A preparation method of an anode intercalation-mediated transition metal halide nanoroll

Abstract

The application discloses a preparation method of transition metal halide nanorolls based on anode intercalation mediation, and first prepares a transition metal halide single crystal material, then prepares an electrolyte for electrochemical anode intercalation, and uses M3X8 and M3QX7 single crystal samples as working electrodes, and uses an inert electrode as a counter electrode to construct an electrochemical anode intercalation device; then, a working voltage is applied, cations in the electrolyte intercalate the M3X8 and M3QX7 single crystals, expansion, curling and peeling occur, and after shaking, one-dimensional M3X8 and M3QX7 nanorolls dispersed in a solution are obtained; finally, the obtained dispersion is centrifuged, washed and dried to obtain M3X8 and M3QX7 nanoroll powder samples. The preparation process is simple, the experimental parameters are controllable, the preparation efficiency is high, the universality is strong, the prepared M3X8 and M3QX7 nanorolls have good compactness and high crystallinity, and the M3X8 and M3QX7 nanorolls have a good application prospect in the fields of optics and electricity.

Description

Technical Field

[0001] This invention relates to a method for preparing one-dimensional nanoroll materials, and more particularly to a method for preparing transition metal halide nanorolls based on anodic intercalation. Background Technology

[0002] Rolling two-dimensional materials into one-dimensional coaxial van der Waals nanorolls offers a unique method for controlling the intrinsic physical properties of materials, opening new avenues for exploring exotic physical properties and functional applications in the one-dimensional limit. Unlike two-dimensional planar structures, one-dimensional nanorolls can introduce new degrees of freedom such as curvature, chirality, and deformation to manipulate the symmetry and electronic structure of the original two-dimensional material, leading to a host of new physical phenomena, such as semiconductor-metal transitions, non-reciprocal superconductivity, bulk photovoltaic effects, and unidirectional magnetic waveguides. Therefore, rolling two-dimensional materials into one-dimensional nanorolls provides a groundbreaking method for controlling materials, promising to generate new phenomena and unique functions beyond the reach of existing materials.

[0003] Currently, the main method for preparing one-dimensional nanorolls is to artificially introduce external driving forces to induce the curling of two-dimensional materials. For example, using carbon nanotubes and choline tubes as soft templates, nanorolls of graphene, MoS2, and BN can be prepared in solution. Anchoring nanoparticles on the surface of two-dimensional materials and utilizing the interactions between these nanoparticles can induce the curling of the two-dimensional material. Recently, based on the stress gradient between the two-dimensional material and the substrate, researchers have discovered that by utilizing capillary liquid intercalation to release stress, two-dimensional materials on a substrate can be curled into one-dimensional nanorolls. Although these methods can prepare one-dimensional nanorolls, the yield, production volume, size, reproducibility, and uniformity are difficult to control, limiting their application in scientific research and functional devices. Furthermore, the material systems for preparing one-dimensional nanorolls to date remain limited, mainly focusing on graphene, BN, and transition metal chalcogenides.

[0004] Therefore, the controllable and large-scale preparation of novel one-dimensional nanoroll material systems remains a huge challenge. Summary of the Invention

[0005] Purpose of the invention: The purpose of this invention is to provide a controllable and large-scale preparation method for transition metal halide nanorolls based on anodic intercalation.

[0006] Technical solution: The preparation method of transition metal halide nanorolls based on anodic intercalation mediated by the present invention includes the following steps:

[0007] (1) Preparation of single-crystal transition metal halide materials;

[0008] (2) Prepare an electrolyte for electrochemical anode intercalation, and use M3X8 and M3QX7 single crystal samples as working electrodes and an inert electrode that does not react with the electrolyte as the counter electrode to construct an electrochemical anode intercalation device.

[0009] (3) When a working voltage is applied, the cation-intercalated M3X8 and M3QX7 single crystals in the electrolyte expand, curl, and fall off. After shaking, one-dimensional M3X8 and M3QX7 nanorolls dispersed in the solution are obtained.

[0010] (4) Centrifuge, wash and dry the dispersion obtained in step (3) to obtain M3X8 and M3QX7 nanofiber powder samples.

[0011] In step (1), the transition metal halide single crystal material is a layered M3X8 and M3QX7 with a Kagome lattice, wherein M = Nb, Ta; X = Cl, Br, I; Q = S, Se, Te.

[0012] The M3X8 includes Nb3Cl8, Nb3Br8, Nb3I8, and Nb alloys. 3-x Ta x I8、Nb 3-x Ta x At least one of Cl8.

