Preparation method of ammonium ion intercalation two-dimensional material
By heating two-dimensional materials in ammonium iodide solution, the problems of complex intercalation process and high equipment requirements in the existing technology of two-dimensional material intercalation are solved. This method enables rapid, efficient, and low-cost mass production of uniform intercalation materials with good reversibility.
Patent Information
- Application Number
- CN202511168105.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-20
- Publication Date
- 2025-12-12
AI Technical Summary
Existing two-dimensional material intercalation methods suffer from problems such as harsh reaction conditions, high equipment requirements, high cost, unstable products, and difficulty in large-scale preparation, making it difficult to achieve a rapid and efficient intercalation process.
A two-dimensional material composite with ammonium ion intercalation was prepared by immersing the two-dimensional material in an ammonium iodide solution and heating it to achieve a spontaneous intercalation reaction of ammonium ions through diffusion. Combined with ethanol washing and vacuum drying, the composite was prepared.
It achieves a rapid and efficient intercalation process, with simple and safe equipment, enabling the mass production of intercalation complexes with high uniformity, low cost, good reversibility of the intercalation process, and energy saving.
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Figure CN121110190A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of two-dimensional material preparation, and particularly relates to a preparation method of an ammonium ion intercalated two-dimensional material. BACKGROUND
[0002] Two-dimensional materials have unique physical and chemical properties, and have wide application prospects in the fields of electronics, optics, catalysis, etc. However, two-dimensional materials often face problems such as poor structural stability, poor compatibility with other materials, and limited carrier mobility in practical applications. The intercalation method of two-dimensional materials can enhance the stability of two-dimensional materials and improve the carrier mobility by adjusting the atomic spacing, introducing new active sites, and improving the electronic structure, thereby providing a solution to break through the application bottleneck of two-dimensional materials.
[0003] Two-dimensional material intercalation refers to the process of inserting foreign atoms, molecules or ions into the interlayer of two-dimensional materials, thereby changing its structure and properties. Through intercalation, the electronic structure, optical properties, and magnetic properties of two-dimensional materials can be changed to meet the needs of different applications. For example, inserting lithium ions into graphene can improve its electrical conductivity and lithium ion storage capacity. In addition, intercalation can introduce new functional groups or nanoparticles into two-dimensional materials to form nanocomposites with special properties. For example, inserting nanoscale multiferroic spacers into the interlayer of two-dimensional MXene can prepare two-dimensional multiferroic materials with excellent electromagnetic properties.
[0004] Currently, the main methods for intercalating two-dimensional materials are chemical vapor transport, hydrothermal synthesis, and electrochemical intercalation. Among them, chemical vapor transport is a method of transporting intercalation materials to the interlayer of two-dimensional materials through chemical vapor reaction. At high temperature, the vapor of the intercalation material reacts with the two-dimensional material to achieve intercalation. However, this method has harsh reaction conditions, usually requiring high temperature, high vacuum, etc., and has high requirements for equipment, long reaction period, and unstable product quality and performance. In addition, the growth process is difficult to control accurately, and the cost is high and the energy consumption is large. Hydrothermal synthesis is a chemical reaction method carried out at high temperature and high pressure, which can insert foreign substances into the interlayer of two-dimensional materials. However, this method also has the problem of harsh reaction conditions, and requires precise control of temperature, pressure and reaction time, etc. The reaction often involves different types of dangerous chemicals, which has certain danger and pollution, and the purity of the product cannot be controlled, impurities may appear, and it is not suitable for some water-sensitive two-dimensional materials. Electrochemical intercalation is a method of inserting ions into the interlayer of two-dimensional materials by applying an electric field in an electrolyte solution. However, this method has high requirements for electrode materials and electrolytes, involves expensive and precise equipment, and requires harsh current sources, otherwise it is difficult to control the degree and uniformity of intercalation, and may even cause structural changes or damage to two-dimensional materials, and cannot be mass-produced.
[0005] In summary, it is still a great challenge to prepare large-area high-quality two-dimensional materials, especially ion intercalation type two-dimensional materials, quickly and efficiently. SUMMARY
[0006] The technical problem to be solved by the present application is to provide a preparation method of ammonium ion intercalated two-dimensional material, which realizes a rapid and efficient intercalation process by soaking the two-dimensional material in a solution, and the intercalation ions are transferred by diffusion, and realizes a spontaneous reaction without the need for prior preparation of the device, and can be mass produced.
