1 Tapos, 1 Tapos; phase intercalation material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of composite materials, in particular to a 1T'phase intercalation material and a preparation method and application thereof. Comprising a two-dimensional layered material and an embedded material, the two-dimensional layered material comprises a 1T'phase transition metal chalcogenide compound with the chemical formula of MX2, M in MX2 comprises a transition metal element, and X comprises a first chalcogenide element; the embedded material is embedded in the interlayer of the 1T'phase transition metal chalcogenide, the chemical formula of the embedded material is D2Z, D in the D2Z comprises an alkali metal element, and Z comprises a second chalcogenide element. The preparation method comprises the following steps: in a reducing atmosphere, carrying out 1T'phase heat treatment on H2X and DaMbOc to generate a 1T 'phase intercalation material. The 1T'phase intercalation material is good in stability and not prone to phase change, the purity of the material prepared through the preparation method is high, and the material can be used for electrochemical catalysts, energy storage devices, superconducting materials and synaptic transistors.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of composite materials, in particular to a 1T' phase intercalation material and a preparation method and application thereof. BACKGROUND

[0002] Transition metal dichalcogenides, abbreviated as TMDs, are a new two-dimensional material, and its chemical formula is usually represented as MX2, such as MoS2. TMDs have multiple crystal structures, which are formed by different coordination geometries of transition metal atoms, among which the typical ones are 1T (octahedral), 2H (trigonal prism) and 3R (orthorhombic hexahedron). The diversity of structures leads to diverse electronic properties, for example, 2H-MoS2 exhibits semiconductor properties, while 1T-MoS2 exhibits metallic properties. Among them, some TMDs also have a special distorted octahedral structure, which is called 1T' (distorted octahedron).

[0003] TMDs in 1T' phase have good electrochemical catalysis and electrochemical energy storage performance, and have very wide applications in electrochemical catalysis, energy storage devices and other fields. However, TMDs in 1T' phase are in metastable state, and TMDs in 2H phase are relatively stable. In a conventional environment, the intrinsic 1T' phase will gradually transform into 2H phase, or immediately transform into 2H phase when the temperature exceeds 97.2℃. Therefore, TMDs in 1T' phase have poor stability and short service life. For this reason, some studies have reported the insertion of alkali metals between the layers of TMDs, but the alkali metals and transition metals are easily oxidized in air, thereby losing their effectiveness. Some studies have also reported the insertion of zinc ions, but the improvement is limited. Some studies have also reported the insertion of sodium hydride and lithium hydride, but the service life can only be extended to at most three months, which is still limited.

[0004] In addition, although existing liquid phase methods and other methods can produce TMDs in 1T' phase, the purity of TMDs in 1T' phase is not high, and the highest purity can only reach the interval of 80% to 90%. The product is often doped with other phases or other components, which leads to the fact that the prepared TMDs cannot exhibit the performance of high-purity 1T' phase TMDs, such as superconductivity and topological field effect transistor. Moreover, the preparation method is complex and is not suitable for large-scale production. Therefore, it is urgent to improve the stability, service life and purity of TMDs in 1T' phase to facilitate the expansion of applications. SUMMARY

[0005] The present application aims to provide a 1T' phase intercalation material and a preparation method and application thereof, and aims to solve the technical problems of poor stability and short service life of TMDs in 1T' phase in the prior art.

[0006] To achieve the above application purposes, the technical solutions adopted by the present application are as follows:

[0007] In a first aspect, the present application provides a 1T' phase intercalation material, comprising:

[0008] a two-dimensional layered material, the two-dimensional layered material comprising a 1T' phase transition metal chalcogenide compound having a chemical formula MX2, wherein M in MX2 comprises a transition metal element, and X comprises a first chalcogen element;

[0009] an intercalation material, the intercalation material being intercalated between layers of the 1T' phase transition metal chalcogenide compound, the intercalation material having a chemical formula D2Z, wherein D in D2Z comprises an alkali metal element, and Z comprises a second chalcogen element.

[0010] The 1T' phase intercalation material of the present application contains the two-dimensional layered material and the intercalation material, and the intercalation material has a chemical formula D2Z, and the intercalation material is intercalated between layers of the 1T' phase transition metal chalcogenide compound to form a 1T' phase intercalation material in combination with the 1T' phase transition metal chalcogenide compound, so that the 1T' phase intercalation material has extremely high stability, maintains good inertness in common environments such as water, air, and ethanol, and the 1T' phase transition metal chalcogenide compound is not prone to phase transition at high temperatures or after long-term use, and can maintain the 1T' phase for a long time, thereby improving the service life.

[0011] In a second aspect, the present application provides a preparation method of a 1T' phase intercalation material, comprising the following steps:

[0012] subjecting H2X and D a M b O c to 1T' phase heat treatment to generate the 1T' phase intercalation material;

[0013] wherein X comprises a chalcogen element, D comprises an alkali metal element, M comprises a transition metal element, 1≤a≤2, b is 1, and 3≤c≤4.

[0014] The preparation method of the present application subjects H2X and D a M b O c to 1T' phase heat treatment, so that H2X and D a M b O c react chemically under a reducing atmosphere and at a certain temperature, and a 1T' phase transition metal chalcogenide compound having a chemical formula MX2 is generated in the heat treatment process, and an intercalation material having a chemical formula D2X is also generated in situ, the intercalation material being intercalated between layers of the 1T' phase transition metal chalcogenide compound to obtain the 1T' phase intercalation material. The 1T' phase intercalation material prepared by the preparation method has good stability, a long service life, and is not prone to phase transition; and has a high yield, wherein the purity of the 1T' phase is high, the preparation method is controllable, and is suitable for large-scale production.

[0015] In a third aspect, the present application provides an application of the 1T' phase intercalation material or the 1T' phase intercalation material prepared by the preparation method of the present application. The 1T' phase intercalation material is applied in at least one of an electrochemical catalyst, an energy storage device, a superconducting material, and a synaptic transistor.

