composite aerogel serving as an electrode material of a supercapacitor can reach 246.6F/g. However, the carbon nanotube material has high price and complex production process, so that the application of the carbon nanotube material is limited to a certain extent. The invention aims to apply plant cellulose with rich sources as the source of the carbon nano-fiber to the graphene-based composite aerogel instead of carbon nano-tube materials. The cost of the composite aerogel material is reduced, and the capacitance performance of the composite aerogel material is improved.
Disclosure of Invention
The invention provides a preparation method of nitrogen-doped carbon nanofiber/graphene aerogel, and aims to prepare an electrode material with high capacitance, high power density, high energy density and long cycle life, and the electrode material is applied to a super capacitor.
The technical solution of the invention is as follows: a preparation method of nitrogen-doped carbon nanofiber/graphene aerogel comprises the following process steps: the method comprises the following process steps: a) preparing nano-cellulose by using natural fibers as raw materials through a chemical mechanical method; b) mixing nano-cellulose, graphene oxide and different amino compounds, and preparing composite hydrogel by a hydrothermal method at the temperature of 50-300 ℃ for 4-24 hours; c) after freezing the composite hydrogel by using a liquid nitrogen or ultralow temperature refrigerator, placing the composite hydrogel in a vacuum freeze dryer for de-icing and drying for 24-48 h, placing the frozen aerogel into a tubular furnace, and carbonizing the aerogel at the high temperature of 500-800 ℃ for 1-3 h by using argon as protective gas to obtain the nitrogen-doped carbon nanofiber/graphene aerogel.
The preparation method of the nitrogen-doped carbon nanofiber/graphene aerogel further comprises the following preferred scheme.
In a preferred embodiment of the present invention, the natural fiber in step a) is 10-100 mesh bamboo powder, wood powder, wheat straw, peanut shell, etc., and the cellulose is obtained by purifying with chemical reagents such as hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, etc. In a preferred embodiment of the present invention, the mechanical treatment in step a) is mechanical grinding with a grinder for 5 to 30 minutes.
In a preferable scheme of the invention, the concentration of the graphene oxide in the step (1) is 1-10 mg/ml.
In a preferable embodiment of the present invention, the mass of the nanocellulose in the step (2) is 10 to 100 mg.
In a preferred embodiment of the present invention, the amount of the amino compound added in step (3) is 20 to 100 uL.
In the preferable scheme of the invention, in the step (5), the composite hydrogel is soaked in deionized water for 1-2 days, and is washed for 5-10 times by changing water.
In a preferred embodiment of the present invention, the freeze-drying time in step (6) is 24-48 h.
In the preferable scheme of the invention, in the step (7), argon is introduced into the tubular furnace as the protective gas, the temperature of the tubular furnace is firstly raised to 500-800 ℃ at the speed of 1-5 ℃/min, the temperature is kept for 1-5h, then the temperature is lowered to 50-100 ℃ at the speed of 5-10 ℃/min, and finally the temperature is naturally lowered to the room temperature; the pressure in the tube furnace is kept constant.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the nano-cellulose is prepared by using the biomass raw materials such as bamboo powder, wood powder, wheat straw, peanut shell and other precursors, so that the environmental pollution is reduced, and the cost is reduced;
(2) combining the prepared nano-cellulose with graphene oxide, introducing amino compounds, and performing self-assembly by using a hydrothermal method to form composite hydrogel; the nitrogen-doped carbon nanofiber/graphene aerogel prepared from the hydrogel by means of freeze drying combined with high-temperature carbonization treatment is simple in method and easy for large-scale production;
(3) the obtained nitrogen-doped carbon nanofiber/graphene aerogel has excellent electrochemical properties (large capacitance, small internal resistance, good cycle stability and the like) and can be used as a stable and efficient electrode material of a super capacitor.
Drawings
FIG. 1 is a macro-topography diagram of composite hydrogel prepared according to examples 1 and 2 and comparative example of the present invention;
fig. 2 is an electron microscope image of the nanocellulose, the graphene oxide and the composite aerogel in example 2, which are provided in examples 1 to 5 of the present invention;
FIG. 3 is a photoelectron spectrum of a composite aerogel provided in example 5 of the present invention;
FIG. 4 is a cyclic voltammetry curve of the composite aerogel provided in example 1 of the present invention at different scanning speeds;
fig. 5 is a constant current charge and discharge curve of the composite aerogel provided in example 2 of the present invention at different current densities;
FIG. 6 is a cyclic voltammetry curve of a composite aerogel provided in example 3 of the present invention at different scanning speeds;
fig. 7 is a constant current charging and discharging curve of the composite aerogel provided in example 4 of the present invention under different current densities.