[0007] The present application provides a preparation method of ammonium ion intercalated two-dimensional material, comprising the following steps:
[0008] The two-dimensional material single crystal is used as raw material, ammonium iodide is used as intercalation agent, the two-dimensional material single crystal is placed in the ammonium iodide solution for heating treatment, and after cooling, cleaning and vacuum drying, the ammonium ion intercalated two-dimensional material composite is obtained.
[0009] Preferably, the two-dimensional material single crystal is millimeter level.
[0010] Preferably, the mass concentration of the ammonium iodide solution is 0.1-1.5g / mL.
[0011] Preferably, the heating temperature is set between room temperature and the decomposition temperature of ammonium iodide, and the heating treatment time is 2-48 hours.
[0012] Preferably, the heating treatment process is carried out in the dark.
[0013] Preferably, the cleaning is carried out by using ethanol. Ethanol cleaning can remove residual impurities and unintercalated ammonium iodide and the like.
[0014] Preferably, the vacuum drying temperature is 20-50℃, and the vacuum drying time is 2-24 hours.
[0015] Further, the ammonium ion intercalated two-dimensional material composite has reversibility. Through repeated cooling and heating operations, i.e. from room temperature to low temperature (4K) and then to room temperature, the intercalated ammonium ions can be deintercalated, and the intercalated two-dimensional material composite can be restored to the original two-dimensional material single crystal state.
[0016] Advantages
[0017] (1) The present application realizes a rapid and efficient intercalation process by soaking the two-dimensional material in a solution, and the intercalation ions are transferred by diffusion, and realizes a spontaneous reaction without the need for prior preparation of the device, and can be mass produced.
[0018] (2) The intercalation agent of the present application is uniformly distributed in the layered material, which helps to obtain an intercalation compound with high uniformity.
[0019] (3) The preparation process of the present application requires simple equipment, mild and safe experimental conditions, does not involve high temperature and high pressure environment, does not involve dangerous organic solvents, is easy to operate, saves energy and cost, and is green and environmentally friendly. Compared with room temperature soaking, the low temperature heating process can accelerate intercalation and improve the intercalation efficiency by 30 times.
[0020] (4) The intercalation material of the present application has reversibility. Through repeated cooling and heating, i.e. the process of reducing room temperature to low temperature (4K) and then rising to room temperature, the intercalated ammonium ions can be deintercalated, and the two-dimensional material composite after intercalation can be restored to a two-dimensional material single crystal. BRIEF DESCRIPTION OF DRAWINGS
[0021] Figure 1 It is a scanning electron microscope image of CrSiTe3 single crystal and ammonium ion intercalated CrSiTe3 single crystal compound (NH4) H2O CrSiTe3. (a) is CrSiTe3 single crystal, and (b) is (NH4) H2O CrSiTe3.
[0022] Figure 2 It is an X-ray diffraction pattern of CrSiTe3 single crystal and ammonium ion intercalated CrSiTe3 single crystal compound (NH4) H2O CrSiTe3.
[0023] Figure 3 It is a Raman spectrum test diagram of CrSiTe3 single crystal and ammonium ion intercalated CrSiTe3 single crystal compound (NH4) H2O CrSiTe3.
[0024] Figure 4 It is an X-ray diffraction pattern of ammonium ion intercalated CrSiTe3 single crystal compound (NH4) H2O CrSiTe3 after cooling and then heating back to CrSiTe3 single crystal.
[0025] Figure 5 It is an X-ray diffraction pattern of CrInSiTe6 single crystal and ammonium ion intercalated CrInSiTe6 single crystal compound (NH4) H2O CrInSiTe6.
[0026] Figure 6 It is an X-ray diffraction pattern of Bi2Te3 single crystal and ammonium ion intercalated Bi2Te3 single crystal compound (NH4) H2O Bi2Te3. Figure 7 It is an X-ray diffraction pattern of CrGeTe3 single crystal and ammonium ion intercalated CrGeTe3 single crystal compound (NH4) H2O CrGeTe3.
