A method for efficiently and controllably preparing a novel two-dimensional antimony oxide by using liquid-phase ultrasonic exfoliation technology in pure water

Abstract

The application belongs to the technical field of novel inorganic two-dimensional material preparation, and particularly relates to a method for efficiently and controllably preparing antimony oxide ene in pure water by using a liquid-phase ultrasonic exfoliation method. The method uses high-purity antimony particles as raw materials, and uses a simple liquid-phase exfoliation method to exfoliate the antimony powder to obtain few-layer antimony oxide ene. The preparation method is green, environmentally friendly, simple and easy to operate, can greatly reduce the preparation cost, and the prepared antimony oxide ene has the characteristics of high quality, good dispersity, high yield and high oxidation degree, so as to overcome the technical defects of the prior art method, such as relatively poor quality of the antimony oxide ene sample and environmental pollution in the preparation method.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of preparation of novel inorganic two-dimensional materials, and particularly relates to a method for efficiently and controllably preparing novel two-dimensional antimonyene by using liquid-phase ultrasonic exfoliation technology in pure water. BACKGROUND

[0002] Due to the low cost, high absorption coefficient, adjustable band gap, high carrier mobility, low exciton binding energy and long carrier diffusion distance of metal halide perovskite, the energy conversion efficiency (PCE) of perovskite solar cells (PSCs) using metal halide perovskite as light absorber has been rapidly improved. So far, the PCE of PSCs has exceeded 25%, which is comparable to the most advanced silicon solar cells. In addition, the low-temperature solution processing characteristics of metal halide perovskite make it particularly suitable for roll-to-roll production processes and flexible PSCs (f-PSCs), which can effectively reduce the production cost of PSCs and expand the application range, thereby improving its potential competitiveness with traditional photovoltaic technology. Therefore, in recent years, the development and application of large-area high-efficiency f-PSCs have become a research hotspot in the field of photovoltaics.

[0003] Although great progress has been made in the research of f-PSCs, such as the PCE of single-junction f-PSCs has been improved to more than 22% (L. Zhang, C. Fu, S. Wang, M. Wang, R. Wang, S. Xiang, Z. Wang, J. Liu, H. Ma, Y. Wang, Y. YAN, M. Chen, L. Shi, Q. Dong, J. Bian, Y. Shi, Amorphous F-doped TiO xCaulked SnO2 Electron Transport Layer for Flexible Perovskite Solar Cells with Efficiency Exceeding 22.5%, Adv. Funct. Mater., 2023, 2213961.) However, the commercial application of f-PSCs still faces some major challenges, such as relatively low efficiency, poor stability, and the incompatibility of common high-efficiency electron transport layers (ETLs) with low-temperature processing. To overcome these difficulties and further promote the industrialization of f-PSCs, researchers have conducted extensive exploratory research on strategies. Among them, the use and optimization strategies of low-temperature solution-processed cathode interfacial modification layers are crucial for improving the power conversion efficiency, stability, and large-scale preparation of flexible photovoltaic devices. However, the commonly used electron transport layer materials (such as TiO2) often require high-temperature annealing or sintering processes to improve their charge transport performance and reduce defects, which are incompatible with the manufacturing philosophy of high-efficiency flexible photovoltaic devices.

[0004] Antimonene oxide has shown great application prospects in acting as a cathode interfacial modification layer for n-i-p type flexible perovskite solar cells to improve their performance and in other electronic device applications due to its high electron mobility, tunable band gap, low-temperature solution processing, and structural stability. The prior art discloses the preparation of antimonene oxide, for example, A.C. Lazanas, M.I. Prodromidis, Electrochemical Performance of Passivated Antimonene Nanosheets and of In-Situ Prepared Antimonene Oxide-PEDOT:PSS Modified Screen-Printed Graphite Electrodes, Electrochim. Acta, 2022, 410: 140033., which obtains a discontinuous antimonene oxide sample; and for another example, J.J. He, F. Zhang, Y.R. Xiang, J.R. Lian, X. Wang, Y.M. Zhang, X. Peng, P.J. Zeng, J.L. Qu, J. Song, Preparation of Low-Dimensional Antimonene Oxides and Their Application in Cu:NiO xBased Planar p-i-n Perovskite Solar Cells, J. Power Sources, 2019, 435:226819, from the XRD diagram provided in this work, the sample body is still antimonene, indicating that the degree of oxidation is low, and in addition, the existing technology method often uses organic reagents, which can cause environmental pollution or high cost, so there is currently a lack of green, efficient and controllable preparation method for preparing oxidized antimonene. SUMMARY