Detailed Description
Example 1
a) Preparing nano-cellulose by using bamboo powder as a raw material through a chemical mechanical method; b) mixing nano-cellulose, graphene oxide and an amino compound, and preparing the composite hydrogel by using a hydrothermal method, wherein the hydrothermal method comprises the following steps: (1) accurately taking a certain mass of graphene oxide, dispersing the graphene oxide in deionized water, preparing a graphene oxide solution with the concentration of 2mg/ml, and fully dispersing by utilizing magnetic stirring and ultrasonic treatment to obtain a uniform graphene oxide aqueous solution; (2) weighing 30mg of nano-cellulose, adding the nano-cellulose into the graphene oxide aqueous solution obtained in the step (1), and stirring the mixture for 10 minutes by using a glass rod; (3) and (3) adding 20uL of acetamide solution into the mixed solution obtained in the step (2), and treating for 35 minutes by using ultrasonic waves, wherein the solution after ultrasonic waves is in a uniformly dispersed state. (4) Adding the mixed solution obtained in the step (3) into a 25ml polytetrafluoroethylene reaction kettle, putting the reaction kettle into an oven, and keeping the temperature at 90 ℃ for 12 hours to obtain composite hydrogel; (5) taking out the prepared composite hydrogel, soaking for 2 days with deionized water for multiple times, and cleaning for 10 times; (6) taking out the composite hydrogel, putting the composite hydrogel into a clean container, slicing the hydrogel, and freezing the sliced hydrogel by using liquid nitrogen; c) putting the frozen aerogel into a tubular furnace, introducing argon gas into the tubular furnace as protective gas, firstly heating the tubular furnace to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 3 hours, then cooling to 100 ℃ at the speed of 10 ℃/min, and finally naturally cooling to room temperature; keeping normal pressure in the tube furnace;
comparative example 1: this example is one of the comparative examples of example 1 above;
in the embodiment, the hydrothermal reaction temperature is 120 ℃, and the specific preparation method is basically the same as that in the embodiment 1;
comparative example 2: this example is the second comparative example of example 1 above;
in the embodiment, the hydrothermal reaction temperature is 150 ℃, and the specific preparation method is basically the same as that in the embodiment 1;
comparative example 3: this example is the third comparative example of example 1 above;
in this example, the hydrothermal reaction temperature was 180 ℃, and the specific preparation method was substantially the same as that in example 1.
Example 2
a) Preparing nano-cellulose by using bamboo powder as a raw material through a chemical mechanical method; b) mixing nano-cellulose, graphene oxide and an amino compound, and preparing the composite hydrogel by using a hydrothermal method, wherein the hydrothermal method comprises the following steps: (1) accurately taking a certain mass of graphene oxide, dispersing the graphene oxide in deionized water, preparing a graphene oxide solution with the concentration of 2mg/ml, and fully dispersing by utilizing magnetic stirring and ultrasonic treatment to obtain a uniform graphene oxide aqueous solution; (2) weighing 30mg of nano-cellulose, adding the nano-cellulose into the graphene oxide aqueous solution obtained in the step (1), and stirring the mixture for 10 minutes by using a glass rod; (3) and (3) adding 20uL of acetamide solution into the mixed solution obtained in the step (2), and treating for 35 minutes by using ultrasonic waves, wherein the solution after ultrasonic waves is in a uniformly dispersed state. (4) Adding the mixed solution obtained in the step (3) into a 25ml polytetrafluoroethylene reaction kettle, putting the reaction kettle into an oven, and keeping the temperature for 6 hours at the constant temperature of 150 ℃ to obtain composite hydrogel; (5) taking out the prepared composite hydrogel, soaking for 2 days with deionized water for multiple times, and cleaning for 10 times; (6) taking out the composite hydrogel, putting the composite hydrogel into a clean container, slicing the hydrogel, and freezing the sliced hydrogel by using liquid nitrogen; c) putting the frozen aerogel into a tubular furnace, introducing argon gas into the tubular furnace as protective gas, firstly heating the tubular furnace to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 3 hours, then cooling to 100 ℃ at the speed of 10 ℃/min, and finally naturally cooling to room temperature; keeping normal pressure in the tube furnace;
comparative example 1: this example is one of the comparative examples of example 2 above;
in the embodiment, the hydrothermal reaction time is 12 hours, and the specific preparation method is basically the same as that in the embodiment 1;
comparative example 2: this example is the second comparative example of example 2 above;
in the embodiment, the hydrothermal reaction time is 18h, and the specific preparation method is basically the same as that in the embodiment 1;
comparative example 3: this example is the third comparative example of example 2 above;
in this example, the hydrothermal reaction time was 24 hours, and the specific preparation method was substantially the same as that in example 1.