[0027] Figure 8 X-ray diffraction pattern of BiSiTe3 single crystal and (NH4)·H2O·BiSiTe3 composite obtained after intercalating ammonium ions into BiSiTe3 single crystal. DETAILED DESCRIPTION
[0028] The application will be further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate the application and not used to limit the scope of the application. Furthermore, it should be understood that after reading the content taught by the application, those skilled in the art can make various modifications or changes to the application, and these equivalent forms also fall within the scope defined by the appended claims.
[0029] Example 1
[0030] Example material: CrSiTe3 single crystal.
[0031] This example takes the intercalation of ammonium ions into CrSiTe3 single crystal as an example to illustrate the specific implementation steps of the method for obtaining the composite of the ammonium ion intercalated two-dimensional material single crystal by simple intercalation according to the application:
[0032] First step: millimeter size CrSiTe3 single crystal is used as raw material, the mass is 5 mg, and the single crystal size is 4 mm x 4 mm, which is placed in a 5 ml glass sample bottle.
[0033] Second step: ammonium iodide and deionized water are mixed and stirred according to a mass ratio of 4:5, wherein 40 g of intercalation agent ammonium iodide and 50 ml of deionized water are used. The solution is mixed uniformly by stirring and ultrasonic. Then, 2 ml of ammonium iodide solution is taken out and dropped into the glass sample bottle containing the CrSiTe3 single crystal.
[0034] Third step: the glass sample bottle containing the CrSiTe3 single crystal and the ammonium iodide solution is placed on a heating table and heated to 40℃ for intercalation treatment. A piece of hat-shaped tin paper is needed to cover the top of the glass sample bottle for shading treatment during heating, and the intercalation duration is 48 hours.
[0035] Fourth step: after the reaction is completed, the single crystal is naturally cooled to room temperature, washed with ethanol for 3-5 times, and then placed in a vacuum drying oven. The drying time of the vacuum drying oven is 24 hours, and the temperature is 30℃. The intercalated CrSiTe3 is dried to obtain the ammonium ion intercalated CrSiTe3 composite (NH4)·H2O·CrSiTe3.
[0036] Figure 1 (a) shows the SEM image of the raw material CrSiTe3, which shows that the CrSiTe3 before exfoliation is a millimeter level sheet-like structure with large thickness, and the sample surface is smooth with metallic luster. Figure 1(b) SEM image of the prepared ammonium ion intercalated CrSiTe3 composite (NH4) H2O CrSiTe3. The image shows that the intercalated sample also has a millimeter-sized layered structure, and the interlayer thickness is expanded, and the sample surface appears granular.
[0037] See Figure 2 As shown by comparison, the diffraction characteristic spectrum of the prepared (NH4) H2O CrSiTe3 composite has changed significantly compared with the CrSiTe3 raw material. Specifically, the main peak originally located at 25.9° in the single crystal sample shifts to 27.7° after intercalation, and other peak positions also show obvious changes in intensity and position. These changes fully indicate that after low-temperature intercalation treatment, ammonium ions have been successfully inserted into the CrSiTe3 single crystal structure.
[0038] See Figure 3 As shown, the Raman characteristic spectrum of CrSiTe3 is consistent with existing experimental and theoretical reports, proving that the intercalation treatment does not destroy the crystal structure of CrSiTe3. In Figure 3 , the Eg1, Eg3, Ag3 mode peak positions of CrSiTe3 single crystal are 97.7 cm -1 , 125.9 cm -1 , 141.1 cm -1 , respectively, while after intercalation of CrSiTe3 single crystal, the peak positions of these three modes are reduced to 88.2 cm -1 , 118.4 cm -1 , 137.2 cm -1 , respectively.
[0039] See Figure 4 As shown, through temperature rising and falling treatment, ammonium ions are successfully deintercalated from CrSiTe3 single crystal, making the composite return to the original CrSiTe3 single crystal structure, confirming the reversibility of the intercalation process.
[0040] Example 2
[0041] Example material: CrInSiTe6 single crystal.
[0042] The specific implementation steps of intercalating ammonium ions into CrInSiTe6 single crystal are as follows:
[0043] First step: millimeter-sized CrInSiTe6 single crystal is used as raw material, with a mass of 3 mg and a single crystal size of 2 mm x 2 mm, which is placed in a 5 ml glass sample bottle.