[0005] In view of the above problems in the prior art, the present application provides a method for efficiently and controllably preparing a novel two-dimensional oxidized antimonene in pure water by using liquid-phase ultrasonic exfoliation technology. The present application uses high-purity antimony particles as raw materials, and uses a simple liquid-phase exfoliation method to exfoliate the antimony powder to obtain few-layer oxidized antimonene. The preparation method of the present application is green and environmentally friendly, simple and easy to operate, and can greatly reduce the preparation cost. The prepared oxidized antimonene has the characteristics of high quality, good dispersity, high yield and high degree of oxidation, so as to overcome the technical defects of the prior art method, such as relatively poor quality of the oxidized antimonene sample and environmental pollution in the preparation method.

[0006] To achieve the above-mentioned purpose, the technical scheme of the present application is as follows:

[0007] A method for efficiently and controllably preparing a novel two-dimensional oxidized antimonene in pure water by using liquid-phase ultrasonic exfoliation technology, comprising the following steps:

[0008] (1) crushing high-purity antimony particles, and then grinding them into powder to obtain antimony powder material;

[0009] (2) placing the antimony powder material of step (1) in pure water to obtain an antimony aqueous solution, and then performing two-step ultrasonic exfoliation on the antimony aqueous solution to obtain an aqueous solution containing oxidized antimony material:

[0010] The first step of the two-step ultrasonic exfoliation uses point ultrasonic method to preliminarily exfoliate the antimony aqueous solution to obtain multi-layer antimony material, and the second step uses water bath ultrasonic method or standing method to twice exfoliate the multi-layer antimony material to obtain the aqueous solution containing oxidized antimony material;

[0011] (3) separating and purifying the aqueous solution containing oxidized antimony material of step (2) by stepwise centrifugation to obtain oxidized antimonene with different sizes.

[0012] Preferably, the particle size of the crushed particles in step (1) is 0.1-1mm, and if a agate mortar is used to grind the crushed antimony particles, the grinding time is 0.5-2h;

[0013] If the ball mill is used to grind the crushed antimony particles, the grinding tank and the grinding ball are made of zirconia, the grinding ball is composed of the particle size 5mm grinding ball and the particle size 3mm grinding ball, the number ratio of the two is 1:1, the rotation speed of the ball mill is 900-1100rpm, and the grinding time is 10-30min.

[0014] Preferably, the mass-volume ratio of the antimony aqueous solution in the step (2) is 0.5-1.5g / L.

[0015] Preferably, the step of the point ultrasonic method in the step (2) is: ultrasonic treatment for 4-7h under the ice bath environment, and the ultrasonic power is 650-900W.

[0016] Preferably, the step of the water bath ultrasonic method in the step (2) is: ultrasonic treatment for 3-6h at room temperature under the condition that the ultrasonic power is 80-120W, and then the multilayer antimony material in the step (1) is statically treated for 6-12h to obtain the aqueous solution containing the antimony oxide material.

[0017] Preferably, the step of the static treatment method in the step (2) is: the multilayer antimony material in the step (1) is statically treated for 12-72h to obtain the aqueous solution containing the antimony oxide material.

[0018] Preferably, the step of the stepwise centrifugation in the step (3) is:

[0019] S1, centrifuging the aqueous solution containing the antimony oxide material at 3000rpm for 10-15min, and taking the supernatant I;

[0020] S2, centrifuging the supernatant I obtained in the step S1 at 5000rpm for 20min to obtain the precipitate I and the supernatant II;

[0021] S3, redispersing the precipitate I obtained in the step S2 in anhydrous ethanol or pure water, and freeze-drying to obtain the powder antimony oxide material I;

[0022] S4, centrifuging the supernatant II obtained in the step S2 at 9000rpm for 30min to obtain the precipitate II, redispersing the precipitate II in anhydrous ethanol or pure water, and freeze-drying to obtain the powder antimony oxide material II.

[0023] The application also protects the two-dimensional antimony oxide ene prepared by the above preparation method, and the lateral size of the two-dimensional antimony oxide ene is 50-800nm.

[0024] The application also protects the application of the two-dimensional antimony oxide ene in the preparation of the flexible perovskite or organic solar cell cathode interface modification layer.