Example 3
a) Preparing nano-cellulose by using bamboo powder as a raw material through a chemical mechanical method; b) mixing nano-cellulose, graphene oxide and an amino compound, and preparing the composite hydrogel by using a hydrothermal method, wherein the hydrothermal method comprises the following steps: (1) accurately taking a certain mass of graphene oxide, dispersing the graphene oxide in deionized water, preparing a graphene oxide solution with the concentration of 4mg/ml, and fully dispersing by utilizing magnetic stirring and ultrasonic treatment to obtain a uniform graphene oxide aqueous solution; (2) weighing 40mg of nano-cellulose, adding the nano-cellulose into the graphene oxide aqueous solution obtained in the step (1), and stirring the mixture for 10 minutes by using a glass rod; (3) and (3) adding 20uL of ethylenediamine solution into the mixed solution obtained in the step (2), and treating for 35 minutes by using ultrasonic waves, wherein the solution after ultrasonic waves is in a uniformly dispersed state. (4) Adding the mixed solution obtained in the step (3) into a 25ml polytetrafluoroethylene reaction kettle, putting the reaction kettle into an oven, and keeping the temperature at 150 ℃ for 12 hours to obtain composite hydrogel; (5) taking out the prepared composite hydrogel, soaking for 2 days with deionized water for multiple times, and cleaning for 10 times; (6) taking out the composite hydrogel, putting the composite hydrogel into a clean container, slicing the hydrogel, and freezing the sliced hydrogel by using liquid nitrogen; c) putting the frozen aerogel into a tubular furnace, introducing argon gas into the tubular furnace as protective gas, firstly heating the tubular furnace to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 5 hours, then cooling to 100 ℃ at the speed of 10 ℃/min, and finally naturally cooling to room temperature; the pressure in the tube furnace is kept constant.
Example 4
a) Preparing nano cellulose by using wood powder as a raw material through a chemical mechanical method; b) mixing nano-cellulose, graphene oxide and an amino compound, and preparing the composite hydrogel by using a hydrothermal method, wherein the hydrothermal method comprises the following steps: (1) accurately taking a certain mass of graphene oxide, dispersing the graphene oxide in deionized water, preparing a graphene oxide solution with the concentration of 2mg/ml, and fully dispersing by utilizing magnetic stirring and ultrasonic treatment to obtain a uniform graphene oxide aqueous solution; (2) weighing 30mg of nano-cellulose, adding the nano-cellulose into the graphene oxide aqueous solution obtained in the step (1), and stirring the mixture for 10 minutes by using a glass rod; (3) and (3) adding 20uL of ethylenediamine solution into the mixed solution obtained in the step (2), and treating for 35 minutes by using ultrasonic waves, wherein the solution after ultrasonic waves is in a uniformly dispersed state. (4) Adding the mixed solution obtained in the step (3) into a 25ml polytetrafluoroethylene reaction kettle, putting the reaction kettle into an oven, and keeping the temperature at 150 ℃ for 12 hours to obtain composite hydrogel; (5) taking out the prepared composite hydrogel, soaking for 2 days with deionized water for multiple times, and cleaning for 10 times; (6) taking out the composite hydrogel, putting the composite hydrogel into a clean container, slicing the hydrogel, and freezing the sliced hydrogel by using liquid nitrogen; c) putting the frozen aerogel into a tubular furnace, introducing argon gas into the tubular furnace as protective gas, firstly heating the tubular furnace to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 3 hours, then cooling to 100 ℃ at the speed of 10 ℃/min, and finally naturally cooling to room temperature; the pressure in the tube furnace is kept constant.
Example 5
a) Preparing nano-cellulose by using bamboo powder as a raw material through a chemical mechanical method; b) mixing nano-cellulose, graphene oxide and an amino compound, and preparing the composite hydrogel by using a hydrothermal method, wherein the hydrothermal method comprises the following steps: (1) accurately taking a certain mass of graphene oxide, dispersing the graphene oxide in deionized water, preparing a graphene oxide solution with the concentration of 2mg/ml, and fully dispersing by utilizing magnetic stirring and ultrasonic treatment to obtain a uniform graphene oxide aqueous solution; (2) weighing 30mg of nano-cellulose, adding the nano-cellulose into the graphene oxide aqueous solution obtained in the step (1), and stirring the mixture for 10 minutes by using a glass rod; (3) and (3) adding 20uL of triethylamine solution into the mixed solution obtained in the step (2), and treating for 35 minutes by using ultrasonic waves, wherein the solution after ultrasonic waves is in a uniformly dispersed state. (4) Adding the mixed solution obtained in the step (3) into a 25ml polytetrafluoroethylene reaction kettle, putting the reaction kettle into an oven, and keeping the temperature at 150 ℃ for 12 hours to obtain composite hydrogel; (5) taking out the prepared composite hydrogel, soaking for 2 days with deionized water for multiple times, and cleaning for 10 times; (6) taking out the composite hydrogel, putting the composite hydrogel into a clean container, slicing the hydrogel, and freezing the sliced hydrogel by using liquid nitrogen; c) putting the frozen aerogel into a tubular furnace, introducing argon gas into the tubular furnace as protective gas, firstly heating the tubular furnace to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 4 hours, then cooling to 100 ℃ at the speed of 10 ℃/min, and finally naturally cooling to room temperature; the pressure in the tube furnace is kept constant.
