Basalt nanosheet with high aspect ratio and preparation method thereof

Abstract

The application provides a high-aspect-ratio basalt nanosheet and a preparation method thereof, which utilizes basalt flake as raw material, and makes the lamellar structure on the surface of the basalt flake finally fall off to form the basalt nanosheet through cavitation effect generated by a cell crusher. The basalt flake which is not peeled off will have intense cavitation effect between the layers of the basalt flake under the action of mechanical stirring combined with ultrasonic, so that the basalt flake is peeled off again to form a large amount of basalt nanosheets. The mixed liquid obtained by mixing the basalt nanosheets prepared by the above two methods is subjected to gradient centrifugation, different centrifugal forces are used to screen the basalt nanosheets with different sizes, and the basalt nanosheet with high aspect ratio is obtained. The application provides a new idea for large-scale preparation of the basalt nanosheet, reuses the waste basalt flake after initial peeling, and prepares a large amount of basalt nanosheets through a chemical and mechanical method, thereby enriching the preparation system of the basalt nanosheet.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of inorganic nanosheet material preparation, and particularly relates to a basalt nanosheet with a high aspect ratio and a preparation method thereof. BACKGROUND

[0002] The continuous progress and development of insulating materials began in the early 20th century, which inspired the creation of new electrical devices. With the advancement of the modernization process around the world, the modern electrical industry is rapidly developing towards high frequency, high voltage, and high power, and the demand for electrical devices is steadily increasing. Obviously, the performance of electrical devices and components depends largely on the performance of their insulating materials, which in turn drives the rapid expansion of the field of insulating materials. The initial insulating materials were mainly derived from natural substances such as cotton, silk, rubber, and asphalt. These materials are directly extracted from plants, minerals, or other inorganic substances, and their electrical properties are poor. Due to their low resistivity and breakdown strength, they limit the improvement of insulating capacity and power level of electrical devices, as well as the ability to use dielectric materials in specialized electrical instruments. With the development of power systems and electrical devices, many valuable discoveries and improvements have been made in insulating materials. To date, silicate minerals have been widely used in modern electrical insulation due to their unique physical properties, abundance, low cost, and environmental friendliness. With the increasing demand for insulating materials, more and more nanoscale insulating materials, especially silicate nanosheets (such as montmorillonite nanosheets, mica nanosheets, vermiculite nanosheets, and ledikite nanosheets), have been produced. These silicate nanosheets are considered as nanoscale fillers, which are added to polymer matrices to manufacture composites with better electrical, thermal, and mechanical properties. Currently, these silicate nanosheet-added composites have been widely used in devices with high insulating performance requirements and have achieved remarkable results.

[0003] However, some studies have found that factors limiting the further improvement of the insulating performance of the above composites are related to the shape and size of the nanosheets. Generally, silicate nanosheets with a large aspect ratio are considered to be ideal insulating materials, but the aspect ratio of the above silicate nanosheets is not high enough (almost less than 500), which cannot meet the actual requirements of high-grade insulating materials. Therefore, it is of great significance to develop a simple and inexpensive exfoliation method to prepare new silicate nanosheets with a high aspect ratio for the development of insulating materials.

[0004] Basalt flakes (BS) as one of the most abundant silicate minerals, due to its unique chemical composition and structure, has excellent thermal stability, chemical stability, and sound absorption performance, especially in mechanical and electrical insulation performance. However, despite the outstanding physical and chemical properties of BS, it has not been applied in the field of electrical insulation to date. SUMMARY

[0005] In view of the problems in the prior art, the basalt nanosheet with high aspect ratio and a preparation method thereof are provided to fill the current industry technical blank, successfully prepare the basalt nanosheet with high aspect ratio, enrich the preparation system of the basalt nanosheet, and lay a foundation for the preparation of the basalt nanomaterial.

[0006] The present application is realized by the following technical solutions:

[0007] The preparation method of the basalt nanosheet with high aspect ratio comprises the following steps:

[0008] S1, after the surface etching reaction of the basalt flake is carried out by using acid, the lithium ion intercalation is carried out on the preliminarily surface etched basalt flake, the intercalated basalt flake is obtained, and the intercalated basalt flake is subjected to cavitation to obtain basalt nanosheet A and basalt flake waste;

[0009] S2, the basalt flake waste is placed in a mixed liquid system of hydrogen peroxide and organic acid in proportion, and is subjected to ultrasonic treatment to obtain basalt nanosheet B;

[0010] S3, after the basalt nanosheet A and the basalt nanosheet B are mixed, gradient centrifugation is carried out, different sizes of the basalt nanosheet are screened by different centrifugal forces, and the basalt nanosheet with high aspect ratio is obtained.

[0011] Preferably, the specific process of S1 is as follows:

[0012] The basalt flake is placed in an acid solution, and the surface etching reaction is carried out by stirring at a set temperature, the basalt flake is subjected to suction filtration and washing until neutral after the reaction is completed, and the preliminarily surface etched basalt flake is obtained; the preliminarily surface etched basalt flake is placed in a sodium chloride solution, and the stirring reaction is carried out at a set temperature, the basalt flake is subjected to suction filtration and washing after the reaction is completed, the basalt flake after the reaction is placed in a lithium ion solution, the stirring reaction is carried out at a set temperature, the basalt flake is dried after the reaction is completed, the intercalated basalt flake is obtained; the intercalated basalt flake is dispersed in anhydrous ethanol, and then is placed in a cell crusher, the reaction is carried out at a set power and time, the mixed liquid after the reaction is placed, the upper turbid liquid is taken out, and the basalt nanosheet A is obtained after drying, and the lower precipitate is the basalt flake waste.

[0013] Preferably, the concentration of the acid solution in S1 is 1moL / L-3moL / L, the dosage ratio of the basalt flake to the acid solution is 1g:100mL-200mL, the acid solution comprises an acetic acid solution or a hydrochloric acid solution, the reaction time of the surface etching reaction is 4-12h, and the reaction temperature is 25℃-80℃.

[0014] Preferably, the sodium chloride is a saturated sodium chloride solution, the basalt flake and the sodium chloride solution are used in a ratio of 1g:200mL, the reaction time is 4-8h, and the reaction temperature is 60-120℃.