[0013] The M3QX7 includes Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb alloy. 3-x Ta x SeI7, Nb3Se 1-x Te x At least one of I7.

[0014] In step (2), the electrolyte used to prepare the anode intercalation electrolyte is a soluble tetraalkylammonium salt and / or an inorganic metal salt.

[0015] In step (2), the electrolyte used to prepare the anode intercalation electrolyte is at least one of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrahexylammonium chloride, tetrahexylammonium bromide, tetraoctylammonium chloride, tetraoctylammonium bromide, tetradecylammonium chloride, tetradecylammonium bromide, tetraheptylammonium chloride, tetraheptylammonium bromide, tetrapentylammonium chloride, tetrapentylammonium bromide, tetrapropylammonium chloride, and tetrapropylammonium bromide.

[0016] The salt concentration in the electrolyte used to prepare the anode intercalation electrolyte is approximately 0.001–0.1 mol / L.

[0017] In step (2), the solvent for preparing the anode intercalation electrolyte is one of propylene carbonate, N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, and N-methylpyrrolidone.

[0018] In step (2), the non-reactive electrode is preferably platinum, gold, or graphite.

[0019] In step (3), the voltage of the working electrode is approximately -2.5 to -7V.

[0020] In step (3), the intercalation expansion time of the M3X8 and M3QX7 single crystals is approximately 0.5–5 h; the expanded sample can be manually shaken to obtain a well-dispersed M3X8 and M3QX7 nanoroll dispersion with a yield of approximately 100%. The prepared M3X8 and M3QX7 nanorolls have a length of approximately 1 μm–30 μm and a diameter of approximately 30 nm–100 nm, exhibiting high density of curling.

[0021] In step (4), vacuum drying is used for drying at a temperature of 40 to 100°C for a time of 0.5 to 5 hours.

[0022] Beneficial Effects: Compared with existing technologies, this invention achieves the following significant effects: 1. By employing an anode intercalation-assisted strategy, layered M3X8 and M3QX7 single crystals are directly intercalated and exfoliated, enabling the large-scale preparation of M3X8 and M3QX7 nanorolls. The length of the nanorolls can reach tens of micrometers, and the diameter is approximately tens of nanometers, which is expected to be used in the development and functional applications of novel low-dimensional electrical and optical devices. 2. The M3X8 and M3QX7 nanorolls prepared by the method of this invention are obtained by directly rolling up the single crystal matrix, exhibiting high crystallinity. Furthermore, the rolled structure protects the internal lattice from damage, allowing the nanorolls to maintain excellent stability. 3. The preparation method of this invention is convenient and feasible, with simple steps. The size, speed, and yield of the prepared nanorolls can be controlled by the intercalation voltage, the size of the cations in the electrolyte, and the intercalation time, which is beneficial for large-scale production. 4. The tetraalkylammonium cation used in the anode intercalation of this invention has good structural flexibility, low intercalation voltage, and less damage and contamination to the sample. The rolled-up M3X8 and M3QX7 nanorolls have smooth surfaces, dense curling, and uniform morphology, providing high-quality samples for the manufacture of low-dimensional optoelectronic devices. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the preparation process of the present invention;

[0024] Figure 2 These are the optical and XRD patterns of the M3X8 and M3QX7 single crystals prepared in Example 1;

[0025] Figure 3 Optical images of the M3X8 and M3QX7 nanorolls prepared in Example 1;

[0026] Figure 4These are SEM images of the M3X8 and M3QX7 nanorolls prepared in Example 1;

[0027] Figure 5 These are TEM images of the M3X8 and M3QX7 nanorolls prepared in Example 1;

[0028] Figure 6 These are HRTEM images of the M3X8 and M3QX7 nanorolls prepared in Example 1. Detailed Implementation

[0029] The present invention will now be described in further detail.

[0030] Example 1

[0031] The first step involves growing layered Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb crystals with Kagome lattice structures using existing chemical vapor transport methods. 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystal sample;

[0032] The second step is to prepare a 0.001 mol / L electrolyte solution by mixing tetrabutylammonium chloride and propylene carbonate.

[0033] The third step involves using Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb... 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals were used as the working electrode and immersed in an electrolyte solution, with a platinum electrode as the counter electrode to construct an electrochemical anode intercalation device.

[0034] The fourth step involves applying a -7V voltage to the working electrode and maintaining it for 5 hours. This process yields Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb... 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Tax I8 and Nb 3-x Ta x Cl8 single crystals completely expand, curl, and detach;

[0035] Fifth step: The system obtained in step three is manually shaken to obtain a solution dispersion of one-dimensional Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb. 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 nanofibers;

[0036] Step 6: The product obtained in step 5 is centrifuged, washed, and vacuum dried to obtain Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 nanoparticle powder sample.