[0016] Since the 1T' phase intercalation material has high stability, is not prone to phase transition during long-term use, and can maintain the 1T' phase for a long time, the performance of the 1T' phase TMDs in electrochemical energy storage and electrochemical catalysis can be fully utilized, and the 1T' phase intercalation material can be used in at least one of an electrochemical catalyst, an energy storage device, a superconducting material, and a synaptic transistor. BRIEF DESCRIPTION OF DRAWINGS

[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiments or prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0018] Figure 1 is an SEM image of the 1T' phase intercalation material of Example 1 of the present application;

[0019] Figure 2 is the Raman spectrum test result of the sample of Example 1, Example 14, and Comparative Example 5 of the present application;

[0020] Figure 3 is the XRD test result of the sample of Example 1 of the present application;

[0021] Figure 4 is a schematic diagram of the XRD test result and the simulation result of the sample of Example 1 of the present application;

[0022] Figure 5 is the test result of Mo and S in the XPS test of the sample of Example 1;

[0023] Figure 6 is the test result of K in the XPS test of the sample of Example 1;

[0024] Figure 7 is the overall test result of the XPS test of the sample of Example 1;

[0025] Figure 8 is the TEM test result of the sample of Example 1;

[0026] Figure 9 is the inverse space scale test result of the TEM test of the sample of Example 1, with a scale length of 5 and a unit of 1 / nm;

[0027] Figure 10 is a graph of the thermal gravimetric stability test results of the sample of Example 1;

[0028] Figure 11 is a graph of the Raman spectra of the sample of Example 1 after solvent resistance, aging resistance, and high temperature resistance performance tests;

[0029] Figure 12 is a graph of the XPS test results of the sample of Example 1 after high temperature heating;

[0030] Figure 13 is a graph of the overpotential test results of the sample of Example 15 and a commercial Pt / C catalyst;

[0031] Figure 14 is a graph of the Tafel slope test results of the sample of Example 15 and a commercial Pt / C catalyst;

[0032] Figure 15 is a graph of the long-term stability test results of the catalytic performance of the sample of Example 15. DETAILED DESCRIPTION

[0033] In order to make the technical problems, technical solutions and beneficial effects to be solved in the present application more clear and understandable, the present application will be further described in detail below in combination with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and do not limit the present application.

[0034] In the present application, the term "and / or" describes the association relationship of the associated objects, which means that there can be three kinds of relationships, for example, A and / or B can mean that A exists alone, A and B exist together, and B exists alone. Wherein A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after it.

[0035] In the present application, "at least one" means one or more, and "multiple" means two or more. "At least one of the following" or the like means any combination of these items, including any combination of single item or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can mean a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple.

[0036] It should be understood that in various embodiments of the present application, the size of the sequence number of the above-mentioned processes does not mean the order of execution, and part or all of the steps can be executed in parallel or in sequence, and the execution order of the processes should be determined according to its function and inherent logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0037] The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. As used in the description of the embodiments of the present application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0038] The weight of the related components mentioned in the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of each component. Therefore, as long as the content of the related components in the embodiments of the present application is proportionally enlarged or reduced, it is within the scope disclosed in the embodiments of the present application. Specifically, the mass in the embodiments of the present application can be μg, mg, g, kg and other mass units commonly known in the chemical field.

[0039] The terms "first", "second", etc. are only used for descriptive purposes and are used to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX can also be referred to as the second XX, and similarly, the second XX can also be referred to as the first XX. Therefore, the features limited by "first" and "second" can explicitly or implicitly include one or more of the features.

[0040] The two-dimensional layered material in the present application refers to a material composed of several atomic layers or molecular layers. The layers are generally connected by strong covalent bonds or ionic bonds, and the layers are generally combined by weak van der Waals forces, such as graphene, topological insulator, transition metal dichalcogenide (TMDs), etc.

[0041] Chalcogen elements generally refer to sulfur (S), selenium (Se), and tellurium (Te) elements.

[0042] The first aspect of the embodiments of the present application provides a 1T' phase intercalation material. The 1T' phase intercalation material of the embodiments of the present application includes a two-dimensional layered material and an intercalation material, wherein,

[0043] The two-dimensional layered material includes a 1T' phase transition metal dichalcogenide with a chemical formula MX2, M in MX2 includes a transition metal element, and X includes a first chalcogen element;

[0044] The intercalation material is embedded in the interlayer of the 1T' phase transition metal dichalcogenide (hereinafter referred to as 1T' phase TMDs). The chemical formula of the intercalation material is D2Z, wherein D in D2Z includes an alkali metal element, and Z includes a second chalcogen element.

[0045] The intercalation material of the 1T' phase in the embodiment 1T' of the present application contains an intercalation material with a chemical formula of D2Z, and the intercalation material is intercalated in the interlayer of the 1T' phase transition metal chalcogenide, thereby being combined with the 1T' phase transition metal chalcogenide to form a 1T' phase intercalation material, which has extremely high stability and remains inert in common environments such as water, air, and ethanol. The 1T' phase transition metal chalcogenide is not prone to phase transition at high temperatures or after long-term use, and can remain in the 1T' phase for a long time, thereby improving the service life.

[0046] Regarding the intercalation material:

[0047] The D in the chemical formula D2Z of the intercalation material includes an alkali metal element. In an exemplary embodiment, the alkali metal element includes at least one of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). In an optional embodiment, the alkali metal element includes at least one of Li, Na, and K. Z includes a second chalcogen element. In an exemplary embodiment, the second chalcogen element includes at least one of sulfur (S), selenium (Se), and tellurium (Te). The alkali metal element and the second chalcogen element can form the intercalation material, which can improve the stability of the 1T' phase intercalation material.

[0048] In some embodiments, the alkali metal element includes at least one of Li, Na, and K, and the second chalcogen element includes at least one of S, Se, and Te.

[0049] Based on the optional types of the alkali metal element and the second chalcogen element, in some embodiments, the intercalation material can include at least one of Li2S, Na2S, K2S, Na2Se, or Na2Te. Compared with the prior art of intercalating alkali metal, sodium hydride, lithium hydride, and zinc ions in the interlayer of the intrinsic 1T' phase TMDs, the intercalation material in the embodiment of the present application is intercalated in the interlayer of the 1T' phase TMDs, which can significantly improve the stability of the 1T' phase TMDs. The 1T' phase TMDs remain stable at 750°C or even higher temperatures, remain inert in common environments such as water, air, and ethanol, and remain in the 1T' phase for a long time without being converted into other crystal forms after being used for up to 8 months.

[0050] Regarding the two-dimensional layered material:

[0051] The two-dimensional layered material can be all 1T' phase TMDs or contain 1T' phase TMDs and other layered materials. However, some properties of 1T' phase TMDs can only be realized at high purity, such as superconductivity, topological field effect transistor, etc. In addition, high purity is also conducive to improving the stability of 1T' phase intercalation material and the performance of electrochemical catalysis and electrochemical energy storage. Therefore, the two-dimensional layered material is ideally high-purity 1T' phase TMDs. In some embodiments, the molar ratio of 1T' phase transition metal chalcogenide in the two-dimensional layered material is 90% to 100%, and can be 100%. In the demonstration example, it can include any value or range between any two values of 90%, 93%, 95%, 98%, and 100%. At these molar ratios, the 1T' phase intercalation material exhibits ideal electrochemical catalysis and electrochemical energy storage performance, and has good stability. In high temperature and long time use, the content of these 1T' phase TMDs in the 1T' phase intercalation material hardly decreases. In some embodiments, the above-mentioned molar ratio is 90% to 100%, and can be 95% to 100%. At these molar ratios, high-purity 1T' phase TMDs can be obtained, which is conducive to stability and the realization of high-purity properties.