[0015] Preferably, the lithium ion solution has a concentration of 0.5-3mol / L, the basalt flake and the lithium ion solution are used in a ratio of 1g:50-200mL, the reaction time is 4-8h, and the reaction temperature is 60-120℃, and the lithium ion solution is a lithium chloride solution or a butyl lithium solution.

[0016] Preferably, the mass ratio of the intercalated basalt flake and the anhydrous ethanol is 1g:200-400mL, the power of the cell crusher is 600-1000W, and the reaction time is 20-60min.

[0017] Preferably, the mass fraction of the hydrogen peroxide in S2 is 10-30wt%, the amount of the added organic acid is 0.5-2g, the organic acid is maleic acid or oxalic acid, the rotation speed of the mechanical stirring is 500-2500rpm, the ultrasonic power is 500-1000W, and the reaction time is 20-60min.

[0018] Preferably, the specific process of S3 is as follows:

[0019] The basalt nanosheet A and the basalt nanosheet B are mixed to obtain a basalt nanosheet C, which is then centrifuged at a rotation speed of 500rpm, and then the supernatant A and the precipitate A are collected; the lower layer precipitate A is dispersed in anhydrous ethanol for ultrasonic dispersion, and then the dispersion liquid is centrifuged at a rotation speed of 1000rpm, and then the supernatant B and the precipitate B are collected; the lower layer precipitate B is dispersed in anhydrous ethanol for ultrasonic dispersion, and then the dispersion liquid is centrifuged at a rotation speed of 2000rpm, and then the supernatant C and the precipitate C are collected; the lower layer precipitate C is dispersed in anhydrous ethanol for ultrasonic dispersion, and then the dispersion liquid is centrifuged at a rotation speed of 3000rpm, and then the supernatant D and the precipitate D are collected; the lower layer precipitate D is dispersed in anhydrous ethanol for ultrasonic dispersion, and then the basalt nanosheet with a high aspect ratio is obtained by screening the basalt nanosheet with different sizes through different centrifugal forces.

[0020] A basalt nanosheet with a high aspect ratio is prepared by the above preparation method.

[0021] Preferably, the basalt nanosheet with a high aspect ratio has a thickness of 1.172-266.83nm, a lateral length of 0.278-4.625μm, and an aspect ratio of 21.5-1310.3.

[0022] Compared with the prior art, the present application has the following beneficial technical effects:

[0023] The present application provides a method for large-scale preparation of basalt nanosheets with high aspect ratio, which fills the current technical gap in the industry. The present application uses basalt flakes as raw material, performs preliminary surface etching with acid to remove part of the metal oxides and impurities on the surface, forms pores on the surface for subsequent modification. Then, lithium ions with small atomic radius are used for intercalation of the basalt flakes. Due to the ion reverse osmosis effect, the basalt flakes intercalated with lithium ions swell and form a layered structure. The cell crusher generates cavitation effect to make the surface layer structure of the basalt flakes finally fall off and form basalt nanosheets. The unpeeled basalt flakes are usually treated as waste, but in the present application, the waste basalt is placed in a hydrogen peroxide and organic acid mixed liquid system. Hydrogen peroxide can enter the interlayer domain of the basalt flakes by replacing water molecules or forming dimers, and can react with the hydrated cations in the interlayer domain through Fenton reaction with water molecules as medium to generate oxygen in situ. And hydrogen peroxide can accelerate the decomposition rate under the catalysis of organic acid to generate more oxygen. These gases will undergo intense cavitation in the interlayer of the basalt flakes under the action of mechanical stirring combined with ultrasonic, causing the basalt flakes to peel off again and form a large amount of basalt nanosheets. The basalt nanosheets prepared by the above two methods are mixed and then subjected to gradient centrifugation to separate basalt nanosheets of different sizes using different centrifugal forces, obtaining basalt nanosheets with high aspect ratio. This method provides a new idea for large-scale preparation of basalt nanosheets, reuses the waste basalt flakes peeled off for the first time, and prepares a large amount of basalt nanosheets through chemical and mechanical methods, enriching the preparation system of basalt nanosheets and laying a foundation for the preparation of basalt nanomaterials.

[0024] Further, the basalt nanosheets prepared by the present application have a thickness of 1.172 nm to 266.83 nm, a lateral length of 0.278 μm to 4.625 μm, and an aspect ratio of 21.5 to 1310.3.

[0025] Further, the present application first reuses the waste basalt flakes peeled off for the first time to prepare a large amount of basalt nanosheets through chemical and mechanical methods, enriching the preparation system of basalt nanosheets.

[0026] Further, the present application first separates basalt nanosheets with high aspect ratio from the prepared basalt nanosheets through gradient centrifugation, which has high stability and strong application prospect in the electrical industry and mechanical reinforcement field.

[0027] Further, the application adopts a simple and effective preparation method to prepare basalt nanosheets with high aspect ratio, the raw material is low, the preparation method is simple and easy to operate, without large equipment, industrialization is relatively easy to realize, and the possibility of industrialized batch production is improved. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 A schematic diagram for the preliminary preparation of basalt nanosheets;

[0029] Figure 2 A schematic diagram for preparing basalt nanosheets from waste basalt flakes;

[0030] Figure 3 A practical operation diagram for preparing basalt nanosheets from waste basalt flakes;

[0031] Figure 4 Optical photographs and Tyndall effect diagrams of basalt nanosheets, wherein Figure (a) is an organic acid; Figure (b) is hydrogen peroxide;

[0032] Figure 5 A schematic diagram of gradient separation of basalt nanosheets;

[0033] Figure 6 SEM diagrams and particle size distribution diagrams of basalt nanosheets of Example 5; wherein Figure (a) is an SEM diagram of BSNs-3, Figure (b) is a particle size distribution diagram of BSNs-3; Figure (c) is an SEM diagram of BSNs-3-500, Figure (d) is a particle size distribution diagram of BSNs-3-500; Figure (e) is an SEM diagram of BSNs-3-1000, Figure (f) is a particle size distribution diagram of BSNs-3-1000; Figure (g) is an SEM diagram of BSNs-3-2000, Figure (h) is a particle size distribution diagram of BSNs-3-2000; Figure (i) is an SEM diagram of BSNs-3-3000, Figure (j) is a particle size distribution diagram of BSNs-3-3000; Figure (k) is a yield ratio diagram of basalt nanosheets of different sizes;

[0034] Figure 7 AFM diagrams and aspect ratio diagrams of basalt nanosheets of Example 6; wherein Figure (a) is a scanning electron microscope diagram, Figure (b) is a 1.433 nm thickness diagram, Figure (c) is a 1.276 nm thickness diagram, Figure (d) is a 1.172 nm thickness diagram, Figure (e) is an aspect ratio diagram of basalt nanosheets of different sizes, and Figure (f) is a comparison diagram of other literatures. DETAILED DESCRIPTION

[0035] The application will be further described in detail below in conjunction with specific examples, which are an explanation of the application rather than a limitation.

