CN111341569A - Green controllable preparation method of nitrogen-doped graphene-based iron oxide supercapacitor material - Google Patents

Green controllable preparation method of nitrogen-doped graphene-based iron oxide supercapacitor material Download PDF

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CN111341569A
CN111341569A CN202010268165.2A CN202010268165A CN111341569A CN 111341569 A CN111341569 A CN 111341569A CN 202010268165 A CN202010268165 A CN 202010268165A CN 111341569 A CN111341569 A CN 111341569A
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nitrogen
iron oxide
doped graphene
amino acid
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王涛
吴冬玲
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Xinjiang University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • 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

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Abstract

The invention discloses a green controllable preparation method of a nitrogen-doped graphene-based iron oxide supercapacitor material, which is characterized in that iron oxide and amino acid which are good in environment and rich in resources are utilized, GO is used as a precursor, a one-step hydrothermal method is used for preparing the nitrogen-doped graphene-based iron oxide composite material, the iron oxide is controllable in shape due to complexation of the amino acid and iron salt, and the prepared electrode material which can be used for a supercapacitor is superior to most reported iron oxide-based heteroatom-doped graphene materials.

Description

Green controllable preparation method of nitrogen-doped graphene-based iron oxide supercapacitor material
Technical Field
The invention relates to the field of novel energy storage materials, in particular to a green controllable preparation method of a high-performance nitrogen-doped graphene-based iron oxide supercapacitor material.
Background
The economy of the world is rapidly increased, the demand for energy is more and more, and the problem of energy shortage is more and more severe. Therefore, the development of various renewable green and clean energy sources, such as super capacitors and the like, has positive effects on relieving energy shortage and reducing environmental pollution.
The performance of supercapacitors depends to a large extent on the electrode material. Therefore, the development of an electrode material with low price, environmental friendliness and high capacity is the focus of current research. The carbon material with double capacitance characteristics has the characteristics of excellent conductivity, large specific surface area, stable structure and the like, so that the carbon material can be used as a carrier of a composite material, the conductivity of the material can be improved by compounding the carbon material with a transition metal oxide, the agglomeration of a nanometer transition metal oxide is reduced, and the like, and further the complementary advantages and the synergistic effect of the carbon material and a pseudocapacitance material are realized through the synergistic effect of the carbon material and the pseudocapacitance material.
Among them, the research of nitrogen-doped graphene-based iron oxide composite becomes a research hotspot. The super capacitor electrode material with high specific capacity, large energy density and high stability is prepared by combining the characteristics of low price, environmental friendliness, high pseudocapacitance and the like of iron oxide and the advantages of excellent conductivity, large surface area, stability and the like of the nitrogen-doped graphene. In the conventional process for preparing nitrogen-doped graphene by hydrothermal synthesis, most commonly used nitrogen sources (hydrazine hydrate, pyrrole and ammonia water) have toxicity, and the shape of the nitrogen sources is uncontrollable in the process of preparing iron oxide by hydrothermal synthesis.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a green controllable preparation method of a nitrogen-doped graphene-based iron oxide supercapacitor material, which solves the problems, wherein green and environment-friendly amino acid is used as a nitrogen source, the iron oxide is controllable in shape due to complexation of the amino acid and an iron salt, and the prepared electrode material of the supercapacitor has high specific capacity and excellent conductivity.
In order to achieve the purpose, the invention provides the following technical scheme:
the green controllable preparation method of the nitrogen-doped graphene-based iron oxide supercapacitor material comprises the following steps:
1) dissolving amino acid in water, adding iron salt, and continuously stirring for 0.5-10 hours; mixing an amino acid coordinated iron salt solution with a graphene oxide aqueous solution with the concentration of 0.5-20 mg/mL, and keeping stirring, wherein the mass ratio of amino acid to GO is 1: 5-5: 1, and the mass ratio of iron salt to GO is 1: 2-20: 1;
2) putting the mixed solution into a reaction kettle, and carrying out high-temperature treatment in an oven at 100-250 ℃ for 2-24 hours, wherein the temperature rise speed is controlled at 2-10 ℃/min in the process;
3) and naturally cooling the reaction kettle, taking out the prepared hydrogel or black powder, and repeatedly washing the hydrogel or black powder with ethanol and distilled water to obtain the nitrogen-doped graphene-based iron oxide material.
Further, the amino acid in step 1) refers to one of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine and histidine, and derivatives thereof.
Still further, the amino acid in step 1) is an acidic amino acid. The acidic amino acid is aspartic acid or glutamic acid.
Further, in the step 1), the ferric salt is one of ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferric citrate, ferric acetylacetonate and ferrocene.