[0025] Compared with the prior art, the application has the following beneficial effects:

[0026] 1. The application provides a novel preparation method of two-dimensional structure antimonyene material, specifically: taking high-purity antimony particles as raw material, grinding the same into powder material, then using liquid phase stripping technology to strip the antimony powder material in pure water through ultrasonic stripping, and through simple control of ultrasonic conditions, the stripping and oxidation of the antimony powder material can be realized synchronously, and the antimonyene material (AM-O) with different lateral size and thickness can be efficiently and controllably prepared.

[0027] The ultrasonic process is divided into two steps: first, high-intensity point ultrasonic is used to obtain multilayer antimony material with certain lateral size by controlling the ultrasonic conditions; second, mild water bath ultrasonic is used to further strip and oxidize the multilayer antimony to obtain thinner two-dimensional antimony oxide material with high oxidation degree; finally, AM-O with specific lateral size and thickness is obtained through fractional centrifugation.

[0028] 2. The application uses high-purity antimony particles as raw material, and uses a simple liquid phase stripping method to strip the antimony powder to obtain few-layer (1-10 layers) antimonyene, the preparation method is green, environmentally friendly, simple and easy to operate, can greatly reduce the preparation cost, and the prepared antimonyene has the characteristics of high quality, good dispersity, high yield and high oxidation degree, so as to overcome the technical defects of the prior art method that the quality of the prepared antimonyene sample is relatively poor. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 (a) low-magnification TEM image (insert: optical picture of the sample redispersed in anhydrous ethanol for three months), (b) single sample TEM image, (c) distribution map corresponding to O element, (d) distribution map corresponding to Sb element of AM-O prepared at 5000 rpm in Example 1 of the application; (e) low-magnification TEM image, (f) single sample TEM image (insert: corresponding selected area diffraction pattern), (g) distribution map corresponding to O element, (h) distribution map corresponding to Sb element of AM-O prepared at 9000 rpm;

[0030] Figure 2 Sb element high-resolution XPS spectrum of the AM-O sample prepared at 5000 rpm in Example 1 of the application.

[0031] Figure 3 XRD spectrum of the AM-O sample prepared at 5000 rpm in Example 1 of the application. DETAILED DESCRIPTION

[0032] The specific embodiments of the present application are described in detail below, but it should be understood that the scope of protection of the present application is not limited by the specific embodiments. Based on the examples in the present application, all other examples obtained by those of ordinary skill in the art without creative labor are within the scope of protection of the present application. The experimental methods described in the embodiments of the present application are conventional methods unless otherwise specified.

[0033] The following experimental methods and detection methods are conventional methods unless otherwise specified; the following reagents and raw materials are commercially available unless otherwise specified.

[0034] Example 1

[0035] A method for efficiently and controllably preparing a novel two-dimensional antimony oxide by using liquid-phase ultrasonic exfoliation technology in pure water, comprising the following steps:

[0036] (1) The high-purity antimony particles are crushed, and then placed in a marquis mortar and ground for 1 h to obtain an antimony powder material;

[0037] (2) The antimony powder material of step (1) is placed in pure water to prepare an antimony aqueous solution with a concentration of 1.0 g / L, and then the antimony aqueous solution is subjected to ultrasonic exfoliation, which is divided into two steps to prepare an aqueous solution containing an antimony oxide material, specifically:

[0038] First step: The antimony aqueous solution is subjected to preliminary exfoliation by point ultrasonic, i.e. ultrasonic for 5 h under ice bath environment, with an ultrasonic power of 800 W, to obtain a multi-layered antimony material;

[0039] Second step: The multi-layered antimony material obtained in the first step is subjected to further exfoliation and oxidation by ordinary water bath ultrasonic, i.e. ultrasonic for 3 h at room temperature, with an ultrasonic power of 100 W, and after the ultrasonic is stopped, the multi-layered antimony material is allowed to stand for 6 h for full oxidation to prepare an aqueous solution containing an antimony oxide material;

[0040] (3) The aqueous solution containing the antimony oxide material of step (2) is subjected to separation and purification by stepwise centrifugation to prepare antimony oxide with different sizes, specifically:

[0041] S1, centrifuge the aqueous solution containing the antimony oxide material at 3000 rpm for 10 min, and take the supernatant I;

[0042] S2, centrifuge the supernatant I of step S1 at 5000 rpm for 20 min to obtain a precipitate I and a supernatant II;

[0043] S3, disperse the precipitate I of step S2 in anhydrous ethanol again, and freeze-dry to obtain a powder antimony oxide material, which is denoted as 5000 rpm precipitate AM-O;

[0044] Centrifuge the supernatant II of step S2 at 9000 rpm for 30 min to obtain a precipitate II, re-disperse the precipitate II in pure water, and freeze-dry to obtain a powder antimony oxide material, denoted as 9000 rpm precipitate AM-O.