[0052] The chemical formula of 1T' phase TMDs in the two-dimensional layered material is MX2, wherein M includes common transition metal elements, and X includes common chalcogen elements. In some embodiments, the transition metal elements include at least one of Mo, W, Ti, Nb, V, Ta, and Re; and the first chalcogen elements include at least one of S, Se, and Te. In the demonstration example, MX2 can include but is not limited to at least one of MoS2, MoSe2, MoTe2, WS2, WSe2, and TiS2. The above-mentioned transition metal elements and first chalcogen elements can form 1T' phase TMDs, and cooperate with the intercalation material embedded in the interlayer to form 1T' phase intercalation material, which can greatly improve the stability and service life.

[0053] It is detected that in some embodiments, the interlayer spacing of 1T' phase TMDs is 0.8 to 1.2 nm; in the demonstration example, it can include but is not limited to any value or range between any two values of 0.8 nm, 0.9064 nm, 1.0 nm, 1.1 nm, 1.196 nm, and 1.2 nm. Since the micro-morphology of 1T' phase TMDs is periodic layers, the interlayer spacing here refers to the length of a single period of periodic stacking, including the thickness sum of one MX2 layer and one adjacent interlayer forming a periodic repeating unit. Due to the presence of the intercalation material, the above-mentioned interlayer spacing is often larger than that of 1T' phase TMDs without the intercalation material. The 1T' phase intercalation material obtained in this way greatly improves the stability and service life.

[0054] In some embodiments, the 1T' phase TMDs have a number of layers of at least 2, and in exemplary embodiments, can include but are not limited to 2, 10, 100, 500, 1000, 2000, or any range between any two of the values. The 1T' phase TMDs with these numbers of layers impart good electrochemical catalysis, electrochemical energy storage, and other properties to the 1T' phase intercalation material, and also provide high stability and long service life.

[0055] Regarding the 1T' phase TMDs:

[0056] In some embodiments, the 1T' phase TMDs and the intercalation material have a molar ratio of (3-10): 1. In exemplary embodiments, this can include but is not limited to 3:1, 4:1, 5.56:1, 8:1, 10:1, or any range between any two of the values. The 1T' phase TMDs and the intercalation material in these ratios impart high stability and long service life to the 1T' phase intercalation material formed.

[0057] In some embodiments, the first chalcogen element is the same as the second chalcogen element, i.e., the element represented by X in the chemical formula MX2 of the 1T' phase TMDs is the same as the element represented by Z in the chemical formula D2Z of the intercalation material. In exemplary embodiments, MX2 can be MoS2 and D2Z can be Na2S, both of which contain the same sulfur element. In another embodiment, MX2 can be MoSe2 and D2Z can be Na2Se, both of which contain the same selenium element. In another embodiment, MX2 can be MoTe2 and D2Z can be Na2Te, both of which contain the same tellurium element. Having the same element in the 1T' phase TMDs and the intercalation material facilitates the formation of a 1T' phase intercalation material with high stability and long service life.

[0058] A second aspect of embodiments of the present application provides a method for preparing the 1T' phase intercalation material described above in the first aspect of embodiments of the present application. The method for preparing the 1T' phase intercalation material of embodiments of the present application includes the following steps:

[0059] S10: in a reducing atmosphere, mixing H2X and D a M b O c performing heat treatment of the 1T' phase to form the 1T' phase intercalation material;

[0060] wherein X includes a chalcogen element, D includes an alkali metal element, M includes a transition metal element, 1≤a≤2, b is 1, and 3≤c≤4.

[0061] The method for preparing the 1T' phase intercalation material of embodiments of the present application mixes H2X and D a M b O c performs heat treatment of the 1T' phase to form the 1T' phase intercalation material; a M b O cThe chemical reaction occurs in a reducing atmosphere and at a certain temperature. During the heat treatment process, 1T' phase transition metal chalcogenide of formula MX2 is generated, and intercalation material of formula D2X is also generated in situ. The intercalation material is intercalated into the interlayer of the 1T' phase transition metal chalcogenide to obtain 1T' phase intercalation material. The 1T' phase intercalation material prepared by the preparation method has good stability, long service life, and is not prone to phase change. In addition, the yield is high, the purity of the 1T' phase is high, the preparation method is controllable, and it is suitable for large-scale production.

[0062] Regarding the raw material H2X:

[0063] X includes chalcogen elements. In some embodiments, the chalcogen elements include at least one of S, Se, and Te. In exemplary embodiments, H2X includes at least one of H2S, H2Se, and H2Te. In embodiments, X in H2X can be one chalcogen element, such as any one of H2S, H2Se, and H2Te. It can also be multiple chalcogen elements, such as a mixture of H2S, H2Se, and H2Te formed by two or more of them. Therefore, X in D2X in the generated 1T' phase intercalation material can be the same as or different from that in MX2. For example, in embodiments, 1T' phase intercalation material with 1T' phase TMDs of MoS2 and intercalation material of K2Se, and 1T' phase intercalation material with 1T' phase TMDs of MoSe2 and intercalation material of K2S, etc. can be obtained.

[0064] These raw materials can be mixed with D a M b O c to react, and D a M b O c is generated by sulfidation, selenization, or tellurization. In addition, under certain temperature and environment, based on the type of chalcogen element represented by X and the characteristics of H2X, the H2X is generally gaseous in the heat treatment environment, which is conducive to sufficient reaction and improves the yield and purity of the generated 1T' phase intercalation material.

[0065] The 1T' phase intercalation material prepared by the preparation method generates not only layered 1T' phase TMDs but also intercalation material during heat treatment, and the intercalation material is intercalated into the interlayer of the 1T' phase TMDs. The chemical formula of the 1T' phase TMDs can be represented as MX2, and the chemical formula of the intercalation material can be represented as D2X, which is conducive to further improving the stability and purity of the prepared 1T' phase intercalation material.