[0036] A method for preparing basalt nanosheets with high aspect ratio on a large scale, comprising the following steps:

[0037] Step (1) preliminary preparation of basalt nanosheets:

[0038] 1.1 Put untreated basalt flakes into an acetic acid, hydrochloric acid solution, and stir at a set temperature to perform surface etching reaction. After the reaction is completed, perform suction filtration and washing until neutral to obtain preliminarily surface-etched basalt flakes;

[0039] 1.2 Put the preliminarily surface-etched basalt flakes into a sodium chloride solution, and stir at a set temperature to perform reaction. After the reaction is completed, perform suction filtration and washing,

[0040] 1.3 Put the reacted basalt flakes into a lithium chloride or butyl lithium solution, and stir at a set temperature to perform reaction. After the reaction is completed, dry and obtain intercalated basalt flakes.

[0041] 1.4 Disperse the basalt flakes in anhydrous ethanol at a certain concentration, then put them into a cell crusher, and perform reaction at a set power and time. After the reaction, let the mixed solution stand, take out the upper turbid liquid, dry it, and obtain basalt nanosheets A. The lower precipitate is basalt flake waste.

[0042] Step (2) large-scale preparation of basalt nanosheets: put the basalt flake waste in step (1) into a mixed solution of hydrogen peroxide and maleic acid or oxalic acid in proportion, and perform mechanical stirring combined with ultrasonic treatment, then obtain basalt nanosheets B.

[0043] Step (3) size screening of basalt nanosheets: mix basalt nanosheets A and basalt nanosheets B to obtain basalt nanosheets C, then put them into a centrifuge and perform centrifugation at a speed of 500 rpm, then collect supernatant A and precipitate A. Supernatant A is named BSNs-500. Disperse the lower precipitate A in anhydrous ethanol and perform ultrasonic dispersion, then put the dispersion into a centrifuge and perform centrifugation at a speed of 1000 rpm, then collect supernatant B and precipitate B. Supernatant B is named BSNs-1000. Disperse the lower precipitate B in anhydrous ethanol and perform ultrasonic dispersion, then put the dispersion into a centrifuge and perform centrifugation at a speed of 2000 rpm, then collect supernatant C and precipitate C. Supernatant C is named BSNs-2000. Disperse the lower precipitate C in anhydrous ethanol and perform ultrasonic dispersion, then put the dispersion into a centrifuge and perform centrifugation at a speed of 3000 rpm, then collect supernatant D and precipitate D. Supernatant D is named BSNs-3000. Disperse the lower precipitate D in anhydrous ethanol and perform ultrasonic dispersion, and name it BSNs-M3000.

[0044] Preferably, the concentration of the acetic acid solution or hydrochloric acid solution in step 1.1 is 1-3 moL / L, the ratio of basalt flake to acetic acid solution or hydrochloric acid solution is 1g:100-200 mL, the reaction time is 4-12 h, the reaction temperature is 25-80℃, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm.

[0045] Preferably, the sodium chloride in step 1.2 is a saturated sodium chloride solution, the ratio of basalt flake to sodium chloride solution is 1g:200 mL, the reaction time is 4-8 h, the reaction temperature is 60-120℃, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm.

[0046] Preferably, the concentration of the lithium chloride or butyl lithium solution in step 1.3 is 0.5-3 mol / L, the ratio of basalt flake to lithium chloride or butyl lithium solution is 1g:50-200 mL, the reaction time is 4-8 h, the reaction temperature is 60-120℃, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm.

[0047] Preferably, the mass ratio of the intercalated basalt flake to ethanol in step 1.4 is 1g:200-400 mL, the power of the cell crusher is 600-1000 W, and the reaction time is 20-60 min.

[0048] Preferably, the mass fraction of hydrogen peroxide in step (2) is 10-30 wt%, the addition amount of maleic acid or oxalic acid is 0.5-2 g, the ratio of waste basalt flake to the mixed solution of hydrogen peroxide and organic acid is 1g:300-500 mL, the mechanical stirring speed is 500-2500 rpm, the ultrasonic power is 500-1000 W, and the reaction time is 20-60 min.

[0049] Preferably, the amount of anhydrous ethanol used for dispersion and precipitation in step (3) is 200 mL, the ultrasonic power is 500 W, and the ultrasonic time is 2 min.

[0050] A basalt nanosheet with a high aspect ratio can be prepared on a large scale by the preparation method described above.

[0051] Preferably, the thickness of the basalt nanosheet is 1.172-266.83 nm, the lateral length is 0.278-4.625 μm, and the aspect ratio is 21.5-1310.3.

[0052] The embodiments of the present application are described in further detail as follows:

[0053] (1) The preliminary preparation of basalt nanosheets: a certain amount of basalt flakes is placed in a three-necked flask, and acetic acid or hydrochloric acid solution is added, the concentration of acetic acid or hydrochloric acid solution is 1 mol / L-3 mol / L, the dosage ratio of basalt flakes to acetic acid solution is 1 g: 100 mL-200 mL, the reaction time is 4-12 h, the reaction temperature is 25℃-80℃, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, it is filtered and washed to neutral (tested by pH paper), and dried by vacuum drying, oven drying and freeze drying to obtain the basalt flakes with preliminary surface etching. Then a certain amount of the basalt flakes with preliminary surface etching is placed in a three-necked flask, and the prepared saturated sodium chloride solution is added, the dosage ratio of basalt flakes to sodium chloride solution is 1 g: 200 mL, the reaction time is 4-8 h, the reaction temperature is 60℃-120℃, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, it is filtered and washed to be free of sodium chloride (tested by AgCl solution), and dried by vacuum drying, oven drying and freeze drying. Then a certain amount of the above basalt flakes is added, and the prepared lithium chloride or butyl lithium solution with a concentration of 0.5 mol / L-3 mol / L is added, the dosage ratio of basalt flakes to solution is 1 g: 50 mL-200 mL, the reaction time is 4-8 h, the reaction temperature is 60℃-120℃, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, it is filtered and washed to neutral (tested by pH paper), and dried by vacuum drying, oven drying and freeze drying to obtain the ion intercalated basalt flakes. The intercalated basalt flakes are dispersed in anhydrous ethanol at a mass ratio of basalt flakes to ethanol of 1 g: 200 mL-400 mL, and then placed in a cell crusher for reaction at a power of 600 W-1000 W for 20 min-60 min. The mixture after reaction is left to stand, and the upper turbid liquid is taken out and dried to obtain basalt nanosheets A (named as BSNs-1), and the lower precipitate is basalt flakes waste.