[0045] Example 2

[0046] A method for efficiently and controllably preparing a novel two-dimensional antimony oxide ene in pure water by using a liquid-phase ultrasonic exfoliation technology, comprising the following steps:

[0047] (1) Grind high-purity antimony particles, then put them in a ball mill for sufficient grinding to a powder to obtain an antimony powder material;

[0048] The ball mill uses a zirconia material grinding tank and ball milling balls, the particle size of the grinding balls is 5 mm and 3 mm, both are used in combination (the number ratio of the two is 1:1), the rotation speed of the ball mill is 1000 rpm, and the grinding time is 20 min;

[0049] (2) Put the antimony powder material of step (1) into pure water to obtain an antimony aqueous solution with a concentration of 1.0 g / L, then perform ultrasonic exfoliation on the above solution, which is divided into two steps to obtain an aqueous solution containing an antimony oxide material, specifically:

[0050] First step: use point ultrasonic to preliminarily exfoliate the antimony aqueous solution, i.e. ultrasonic for 5 h under ice bath environment, the ultrasonic power is 800 W, to obtain a multi-layer antimony material;

[0051] Second step: directly stand the multi-layer antimony material obtained in the first step for 24 h to make the multi-layer antimony material be fully exfoliated and oxidized to obtain an aqueous solution containing an antimony oxide material;

[0052] (3) Use a step-by-step centrifugation method to separate and purify the aqueous solution containing the antimony oxide ene material of step (2) to obtain antimony oxide enes with different sizes, specifically:

[0053] S1, centrifuge the aqueous solution containing the antimony oxide material at 3000 rpm for 10 min to obtain supernatant I;

[0054] S2, centrifuge the supernatant I obtained in step S1 at 5000 rpm for 20 min to obtain a precipitate I and a supernatant II;

[0055] S3, re-disperse the precipitate I in pure water, and freeze-dry to obtain a powder antimony oxide material, denoted as 5000 rpm precipitate AM-O;

[0056] Centrifuging supernatant II at 9000 rpm for 30 min to obtain precipitate II, re-dispersing precipitate II in anhydrous ethanol, and freeze-drying to obtain powder antimony oxide material, recorded as 9000 rpm precipitate AM-O.

[0057] Example 3

[0058] The method for efficiently and controllably preparing novel two-dimensional antimony oxide ene by using liquid-phase ultrasonic exfoliation technology in pure water comprises the following steps:

[0059] (1) crushing high-purity antimony particles, and then grinding them in a ball mill to obtain antimony powder material;

[0060] The ball mill uses a zirconia material grinding tank and ball milling balls, the particle size of the grinding balls is 5 mm and 3 mm, and the two are used in combination (the number ratio of the two is 1:1), the rotation speed of the ball mill is 1000 rpm, and the grinding time is 20 min;

[0061] (2) placing the antimony powder material of step (1) in pure water to obtain an antimony aqueous solution with a concentration of 1.0 g / L, and then performing ultrasonic exfoliation on the antimony aqueous solution, which is divided into two steps to obtain an aqueous solution containing antimony oxide material, specifically:

[0062] First step: performing preliminary exfoliation on the antimony aqueous solution by using point ultrasonic, i.e. ultrasonic for 5 h under ice bath environment, the ultrasonic power is 800 W, and a multilayer antimony material is obtained;

[0063] Second step: further exfoliating and oxidizing the multilayer antimony material obtained in the first step, i.e. ultrasonic for 3 h at room temperature, the ultrasonic power is 100 W, and after the ultrasonic ends, standing for 8 h to allow the multilayer antimony material to be fully oxidized to obtain an aqueous solution containing antimony oxide material;

[0064] (3) using a step-by-step centrifugation method to separate and purify the aqueous solution containing antimony oxide ene material of step (2) to obtain antimony oxide ene with different sizes, specifically:

[0065] S1, centrifuging the aqueous solution containing antimony oxide material of step (2) at 3000 rpm for 10 min to obtain supernatant I;

[0066] S2, centrifuging the supernatant I obtained in step S1 at 5000 rpm for 20 min to obtain precipitate I and supernatant II;

[0067] S3, re-dispersing the precipitate I of step S2 in anhydrous ethanol, and freeze-drying to obtain powder antimony oxide material, recorded as 5000 rpm precipitate AM-O;

[0068] The supernatant II of step S2 is centrifuged at 9000 rpm for 30 min to obtain a precipitate II, the precipitate II is re-dispersed in anhydrous ethanol, and the powder antimony oxide material is obtained by freeze-drying, which is recorded as 9000 rpm precipitate AM-O.