[0066] Regarding the raw material D a M b O c :

[0067] D includes alkali metal elements, in some embodiments, the alkali metal elements include at least one of Li, Na, K, Rb, Cs, Fr, and in exemplary embodiments, at least one of Li, Na, K. M includes common transition metal elements, in some embodiments, the transition metal elements include at least one of Mo, W, Ti, Nb, V, Ta, Re. And, 1≤a≤2, b is 1, 3≤c≤4. In exemplary embodiments, the above D a M b O c may include, but not limited to, at least one of Li2MoO4, Na2MoO4, K2MoO4, Na2WO4, K2WO4, K2TiO3. These D a M b O c may react with the above H2X to form corresponding 1T' phase intercalation material, D a M b O c is in solid state, which is optional in powder form, which is beneficial to reaction, and improves yield of the preparation method and purity of 1T' phase. There is no special requirement for particle size and specific surface area of the powder particles, and the preparation method has strong applicability and is suitable for large-scale production.

[0068] According to different raw materials D a M b O c , the above heat treatment can be carried out in a reducing atmosphere. The reducing atmosphere can include reducing gas such as hydrogen, and can also include mixed gas of protective gas and reducing gas, and the volume ratio of protective gas to reducing gas can be 1:(2-10), and in exemplary embodiments, the protective gas includes at least one of helium, neon, argon, nitrogen; and the reducing gas can include hydrogen. In exemplary embodiments, the mixed gas can include mixed gas atmosphere formed by hydrogen and argon with a volume ratio of 15:35, which can reduce side reactions and improve yield of the preparation method and purity of 1T' phase.

[0069] The temperature of heat treatment is a key to prepare 1T' phase intercalation material, for example, when the temperature of heat treatment is low, such as temperature <500℃, the above H2X and D a M b O cAlmost no 1T' phase is generated, and almost all 2H phase is generated, so the heat treatment should be relatively strict to be able to generate 1T' phase at the temperature. With the increase of temperature, when a certain reaction temperature is reached, such as the temperature is greater than or equal to 500℃ and less than 650℃, the 1T' phase and the 2H phase exist at the same time in the product, and the product also has the 2H phase. At the above two temperatures, some raw materials may not be completely reacted, or the product may also contain other products that are not completely vulcanized. Therefore, the temperature of the heat treatment should be avoided to be less than 500℃. In addition, in order to increase the content of the 1T' phase in the product, the heat treatment should be carried out at a temperature greater than or equal to 650℃ as much as possible.

[0070] In some embodiments, the temperature of the heat treatment is ≥650℃, which can be optionally 650-800℃, 700-750℃, and in exemplary embodiments, can include but not limited to any one of 650℃, 680℃, 700℃, 720℃, 750℃, 800℃, 850℃, 900℃, 950℃, 1000℃ or a range between any two of them, which is conducive to the full reaction and the preparation of high-purity and high-stability 1T' phase intercalation material. The heating rate of the reaction environment to the heat treatment can be optionally 10-40℃ / min.

[0071] In exemplary embodiments, when D a M b O c When K2MoO4 is included, the following chemical reactions can occur at the above-mentioned heat treatment temperature:

[0072] K2MoO4+3H2S+H2→(K2S) d MoS2+K2S (1-d) +4H2O; wherein 0

[0073] In exemplary embodiments, when D a M b O c When K2TiO3 is included, the following chemical reactions can occur at the above-mentioned heat treatment temperature:

[0074] K2TiO3+3H2S→(K2S) d TiS2+K2S (1-d) +3H2O; wherein 0

[0075] In some embodiments, the time of the heat treatment is 3-6h, and in exemplary embodiments, can include but not limited to any one of 3h, 4h, 5h, 6h or a range between any two of them, which is conducive to the full reaction and the preparation of high-purity and high-stability 1T' phase intercalation material.

[0076] In some embodiments, the above-mentioned heat treatment can include the following steps:

[0077] S11: heat volatilization treatment is performed on the solid X element to obtain gaseous X element;

[0078] S12: redox reaction is performed between the gaseous X element and reducing gas to obtain H2X;

[0079] S13: H2X and D a M b O c are heated to the heat treatment temperature respectively, and then H2X and reducing gas are introduced into the environment where D a M b O c are located to perform reaction.

[0080] Through the above three steps, the gaseous H2X generated by the reaction of X element can be reacted with D a M b O c in advance, and then the reaction occurs, so as to improve the purity and stability of the prepared 1T' phase intercalation material.

[0081] In step S11, the solid X element is changed into gaseous X element through heat volatilization treatment. In the demonstration example, the solid sulfur powder can be heat volatilized into sulfur gas at 135°C. Then in step S12, the gaseous X element is reacted with reducing gas to generate H2X. In the demonstration example, the sulfur gas can be reacted with hydrogen at 700-750°C to generate H2S. Finally, H2X and reducing gas are heated to the heat treatment temperature respectively, and then reacted with D a M b O c to ensure that the reaction occurs at the required heat treatment temperature, so as to improve the purity and stability of the prepared 1T' phase intercalation material.

[0082] In the embodiment, the X element can be an element of a chalcogen group, such as any one of S, Se, and Te; or can be an element of multiple chalcogen groups, which can be multiple elements of a chalcogen group, such as a mixture of two or more of S, Se, and Te. Thus, X in the generated 1T' phase intercalation material D2X can be the same as or different from MX2. For example, in the embodiment, the 1T' phase intercalation material can be obtained, in which the 1T' phase TMDs is MoS2, and the intercalation material is K2Se, or the 1T' phase TMDs is MoSe2, and the intercalation material is K2S, and so on.

[0083] In the demonstration example, a heating furnace with three heating zones can be provided, in which there is a clean quartz tube for placing materials and reaction. Along the direction from one end of the quartz tube to the opposite end of the quartz tube, X element, D a M b Oc powder, and X element, D a M b O c The powders are placed at intervals, and no raw material is placed in the interval region. The region where X element is located, the interval region, and the region where D a M b O c The regions where the powders are located are respectively located in the three heating regions of the furnace, and are sequentially recorded as the left end region, the interval region, and the right end region. The air in the tube is exhausted with a protective gas, and then the protective gas and the reducing gas are introduced in the direction from the left end region to the right end region, which can be 35 sccm of argon and 15 sccm of hydrogen.

[0084] During heating, the temperature of the interval region and the right end region of the quartz tube is first heated to the required heat treatment temperature to reduce the occurrence of side reactions, and then the X element in the left end region is heated for thermal evaporation treatment to complete step S11. The generated gaseous X element will flow to the interval region with the gas flow, and react with the reducing gas to generate H2X, completing step S12; and the gas generated H2X in the interval region has also been heated to the required heat treatment temperature. In the demonstration example, the reducing gas can be excessive, so that the gaseous X element is all generated into H2X gas and flows to the right end region to participate in the reaction. The last step S13 is in the right end region, and H2X and the reducing gas react with D a M b O c 1T' phase intercalation material is generated by reaction at the required heat treatment temperature. This method avoids the low-temperature reaction to generate 2H phase in the right end region during the heating process, so that the reaction only occurs at the set temperature, which can improve the purity of 1T' phase in the product, and is an important feature distinguishing from the preparation method of the prior art, and is also the key to successful preparation.