[0054] (2) Large-scale preparation of basalt nanosheets: the basalt flakes waste in step (1) is placed in a hydrogen peroxide and maleic acid or oxalic acid mixed solution, the mass fraction of hydrogen peroxide is 10wt%-30wt%, the addition amount of maleic acid and oxalic acid is 0.5 g-2 g, and the dosage ratio of waste basalt flakes to mixed solution is 1 g: 300 mL-500 mL. Then mechanical stirring combined with ultrasonic treatment is carried out, the mechanical stirring speed is 500 rpm-2500 rpm, the ultrasonic power is 500 W-1000 W, and the reaction time is 20 min-60 min. After the reaction is completed, basalt nanosheets B (named as BSNs-2) are obtained.

[0055] (3) Size screening of basalt nanosheets: basalt nanosheets A and basalt nanosheets B were mixed to obtain basalt nanosheets C (named as BSNs-3), which was then placed in a centrifuge and centrifuged at a speed of 500 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-500; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 1000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-1000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 2000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-2000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 3000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-3000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min, and the dispersion liquid was named as BSNs-3-M3000.

[0056] In order for those skilled in the art to better understand the present application, the technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor should fall within the scope of protection of the present application.

[0057] Embodiment 1

[0058] 1. A method for mass production of basalt nanosheets with high aspect ratio, comprising the following steps:

[0059] (1) The preliminary preparation of basalt nanosheets: a certain amount of basalt flakes is placed in a three-necked flask, and an acetic acid solution is added thereto, the concentration of the acetic acid solution is 1 mol / L, the dosage ratio of the basalt flakes to the acetic acid solution is 1 g: 100 mL, the reaction time is 12 h, the reaction temperature is 80°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the filtrate is washed to neutral (tested by pH paper) and dried by vacuum drying, oven drying and freeze drying. Then a certain amount of the preliminarily surface-etched basalt flakes is placed in a three-necked flask, and a prepared saturated sodium chloride solution is added thereto, the dosage ratio of the basalt flakes to the sodium chloride solution is 1 g: 200 mL, the reaction time is 8 h, the reaction temperature is 100°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the filtrate is washed to be free of sodium chloride (tested by AgCl solution), and drying is performed by vacuum drying, oven drying and freeze drying. Then a certain amount of the above basalt flakes is added to a prepared lithium chloride solution with a concentration of 3 mol / L, the dosage ratio of the basalt flakes to the lithium chloride solution is 1 g: 100 mL, the reaction time is 8 h, the reaction temperature is 120°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the filtrate is washed to neutral (tested by pH paper), and drying is performed by vacuum drying, oven drying and freeze drying, to obtain ion-intercalated basalt flakes. The intercalated basalt flakes are dispersed in anhydrous ethanol at a mass ratio of basalt flakes to ethanol of 1 g: 200 mL, and then placed in a cell crusher for reaction at a power of 1000 W for 60 min. The mixture after reaction is left to stand, the upper turbid liquid is taken out, and dried to obtain basalt nanosheets A, and the lower precipitate is waste basalt flakes.

[0060] (2) Large-scale preparation of basalt nanosheets: the waste basalt flakes in step (1) are placed in a hydrogen peroxide and maleic acid mixed solution, the mass fraction of hydrogen peroxide is 30 wt%, the amount of maleic acid added is 2 g, and the dosage ratio of the waste basalt flakes to the mixed solution is 1 g: 500 mL. Then mechanical stirring combined with ultrasonic treatment is performed, the mechanical stirring speed is 500 rpm-2500 rpm, the ultrasonic power is 1000 W, and the reaction time is 60 min. After the reaction is completed, basalt nanosheets B (named as BSNs-2) are obtained.

[0061] (3) Size fractionation of basalt nanosheets: basalt nanosheets A and basalt nanosheets B were mixed to obtain basalt nanosheets C (named as BSNs-3), which was then placed in a centrifuge and centrifuged at a speed of 500 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-500; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 1000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-1000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 2000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-2000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 3000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-3000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min, and the dispersion liquid was named as BSNs-3-M3000.

[0062] 2、 Figure 1 A schematic diagram for the preparation of basalt nanosheets in step (1) is shown in Table 1, and the yield of basalt nanosheets was 45.2 mg / h, and the maximum diameter-thickness ratio was 1420.2.

[0063] Example 2

[0064] 1. A method for large-scale preparation of basalt nanosheets with a high diameter-thickness ratio, comprising the following steps:

[0065] (1) The preliminary preparation of basalt nanosheets: a certain amount of basalt flakes is placed in a three-necked flask, hydrochloric acid solution is added, the concentration of the hydrochloric acid solution is 2 mol / L, the dosage ratio of basalt flakes to hydrochloric acid solution is 1 g: 100 mL, the reaction time is 8 h, the reaction temperature is 60°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the filter is washed to neutral (pH test paper test), and the vacuum drying, oven drying and freeze drying methods are used for drying. Then a certain amount of the above basalt flakes is weighed and placed in a three-necked flask, a prepared saturated sodium chloride solution is added, the dosage ratio of basalt flakes to sodium chloride solution is 1 g: 200 mL, the reaction time is 8 h, the reaction temperature is 120°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the filter is washed to be free of sodium chloride (AgCl solution test), and the vacuum drying, oven drying and freeze drying methods are used for drying. Then a certain amount of the above basalt flakes is weighed, a prepared butyl lithium solution with a concentration of 0.5 mol / L to 3 mol / L is added, the dosage ratio of basalt flakes to butyl lithium solution is 1 g: 100 mL, the reaction time is 8 h, the reaction temperature is 120°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the filter is washed to neutral (pH test paper test), and the vacuum drying, oven drying and freeze drying methods are used for drying to obtain ion intercalated basalt flakes. The intercalated basalt flakes are dispersed in anhydrous ethanol according to a mass ratio of basalt flakes to ethanol of 1 g: 300 mL, then they are placed in a cell crusher and reacted at a power of 800 W for 40 min. The mixture after reaction is left to stand, the upper turbid liquid is taken out and dried to obtain basalt nanosheets A, and the lower precipitate is waste basalt flakes.

