CN116022780A - Oligolayer graphene with large interlayer spacing and low-temperature rapid preparation method and application thereof - Google Patents
Oligolayer graphene with large interlayer spacing and low-temperature rapid preparation method and application thereof Download PDFInfo
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- 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
- Y02E60/10—Energy storage using batteries
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Abstract
An oligolayer graphene with a large interlayer distance and a low-temperature rapid preparation method and application thereof. The invention belongs to the field of graphene material preparation. The invention aims to solve the technical problems that the existing high-temperature GO reduction method requires higher temperature and energy consumption, the existing low-temperature GO reduction method takes longer time, and the obtained graphene layer spacing is not large. According to the invention, GO dispersion liquid prepared by a Hummers method is used as a raw material, and the oligolayer graphene with large interlayer spacing is obtained through drying and low-temperature micro-explosion treatment. The graphene with high reduction degree is obtained after further heat treatment, and is applied to the field of negative electrode materials of potassium ion batteries, so that the graphene has the remarkable advantages of excellent potassium storage performance, high structural stability and effective buffering of volume expansion in the electrochemical reaction process.
Description
Technical Field
The invention belongs to the field of graphene material preparation, and particularly relates to an oligolayer graphene with a large interlayer spacing, and a low-temperature rapid preparation method and application thereof.
Background
Graphene refers to single-layer carbon atoms closely stacked into a two-dimensional honeycomb lattice structure, and is a basic structural unit for constructing carbon materials with other dimensions (zero-dimensional fullerenes, one-dimensional carbon nanotubes and three-dimensional graphite). Because of their excellent electrical, thermal and mechanical properties, graphene has received great attention in the fields of high-function nano-electronic devices, transparent conductive films, composite materials, catalytic materials, energy storage materials, field emission materials, gas sensors, gas storage and the like. The macro preparation of graphene is an important precondition for realizing the wide application and performance research of the graphene, so that the development of the macro preparation technology of the graphene is particularly important.
Currently, methods for preparing graphene mainly include a Chemical Vapor Deposition (CVD) method, a crystal epitaxy method, a mechanical lift-off method, and a chemical lift-off method (i.e., oxidation-lift-reduction). The CVD method can meet the requirement of large-scale preparation of high-quality graphene, but has the advantages of higher preparation cost, high requirement on a substrate and complex process. The crystal epitaxial growth method has strict requirements on preparation conditions and low yield, and is difficult to meet the requirements of industrialized and large-scale production. The mechanical stripping method can prepare high-quality graphene with few defects, but can only obtain a very small amount of graphene, has low efficiency and high randomness, is not suitable for preparing a large amount of graphene, and can only be used for laboratory small-scale preparation at present. The chemical stripping method is mainly used for preparing graphene oxide by oxidizing crystalline flake graphite and preparing graphene oxide by stripping and reducing Graphene Oxide (GO) in the follow-up process, has low cost, low equipment requirement and high graphene yield, and is a recognized method capable of realizing macro preparation of graphene.
The most commonly used methods for reduction of GO at present include chemical reduction and high temperature thermal reduction. The chemical reduction method needs to use reducing agents such as hydrazine, sodium borohydride, hydroiodic acid and the like to remove various oxygen-containing functional groups on the surface of GO so as to obtain graphene, but the reducing agents have larger toxicity and higher cost, have larger environmental pollution and can introduce new impurities to influence the quality of the graphene. The high-temperature thermal reduction method is an ideal choice for preparing graphene in large quantity at present because oxygen-containing functional groups on the surface of GO are removed through high-temperature heat treatment without using other toxic and harmful chemical reagents. However, high-temperature reduction of GO requires higher temperature and higher energy consumption, so how to realize low-temperature rapid reduction of GO is still a difficulty and challenge in the field of graphene research at present.
Disclosure of Invention
The invention aims to solve the technical problems that the existing high-temperature reduction of GO requires higher temperature and higher energy consumption, the existing low-temperature reduction of GO takes longer time, and the obtained graphene layer spacing is not large, and provides an oligolayer graphene with a large layer spacing, a low-temperature rapid preparation method and application thereof.
One of the purposes of the invention is to provide a low-temperature rapid preparation method of oligolayer graphene with large interlayer spacing, which comprises the following steps:
step 1: taking GO dispersion liquid prepared by a Hummers method as a precursor, and drying the precursor until the water content is 20% -45% to obtain GO powder;
step 2: and (3) placing the GO powder in a tube furnace, and heating to a certain temperature under a protective atmosphere to generate micro-explosion stripping to obtain the oligolayer graphene with large interlayer spacing.