Further, the graphene oxide aqueous solution in the step 1) is prepared by firstly preparing graphene oxide from natural crystalline flake graphite by a Hummer's method and then dissolving the graphene oxide in water.
Further, the iron salt solution coordinated by the amino acid in the step 1) is dropwise added into the graphene oxide aqueous solution.
In a further improvement scheme, the filling degree of the reaction kettle in the step 2) is less than or equal to 80 percent.
The invention has the beneficial effects that:
aiming at the lack of green preparation technology of high-performance supercapacitor electrode materials, the electrode materials which can be used for the supercapacitor are prepared by using iron oxide and amino acid which are good in environment and rich in resources and taking GO as a precursor, and are superior to most reported iron oxide-based heteroatom-doped graphene materials (151-618F g)-1) Especially under the preparation conditions of example 1, Fe2O3The nanoparticles are spindle-shaped, and the overall composite sample has a loose and cross-linked structure, as shown in 1A g-1The specific capacitance value of the material can reach 1060F g under the condition of small current density-1. The high specific capacity of the ferric oxide and the excellent conductivity of the nitrogen-doped graphene are combined, so that the good super-capacitance of the material is realizedCan be used.
Drawings
FIG. 1 is an XRD pattern of FeO-NG-A in example 1;
FIG. 2 is an SEM morphology photograph of FeO-NG-A in example 1;
FIG. 3 is an XPS plot of N in FeO-NG-A in example 1;
FIG. 4 is a cross-current charge-discharge diagram of FeO-NG-A in example 1;
FIG. 5 is an SEM morphology picture of FeO-NG-N in example 2;
FIG. 6 is a thermogravimetric plot of FeO-NG-N in example 2;
FIG. 7 is a cross-current charge-discharge diagram of FeO-NG-N in example 2;
FIG. 8 is an SEM morphology photograph of FeO-NG-B in example 3;
FIG. 9 is a Raman diagram of FeO-NG-B in example 3;
FIG. 10 is a cross-current charge-discharge diagram of FeO-NG-B in example 3;
FIG. 11 is a scanning electron micrograph of FeO-NG-A1 in example 4;
FIG. 12 is a cross-current charge-discharge diagram of FeO-NG-A1 in example 4;
FIG. 13 is a scanning electron micrograph of FeO-NG-B1 in example 5;
FIG. 14 is a cross-current charge/discharge diagram of FeO-NG-B1 in example 5.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
Example 1
Using glutamic acid as a nitrogen source, dissolving 30 mg of GO in 10 mL of deionized water to prepare a GO solution, performing ultrasonic dispersion, and uniformly stirring for 2 hours to form a GO suspension; FeCl is added3•6H2O (100 mg) and glutamic acid (acidic amino acid, 81 mg) were dissolved in 5 mL of deionized water, and continuously stirred for 2 hours to form a Fe-glutamic acid complex solution. Then, the above solution was added drop-wise to the continuously stirred GO suspension, stirred well to form a mixed solution. The mixture was then sealed in a 25 mL autoclave and placed in a constant temperature forced air drying cabinetReacting at 160 ℃ for 12 h at constant temperature, and the heating rate is 5 ℃/min. And after the heat preservation is finished, naturally cooling the reaction kettle to room temperature. Subsequently, the obtained black hydrogel was washed with deionized water to obtain iron oxide/nitrogen-doped graphene (Fe)2O3/NG), this sample was named FeO-NG-A. The XRD pattern (figure 1) of FeO-NG-A shows that the diffraction peak of the composite material is combined with a-Fe2O3(JCP DS No. 33-0664) and a-Fe was determined2O3Is present. From the SEM results (FIG. 2), Fe was found2O3The nanoparticles were spindle-shaped, approximately 200 nm long and 100 nm wide (fig. 2 left), and the bulk sample of the composite exhibited a loose, cross-linked structure (fig. 2 right). XPS results showed that the doped nitrogen was mainly pyridine nitrogen, pyrrole nitrogen and graphitized nitrogen (fig. 3). At 1A g-1At a low current density of 1060, the specific capacitance value of the material is 1060F g-1. (FIG. 4).
Example 2
Fe was prepared in the same manner as in example 1, except that alanine (neutral amino acid) was used as the nitrogen source and the mass of the amino acid was changed to 162 mg2O3The sample was named FeO-NG-N. The XRD pattern of FeO-NG-N is similar to that of FeO-NG-A, and a-Fe in the compound is determined2O3Is present. From the SEM results (FIG. 5), Fe was found2O3The morphology of the nano particles is that the whole of a nearly cubic sample is in an agglomerated state (left side of figure 5), NG in the compound is agglomerated (right side of figure 5), and a cross-linked porous structure is not seen. The thermogravimetric results showed an iron oxide content of 43% (fig. 6). At 1A g-1Has a specific capacitance value of 860F g-1(FIG. 7).
Example 3
Histidine (basic amino acid) is used as a nitrogen source, and the hydrothermal temperature is changed to 120oC, other preparation of Fe by the same method as example 12O3The sample was named FeO-NG-B. The XRD pattern of FeO-NG-B is similar to that of FeO-NG-A, and a-Fe in the compound is determined2O3Is present. From the SEM results (FIG. 8), Fe was found2O3The shape of the nano particles is that the whole of a nearly cubic sample is agglomeratedIn this state (left in FIG. 8), the NG agglomeration in the complex was severe (right in FIG. 8). FIG. 9 Raman spectrum showing Fe2O3A of (A)1gSymmetric vibration (about 219 cm)-1) And EgSymmetric vibration (about 285 cm)-1) Also, a D peak (about 1350 cm) of the carbon material was observed-1) And G peak of order degree (about 1580 cm)-1) Illustrating Fe in the composite material2O3And the presence of graphene. At 1A g-1Has a specific capacitance value of 770F g-1(FIG. 10).
Example 4