[0066] (2) Large-scale preparation of basalt nanosheets: the waste basalt flakes in step (1) are placed in a hydrogen peroxide and oxalic acid mixed solution, the mass fraction of hydrogen peroxide is 20 wt%, the addition amount of oxalic acid is 2 g, the dosage ratio of waste basalt flakes to mixed solution is 1 g: 500 mL, then mechanical stirring combined with ultrasonic treatment is performed, the mechanical stirring speed is 500 rpm to 2500 rpm, the ultrasonic power is 1000 W, and the reaction time is 60 min. After the reaction is completed, basalt nanosheets B (named BSNs-2) are obtained.

[0067] (3) Size screening of basalt nanosheets: basalt nanosheets A and basalt nanosheets B were mixed to obtain basalt nanosheets C (named as BSNs-3), which was then placed in a centrifuge and centrifuged at a speed of 500 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-500; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 1000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-1000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 2000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-2000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 3000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-3000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min, and the dispersion liquid was named as BSNs-3-M3000.

[0068] 2、 Figure 2 、 Figure 3 A schematic diagram for large-scale preparation of basalt nanosheets in step (2), Figure 4 An optical photograph and a Tyndall effect diagram of basalt nanosheets, from Figure 4 It can be found that the basalt nanosheet solution produces obvious Tyndall effect, indicating that the size is small and the dispersibility is good, and from Table 1, the yield of basalt nanosheets is 59.1 mg / h, and the maximum diameter-thickness ratio is 1359.4.

[0069] Example 3

[0070] 1. A method for large-scale preparation of basalt nanosheets with a high diameter-thickness ratio, comprising the following steps:

[0071] (1) The preliminary preparation of basalt nanosheets: a certain amount of basalt flakes is placed in a three-necked flask, and an acetic acid solution is added thereto, the concentration of the acetic acid solution is 2 mol / L, the dosage ratio of the basalt flakes to the acetic acid solution is 1 g: 200 mL, the reaction time is 12 h, the reaction temperature is 80°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the product is washed by suction filtration until it is neutral (tested by pH paper), and then it is dried by vacuum drying, oven drying and freeze-drying. Then a certain amount of the preliminarily surface-etched basalt flakes is placed in a three-necked flask, and a prepared saturated sodium chloride solution is added thereto, the dosage ratio of the basalt flakes to the sodium chloride solution is 1 g: 200 mL, the reaction time is 8 h, the reaction temperature is 100°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the product is washed by suction filtration until it is free of sodium chloride (tested by AgCl solution), and then it is dried by vacuum drying, oven drying and freeze-drying. Then a certain amount of the above basalt flakes is placed, and a prepared butyl lithium solution with a concentration of 2 mol / L is added thereto, the dosage ratio of the basalt flakes to the butyl lithium solution is 1 g: 200 mL, the reaction time is 6 h, the reaction temperature is 100°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the product is washed by suction filtration until it is neutral (tested by pH paper), and then it is dried by vacuum drying, oven drying and freeze-drying, thereby obtaining ion-intercalated basalt flakes. The intercalated basalt flakes are dispersed in anhydrous ethanol at a mass ratio of basalt flakes to ethanol of 1 g: 300 mL, and then they are placed in a cell crusher and reacted at a power of 600 W for 40 min. After the reaction, the mixture is allowed to stand, the upper turbid liquid is taken out, and the basalt nanosheets A are obtained after drying. The lower precipitate is waste basalt flakes.

[0072] (2) Large-scale preparation of basalt nanosheets: the waste basalt flakes in step (1) are placed in a hydrogen peroxide and oxalic acid mixed solution, the mass fraction of hydrogen peroxide is 20 wt%, the amount of oxalic acid added is 2 g, the dosage ratio of the waste basalt flakes to the mixed solution is 1 g: 500 mL, and then mechanical stirring combined with ultrasonic treatment is performed, the mechanical stirring speed is 500 rpm-2500 rpm, the ultrasonic power is 600 W, and the reaction time is 60 min. After the reaction is completed, basalt nanosheets B (named as BSNs-2) are obtained.

[0073] (3) Size screening of basalt nanosheets: basalt nanosheets A and basalt nanosheets B were mixed to obtain basalt nanosheets C (named as BSNs-3), which was then placed in a centrifuge and centrifuged at a speed of 500 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-500; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 1000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-1000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 2000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-2000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 3000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-3000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min, and the dispersion liquid was named as BSNs-3-M3000.

[0074] 2、 Figure 5 A schematic diagram for size screening of basalt nanosheets in step (3), and from Table 1, the yield of basalt nanosheets was 60.2 mg / h, and the maximum diameter-thickness ratio was 1465.7.

[0075] Example 4

[0076] 1. A method for large-scale preparation of basalt nanosheets with a high diameter-thickness ratio, comprising the following steps:

[0077] (1) The preliminary preparation of basalt nanosheets: a certain amount of basalt flakes is placed in a three-necked flask, hydrochloric acid solution is added, the concentration of the hydrochloric acid solution is 2 mol / L, the amount ratio of basalt flakes to hydrochloric acid solution is 1 g: 100 mL, the reaction time is 6 h, the reaction temperature is 60°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the filtrate is washed to neutral (tested by pH paper), and the preliminary surface etched basalt flakes are obtained by vacuum drying, oven drying and freeze drying. Then a certain amount of the preliminary surface etched basalt flakes is placed in a three-necked flask, and a prepared saturated sodium chloride solution is added, the amount ratio of basalt flakes to sodium chloride solution is 1 g: 200 mL, the reaction time is 4 h, the reaction temperature is 80°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the filtrate is washed to be free of sodium chloride (tested by AgCl solution), and the dried product is obtained by vacuum drying, oven drying and freeze drying. Then a certain amount of the above basalt flakes is added, a prepared lithium chloride solution with a concentration of 2 mol / L is added, the amount ratio of basalt flakes to lithium chloride solution is 1 g: 100 mL, the reaction time is 6 h, the reaction temperature is 120°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the filtrate is washed to neutral (tested by pH paper), and the ion intercalated basalt flakes are obtained by vacuum drying, oven drying and freeze drying. The intercalated basalt flakes are dispersed in anhydrous ethanol at a mass ratio of basalt flakes to ethanol of 1 g: 400 mL, and then placed in a cell crusher for reaction at a power of 8000 W for 20 min. The mixture after reaction is left to stand, the upper turbid liquid is taken out, dried, and basalt nanosheets A are obtained, and the lower precipitate is waste basalt flakes.