[0085] In some embodiments, D a M b O c In addition to the raw material in the form of powder and the preparation of the 1T' phase intercalation material in the form of powder, the raw material can also be in the form of nanosheet and the 1T' phase intercalation material can be prepared in the form of nanosheet. In the demonstration example, D a M b O c The nanosheet is formed, and other preparation steps are the same as the above steps. After the reaction is completed, the nanosheet of the 1T' phase intercalation material can be prepared.

[0086] In some embodiments, D a M b O c The solution of D a M b O cThe 1T' phase intercalation material is attached to the substrate, and other preparation steps are the same as the above steps. After the reaction is completed, the substrate with the 1T' phase intercalation material attached can be prepared, and can be used in subsequent electrochemical catalysis and other applications.

[0087] The third aspect of the embodiments of the present application provides an application of the 1T' phase intercalation material or the 1T' phase intercalation material prepared by the preparation method of the above embodiments of the present application. The 1T' phase intercalation material is applied in at least one of an electrochemical catalyst, an energy storage device, a superconducting material, and a synaptic transistor.

[0088] Since the 1T' phase intercalation material has high stability, it is not easy to change phase for a long time, and can maintain the 1T' phase for a long time. Therefore, the performance of the 1T' phase TMDs in electrochemical energy storage and electrochemical catalysis can be fully utilized, and the 1T' phase intercalation material can be used in at least one of an electrochemical catalyst, an energy storage device, a superconducting material, and a synaptic transistor.

[0089] In some embodiments, when used in an electrochemical catalyst, the electrochemical catalyst can include an electrochemical hydrogen evolution catalyst. The hydrogen evolution reaction (HER) is the cathodic half-reaction of water splitting. The 1T' phase TMDs in the 1T' phase intercalation material are good HER catalysts. On the one hand, they are semimetals, have low resistivity, are conducive to electron transport, and have high-density catalytically active sites, and have excellent HER catalytic performance. The 1T' phase intercalation material containing the intercalation material has a Tafel slope (39.3 mV / dec) and an overpotential (-73 mV, current density: 10 mA / cm 2 ) close to a platinum-carbon catalyst. On the other hand, due to the high stability brought by intercalation, the HER stability is much higher than that of 1T' or 1T phase TMDs prepared by other methods. No performance degradation is observed after 1000 hours of continuous work at a current density of 50 mA / cm 2 ).

[0090] In some embodiments, when used in an energy storage device, the energy storage device includes at least one of a metal-sulfur battery and a supercapacitor. The use of the 1T' phase intercalation material as a cathode can effectively improve the capacity of the battery. The 1T' phase purity and stability greatly affect the performance of the battery. Therefore, the 1T' phase intercalation material prepared by the preparation method of the embodiments of the present application has great advantages over materials prepared by other methods. In the exemplary examples, the metal-sulfur battery can be a lithium-sulfur battery, a sodium-sulfur battery, a potassium-sulfur battery, etc. The 1T' phase intercalation material can also be used as an electrode material for a supercapacitor, which can greatly improve the capacitance value and be suitable for various aqueous electrolytes. In the embodiments, it can match a high voltage of 3.5 V, and the capacitance value can be from 400 to 700 F / cm 3Graphene is used as electrode material for supercapacitor, with capacitance of about 300F / cm 3 .

[0091] In some embodiments, when used as superconducting material, especially 1T' intercalation material, the purity is high and the crystallinity is good, which can exhibit superconducting effect below 10K.

[0092] In some embodiments, the topological field effect transistor constructed by 1T' intercalation material formed by high-purity 1T' MoS2 can realize high-speed switching of the on-off state, which can greatly reduce power consumption and improve response speed compared with traditional structure field effect transistor.

[0093] The following will be described in conjunction with specific embodiments.

[0094] Embodiment 1

[0095] This embodiment provides a 1T' intercalation material and a preparation method thereof. The 1T' intercalation material includes 1T' phase TMDs, with a chemical formula of MoS2, and also includes an intercalation material, with a chemical formula of K2S, which is embedded in the interlayer of the 1T' phase TMDs.

[0096] The preparation method includes the following steps:

[0097] S1. Raw material preparation:

[0098] A heating furnace containing a clean quartz tube with a length of one meter is provided, and there are three heating zones from the left end inlet to the right end outlet of the quartz tube, which are referred to as left zone, middle zone and right zone respectively.

[0099] Sulfur powder is placed on an alumina substrate and placed in the left zone. The middle zone is left without any raw material. K2MoO4 powder is uniformly coated on the exposed sapphire substrate and placed in the right zone.

[0100] S2. Reaction condition preparation:

[0101] The quartz tube is pumped to eliminate the air inside, then argon is introduced from the left end until the tube reaches atmospheric pressure, then argon and hydrogen are introduced, with a flow rate of 35sccm of argon and 15sccm of hydrogen respectively.

[0102] The middle zone and the right zone are heated to 750℃ at a heating rate of 15℃ / min and kept, and the left zone is kept at room temperature.

[0103] S3. Reaction:

[0104] The left zone is heated to 135°C at a ramp rate of 30°C / min to thermally volatilize the sulfur to form sulfur vapor and react with the gas stream in the middle zone to form hydrogen sulfide, and finally react in the right zone to form the 1T' phase intercalated material in a powder form. After 4 hours of reaction, the thermal volatilization of sulfur in the left zone is complete, the reaction in the right zone is complete, and all three zones are allowed to cool to room temperature naturally. The sapphire substrate and the 1T' phase intercalated material are removed from the right zone without any post-treatment. The used quartz tube is cleaned thoroughly to remove any residual sulfur in the middle and right zones to avoid low temperature reaction in the right zone in subsequent uses.

[0105] Example 2

[0106] Example 2 provides a 1T' phase intercalated material and a method of making the same, which differs from Example 1 only in that the intercalation material is changed to Li2S. The method of making differs only in that K2MoO4 is changed to Li2MoO4, and the rest is the same.

[0107] Example 3

[0108] Example 3 provides a 1T' phase intercalated material and a method of making the same, which differs from Example 1 only in that the intercalation material is changed to Na2S. The method of making differs only in that K2MoO4 is changed to Na2MoO4, and the rest is the same.

[0109] Example 4

[0110] Example 4 provides a 1T' phase intercalated material and a method of making the same, which differs from Example 1 only in that the intercalation material is changed to Na2S. The method of making differs only in that K2MoO4 is changed to Na2MoO4, and the temperature in the middle and right zones is changed from 750°C to 700°C, and the rest is the same.