Modification of FeCl Using glutamic acid as Nitrogen Source (acidic amino acid) as Nitrogen Source3•6H2Fe was prepared by adjusting the amount of O added to 1g in the same manner as in example 12O3This sample was designated FeO-NG-A1. From the SEM results, Fe in the composite2O3Agglomeration was severe (fig. 11) and separated from the nitrogen-doped graphene, which may be due to FeCl3•6H2Too large amount of O is added. The capacitance performance test shows that the capacitance performance is 1A g-1The specific capacitance value of the material is 590F g at the current density of-1(FIG. 12). The capacitance of the material is relatively small, which is in contrast to FeCl3•6H2Excessive addition of O, Fe in the composite2O3The agglomeration is severe and separates from the nitrogen-doped graphene, causing a reduction in the conductivity of the material and thus reducing the capacitive properties of the composite.
Example 5
Histidine (basic amino acid) is used as a nitrogen source, and the hydrothermal temperature is changed to 270oC, other preparation of Fe by the same method as example 12O3This sample was designated FeO-NG-B1. From the SEM results, it can be seen that the nitrogen-doped graphene in the composite was heavily agglomerated (fig. 13), and Fe2O3The agglomerated graphene is wrapped, which is probably caused by overlarge hydrothermal temperature addition amount, the reduction degree of the graphene oxide is increased, oxygen-containing functional groups are reduced, and the repulsive force between sheet layers is reduced at higher temperature. The capacitance performance test shows that the capacitance performance is 1A g-1At a current density of (2), the specific capacitance value of the material is569 F g-1(FIG. 14). The capacitance of the material is relatively small, which is related to overlarge hydrothermal temperature, the reduction degree of the nitrogen-doped graphene at high temperature is increased, and the agglomeration is serious, so that the capacitance performance of the compound is reduced.
Comparative example:
wang (J. Phys. chem. C2014, 118, 31, 17231-17239.) and the like use ammonia water as a nitrogen source to prepare irregular Fe2O3The nitrogen-doped graphene composite material has the advantages that the nitrogen-doped graphene does not have a loose porous structure, and the specific capacitance of the composite material is 618F g–1（0.5A g-1). Ren (Journal of Alloys and Compounds, 2014,604,87-93.) et al prepared 20-100 nm Fe using hydrazine hydrate, urea as nitrogen source2O3The particle nitrogen-doped graphene composite material has the nitrogen-doped graphene which does not have a loose porous structure, and the specific capacity of the composite material is 260.1F g–1（2 A g-1）。
The above examples 1-3 show that Fe with different morphologies can be prepared by changing the charge ratio and the reaction temperature2O3And nitrogen-doped graphene. The nitrogen in the material exists in the modes of pyridine nitrogen, pyrrole nitrogen and graphitized nitrogen, and the content of iron oxide in the material can reach 43 percent. The composite materials with different doping ratios and different electrochemical properties can be obtained in the examples 1, 2 and 3. The capacitance performance of the material is superior to that of most reported iron oxide-based heteroatom-doped graphene materials (151-618F g)-1). In the embodiment 4, the adding amount of the nitrogen source and the hydrothermal temperature in the embodiment 5 exceed the limited conditions of the invention, and the prepared product has obviously poor appearance and specific capacitance. The material prepared by adopting ammonia water, hydrazine hydrate and urea as nitrogen sources has poorer performance.
The pH of the mixture solution before and after the reaction is about 5.1, obviously, the pH of the mixed solution is higher than the isoelectric point (pI value is 3.22) of glutamic acid but lower than the isoelectric point (pI value is 6.02) of alanine and the isoelectric point (pI value is 7.59) of histidine, therefore, glutamic acid in the solution is negatively charged, other two amino acids are positively charged, the electrostatic repulsion between negatively charged aspartic acid and negatively charged aspartic acid is prevented in the hydrothermal reaction, the aggregation between graphene sheets is prevented, a porous network structure formed by graphene loose sheets is formed, and the final three-dimensional electrostatic repulsion of FeO-GO-NG material is reduced, so that the composite material is subjected to the three-dimensional electrostatic repulsion of FeO-G-and FeO-NG-G-which are attracted by the composite material.
At the same time, Fe is present3+And amino acid, in the hydrothermal synthesis process, the formed chelate is hydrolyzed to form FeOOH, and then the FeOOH is further converted into Fe2O3The polymerization and recrystallization of nuclei, then predominantly nanocrystals, form Fe of different morphologies2O3And (3) nanoparticles. In the FeO-NG-A sample, the acidic amino acid contained a carbon-oxygen double bond in the R group (C = O) and was negatively charged in the reaction solution (pH)>pI), negatively charged glutamic acid promoted Fe2O3Formation of nuclei, possibly acidic amino acids, altering Fe2O3The growth rate of different crystal faces of atomic nucleus is long, so that the crystal faces are changed to be polymerized into initial nano crystals, and finally spindle-shaped Fe is formed by assembling2O3And (3) nanoparticles. In the FeO-NG-N and FeO-NG-B samples, alanine and histidine were positively charged. During the formation of these two complexes, the amino acid coordination-chelation also alters Fe2O3The growth rates of different crystal planes finally form Fe similar to a cube2O3Nanoparticles.
Therefore, the material obtained by complexing the acid amino acid in the example 1 has the optimal capacitance performance which can reach 1060F g-1。