[0078] (2) Large-scale preparation of basalt nanosheets: the waste basalt flakes in step (1) are placed in a hydrogen peroxide and maleic acid mixed solution, the mass fraction of hydrogen peroxide is 10 wt%, the amount of maleic acid added is 1 g, the amount ratio of waste basalt flakes to mixed solution is 1 g: 400 mL, and then mechanical stirring combined with ultrasonic treatment is performed, the mechanical stirring speed is 500 rpm-2500 rpm, the ultrasonic power is 500 W, the reaction time is 20 min, and basalt nanosheets B (named BSNs-2) are obtained after the reaction is completed.

[0079] (3) Size screening of basalt nanosheets: basalt nanosheets A and basalt nanosheets B were mixed to obtain basalt nanosheets C (named as BSNs-3), which was then placed in a centrifuge and centrifuged at a speed of 500 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-500; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 1000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-1000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 2000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-2000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 3000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-3000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min, and the dispersion liquid was named as BSNs-3-M3000.

[0080] 2, It can be seen from Table 1 that the yield of basalt nanosheets is 66.3 mg / h, and the maximum diameter-thickness ratio is 1310.3.

[0081] Example 5

[0082] 1. A method for large-scale preparation of basalt nanosheets with high diameter-thickness ratio, comprising the following steps:

[0083] (1) The preliminary preparation of basalt nanosheets: a certain amount of basalt flakes is placed in a three-necked flask, hydrochloric acid solution is added, the concentration of the hydrochloric acid solution is 1 mol / L to 3 mol / L, the amount ratio of basalt flakes to hydrochloric acid solution is 1 g: 150 mL, the reaction time is 6 hours, the reaction temperature is 40°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the product is washed by suction filtration until it is neutral (tested by pH paper), and then dried by vacuum drying, oven drying and freeze drying. Then a certain amount of the preliminarily surface-etched basalt flakes is placed in a three-necked flask, and a prepared saturated sodium chloride solution is added, the amount ratio of basalt flakes to sodium chloride solution is 1 g: 200 mL, the reaction time is 6 hours, the reaction temperature is 80°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the product is washed by suction filtration until there is no sodium chloride (tested by AgCl solution), and then dried by vacuum drying, oven drying and freeze drying. Then a certain amount of the above basalt flakes is added, a prepared butyl lithium solution with a concentration of 1 mol / L is added, the amount ratio of basalt flakes to butyl lithium solution is 1 g: 100 mL, the reaction time is 4 hours, the reaction temperature is 60°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the product is washed by suction filtration until it is neutral (tested by pH paper), and then dried by vacuum drying, oven drying and freeze drying, to obtain ion-intercalated basalt flakes. The intercalated basalt flakes are dispersed in anhydrous ethanol at a mass ratio of basalt flakes to ethanol of 1 g: 300 mL, and then placed in a cell crusher for reaction at a power of 600 W for 30 minutes. The mixture after reaction is left to stand, the upper turbid liquid is taken out and dried to obtain basalt nanosheets A, and the lower precipitate is waste basalt flakes.

[0084] (2) Large-scale preparation of basalt nanosheets: the waste basalt flakes in step (1) are placed in a hydrogen peroxide and oxalic acid mixed solution, the mass fraction of hydrogen peroxide is 10 wt%, the amount of oxalic acid added is 1.5 g, the amount ratio of waste basalt flakes to mixed solution is 1 g: 300 mL, and then mechanical stirring combined with ultrasonic treatment is performed, the mechanical stirring speed is 500 rpm to 2500 rpm, the ultrasonic power is 600 W, and the reaction time is 40 minutes. After the reaction is completed, basalt nanosheets B (named as BSNs-2) are obtained.

[0085] (3) Size screening of basalt nanosheets: basalt nanosheets A and basalt nanosheets B were mixed to obtain basalt nanosheets C (named as BSNs-3), which was then placed in a centrifuge and centrifuged at a speed of 500 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-500; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 1000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-1000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 2000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-2000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 3000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-3000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min, and the dispersion liquid was named as BSNs-3-M3000.

[0086] 2、 Figure 6 For the SEM images and particle size charts of the basalt nanosheets of different sizes after gradient centrifugation in step (3), it can be found that the size of BSNs-3 is larger, and the size of the nanosheet gradually decreases as the centrifugal force becomes larger, and from Table 1, the yield of basalt nanosheets is 50.1 mg / h, and the maximum diameter-thickness ratio is 1431.1.

[0087] Example 6

[0088] 1. A method for large-scale preparation of basalt nanosheets with high diameter-thickness ratio, comprising the following steps:

[0089] (1) The preliminary preparation of basalt nanosheets: a certain amount of basalt flakes is placed in a three-necked flask, and an acetic acid solution is added thereto, the concentration of the acetic acid solution is 2 mol / L, the dosage ratio of the basalt flakes to the acetic acid solution is 1 g: 150 mL, the reaction time is 8 h, the reaction temperature is 60°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the product is washed by suction filtration until it is neutral (tested by pH paper), and then dried by vacuum drying, oven drying and freeze drying. Then a certain amount of the preliminarily surface-etched basalt flakes is placed in a three-necked flask, and a prepared saturated sodium chloride solution is added thereto, the dosage ratio of the basalt flakes to the sodium chloride solution is 1 g: 200 mL, the reaction time is 6 h, the reaction temperature is 100°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the product is washed by suction filtration until it is free of sodium chloride (tested by AgCl solution), and then dried by vacuum drying, oven drying and freeze drying. Then a certain amount of the above basalt flakes is placed in a three-necked flask, and a prepared butyl lithium solution with a concentration of 2 mol / L is added thereto, the dosage ratio of the basalt flakes to the butyl lithium solution is 1 g: 100 mL, the reaction time is 6 h, the reaction temperature is 100°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the product is washed by suction filtration until it is neutral (tested by pH paper), and then dried by vacuum drying, oven drying and freeze drying, to obtain ion-intercalated basalt flakes. The intercalated basalt flakes are dispersed in anhydrous ethanol at a mass ratio of basalt flakes to ethanol of 1 g: 200 mL, and then placed in a cell crusher for reaction at a power of 1000 W for 60 min. After the reaction, the mixture is allowed to stand, and the upper turbid liquid is taken out and dried to obtain basalt nanosheets A, and the lower precipitate is waste basalt flakes.

