CN112062121A - Method for preparing thermal reduction graphene oxide film by blending sodium lignosulfonate and graphene oxide - Google Patents
Method for preparing thermal reduction graphene oxide film by blending sodium lignosulfonate and graphene oxide Download PDFInfo
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- CN112062121A CN112062121A CN202010881671.9A CN202010881671A CN112062121A CN 112062121 A CN112062121 A CN 112062121A CN 202010881671 A CN202010881671 A CN 202010881671A CN 112062121 A CN112062121 A CN 112062121A
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- graphene oxide
- sodium lignosulfonate
- thermal reduction
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
Abstract
The invention provides a method for preparing a thermal reduction graphene oxide film by blending sodium lignosulfonate and graphene oxide and then carrying out high-temperature heat treatment. The method comprises the steps of firstly adding sodium lignosulfonate into graphene oxide dispersion liquid, uniformly mixing the sodium lignosulfonate and the graphene oxide dispersion liquid through ultrasonic treatment, then evaporating the mixture on a mold to form a film, and finally treating the composite film at high temperature to obtain the thermal reduction graphene oxide film. The invention makes full use of the waste sodium lignin sulfonate in the paper industry, has low cost and is renewable. The whole preparation process is safe, reliable, economic, environment-friendly and simple to operate, and has suitable industrial popularization and economic value. The thermal reduction graphene oxide film prepared by the method has a more compact structure and high graphitization degree.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a method for preparing a thermal reduction graphene oxide film by blending sodium lignosulfonate and graphene oxide.
Background
Lignin is a natural high molecular polymer with the second content of cellulose and chitin in nature, and can generate about 6 x 10 of lignin every year all over the world14Ton. The lignosulfonate is derived from sulfite pulping in an acid pulping process, is widely applied and is a dominant process in the prior papermaking process. The lignosulfonate has good water solubility due to the introduction of sulfonic acid groups in molecules, so that the reaction capacity of the lignosulfonate is greatly improved, and therefore, sodium lignosulfonate is industrial lignin with rich sources and wide application. The method for preparing the thermal reduction graphene oxide film by blending the sodium lignosulfonate and the graphene oxide realizes high-value utilization of the papermaking industrial waste.
Graphene is a compound represented by sp2A two-dimensional carbon material with a honeycomb lattice structure formed by hybridized carbon atoms promotes great development and innovation in many fields of optics, mechanics, electricity, thermodynamics and the like. With the gradual breakthrough of mass production and large-size problems, the industrial application of graphene is accelerating, and based on existing research results, the field in which the commercial application is first realized may be a plurality of important fields such as mobile devices, aerospace, new energy batteries and the like.
Graphene oxide, which is one of graphene derivatives, has good water dispersibility, is a precursor for preparing graphene, and can be used for preparing graphene through a thermal reduction process. Meanwhile, the graphene oxide is stably dispersed in water, can be easily prepared into films, aerogel or compounded with other functional materials, and then is reduced by high-temperature heat to prepare graphene and related materials with excellent performance. However, during the reduction of graphene oxide, some carbon atoms are inevitably taken away due to the removal of oxygen atoms, so that the defects of the reduced graphene oxide are large. The existence of the defects has great influence on various performances of the reduced graphene oxide. Meanwhile, due to irregular stacking of graphene oxide nanosheets, and decomposition of oxygen-containing functional groups into carbon-containing gas during thermal reduction. Therefore, the structure of the reduced graphene oxide film tends to be loose.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for preparing a thermal reduction graphene oxide film by blending sodium lignosulfonate and graphene oxide, and the prepared thermal reduction graphene oxide film has a more compact structure and high graphitization degree.
A method for preparing a thermal reduction graphene oxide film by blending sodium lignosulfonate and graphene oxide comprises the following steps:
s1, dispersing graphene oxide in water to prepare a graphene oxide dispersion liquid;
s2, adding sodium lignosulphonate into the graphene oxide dispersion liquid, and carrying out ultrasonic treatment for 30-180min at the ultrasonic power of 280-480W;
s3, pouring the mixed liquid obtained in the step S2 into a mold, and baking for 6-24 hours at the temperature of 60-80 ℃ to obtain a composite film;
s4, heating the composite film obtained in the step S3 from room temperature to 600-1000 ℃ at a heating rate of 2-10 ℃/min in an argon atmosphere, preserving the heat for 60-180min, and naturally cooling to room temperature to obtain a thermal reduction graphene oxide film;
the concentration of the graphene oxide dispersion liquid is 3-15mg/L, and the volume/mass ratio of the graphene oxide dispersion liquid to the sodium lignosulfonate is 5-15mL:5-200 mg.