Claims (8)

1. The green controllable preparation method of the nitrogen-doped graphene-based iron oxide supercapacitor material is characterized by comprising the following steps of: the method comprises the following steps:
1) dissolving amino acid in water, adding iron salt, and continuously stirring for 0.5-10 hours; mixing an amino acid coordinated iron salt solution with a graphene oxide aqueous solution with the concentration of 0.5-20 mg/mL, and keeping stirring, wherein the mass ratio of amino acid to GO is 1: 5-5: 1, and the mass ratio of iron salt to GO is 1: 2-20: 1;
2) putting the mixed solution into a reaction kettle, and carrying out high-temperature treatment in an oven at 100-250 ℃ for 2-24 hours, wherein the temperature rise speed is controlled at 2-10 ℃/min in the process;
3) and naturally cooling the reaction kettle, taking out the prepared hydrogel or black powder, and repeatedly washing the hydrogel or black powder with ethanol and distilled water to obtain the nitrogen-doped graphene-based iron oxide material.
2. The green controllable preparation method of the nitrogen-doped graphene-based iron oxide supercapacitor material according to claim 1, which is characterized by comprising the following steps: the amino acid in the step 1) refers to one of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine and histidine and derivatives thereof.
3. The green controllable preparation method of the nitrogen-doped graphene-based iron oxide supercapacitor material according to claim 1, which is characterized by comprising the following steps: the amino acid in step 1) is an acidic amino acid.
4. The green controllable preparation method of the nitrogen-doped graphene-based iron oxide supercapacitor material according to claim 3, characterized by comprising the following steps: the acidic amino acid is aspartic acid or glutamic acid.
5. The green controllable preparation method of the nitrogen-doped graphene-based iron oxide supercapacitor material according to claim 1, which is characterized by comprising the following steps: in the step 1), the ferric salt is one of ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferric citrate, ferric acetylacetonate and ferrocene.
6. The green controllable preparation method of the nitrogen-doped graphene-based iron oxide supercapacitor material according to claim 1, which is characterized by comprising the following steps: the graphene oxide aqueous solution in the step 1) is prepared by firstly preparing graphene oxide from natural crystalline flake graphite by a Hummer's method and then dissolving the graphene oxide in water.
7. The green controllable preparation method of the nitrogen-doped graphene-based iron oxide supercapacitor material according to claim 1, which is characterized by comprising the following steps: step 1), dropwise adding an amino acid coordinated iron salt solution into a graphene oxide aqueous solution.
8. The green controllable preparation method of the nitrogen-doped graphene-based iron oxide supercapacitor material according to claim 1, which is characterized by comprising the following steps: the filling degree of the reaction kettle in the step 2) is less than or equal to 80 percent.
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CN112079349A (en) * 2020-08-25 2020-12-15 中国科学院兰州化学物理研究所 Method for preparing nitrogen-doped porous graphene nano material through limited-area combustion and application
CN114171326A (en) * 2021-12-06 2022-03-11 西北大学 Preparation method of nitrogen-doped ultrathin 2D porous carbon nanosheet

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CN112079349A (en) * 2020-08-25 2020-12-15 中国科学院兰州化学物理研究所 Method for preparing nitrogen-doped porous graphene nano material through limited-area combustion and application
CN114171326A (en) * 2021-12-06 2022-03-11 西北大学 Preparation method of nitrogen-doped ultrathin 2D porous carbon nanosheet

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