[0111] Example 5

[0112] Example 5 provides a 1T' phase intercalated material and a method of making the same, which differs from Example 1 only in that the intercalation material is changed to Na2S. The method of making differs only in that K2MoO4 is changed to Na2MoO4, and the temperature in the middle and right zones is changed from 750°C to 650°C, and the rest is the same.

[0113] Example 6

[0114] Example 6 provides a 1T' phase intercalated material and a method of making the same, which differs from Example 1 only in that the 1T' phase TMDs is changed to a state where both 2H phase TMDs and 1T' phase TMDs exist, and the 2H phase to 1T' phase molar ratio is about 1:1. The intercalation material is intercalated in the interlayer of the 2H phase TMDs and the 1T' phase TMDs.

[0115] The preparation method of the present comparative example is different from that of Example 1 only in that the temperature of the middle zone and the right zone in step S2 is changed to heating to 600°C and keeping, and others are the same.

[0116] Example 7

[0117] Example 7 provides a 1T' phase intercalation material and a preparation method thereof, which is different from Example 1 only in that the 1T' phase TMDs is changed to WS2. The difference of the preparation method is only that K2MoO4 is changed to K2WO4, and the temperature of the middle zone and the right zone is changed from 750°C to 850°C, and others are the same.

[0118] Example 8

[0119] Example 8 provides a 1T' phase intercalation material and a preparation method thereof, which is different from Example 1 only in that the 1T' phase TMDs is changed to TiS2. The difference of the preparation method is only that K2MoO4 is changed to K2TiO3, and the temperature of the middle zone and the right zone is changed from 750°C to 900°C, and others are the same.

[0120] Example 9

[0121] Example 9 provides a 1T' phase intercalation material and a preparation method thereof, which is different from Example 1 only in that the 1T' phase TMDs is changed to MoSe2, and the intercalation material is changed to Na2Se. The difference of the preparation method is only that sulfur is changed to selenium powder, the temperature of the left zone is changed to 230°C, so that the selenium powder can be hot volatilized, K2MoO4 is changed to Na2MoO4, and others are the same.

[0122] Example 10

[0123] Example 10 provides a 1T' phase intercalation material and a preparation method thereof, which is different from Example 1 only in that the 1T' phase TMDs is changed to MoTe2, and the intercalation material is changed to K2Te. The difference of the preparation method is only that sulfur is changed to tellurium powder, the temperature of the left zone is changed to 500°C, so that the tellurium powder can be hot volatilized, and others are the same.

[0124] Example 11

[0125] Example 11 provides a 1T' phase intercalation material and a preparation method thereof, which is different from Example 1 only in that the 1T' phase TMDs is changed to both MoS2 and MoSe2, and the intercalation material is changed to both K2S and K2Se. The difference of the preparation method is only that sulfur is changed to sulfur powder and selenium powder, the temperature of the left zone is changed to 230°C, so that the sulfur powder and the selenium powder can be hot volatilized, and others are the same. A part of K2S is intercalated into MoS2, and a part of K2S is intercalated into MoSe2, a part of K2Se is intercalated into MoS2, and a part of K2Se is intercalated into MoSe2.

[0126] Example 12

[0127] Example 12 provides a 1T' phase intercalation material and a preparation method thereof, which is only different from example 1 in that the 1T' phase TMDs are changed to both MoS2 and MoTe2, and the intercalation material is changed to both K2S and K2Te. The difference of the preparation method is only that the sulfur powder is changed to sulfur powder and tellurium powder, and the temperature of the left zone is changed to 500℃, so that the sulfur powder and the tellurium powder can be thermally volatilized, and the others are the same. A part of K2S is intercalated into MoS2, and a part of K2S is intercalated into MoTe2. A part of K2Te is intercalated into MoS2, and a part of K2Te is intercalated into MoTe2.

[0128] Example 13

[0129] Example 13 provides a 1T' phase intercalation material and a preparation method thereof, which is only different from example 1 in that the step S1 does not place sulfur powder, the step S2 heats the left zone, the middle zone and the right zone to 750℃ and keeps, the step S3 is different from example 1 in that, in addition to the 35sccm argon gas and the 15sccm hydrogen gas, 15sccm hydrogen sulfide gas is also introduced from the left end, and the others are the same.

[0130] Example 14

[0131] Example 14 provides a 1T' phase intercalation material and a preparation method thereof, which is only different from example 1 in that the intercalation material is changed to Na2S, and is not in the form of powder, but in the form of nanosheet.

[0132] The difference of the preparation method from example 1 is only that the K2MoO4 powder in the step S1 is changed to a Na2MoO4 film, which is deposited on a sapphire substrate by sputtering deposition. The specific parameters are as follows: sputtering object Na2MoO4, power 50W, time 600s, environment 20sccm Ar / 10sccm O2. The others are the same, and finally a nanosheet film of the 1T' phase intercalation material is prepared.

[0133] Example 15

[0134] Example 15 provides a 1T' phase intercalation material and a preparation method thereof, which is only different from example 1 in that the 1T' phase intercalation material is not in the form of powder, but is combined on a carbon cloth.

[0135] The preparation method is different from that of Example 1 only in that the K2MoO4 powder in step S1 is placed on the sapphire substrate in the following way: first, the carbon cloth is dried on a hot plate at 130°C, and a few drops of ethanol are dropped on the carbon cloth to soak the carbon cloth, then 10 drops of saturated K2MoO4 solution are dropped on the carbon cloth drop by drop within 1 minute. Then the carbon cloth is dried on a hot plate at 130°C for 20 minutes to make the solid K2MoO4 evenly adhere to the carbon cloth, and the carbon cloth is used to replace the K2MoO4 powder and the sapphire substrate in Example 1, and the intercalation material of the 1T' phase on the carbon cloth has a mass of 22.7 mg / cm2. 2 The other steps are the same. Finally, the 1T' phase intercalation material film combined on the carbon cloth is obtained.

[0136] Comparative Example 1

[0137] This comparative example provides an intercalation material and a preparation method thereof, which is different from Example 1 only in that the 1T' phase TMDs is replaced by 2H phase TMDs, and the intercalation material is embedded in the interlayer of the 2H phase TMDs.

[0138] The preparation method of this comparative example is different from that of Example 1 only in that the middle and right zones of step S2 are heated to 450°C and kept, and the other steps are the same.

[0139] Comparative Example 2

[0140] This comparative example provides an intercalation material, which is sodium atoms embedded in the interlayer of the prior art 1T' phase MoS2.

[0141] Comparative Example 3

[0142] This comparative example provides an intercalation material, which is lithium hydride embedded in the interlayer of the prior art 1T' phase MoS2.