Further defined, the concentration of GO dispersion in step 1 is 0.1-10 mg/mL.
Further defined, the drying in step 1 is natural drying, forced air drying, vacuum drying or freeze drying.
Further defined, the temperature of drying in step 1 is less than or equal to 50 ℃.
Further defined, the freeze-drying time is 2 to 32 hours, and the vacuum pressure value is 1 to 500Pa.
Further limited, the protective atmosphere in the step 2 is any one or a mixture of a plurality of gases of hydrogen, argon and nitrogen according to any ratio.
Further limited, the temperature rising rate in the step 2 is more than or equal to 5 ℃/min, and the certain temperature is 150-220 ℃.
The second object of the present invention is to provide an oligolayer graphene with a large interlayer spacing prepared by the above method.
Further defined, the angle corresponding to the diffraction peak of the (002) crystal face of the graphene is 21.5 DEG to 22.5 DEG, the interlayer spacing is 0.395 to 0.413nm, and the specific surface area is 300 to 800m 2 /g。
The invention further aims to provide a preparation method of the high-reduction-degree oligolayer graphene with a large interlayer spacing, which comprises the following steps of:
and carrying out heat treatment on the oligolayer graphene with the large interlayer spacing, so as to obtain the oligolayer graphene with the large interlayer spacing and high reduction degree.
Further limited, the heat treatment temperature is 300-1000 ℃ and the temperature rising rate is 2-10 ℃/min.
The fourth object of the invention is to provide an application of the high-reduction-degree oligolayer graphene with large interlayer spacing prepared by the method in a cathode material of a potassium ion battery.
The invention aims to provide a negative electrode material of a potassium ion battery, which is prepared by adopting the method, and the high-reduction-degree oligolayer graphene with a large interlayer spacing is used as an active material.
Compared with the prior art, the invention has the remarkable effects that:
(1) The invention provides a new method for preparing graphene in a macro amount, which not only can obtain graphene with large interlayer spacing, rich folds and high specific area, but also has low equipment requirement and cost, and simultaneously has the advantages of short preparation time, low reduction temperature, energy saving, economy and environmental protection, and further omits complicated processes of suction filtration, centrifugation, washing and the like for removing chemical impurities.
(2) According to the method, the preparation process parameters are strictly controlled, under the conditions of inert gas protection, specific heating rate and certain water content, the graphene oxide is subjected to micro-explosion stripping, and the ultra-thin, loose, large-layer-spacing, rich-fold and high-specific-area oligolayer graphene is prepared after subsequent thermal reduction, so that the oligolayer graphene is applied to the field of anode materials of potassium ion batteries, and has the remarkable advantages of excellent potassium storage performance, high structural stability and effective buffering of volume expansion in the electrochemical reaction process.
Drawings
FIG. 1 is a comparative photograph showing the volume change of the sample obtained in example 1 before and after the micro-explosion peeling; (A) GO, (B) example 1;
FIG. 2 is an X-ray diffraction pattern (XRD) spectrum of the GO precursor, samples obtained in example 1 and example 2;
FIG. 3 is XRD patterns of samples obtained in example 2 and comparative example 6;
FIG. 4 is a Transmission Electron Microscope (TEM) photograph of the sample obtained in example 2;
FIG. 5 is a graph showing the adsorption and desorption isotherms of nitrogen for the samples obtained in example 2 and comparative example 6;
fig. 6 is a graph showing the ratio performance of half cells assembled using the samples obtained in example 2 and comparative example 6.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. In the present specification and claims, the range limitations may be combined and/or interchanged, such ranges including all the sub-ranges contained therein if not expressly stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Example 1:
the low-temperature rapid preparation method of the oligolayer graphene with the large interlayer spacing comprises the following steps:
step 1:
firstly, taking GO dispersion liquid prepared by a Hummers method as a precursor, wherein the concentration of the GO dispersion liquid is 0.5mg/mL, and then performing ultrasonic dispersion for 2 hours; drying with air at 40deg.C for 12 hr to obtain GO powder (200 mg) with water content of 34.1%;
step 2:
GO powder (200 mg) is placed in a tube furnace, and heated to 180 ℃ at a speed of 10 ℃/min under nitrogen atmosphere, and micro-explosion occurs, so that the oligolayer graphene with large interlayer spacing is obtained.