[0044] Second step: mix ammonium iodide and deionized water with a mass ratio of 2:3, where the intercalation agent ammonium iodide is 40 g and the deionized water is 60 ml. Stir and use ultrasonic method to mix the solution uniformly. Then, take 2 ml of the ammonium iodide solution and drop it into the glass sample bottle containing the CrInSiTe6 single crystal.
[0045] Third step: place the glass sample bottle containing the CrInSiTe6 single crystal and the ammonium iodide solution on a heating table and heat to 40℃ for intercalation treatment. A piece of hat-shaped tin paper needs to be placed on top of the glass sample bottle during heating to block light. The intercalation duration is 39 hours.
[0046] Fourth step: after the reaction is completed, naturally cool to room temperature, take out the single crystal, wash the sample with ethanol for 3-5 times, and then place it in a vacuum drying oven. The drying time in the vacuum drying oven is 24 hours and the temperature is 30℃. Dry the intercalated CrInSiTe6 to obtain the (NH4)·H2O·CrInSiTe6 complex.
[0047] See Figure 5 As shown in the figure, the diffraction characteristic spectrum of the prepared (NH4)·H2O·CrInSiTe6 complex is obviously changed compared with the CrInSiTe6 raw material, and the diffraction peak is shifted, indicating that the ammonium ion is successfully intercalated into the CrInSiTe6 single crystal after low-temperature intercalation.
[0048] Example 3
[0049] Example material: Bi2Te3 single crystal.
[0050] The specific implementation steps of intercalating ammonium ions into Bi2Te3 single crystal are as follows:
[0051] First step: use a millimeter-sized Bi2Te3 single crystal as raw material, with a mass of 3.5 mg and a single crystal size of 3 mm x 3.7 mm, and place it in a 5 ml glass sample bottle.
[0052] Second step: mix ammonium iodide and deionized water with a mass ratio of 6:5, where the intercalation agent ammonium iodide is 16.8 g and the deionized water is 14 ml. Stir and use ultrasonic method to mix the solution uniformly. Then, take 2 ml of the ammonium iodide solution and drop it into the glass sample bottle containing the Bi2Te3 single crystal.
[0053] Third step: place the glass sample bottle containing the Bi2Te3 single crystal and the ammonium iodide solution on a heating table and heat to 60℃ for 31 hours after being placed at room temperature for 11 hours. Stop heating and place at room temperature for 27 hours. A piece of hat-shaped tin paper needs to be placed on top of the glass sample bottle during heating to block light.
[0054] Fourth step: After the reaction, the single crystal was taken out, washed with ethanol for 3 times, and then placed in a vacuum drying oven. The drying time of the vacuum drying oven was 24 hours, and the temperature was 30°C. The intercalated Bi2Te3 was dried to obtain the intercalated ammonium ion Bi2Te3 complex (NH4) H2O Bi2Te3.
[0055] See Figure 6 As shown in the figure, the diffraction characteristic spectrum of the prepared (NH4) H2O Bi2Te3 complex was obviously changed compared with the Bi2Te3 raw material, and new diffraction peaks appeared, indicating that the ammonium ion was successfully intercalated into the Bi2Te3 single crystal after low-temperature intercalation of Bi2Te3.
[0056] Example 4
[0057] Example material: CrGeTe3 single crystal.
[0058] The specific implementation steps of intercalating ammonium ions into CrGeTe3 single crystal are as follows:
[0059] First step: millimeter size CrGeTe3 single crystal was used as raw material, with a mass of 0.77 mg and a single crystal size of 1.0 mm x 2.5 mm. It was placed in a 3 ml glass sample bottle.
[0060] Second step: ammonium iodide and deionized water were mixed in a mass ratio of 3:10, wherein 4.8 g of intercalation agent ammonium iodide and 16 ml of deionized water were used. The solution was mixed uniformly by stirring and ultrasonic. Then, 2 ml of ammonium iodide solution was taken out and dropped into the glass sample bottle containing the CrGeTe3 single crystal.
[0061] Third step: the glass sample bottle containing the CrGeTe3 single crystal and the ammonium iodide solution was placed at room temperature for 11 hours, then heated to 70°C on a heating table and kept for 31 hours. The heating was stopped and the sample was placed at room temperature for 27 hours. The glass sample bottle needed to be covered with a cap-shaped tin paper for light shielding during heating.