[0069] Example 4

[0070] A method for efficiently and controllably preparing a novel two-dimensional antimony oxide ene in pure water by using a liquid-phase ultrasonic exfoliation technology, comprising the following steps:

[0071] (1) The high-purity antimony particles are crushed, and then are placed in a ball mill for grinding to obtain an antimony powder material;

[0072] The ball mill uses a zirconia material grinding tank and ball milling balls, the particle size of the grinding balls is 5 mm and 3 mm, and the two are used in combination (the number ratio is 1:1), the rotation speed of the ball mill is 1100 rpm, and the grinding time is 10 min;

[0073] (2) The antimony powder material of step (1) is placed in pure water to obtain an antimony aqueous solution with a concentration of 1.5 g / L, and then the antimony aqueous solution is subjected to ultrasonic exfoliation, which is divided into two steps to obtain an aqueous solution containing an antimony oxide material, specifically:

[0074] First step: The antimony aqueous solution is subjected to preliminary exfoliation by point ultrasonic, i.e. ultrasonic for 4 h under ice bath environment, the ultrasonic power is 900 W, and a multi-layer antimony material is obtained;

[0075] Second step: The multi-layer antimony material obtained in the first step is subjected to further exfoliation and oxidation, i.e. ultrasonic for 6 h at room temperature, the ultrasonic power is 80 W, and after the ultrasonic is finished, the multi-layer antimony material is allowed to stand for 12 h to be fully oxidized to obtain an aqueous solution containing an antimony oxide material;

[0076] (3) The aqueous solution containing the antimony oxide ene material of step (2) is subjected to separation and purification by a step-by-step centrifugation method to obtain antimony oxide enes with different sizes, specifically:

[0077] S1, the aqueous solution containing the antimony oxide material of step (2) is centrifuged at 3000 rpm for 15 min to obtain a supernatant I;

[0078] S2, the supernatant I obtained in step S1 is centrifuged at 5000 rpm for 20 min to obtain a precipitate I and a supernatant II;

[0079] S3, the precipitate I of step S2 is re-dispersed in anhydrous ethanol, and a powder antimony oxide material is obtained by freeze-drying, which is recorded as 5000 rpm precipitate AM-O;

[0080] The supernatant II of step S2 is centrifuged at 9000 rpm for 30 min to obtain a precipitate II, the precipitate II is re-dispersed in anhydrous ethanol, and freeze-drying is performed to obtain a powder antimony oxide material, which is recorded as 9000 rpm precipitate AM-O.

[0081] Example 5

[0082] A method for efficiently and controllably preparing a novel two-dimensional antimony oxide ene in pure water by using a liquid-phase ultrasonic exfoliation technology, comprising the following steps:

[0083] (1) The high-purity antimony particles are crushed, and then are placed in a ball mill for sufficient grinding to a powder to obtain an antimony powder material;

[0084] The ball mill uses a zirconia material grinding tank and ball milling balls, the particle size of the grinding balls is 5 mm and 3 mm, and the two are used in combination (the number ratio of the two is 1:1), the rotation speed of the ball mill is 900 rpm, and the grinding time is 30 min;

[0085] (2) The antimony powder material of step (1) is placed in pure water to prepare an antimony aqueous solution with a concentration of 0.5 g / L, and then the solution is subjected to ultrasonic exfoliation, which is divided into two steps to prepare an aqueous solution containing an antimony oxide material, specifically:

[0086] First step: The antimony aqueous solution is subjected to preliminary exfoliation by point ultrasonic, i.e., ultrasonic is performed for 7 h under ice bath conditions at an ultrasonic power of 650 W to obtain a multi-layered antimony material;

[0087] Second step: The multi-layered antimony material obtained in the first step is subjected to further exfoliation and oxidation, i.e., ultrasonic is performed for 3 h at room temperature at an ultrasonic power of 120 W, and after the ultrasonic is completed, the multi-layered antimony material is allowed to stand for 9 h to allow it to be fully oxidized to prepare an aqueous solution containing an antimony oxide material;