Preferably, the concentration of the graphene oxide dispersion liquid is 5mg/L, and the volume/mass ratio of the graphene oxide dispersion liquid to the sodium lignosulfonate is 7mL:50 mg.
Preferably, the baking temperature of the step S3 is 80 ℃.
Preferably, the temperature rising rate of the step S4 is 2 ℃/min, and the temperature rises from room temperature to 900 ℃.
Compared with the prior art, the invention has the following technical effects:
(1) according to the invention, sodium lignosulfonate is added in the process of thermally reducing the graphene oxide film, and the sodium lignosulfonate has the property of a surfactant, so that the structure is more compact in the evaporation film forming process of the graphene oxide. Meanwhile, in the thermal reduction process, sodium lignosulfonate can be decomposed into small-molecular fragments of activated carbon atoms, and defects generated in the thermal reduction process can be compensated. Therefore, the thermal reduction graphene oxide film prepared by the method has high graphitization degree and a more compact structure.
(2) The invention takes sodium lignosulphonate as a raw material, the raw material is rich and renewable, and the reutilization of the wastes in the papermaking industry is realized.
(3) The preparation process is simple, and in the high-temperature treatment process, the original shape and structure of the material can be well maintained only by clamping the composite film between the two silicon dioxide sheets. High process feasibility and easy industrial production.
Description of the drawings:
fig. 1 is a raman spectrum of thermally reduced graphene oxide according to the present invention; in the figure, a, b and c are Raman spectra of products of examples 1, 2 and 3, respectively. Wherein the ratio of the intensities of the D peak and the G peak (I)D/IG) Can be used as a measure of the degree of graphitization of the carbon material, with the smaller the value, the higher the degree of graphitization.
FIG. 2 is a scanning electron micrograph of thermally reduced graphene oxide according to the present invention; in the figure, a, b and c are scanning electron micrographs of the products of examples 1, 2 and 3, respectively.
Detailed Description
The process of the present invention is further illustrated below with reference to examples. The embodiments described herein are presently preferred embodiments of the invention, are provided for the purpose of illustration and explanation only and are not intended to be limiting of the invention.
Example 1
A method for preparing a thermal reduction graphene oxide film by blending sodium lignosulfonate and graphene oxide comprises the following steps:
(1) preparing 5mL of graphene oxide water dispersion liquid with the concentration of 3 mg/mL;
(2) 5mg of sodium lignosulfonate was added to the dispersion of graphene oxide water, and ultrasound was performed at 280W for 30 min.
(3) The resulting mixture was poured into a circular polytetrafluoroethylene mold having a diameter of 3 cm. Baking for 6h at 60 ℃ to obtain the composite film.
(4) The obtained composite film is clamped between two silicon dioxide sheets and put into a tubular furnace. Raising the temperature from room temperature to 700 ℃ at the temperature raising rate of 5 ℃/min under the argon atmosphere, and preserving the temperature for 60 min. And then naturally cooling to room temperature to obtain the thermal reduction graphene oxide film.
The raman spectrum of the thermal reduction graphene oxide film prepared in this example is shown in fig. 1(a), ID/IGIs 1.03. Thermal reduction of graphene oxide without addition of sodium lignosulfonate ID/IGGreater than 1.2. The thermal reduction graphene oxide film prepared by the embodiment has high graphitization degree.
A scanning electron microscope image of the thermal reduction graphene oxide film prepared in this embodiment is shown in fig. 2(a), and it can be seen that the thermal reduction graphene oxide film prepared in this embodiment has an obvious layered structure and a small interlayer distance. And the thermal reduction graphene oxide without adding sodium lignosulfonate has fewer scanning electron microscope layered structures and larger interlayer spacing.
Example 2
A method for preparing a thermal reduction graphene oxide film by blending sodium lignosulfonate and graphene oxide comprises the following steps:
(1) preparing 15mL of graphene oxide water dispersion liquid with the concentration of 15 mg/mL;
(2) adding 200mg of sodium lignosulphonate into the dispersion liquid of the graphene oxide water, and carrying out ultrasonic treatment for 180min at the ultrasonic power of 380W.
(3) The resulting mixture was poured into a mold of circular polytetrafluoroethylene with a diameter of 20 cm. Baking for 24h at 70 ℃ to obtain the composite film.