[0062] Fourth step: after the reaction, the sample was washed with ethanol for 3 times, and then placed in a vacuum drying oven. The drying time of the vacuum drying oven was 24 hours, and the temperature was 30°C. The intercalated CrGeTe3 was dried to obtain the intercalated ammonium ion CrGeTe3 complex (NH4) H2O CrGeTe3.
[0063] See Figure 7 As shown in the figure, the diffraction characteristic spectrum of the prepared (NH4) H2O CrGeTe3 complex was obviously changed compared with the CrGeTe3 raw material, and new diffraction peaks appeared, indicating that the ammonium ion was successfully intercalated into the CrGeTe3 single crystal after low-temperature intercalation of CrGeTe3.
[0064] Example 5
[0065] Example material: BiSiTe3 single crystal.
[0066] The specific implementation steps of the ammonium ion intercalated BiSiTe3 single crystal are as follows:
[0067] First step: take BiSiTe3 single crystal with millimeter size as raw material, the mass is 1.3 mg, and the single crystal size is 3 mm x 5 mm, which is placed in a 3 ml glass sample bottle;
[0068] Second step: prepare an aqueous solution of ammonium iodide with a concentration of 0.8 g / mL, wherein 14.4 g of intercalation agent ammonium iodide and 18 mL of deionized water are stirred uniformly. Then, 2 mL of ammonium iodide solution is taken out and dropped into the glass sample bottle containing the BiSiTe3 single crystal.
[0069] Third step: heat the glass sample bottle containing the BiSiTe3 single crystal and the ammonium iodide solution on a heating table to 40℃, keep for 49 hours, stop heating, and place at room temperature for 2 hours. The glass sample bottle needs to be covered with a cap-shaped tin paper for light shielding during heating.
[0070] Fourth step: after the reaction is completed, the sample is washed with ethanol for 3 times, then placed in a vacuum drying box, the vacuum drying time is 24 hours, the temperature is 30℃, and the intercalated BiSiTe3 is dried to obtain the intercalated ammonium ion BiSiTe3 composite (NH4)·H2O·BiSiTe3.
[0071] See Figure 8 As shown in the figure, the diffraction characteristic spectrum of the prepared (NH4)·H2O·BiSiTe3 composite is obviously changed compared with the BiSiTe3 raw material, and new diffraction peaks appear, indicating that the ammonium ion is successfully intercalated into the BiSiTe3 single crystal after low-temperature intercalation of CrGeTe3.
[0072] For those skilled in the art to which the present application belongs, without departing from the concept of the present application, a number of equivalent substitutions or obvious modifications can be made, and the performance or use is the same, which should be considered as belonging to the protection scope of the present application.
[0073] Those skilled in the art can easily understand that the above description is only a preferred embodiment of the present application, and is not used to limit the present application, and any modification, equivalent substitution and improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims
1. A method for preparing an ammonium ion intercalated two-dimensional material, comprising the following steps: Using two-dimensional material single crystals as raw materials and ammonium iodide as intercalating agent, the two-dimensional material single crystals were placed in an ammonium iodide solution for heating treatment, and after cooling, they were washed and vacuum dried to obtain a two-dimensional material composite with ammonium ion intercalation.
2. The preparation method according to claim 1, characterized in that: The two-dimensional material has single crystals on the millimeter scale.
3. The preparation method according to claim 1, characterized in that: The ammonium iodide solution has a mass concentration of 0.1–1.5 g / mL.
4. The preparation method according to claim 1, characterized in that: The heating temperature is set between room temperature and the decomposition temperature of ammonium iodide, and the heating treatment time is 2 to 48 hours.
5. The preparation method according to claim 1, characterized in that: The heat treatment process involves shading from light.
6. The preparation method according to claim 1, characterized in that: The cleaning process uses ethanol.
7. The preparation method according to claim 1, characterized in that: The vacuum drying temperature is 20–50°C, and the vacuum drying time is 2–24 hours.
8. The preparation method according to claim 1, characterized in that: The two-dimensional material composite with ammonium ion intercalation is reversible.