Claims (8)
1. A preparation method of nitrogen-doped carbon nanofiber/graphene aerogel comprises the following process steps: a) preparing nano-cellulose by using natural fibers as raw materials through a chemical method or a mechanical method; b) mixing nano-cellulose, graphene oxide and an amino compound, and preparing composite hydrogel by a hydrothermal method at the temperature of 50-300 ℃ for 4-24 hours; c) after freezing the composite hydrogel by using a liquid nitrogen or ultralow temperature refrigerator, placing the composite hydrogel in a vacuum freeze dryer for de-icing and drying for 24-48 h, placing the frozen aerogel into a tubular furnace, and carbonizing the aerogel at the high temperature of 500-800 ℃ for 1-3 h by using argon as protective gas to obtain the nitrogen-doped carbon nanofiber/graphene aerogel.
2. The preparation method of the nitrogen-doped carbon nanofiber/graphene aerogel according to claim 1, wherein the natural fibers in the step a) are 10-100 mesh bamboo powder, wood powder, wheat straw and peanut shell, and the cellulose is obtained by purifying with chemical reagents such as hydrochloric acid, sulfuric acid, sodium hydroxide and potassium hydroxide.
3. The method for preparing nitrogen-doped carbon nanofiber/graphene aerogel according to claim 1, wherein the mechanical method in step a) is that a grinder is used for mechanical grinding for 5-30 minutes to obtain nanocellulose with the diameter distribution of 10-100 nm.
4. The method for preparing nitrogen-doped carbon nanofiber/graphene aerogel according to claim 1, wherein the nanocellulose, graphene oxide and the amino compound are mixed in the step b), and the composite hydrogel is prepared by a hydrothermal method, wherein the method comprises the following steps:
(1) accurately taking a certain mass of graphene oxide, dispersing the graphene oxide in deionized water, preparing a graphene oxide solution with the concentration of 1-10 mg/ml, and performing magnetic stirring and ultrasonic treatment to obtain a uniformly dispersed graphene oxide aqueous solution;
(2) weighing 10-100 mg of nano-cellulose, adding the nano-cellulose into the graphene oxide aqueous solution obtained in the step (1), and stirring for 5-15 minutes by using a glass rod;
(3) adding a certain volume of amino compound solution into the mixed solution obtained in the step (2), and performing ultrasonic treatment for 10-50 minutes to ensure that the solution after ultrasonic treatment is in a uniformly dispersed state;
(4) adding the mixed solution obtained in the step (3) into a reaction kettle of 25-100 ml of polytetrafluoroethylene, putting the reaction kettle into an oven, and keeping the temperature for 4-24 hours at a constant temperature of 50-300 ℃ to obtain composite hydrogel;
(5) taking out the prepared composite hydrogel, and soaking and cleaning the hydrogel for multiple times by using deionized water;
(6) taking out the composite hydrogel, putting the composite hydrogel into a clean container, slicing the hydrogel, freezing the sliced hydrogel, and then putting the hydrogel into a freeze dryer for freeze drying for 24-48 h.
5. The method for preparing nitrogen-doped carbon nanofiber/graphene aerogel according to claim 1, wherein the nanocellulose, graphene oxide and the amino compound are mixed in the step b), and the composite hydrogel is prepared by a hydrothermal method, wherein the method comprises the following steps: the selected amino compounds mainly comprise urea, melamine, ethylenediamine, triethylamine and acetamide.
6. The preparation method of the nitrogen-doped carbon nanofiber/graphene aerogel according to claim 4, wherein the amount of the amino compound solution added in the step (3) is 20-100 uL.
7. The method for preparing nitrogen-doped carbon nanofiber/graphene aerogel according to claim 4, wherein in the step (5), the composite hydrogel is soaked in deionized water for 1-2 days, and then washed with water for 5-10 times.
8. The method for preparing nitrogen-doped carbon nanofiber/graphene aerogel according to claim 1, wherein the composite hydrogel obtained in step c) is subjected to freeze drying and high-temperature carbonization treatment to obtain nitrogen-doped carbon nanofiber/graphene aerogel, and the method comprises the following steps: putting the hydrogel after freeze drying into a tube furnace; introducing argon gas into the tubular furnace as a protective gas, firstly heating the tubular furnace to 800 ℃ at the speed of 1-5 ℃/min, keeping the temperature for 1-5h, then cooling to 50-100 ℃ at the speed of 5-10 ℃/min, and finally naturally cooling to room temperature; the pressure in the tube furnace is kept constant.
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