Comparative example 1
This comparative example differs from example 1 in that: and (3) heating at a rate of 3 ℃/min in the step (2) to obtain the non-explosive graphene powder. The remaining steps and parameters were the same as in example 1.
Comparative example 2
This comparative example differs from example 1 in that: and 2, taking air as the atmosphere in the step, and obtaining the non-explosive graphene powder. The remaining steps and parameters were the same as in example 1.
Comparative example 3
This comparative example differs from example 1 in that: in the step 1, the drying mode adopts freeze drying, and the specific technological parameters of the freeze drying are as follows: vacuum pressure is 1Pa, and freeze-drying time is 1.5h, so that the non-explosive graphene powder is obtained. The remaining steps and parameters were the same as in example 1.
Comparative example 4
This comparative example differs from example 1 in that: in the step 1, the drying mode adopts freeze drying, and the specific technological parameters of the freeze drying are as follows: vacuum pressure is 1Pa, freeze-drying time is 32h, and the non-explosive graphene powder is obtained. The remaining steps and parameters were the same as in example 1.
Comparative example 5
This comparative example differs from example 1 in that: and in the step 2, heating to 150 ℃ at a speed of 10 ℃/min to obtain the non-explosive graphene powder. The remaining steps and parameters were the same as in example 1.
Example 2
The preparation method of the high-reduction-degree oligolayer graphene with the large interlayer spacing in the embodiment comprises the following steps:
the sample prepared in example 1 was subjected to heat treatment, specifically, heating to 500 ℃ at a heating rate of 3 ℃/min and heat-preserving for 2 hours, to obtain high-reduction oligolayer graphene with a large interlayer spacing.
Comparative example 6
This comparative example differs from example 2 in that: the sample prepared in example 1 was replaced with the sample prepared in comparative example 1. The remaining steps and parameters were identical to those of example 2.
Comparative example 7
This comparative example differs from example 2 in that: the sample prepared in example 1 was replaced with the sample prepared in comparative example 2. The remaining steps and parameters were identical to those of example 2.
Comparative example 8
This comparative example differs from example 2 in that: the sample prepared in example 1 was replaced with the sample prepared in comparative example 3. The remaining steps and parameters were identical to those of example 2.
Comparative example 9
This comparative example differs from example 2 in that: the sample prepared in example 1 was replaced with the sample of comparative example 4 prepared in comparative example 4. The remaining steps and parameters were identical to those of example 2.
Comparative example 11
This comparative example differs from example 2 in that: the sample prepared in example 1 was replaced with the sample prepared in comparative example 5. The remaining steps and parameters were identical to those of example 2.
Detection test
Fig. 1 is a comparison photograph of the volume change of the sample obtained in example 1 before and after micro-explosion peeling (GO mass is 200 mg), and it is seen that the volume of GO after micro-explosion peeling is increased by 9.5 times of the original volume.
(II) FIG. 2 is an X-ray diffraction (XRD) spectrum of the GO precursor, the samples obtained in example 1 and example 2, and it is seen from the figure that the diffraction angle of the (002) crystal face of the sample obtained in example 1 is 21.9 DEG, and the corresponding interplanar spacing is 0.406nm; the diffraction angle of the (002) crystal face of the sample of example 2 was increased to 22.3 degrees, and the corresponding interplanar spacing was 0.398nm, which indicates that the sample was further reduced and graphitized by the subsequent high temperature reduction process.
(III) FIG. 3 shows XRD patterns of the samples obtained in example 2 and comparative example 6. As can be seen from FIG. 3, the diffraction angle of the (002) crystal plane of the sample obtained in comparative example 6 was increased from 22.3 to 25.9℃and the corresponding interplanar spacing was decreased from 0.398nm to 0.344nm, indicating that the interlayer spacing of the samples prepared by micro-explosion delamination was greater than that of the samples obtained in example 2.
(IV) FIG. 4 is a Transmission Electron Microscope (TEM) photograph of the sample obtained in example 2, and it can be seen that the graphene surface prepared by micro-explosion stripping has rich wrinkles.
(fifth) FIG. 5 is a graph showing the nitrogen adsorption/desorption isotherms of the samples obtained in example 2 and comparative example 6, the specific surface area of the sample being 306m 2 Per gram, far greater than the specific surface area of the sample of comparative example 6 (16.3 m 2 According to the ratio of/g), the graphene after the rapid low-temperature micro-explosion thermal stripping process is shown to have larger sizeThe specific surface area is more favorable for potassium ion storage.