(4) The obtained composite film is clamped between two silicon dioxide sheets and put into a tubular furnace. Raising the temperature from room temperature to 1000 ℃ at a heating rate of 10 ℃/min under the atmosphere of argon, and preserving the temperature for 180 min. And then naturally cooling to room temperature to obtain the thermal reduction graphene oxide film.
The raman spectrum of the thermal reduction graphene oxide film prepared in this example is shown in fig. 1(b), ID/IGIs 1.04. Thermal reduction of graphene oxide without addition of sodium lignosulfonate ID/IGGreater than 1.2. The thermal reduction graphene oxide film prepared by the embodiment has high graphitization degree.
A scanning electron microscope image of the thermal reduction graphene oxide film prepared in this embodiment is shown in fig. 2(b), and it can be seen that the thermal reduction graphene oxide film prepared in this embodiment has an obvious layered structure and a small interlayer distance. And the thermal reduction graphene oxide without adding sodium lignosulfonate has fewer scanning electron microscope layered structures and larger interlayer spacing.
Example 3
A method for preparing a thermal reduction graphene oxide film by blending sodium lignosulfonate and graphene oxide comprises the following steps:
(1) preparing 7mL of graphene oxide water dispersion liquid with the concentration of 5 mg/mL;
(2) 50mg of sodium lignosulfonate was added to the dispersion of graphene oxide water, and ultrasound was performed at 480W for 100 min.
(3) The resulting mixture was poured into a circular polytetrafluoroethylene mold having a diameter of 12 cm. Baking at 80 deg.C for 12h to obtain the composite film.
(4) The obtained composite film is clamped between two silicon dioxide sheets and put into a tubular furnace. Raising the temperature from room temperature to 900 ℃ at the temperature raising rate of 2 ℃/min under the argon atmosphere, and preserving the temperature for 120 min. And then naturally cooling to room temperature to obtain the thermal reduction graphene oxide film.
The raman spectrum of the thermal reduction graphene oxide film prepared in this example is shown in fig. 1(c), ID/IG0.94, less than 1, with the highest degree of graphitization.
A scanning electron microscope image of the thermal reduction graphene oxide film prepared in this embodiment is shown in fig. 2(c), and it can be seen that the thermal reduction graphene oxide film prepared in this embodiment has an obvious layered structure and a minimum interlayer distance.
Claims (4)
1. A method for preparing a thermal reduction graphene oxide film by blending sodium lignosulfonate and graphene oxide is characterized by comprising the following steps:
s1, dispersing graphene oxide in water to prepare a graphene oxide dispersion liquid;
s2, adding sodium lignosulphonate into the graphene oxide dispersion liquid, and carrying out ultrasonic treatment for 30-180min at the ultrasonic power of 280-480W;
s3, pouring the mixed liquid obtained in the step S2 into a mold, and baking for 6-24 hours at the temperature of 60-80 ℃ to obtain a composite film;
s4, heating the composite film obtained in the step S3 from room temperature to 600-1000 ℃ at a heating rate of 2-10 ℃/min in an argon atmosphere, preserving the heat for 60-180min, and naturally cooling to room temperature to obtain a thermal reduction graphene oxide film;
the concentration of the graphene oxide dispersion liquid is 3-15mg/L, and the volume/mass ratio of the graphene oxide dispersion liquid to the sodium lignosulfonate is 5-15mL:5-200 mg.
2. The method for preparing the thermal reduction graphene oxide film after blending sodium lignosulfonate and graphene oxide according to claim 1, wherein the concentration of the graphene oxide dispersion liquid is 5mg/L, and the volume/mass ratio of the graphene oxide dispersion liquid to the sodium lignosulfonate is 7mL:50 mg.
3. The method for preparing the thermally reduced graphene oxide film after blending sodium lignosulfonate and graphene oxide according to claim 1, wherein the baking temperature of the step S3 is 80 ℃.
4. The method for preparing the thermally reduced graphene oxide film after blending sodium lignosulfonate and graphene oxide according to claim 1, wherein the temperature rise rate of the step S4 is 2 ℃/min, and the temperature rises from room temperature to 900 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114291813A (en) * | 2022-02-16 | 2022-04-08 | 浙江大学 | Preparation method of independent self-supporting ultrathin graphite film |
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| CN114291813A (en) * | 2022-02-16 | 2022-04-08 | 浙江大学 | Preparation method of independent self-supporting ultrathin graphite film |
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Application publication date: 20201211 |