[0143] Comparative Example 4

[0144] This comparative example provides an intercalation material, which is lithium atoms embedded in the interlayer of the prior art 1T' phase MoS2.

[0145] Comparative Example 5

[0146] This comparative example provides 1T' phase MoS2, which is prepared by the prior art preparation method, taking MoO3 and sulfur powder as precursors, growing 2H phase MoS2 flakes on a SiO2 / Si substrate by CVD, then immersing the sample in a 2 mol / L n-butyl lithium and cyclohexane solution in a glove box with pure nitrogen as a protective gas for 200 hours. After that, the sample is completely washed with cyclohexane and dried to obtain 1T' phase MoS2.

[0147] The 1T' phase intercalation materials of Example 1 to Example 15 and the intercalation materials of Comparative Example 1 to Comparative Example 5 are shown in Table 1.

[0148] Table 1

[0149]

[0150] Related performance test and result analysis

[0151] The 1T' phase intercalation materials of Example 1 to Example 15, and the samples of Comparative Example 1 to Comparative Example 5 were sequentially subjected to the following tests:

[0152] 1. SEM test:

[0153] The SEM image of the 1T' phase intercalation material of Example 1 is shown in Figure 1 , where a large number of trapezoidal flakes can be seen stacked together, and the flake shape indicates a two-dimensional growth trend, with the maximum size of a single flake exceeding 100 μm. Macroscopically, the powder of Example 1 also differs from typical triangular 2H phase MoS2 flakes in that it has a distinct metallic luster.

[0154] 2. Raman spectrum test:

[0155] The test results of Example 1, Example 14, and Comparative Example 5 are shown in Figure 2 , where the characteristic peaks J1 and J3 of the 1T' phase are different from those of the 2H phase MoS2, confirming the existence of the 1T' phase MoS2 with high crystal quality in Example 1 and Example 14, and the absence of the defect-related Raman peak J2 9,22,31,32 , indicating a high crystal quality. The peaks A 1g and E 1g present in both the 2H phase and the 1T' phase MoS2, and the other three Raman peaks A, B, and C are related to intercalation. The Raman peaks of the sample of Comparative Example 5 are significantly weaker than those of the 1T' phase intercalation materials of Example 1 and Example 14, indicating that the crystal quality of the 1T' phase prepared by the prior art is poor.

[0156] 3. XRD test:

[0157] The test results of Example 1 are shown in Figure 3 , Figure 4 , where the total distance d (200) of the interlayer spacing is 0.9064 nm, which is larger than the 0.5876 nm of the intrinsic 1T' phase MoS2 and the 0.6148 nm of the 2H phase MoS2, and the lattice constant is increased from 1.2835 nm to 1.9797 nm. The clear XRD characteristic peak and the same in-plane structure reflect the two-dimensional growth trend.

[0158] 4. XPS test:

[0159] The test results of Example 1 are shown inFigure 5 、 Figure 6 、 Figure 7 as shown in FIG. 4B, FIG. 4C and FIG. 4D, respectively, Figure 5 Mo 3d 5 / 2 and Mo 3d 3 / 2 peaks have lower binding energy (228.00 eV and 231.17 eV), which is almost the same as the intrinsic 1T' phase MoS2. There is only one set of Mo 3d XPS peaks in the fitting results, and the fitting curve is exactly the same as the test results of Example 1, which confirms that the sample prepared in Example 1 has very high 1T' phase purity, and within the error range of XPS measurement, it can be considered that Example 1 is 100% phase pure.

[0160] Figure 6 which confirms the presence of K. According to the energy in Figure 7 , the molar ratio of S to Mo and S to K is calculated to be MoS2 and K2S, which is consistent with the XRD results, indicating that K2S is embedded in the interlayer of MoS2.

[0161] Examples 2 to 15 are listed in Table 1 according to the test results. Among them, Examples 2 to 5, Examples 7 to 15 are also almost 100% phase pure.

[0162] However, in Example 6, because the heat treatment temperature is only 600℃, the 1T' phase intercalation material prepared contains 2H phase in addition to 1T' phase, so its purity is low.

[0163] 5. TEM test:

[0164] The test results of Example 1 are shown in FIG. 5A and FIG. 5B, respectively, Figure 8 and Figure 9 , it can be seen that the Mo atoms in the 1T' phase form zigzag chains in the layer. Combined with Figure 8 and Figure 8 , adjusting the SAED mode of the transmission electron microscope, it can be confirmed that MoS2 is a distorted octahedral structure, which is a 1T' phase. Figure 9 6. Stability test:

[0165]

[0166] It can be seen that the stability of the 1T' phase intercalation material of Example 1 is very good. The DSC (differential scanning calorimetry) test in the temperature range of 50℃ to 380℃ confirms that there is no phase transition in this temperature range. As shown in the TGA curve, there is also no weight loss. The intrinsic 1T' phase MoS2 will be converted to 2H phase when the temperature exceeds 97.2℃. Figure 10

[0167] Figure 11 ​It can be seen from the figure that the sample of Example 1 was divided into several samples, which were washed with deionized water and ethanol, exposed to air at room temperature for one year, and annealed at 750°C, and no degradation was observed after the above treatments, Figure 11 The Raman spectrum measured in the middle did not change significantly, proving the inertness, aging resistance, and high temperature resistance of the sample of Example 1 in the solvent.

[0168] After heating the sample of Example 1 at 750°C, the Raman spectrum and Figure 12 The XPS test results showed no significant change, proving that it can also maintain its 1T' phase purity at high temperatures.

[0169] The stability test results of Examples 2 to 15 are also similar to Example 1.

[0170] The samples of Comparative Examples 1 to 5 were washed with deionized water or ethanol, or left in air. The active alkali metal (Li, Na, etc.) in the intercalation of Comparative Examples 2 and 4 will react with water or ethanol to generate hydrogen, the release of hydrogen will destroy the material structure, at the same time, the 1T' phase TMDs intercalated with alkali metal will gradually transform into 2H phase. In addition, the 1T' phase TMDs intercalated with alkali metal will be oxidized when exposed to air, and need to be stored in an inert atmosphere, which has a large application limitation. The lithium hydride intercalation of Comparative Example 3 also has this problem, but it is relatively stable in air, but the surface can be easily oxidized, and the storage time is less than 3 months. Moreover, the samples of Comparative Examples 2 to 5 all immediately transformed into 2H phase at about 100°C, and had poor thermal stability. The samples prepared in Comparative Example 1 were all 2H phase, which is the thermally stable phase of MoS2, but does not have the electrochemical catalysis, electrochemical energy storage, and superconductivity of the 1T' phase intercalation material.