Application example
The samples prepared in example 2 and comparative example 6 were used as active materials to prepare negative electrode materials for potassium ion batteries, which were assembled into button half cells to evaluate electrochemical properties, and the specific steps were as follows:
step one, preparing an electrode slice
The obtained sample, a conductive agent (Super-P) and a binder (carboxymethyl cellulose CMC) were mixed according to a mass ratio of 75:15:10, uniformly mixing to obtain slurry, coating the slurry on a copper foil by using a coater, and vacuum drying at 60 ℃ for 12 hours to obtain a potassium ion battery negative electrode plate;
step two, preparing a button type half cell:
the electrode slice and the potassium slice obtained in the first step are respectively used as an anode and a cathode to assemble a potassium ion half-cell, and the electrolyte is 0.8mol/L potassium hexafluorophosphate (KPF) 6 ) (the solvent is diethyl carbonate/ethylene carbonate (DEC/EC, 1:1, volume percent)).
Step three, electrochemical test:
constant current charge and discharge test is carried out on the battery by using charge and discharge test equipment, and the test voltage is 0.01-3.0V (vs. K) + and/K) the test current density is 0.05-10A/g.
The test result is shown in fig. 6, and it can be seen from fig. 6 that the micro-explosion graphene powder has excellent rate capability when being used as a cathode material of the potassium ion battery, the capacity can still be kept at 153mAh/g under the high current density of 10A/g, and the capacity can still reach 210mAh/g when the current density returns to 0.2A/g, so that the graphene prepared by the micro-explosion method has the advantages of stable structure and effective buffering of volume expansion in the electrochemical reaction process.
In the foregoing, the present invention is merely preferred embodiments, which are based on different implementations of the overall concept of the invention, and the protection scope of the invention is not limited thereto, and any changes or substitutions easily come within the technical scope of the present invention as those skilled in the art should not fall within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. The low-temperature rapid preparation method of the oligolayer graphene with the large interlayer spacing is characterized by comprising the following steps of:
step 1: taking GO dispersion liquid prepared by a Hummers method as a precursor, and drying the precursor until the water content is 20% -45% to obtain GO powder;
step 2: and (3) placing the GO powder into a tube furnace, and heating to a certain temperature under a protective atmosphere to generate micro-explosion stripping to obtain the oligolayer graphene with large interlayer spacing.
2. The method of claim 1, wherein the GO dispersion in step 1 has a concentration of 0.1-10 mg/mL.
3. The method according to claim 1, wherein the drying in step 1 is natural drying, forced air drying, vacuum drying or freeze drying, the drying temperature is less than or equal to 50 ℃, the freeze drying time is 2-32 h, and the vacuum pressure value is 1-500 Pa.
4. The method according to claim 1, wherein the protective atmosphere in the step 2 is any one or a mixture of a plurality of hydrogen, argon and nitrogen.
5. The method according to claim 1, wherein the temperature rising rate in the step 2 is equal to or higher than 5 ℃/min, and the certain temperature is 150-220 ℃.
6. The oligolayer graphene with large interlayer spacing produced by the method of any one of claims 1 to 5, wherein the angle corresponding to the diffraction peak of the (002) crystal face is 21.5 ° to 22.5 °, the interlayer spacing is 0.395 to 0.413nm, and the specific surface area is 300 to 800m 2 /g。
7. The preparation method of the high-reduction-degree oligolayer graphene with the large interlayer spacing is characterized by comprising the following steps of:
heat-treating the oligolayer graphene having a large interlayer spacing of claim 6 to obtain the oligolayer graphene having a high reduction degree and a large interlayer spacing.
8. The method according to claim 7, wherein the heat treatment temperature is 300 to 1000 ℃ and the temperature rising rate is 2 to 10 ℃/min.
9. The application of the high-reduction-degree oligolayer graphene with large interlayer spacing prepared by the method in the anode material of the potassium ion battery.
10. The negative electrode material of the potassium ion battery is characterized in that the high-reduction-degree oligolayer graphene with large interlayer spacing prepared by the method of claim 7 is adopted as an active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202310049960.6A CN116022780B (en) | 2023-02-01 | 2023-02-01 | Oligolayer graphene with large interlayer spacing and low-temperature rapid preparation method and application thereof |
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