[0090] (2) Large-scale preparation of basalt nanosheets: the waste basalt flakes in step (1) are placed in a hydrogen peroxide and maleic acid mixed solution, the mass fraction of hydrogen peroxide is 30 wt%, the amount of maleic acid added is 1 g, the dosage ratio of the waste basalt flakes to the mixed solution is 1 g: 400 mL, and then mechanical stirring combined with ultrasonic treatment is performed, the mechanical stirring speed is 500 rpm-2500 rpm, the ultrasonic power is 800 W, and the reaction time is 20 min. After the reaction is completed, basalt nanosheets B (named as BSNs-2) are obtained.

[0091] (3) Size screening of basalt nanosheets: basalt nanosheets A and basalt nanosheets B were mixed to obtain basalt nanosheets C (named as BSNs-3), which was then placed in a centrifuge and centrifuged at a speed of 500 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-500; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 1000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-1000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 2000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-2000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min. Then the dispersion liquid was placed in a centrifuge and centrifuged at a speed of 3000 rpm, and then the supernatant and the precipitate were collected, the supernatant was named as BSNs-3-3000; the lower precipitate was dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol used for dispersing the precipitate was 200 mL, the ultrasonic power was 500 W, and the ultrasonic time was 2 min, and the dispersion liquid was named as BSNs-3-M3000.

[0092] 2、 Figure 7 For the thickness diagram, the diameter-thickness ratio diagram and the comparison diagram with other literatures of the basalt flake and nanosheet, it can be found that the size of the basalt flake is large, and as the centrifugal force is larger, the thickness of the nanosheet gradually decreases and the diameter-thickness ratio becomes larger. As shown in Table 1, the yield of the basalt nanosheet is 53.5 mg / h, and the maximum diameter-thickness ratio is 1394.5.

[0093] Example 7

[0094] 1. A method for large-scale preparation of basalt nanosheets with high diameter-thickness ratio, comprising the following steps:

[0095] (1) The preliminary preparation of basalt nanosheets: a certain amount of basalt flakes is placed in a three-necked flask, hydrochloric acid solution is added, the concentration of the hydrochloric acid solution is 2 mol / L, the dosage ratio of basalt flakes to hydrochloric acid solution is 1 g: 100 mL, the reaction time is 4 h, the reaction temperature is 25-80°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the filtrate is washed to neutral (pH test paper test) and dried by vacuum drying, oven drying and freeze drying. Then a certain amount of the above basalt flakes is weighed and placed in a three-necked flask, and a prepared saturated sodium chloride solution is added, the dosage ratio of basalt flakes to sodium chloride solution is 1 g: 200 mL, the reaction time is 4 h, the reaction temperature is 120°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the filtrate is washed to be free of sodium chloride (AgCl solution test), and dried by vacuum drying, oven drying and freeze drying. Then a certain amount of the above basalt flakes is weighed and a prepared lithium chloride solution with a concentration of 1 mol / L is added, the dosage ratio of basalt flakes to lithium chloride solution is 1 g: 100 mL, the reaction time is 6 h, the reaction temperature is 80°C, the stirring mode is magnetic stirring, and the stirring rate is 1000 rpm. After the reaction is completed, the filtrate is washed to neutral (pH test paper test) and dried by vacuum drying, oven drying and freeze drying, to obtain ion-intercalated basalt flakes. The intercalated basalt flakes are dispersed in anhydrous ethanol at a mass ratio of basalt flakes to ethanol of 1 g: 300 mL, then placed in a cell crusher and reacted at a power of 600 W for 40 min. The mixture after reaction is left to stand, and the upper turbid liquid is taken out and dried to obtain basalt nanosheets A, and the lower precipitate is basalt flake waste.

[0096] (2) Large-scale preparation of basalt nanosheets: the basalt flake waste in step (1) is placed in a hydrogen peroxide and oxalic acid mixed solution, the mass fraction of hydrogen peroxide is 30 wt%, the addition amount of oxalic acid is 0.5 g, the dosage ratio of waste basalt flakes to mixed solution is 1 g: 500 mL, then mechanical stirring combined with ultrasonic treatment is carried out, the mechanical stirring speed is 500-2500 rpm, the ultrasonic power is 500 W, the reaction time is 60 min, and basalt nanosheets B (named BSNs-2) are obtained after the reaction is completed.

[0097] (3) Size screening of basalt nanosheets: basalt nanosheets A and basalt nanosheets B are mixed to obtain basalt nanosheets C (named as BSNs-3), which is then placed in a centrifuge and centrifuged at a speed of 500 rpm, and then the supernatant and the precipitate are collected, the supernatant is named as BSNs-3-500; the lower precipitate is dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol for dispersing the precipitate is 200 mL, the ultrasonic power is 500 W, and the ultrasonic time is 2 min. Then the dispersion liquid is placed in a centrifuge and centrifuged at a speed of 1000 rpm, and then the supernatant and the precipitate are collected, the supernatant is named as BSNs-3-1000; the lower precipitate is dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol for dispersing the precipitate is 200 mL, the ultrasonic power is 500 W, and the ultrasonic time is 2 min. Then the dispersion liquid is placed in a centrifuge and centrifuged at a speed of 2000 rpm, and then the supernatant and the precipitate are collected, the supernatant is named as BSNs-3-2000; the lower precipitate is dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol for dispersing the precipitate is 200 mL, the ultrasonic power is 500 W, and the ultrasonic time is 2 min. Then the dispersion liquid is placed in a centrifuge and centrifuged at a speed of 3000 rpm, and then the supernatant and the precipitate are collected, the supernatant is named as BSNs-3-3000; the lower precipitate is dispersed in anhydrous ethanol for ultrasonic dispersion, the amount of anhydrous ethanol for dispersing the precipitate is 200 mL, the ultrasonic power is 500 W, and the ultrasonic time is 2 min, and the dispersion liquid is named as BSNs-3-M3000.