[0171] 7. Electrochemical catalytic performance test:

[0172] The 1T' phase intercalation material of Example 15 combined on carbon cloth was used for HER test. In the HER measurement, the electrochemical configuration of H-type battery was used, 0.5 mol / L H2SO4 solution was used as electrolyte, the sample of Example 15 was used as working electrode, saturated Ag / AgCl was used as reference electrode, and graphite was used as counter electrode. The battery was separated from another battery by Nafion membrane, and the working electrode and the reference electrode were placed in another battery. The electrochemical HER performance of commercially available Pt / C was also tested, and the Pt / C was dropped on glassy carbon and dried, and then covered with Nafion membrane. During the HER test, the sample of Example 15 can be directly immersed in the electrolyte, showing stability to strong acid, which is not available for existing catalysts.

[0173] The polarization curve (iR correction) results are shown in Figure 13 10 mA / cm 2at a very low onset potential of -73 mV, Figure 14 The corresponding Tafel slope of 39.3 mV / dec can be seen in Figure 8. More importantly, Figure 15 It can be seen in Figure 8 that the sample of Example 15 has excellent long-term stability, and the polarization curve does not change significantly even after 30,000 cyclic voltammetry (CV) cycles (overpotential range: -0.25 ~ 0.2 V vs. RHE).

[0174] In order to comprehensively and accurately study its long-term stability, a chronopotentiometric analysis was also carried out. Using the three-electrode electrochemical configuration described above, the sample of Example 15 was operated as an HER electrochemical catalyst at a constant current density of 50 mA / cm 2 for 1000 hours. The overpotential was recorded constantly. In Figure 15, the overpotential vs. time curve fluctuates very little over this 1000 hour period. The sawtooth-like fluctuations are caused by the accumulation and release of hydrogen bubbles on the surface of the sample, which hinders contact with the electrolyte. The sample shows no signs of degradation during the 1000 hour stability test.

[0175] It was tested that the 1T' phase intercalation materials of Examples 2 to 5, Examples 7 to 15 also have good electrochemical catalytic performance.

[0176] However, in Example 6, because the heat treatment temperature is only 600℃, the 1T' phase intercalation material prepared contains 2H phase in addition to 1T' phase, so its purity is low, and its electrochemical catalytic performance is not as good as that of other examples.

[0177] The HER electrochemical catalytic performance is mainly determined by three parameters: Tafel slope, overpotential η, and long-term stability. Table 2 compares the phase purity and HER performance of the TMDs catalysts prepared by the preparation method of Example 1 and the typical preparation methods in the existing literature. The overpotential in Table 2 is measured at a current density of 10 mA / cm 2 .

[0178] Table 2

[0179]

[0180]

[0181] As can be seen from Table 2, compared with the TMDs catalysts prepared by the typical preparation methods in the existing literature, the 1T' phase intercalation material prepared by the preparation method of Example 1 has high purity, low Tafel slope, low overpotential η, and good long-term stability, indicating good HER electrocatalytic performance.

[0182] The above only describes preferred embodiments of the present application and is not used to limit the present application, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A 1T' phase intercalation material, characterized in that, The application relates to a 1T'-phase transition metal chalcogenide compound, which comprises the following components: a two-dimensional layered material, wherein the two-dimensional layered material comprises a 1T'-phase transition metal chalcogenide compound with a chemical formula of MX2, wherein M in the MX2 comprises a transition metal element, and X comprises a first chalcogen element; an intercalation material intercalated in the interlayer of the 1T'-phase transition metal chalcogenide compound, wherein the intercalation material has a chemical formula of D2Z, wherein D in the D2Z comprises an alkali metal element, and Z comprises a second chalcogen element.

2. The 1T' intercalation material of claim 1, wherein: The molar ratio of the 1T'-phase transition metal chalcogenide compound in the two-dimensional layered material is 90%-100%; And / or, the molar ratio of the 1T'-phase transition metal chalcogenide compound to the intercalation material is (3-10):1; And / or, the first chalcogen element is the same as the second chalcogen element.

3. The 1T’ intercalation material of claim 1 or 2, wherein: The alkali metal element comprises at least one of Li, Na and K; And / or, the second chalcogen element comprises at least one of S, Se and Te.

4. The 1T’ intercalation material of claim 1 or 2, wherein: The transition metal element comprises at least one of Mo, W, Ti, Nb, V, Ta and Re; And / or, the first chalcogen element comprises at least one of S, Se and Te.

5. The 1T’ intercalation material of claim 1 or 2, wherein: The interlayer spacing of the 1T'-phase transition metal chalcogenide compound is 0.8-1.2 nm; And / or, the number of layers of the 1T'-phase transition metal chalcogenide compound is at least 2.

6. A method of preparing a 1T' phase intercalation material, characterized by, The application further relates to a preparation method of the 1T'-phase transition metal chalcogenide compound, which comprises the following steps: H2X is reacted with D a M b O c heat treatment of the 1T' phase to generate the 1T' phase intercalation material; wherein X comprises a chalcogen element, D comprises an alkali metal element, M comprises a transition metal element, 1<=a<=2, b is 1, and 3<=c<=4.

7. The method of claim 6, wherein the 1T' phase intercalation material is prepared by: The temperature of the heat treatment is greater than or equal to 650 DEG C; And / or, the time of the heat treatment is 3-6 h.

8. The method of claim 6 or 7, wherein the 1T' phase intercalation material is prepared by: The temperature of the heat treatment is 700-750 DEG C; And / or, the chalcogen element comprises at least one of S, Se and Te; And / or, the alkali metal element comprises at least one of Li, Na and K; And / or, the transition metal element comprises at least one of Mo, W, Ti, Nb, V, Ta and Re.

9. The method for preparing the 1T' phase intercalation material according to claim 6 or 7, characterized in that, The heat treatment comprises the following steps: carrying out thermal volatilization treatment on the solid X element to obtain gaseous X element; carrying out redox reaction on the gaseous X element and a reducing gas to obtain the H2X; The H2X and the D a M b O c Heated to the temperature of the heat treatment, the H2X and reducing gas are introduced into the D a M b O c The reaction is carried out in the environment.

10. Use of the 1T' phase intercalation material according to any one of claims 1 to 5 or of the 1T' phase intercalation material prepared according to the method of any one of claims 6 to 9, characterized in that: The 1T'-phase intercalation material is applied in at least one of electrochemical catalysts, energy storage devices, superconducting materials and synaptic transistors.

11. Use according to claim 10, characterized in that: The electrochemical catalysts comprise electrochemical hydrogen evolution catalysts; And / or, the energy storage devices comprise at least one of metal-sulfur batteries and supercapacitors.

Images