[0088] (3) The aqueous solution containing the antimony oxide ene material of step (2) is subjected to separation and purification by a stepwise centrifugation method to prepare antimony oxide enes with different sizes, specifically:

[0089] S1, centrifuge the aqueous solution containing the antimony oxide material at 3000 rpm for 15 min to obtain supernatant I;

[0090] S2, centrifuge the supernatant I obtained in step S1 at 5000 rpm for 20 min to obtain a precipitate I and a supernatant II;

[0091] S3, re-disperse the precipitate I in pure water, and freeze-drying is performed to obtain a powder antimony oxide material, which is recorded as 5000 rpm precipitate AM-O;

[0092] The supernatant II is centrifuged at 9000 rpm for 30 min to obtain a precipitate II, the precipitate II is re-dispersed in anhydrous ethanol, and the powder antimony oxide material is obtained by freeze-drying, which is recorded as 9000 rpm precipitate AM-O.

[0093] Example 6

[0094] The method for efficiently and controllably preparing a novel two-dimensional antimony oxide ene by using liquid-phase ultrasonic exfoliation technology in pure water comprises the following steps:

[0095] (1) The high-purity antimony particles are crushed, and then placed in a agate mortar, and ground for 0.5 h to obtain an antimony powder material;

[0096] (2) The antimony powder material in step (1) is placed in pure water to prepare an antimony aqueous solution with a concentration of 0.5 g / L, and then the above solution is subjected to ultrasonic exfoliation, which is divided into two steps to prepare an aqueous solution containing an antimony oxide material, specifically:

[0097] First step: The antimony aqueous solution is subjected to preliminary exfoliation by point ultrasonic, i.e. ultrasonic for 6 h under ice bath environment, and the ultrasonic power is 700 W, to obtain a multi-layer antimony material;

[0098] Second step: The multi-layer antimony material obtained in the first step is subjected to further exfoliation and oxidation, i.e. ultrasonic for 4 h at room temperature, and the ultrasonic power is 90 W, and after the ultrasonic ends, it is left to stand for 10 h to allow the multi-layer antimony material to be fully oxidized to prepare an aqueous solution containing an antimony oxide material;

[0099] (3) The aqueous solution containing the antimony oxide ene material in step (2) is subjected to separation and purification by stepwise centrifugation to prepare antimony oxide enes with different sizes, specifically:

[0100] S1, the aqueous solution containing the antimony oxide material is centrifuged at 3000 rpm for 10 min to obtain supernatant I;

[0101] S2, the supernatant I obtained in step S1 is centrifuged at 5000 rpm for 20 min to obtain a precipitate I and a supernatant II;

[0102] S3, the precipitate I is re-dispersed in pure water, and the powder antimony oxide material is obtained by freeze-drying, which is recorded as 5000 rpm precipitate AM-O;

[0103] The supernatant II is centrifuged at 9000 rpm for 30 min to obtain a precipitate II, the precipitate II is re-dispersed in anhydrous ethanol, and the powder antimony oxide material is obtained by freeze-drying, which is recorded as 9000 rpm precipitate AM-O.

[0104] Example 7

[0105] The method for efficiently and controllably preparing a novel two-dimensional antimony oxide by using liquid-phase ultrasonic stripping technology in pure water comprises the following steps:

[0106] (1) high-purity antimony particles are crushed, and then placed in a marquis mortar, and ground for 2 h to obtain an antimony powder material;

[0107] (2) the antimony powder material in step (1) is placed in pure water to prepare an antimony aqueous solution with a concentration of 1.5 g / L, and then the solution is subjected to ultrasonic stripping, which is divided into two steps, to prepare an aqueous solution containing an antimony oxide material, specifically as follows:

[0108] First step: the antimony aqueous solution is subjected to preliminary stripping by using point ultrasonic, i.e. ultrasonic is performed for 5 h under ice bath environment, the ultrasonic power is 750 W, and a multi-layer antimony material is obtained;

[0109] Second step: the multi-layer antimony material obtained in the first step is subjected to further stripping and oxidation, i.e. ultrasonic is performed for 5 h at room temperature, the ultrasonic power is 100 W, and after the ultrasonic ends, the multi-layer antimony material is allowed to stand for 11 h to be fully oxidized, so as to prepare an aqueous solution containing an antimony oxide material;

[0110] (3) the aqueous solution containing the antimony oxide material in step (2) is subjected to separation and purification by using a stepwise centrifugation method, to prepare antimony oxide materials with different sizes, specifically as follows:

[0111] S1, the aqueous solution containing the antimony oxide material is centrifuged at 3000 rpm for 13 min, and the supernatant I is taken;

[0112] S2, the supernatant I obtained in step S1 is centrifuged at 5000 rpm for 20 min, to obtain a precipitate I and a supernatant II;

[0113] S3, the precipitate I is re-dispersed in pure water, and freeze-dried to obtain a powder antimony oxide material, which is recorded as 5000 rpm precipitate AM-O;

[0114] The supernatant II is centrifuged at 9000 rpm for 30 min to obtain a precipitate II, and then the precipitate II is re-dispersed in anhydrous ethanol, and freeze-dried to obtain a powder antimony oxide material, which is recorded as 9000 rpm precipitate AM-O.

[0115] Example 8

[0116] The preparation steps are the same as those in Example 1, except that in step (2), the power of the first step of ultrasonic stripping is 850 W, and the power of the second step of ultrasonic stripping is 110 W.

[0117] In combination with Examples 1-8, the selected conditions are as follows:

[0118] (1) high-purity antimony particles are crushed and then ground into powder material in a marver or a ball mill; if a marver is used, the grinding time is 0.5-2 h; if a ball mill is used, a zirconia grinding tank and an appropriate number of grinding balls are used, the grinding balls have a particle size of 5 mm and 3 mm (a ratio of 1:1), the rotation speed of the ball mill is 900-1100 rpm, and the grinding time is 10-30 min;

[0119] (1) the antimony powder material obtained in step (1) is placed in pure water to obtain an antimony aqueous solution with a concentration of 0.5-1.5 g / L (0.5 g / L, 1.0 g / L, or 1.5 g / L can be used), and then the solution is subjected to ultrasonic stripping, which is divided into two steps:

[0120] First step: the antimony aqueous solution is subjected to preliminary stripping by point ultrasonic, i.e., ultrasonic is applied for 4-7 h (4 h, 5 h, 6 h, or 7 h can be used) in an ice bath, and the ultrasonic power is 650-900 W (650 W, 700 W, 750 W, 800 W, 850 W, or 900 W can be used), to obtain a multilayer antimony material;

[0121] The second step can be divided into two modes: ① the multilayer antimony material obtained in the first step is subjected to further stripping and oxidation by ordinary water bath ultrasonic, i.e., ultrasonic is applied for 3-6 h (3 h, 4 h, 5 h, or 6 h can be used) at room temperature, and the ultrasonic power is 80-120 W (80 W, 90 W, 100 W, 110 W, or 120 W can be used), and after the ultrasonic treatment, the multilayer antimony material is allowed to stand for 6-12 h to allow the material to be fully oxidized to obtain an aqueous solution containing an antimony oxide material; ② the multilayer antimony material obtained in the first step is directly allowed to stand for 12-72 h to allow the material to be fully stripped and oxidized to obtain an aqueous solution containing an antimony oxide material;

[0122] (4) the aqueous solution containing the antimony oxide material obtained in step (2) is subjected to separation and purification by a stepwise centrifugation method to obtain antimony oxide materials with different sizes, specifically:

[0123] S1, the aqueous solution containing the antimony oxide material is centrifuged at 3000 rpm for 10-15 min (10 min or 15 min can be selected), and the supernatant I is taken;

[0124] S2, the supernatant I obtained in step S1 is centrifuged at 5000 rpm for 20 min to obtain a precipitate I and a supernatant II;

[0125] S3, the precipitate I obtained in step S2 is redispersed in anhydrous ethanol for later use, or it is redispersed in pure water and freeze-dried to obtain a powder antimony oxide material, which is denoted as 5000 rpm precipitate AM-O;

[0126] The supernatant II obtained in step S2 is centrifuged at 9000 rpm for 30 min to obtain a precipitate, and the precipitate obtained at 9000 rpm is redispersed in anhydrous ethanol for use, or redispersed in pure water and freeze-dried to obtain a powder antimony oxide material, denoted as 9000 rpm precipitate AM-O.