[0098] 2, It can be seen from Table 1 that the yield of basalt nanosheets is 57.5 mg / h, and the maximum diameter-thickness ratio is 1241.5.

[0099] Table 1 is a basalt nanosheet performance index data table

[0100]

[0101] The above description is only a preferred embodiment of the present application, and does not limit the present application in any form; any ordinary skilled person in the industry can easily implement the present application according to the drawings and the above description; however, any equivalent changes, modifications and evolution made by the skilled person in the art without departing from the technical solution of the present application, using the technical content disclosed above, are equivalent embodiments of the present application; at the same time, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present application are still within the protection scope of the technical solution of the present application.

Claims

1. A method for preparing high aspect ratio basalt nanosheets, characterized in that, The application relates to a method for preparing basalt nanosheets with high aspect ratio. S1, after surface etching reaction of basalt flakes by acid, lithium ion intercalation is carried out on the preliminarily surface-etched basalt flakes to obtain intercalated basalt flakes, and then the intercalated basalt flakes are subjected to cavitation to obtain basalt nanosheets A and basalt flake waste; S2, the basalt flake waste is placed in a mixed solution system of hydrogen peroxide and organic acid, and is subjected to mechanical stirring combined with ultrasonic treatment to obtain basalt nanosheets B; S3, the basalt nanosheets A and the basalt nanosheets B are mixed and subjected to gradient centrifugation, different sizes of the basalt nanosheets are screened through different centrifugal forces, and the basalt nanosheets with high aspect ratio are obtained. The mass fraction of hydrogen peroxide in the mixed solution of hydrogen peroxide and organic acid in S2 is 10wt%-30wt%, and the organic acid is maleic acid or oxalic acid; the rotating speed of mechanical stirring is 500rpm-2500rpm, the ultrasonic power is 500W-1000W, and the reaction time is 20min-60min; The specific process of S3 is as follows: The basalt nanosheets A and the basalt nanosheets B are mixed to obtain basalt nanosheets C, then the basalt nanosheets C are subjected to centrifugation at a rotating speed of 500rpm, and then supernatant A and sediment A are collected; the lower sediment A is dispersed in anhydrous ethanol and subjected to ultrasonic dispersion, then the dispersion liquid is subjected to centrifugation at a rotating speed of 1000rpm, and then supernatant B and sediment B are collected; the lower sediment B is dispersed in anhydrous ethanol and subjected to ultrasonic dispersion, then the dispersion liquid is subjected to centrifugation at a rotating speed of 2000rpm, and then supernatant C and sediment C are collected; the lower sediment C is dispersed in anhydrous ethanol and subjected to ultrasonic dispersion, then the dispersion liquid is subjected to centrifugation at a rotating speed of 3000rpm, and then supernatant D and sediment D are collected, the lower sediment D is dispersed in anhydrous ethanol and subjected to ultrasonic dispersion, and then the basalt nanosheets with high aspect ratio are obtained through screening of different sizes of the basalt nanosheets through different centrifugal forces; The thickness of the basalt nanosheets with high aspect ratio is 1.172nm-266.83nm, the transverse length is 0.278mu m-4.625mu m, and the aspect ratio is 21.5-1310.

3.

2. The method of claim 1, wherein the basalt nanoplatelets have a high aspect ratio. The specific process of S1 is as follows: The basalt flakes are placed in an acid solution, surface etching reaction is carried out under stirring at a set temperature, and after the reaction is completed, the basalt flakes are washed to neutral by suction filtration to obtain preliminarily surface-etched basalt flakes; The preliminarily surface-etched basalt flakes are placed in a sodium chloride solution, stirring reaction is carried out at a set temperature, and after the reaction is completed, the basalt flakes are washed by suction filtration; then the reacted basalt flakes are placed in a lithium ion solution, stirring reaction is carried out at a set temperature, and after the reaction is completed, the basalt flakes are dried by baking; the intercalated basalt flakes are dispersed in anhydrous ethanol, and then the mixture is placed in a cell crusher and subjected to reaction at a set power and time; the reacted mixture is left to stand, the upper turbid liquid is taken out, and after drying, the basalt nanosheets A are obtained, and the lower sediment is the basalt flake waste.

3. The method of claim 2, wherein the basalt nanoplatelets have a high aspect ratio. The concentration of the acid solution of S1 is 1-3 moL / L, the dosage ratio of basalt flake to the acid solution is 1g:100-200 mL, the acid solution comprises acetic acid solution or hydrochloric acid solution; the reaction time of the surface etching reaction is 4-12 h, and the reaction temperature is 25-80 DEG C.

4. The method of claim 2, wherein the basalt nanoplatelets have a high aspect ratio. The sodium chloride is a saturated sodium chloride solution, the dosage ratio of basalt flake to the sodium chloride solution is 1g:200 mL, the reaction time is 4-8 h, and the reaction temperature is 60-120 DEG C.

5. The method of claim 2, wherein the basalt nanoplatelets have a high aspect ratio. The concentration of the lithium ion solution is 0.5-3 mol / L, the dosage ratio of basalt flake to the lithium ion solution is 1g:50-200 mL, the reaction time is 4-8 h, the reaction temperature is 60-120 DEG C, and the lithium ion solution is lithium chloride solution or butyl lithium solution.

6. The method of claim 2, wherein the basalt nanoplatelets have a high aspect ratio. The mass ratio of the intercalated basalt flake to anhydrous ethanol is 1g:200-400 mL, the power of the cell crusher is 600-1000 W, and the reaction time is 20-60 min.

7. A high aspect ratio basalt nanosheet, characterized in that, The high-aspect-ratio basalt nanosheet is prepared by the preparation method according to any one of claims 1-6.

8. The high aspect ratio basalt nanoplatelets of claim 7, wherein, The high-aspect-ratio basalt nanosheet has a thickness of 1.172-266.83 nm, a lateral length of 0.278-4.625 mu m, and an aspect ratio of 21.5-1310.3.

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