[0127] The applicant obtains AM-O with different sizes and thicknesses by using fractional centrifugation on the highly oxidized AM-O. Figure 1 (a)-(d) and (e)-(h) are the characterization of the precipitate samples AM-O obtained by centrifugation at 5000 rpm and 9000 rpm, respectively. The results show that the oxygen element and the antimony element are detected in all samples, and the distribution is uniform and continuous. The inset in figure (a) is an optical picture of the 5000 rpm AM-O sample dispersed in ethanol. It can be seen that the 5000 rpm AM-O sample can maintain a good colloidal state and has a larger concentration even after being dispersed in ethanol for 3 months. This property is crucial for the film preparation by low-temperature solution processing. In addition, an interesting phenomenon can be observed, that is, the lateral size of the 5000 rpm AM-O sample is smaller than that of the 9000 rpm AM-O sample. The applicant analyzes that this may be due to the fact that the 9000 rpm AM-O sample is thinner, and the presence of oxygen elements helps the sample to disperse, etc. Secondly, it can be observed that the 9000 rpm AM-O sample exhibits a morphology similar to that of graphene oxide, and the selected area diffraction shows both diffraction rings and symmetrical diffraction spots, indicating that there may be a local amorphization phenomenon. The above research results show that the oxygen element functionalization may not only play a role in regulating the photoelectric properties of the material, but also play a key role in the preparation process of the AM-O.

[0128] As shown in Figure 2 , the applicant also analyzes the oxidation degree of the 5000 rpm AM-O sample by high-resolution XPS spectrum. The results show that the 5000 rpm AM-O sample is in a highly oxidized state, and more than 90% of the Sb atoms are in the +3 valence state.

[0129] As shown in Figure 3 , the applicant further analyzes the crystal structure of the 5000 rpm AM-O sample by XRD spectrum. The results show that the crystal structure of the 5000 rpm AM-O sample is mainly cubic Sb2O3, further confirming the results of Figure 2 .

[0130] Obviously, those skilled in the art can make various modifications and variations to the present application without departing from the spirit and scope of the present application. Thus, if these modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application also intends to include these modifications and variations.

Claims

1.A method for efficiently and controllably preparing two-dimensional antimonene by liquid-phase ultrasonic exfoliation in pure water, characterized in that, It comprises the following steps: (1) grinding high-purity antimony particles, and then grinding the particles into powder to obtain antimony powder material; (2) placing the antimony powder material of step (1) in pure water to obtain an antimony aqueous solution, and then performing two-step ultrasonic stripping on the antimony aqueous solution to obtain an aqueous solution containing antimony oxide material: The first step of the two-step ultrasonic stripping is to preliminarily strip the antimony aqueous solution by point ultrasonic method to obtain multi-layer antimony material, and the second step is to perform secondary stripping on the multi-layer antimony material by water bath ultrasonic method to obtain an aqueous solution containing antimony oxide material; The step of the point ultrasonic method in step (2) is: ultrasonic for 4-7 h under ice bath environment, and the ultrasonic power is 650-900 W; The step of the water bath ultrasonic method in step (2) is: under the condition of ultrasonic power of 80-120 W, ultrasonic for 3-6 h at room temperature, and then standing for 6-12 h to obtain an aqueous solution containing antimony oxide material; (3) separating and purifying the aqueous solution containing antimony oxide material of step (2) by stepwise centrifugation to obtain antimony oxide materials with different sizes; The mass-volume ratio of the antimony aqueous solution in step (2) is 0.5-1.5 g / L. 2.The method for efficiently and controllably preparing two-dimensional antimonyene by liquid-phase ultrasonic exfoliation in pure water according to claim 1, characterized in that, In step (1), the particle size after grinding is 0.1-1 mm, if agate mortar is used to grind the ground antimony particles, the grinding time is 0.5-2 h; If a ball mill is used to grind the ground antimony particles, a zirconia material grinding tank and ball milling balls are used, which are composed of particle size 5 mm grinding balls and particle size 3 mm grinding balls, and the number ratio of the two is 1:1, the rotation speed of the ball mill is 900-1100 rpm, and the grinding time is 10-30 min. 3.The method of claim 1, wherein, The stepwise centrifugation in step (3) is as follows: S1, centrifuge the aqueous solution containing antimony oxide material at 3000 rpm for 10-15 min, and take the supernatant I; S2, centrifuge the supernatant I obtained in step S1 at 5000 rpm for 20 min to obtain precipitate I and supernatant II; S3, redispersed the precipitate I obtained in step S2 in anhydrous ethanol or pure water, and freeze-dried to obtain powder antimony oxide material I; S4, centrifuge the supernatant II obtained in step S2 at 9000 rpm for 30 min to obtain precipitate II, and redispersed the precipitate II in anhydrous ethanol or pure water, and freeze-dried to obtain powder antimony oxide material II.

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