[0037] Figure 1 This is a schematic diagram of the preparation process of the present invention. Figure 2 Optical and XRD patterns of the prepared M3X8 and M3QX7 single crystals are shown. The single crystal size is on the order of several millimeters and exhibits excellent crystallinity. Figure 3 Optical images of the obtained M3X8 and M3QX7 nanorolls, with lengths ranging from several micrometers to tens of micrometers; Figure 4 SEM images of the prepared M3X8 and M3QX7 nanorolls, with diameters of approximately tens of nanometers; Figure 5 TEM images of the prepared M3X8 and M3QX7 nanorolls, whose multi-layered wall structure at the edges confirms the structure of the nanorolls; Figure 6 HRTEM images of the prepared M3X8 and M3QX7 nanorolls confirm the phase composition.

[0038] Example 2

[0039] The first step involved growing layered Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb crystals with Kagome lattice structures using a chemical vapor transport method. 3-x Tax SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystal sample;

[0040] The second step is to prepare a 0.005 mol / L electrolyte solution by mixing tetrabutylammonium chloride and propylene carbonate.

[0041] The third step involves using Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb... 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals were used as the working electrode and immersed in an electrolyte solution, with a platinum electrode as the counter electrode to construct an electrochemical anode intercalation device.

[0042] Fourth step: Apply a -6V voltage to the working electrode and maintain it for 3 hours. Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, Nb 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals completely expand, curl, and detach;

[0043] Fifth step: The system obtained in step three is manually shaken to obtain a solution dispersion of one-dimensional Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb. 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 nanofibers;

[0044] Step 6: The product obtained in step 5 is centrifuged, washed, and vacuum dried to obtain Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 nanoparticle powder sample.

[0045] Example 3

[0046] The first step involved growing layered Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb crystals with Kagome lattice structures using a chemical vapor transport method. 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystal sample;

[0047] The second step is to prepare a 0.01 mol / L electrolyte solution by mixing tetrabutylammonium chloride and propylene carbonate.

[0048] The third step involves using Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb... 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals were used as the working electrode and immersed in an electrolyte solution, with a platinum electrode as the counter electrode to construct an electrochemical anode intercalation device.

[0049] Fourth step: Apply a voltage of -5.5V to the working electrode and maintain it for 2 hours. Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, Nb 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta xI8 and Nb 3-x Ta x Cl8 single crystals completely expand, curl, and detach;

[0050] Fifth step: The system obtained in step three is manually shaken to obtain a solution dispersion of one-dimensional Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb. 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 nanofibers;

[0051] Step 6: The product obtained in step 5 is centrifuged, washed, and vacuum dried to obtain Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 nanoparticle powder sample.

[0052] Example 4

[0053] The first step involved growing layered Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb crystals with Kagome lattice structures using a chemical vapor transport method. 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystal sample;

[0054] The second step is to prepare a 0.05 mol / L electrolyte solution by mixing tetrahexylammonium chloride and N,N-dimethylformamide.

[0055] The third step involves using Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb... 3-x Ta x SeI7, Nb3Se 1-x Tex I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals were used as the working electrode and immersed in an electrolyte solution, with a platinum electrode as the counter electrode to construct an electrochemical anode intercalation device.

[0056] Fourth step: Apply a -5V voltage to the working electrode and maintain it for 1 hour. Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, Nb 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals completely expand, curl, and detach;

[0057] Fifth step: The system obtained in step three is manually shaken to obtain a solution dispersion of one-dimensional Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb. 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 nanofibers;

[0058] Step 6: The product obtained in step 5 is centrifuged, washed, and vacuum dried to obtain Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 nanoparticle powder sample.

[0059] Example 5

[0060] The first step was to grow layered Nb3Cl8, Nb3I8 and Nb3SeI7 single crystal samples with Kagome lattice structure using chemical vapor transport method;

[0061] The second step is to prepare a 0.1 mol / L electrolyte solution by mixing tetrabutylammonium chloride and N,N-dimethylformamide.

[0062] The third step involves using Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb... 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals were used as the working electrode and immersed in an electrolyte solution, with a platinum electrode as the counter electrode to construct an electrochemical anode intercalation device.

[0063] Fourth step: Apply a -7V voltage to the working electrode and maintain it for 0.5 hours. Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, Nb 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals completely expand, curl, and detach;

[0064] Fifth step: The system obtained in step three is manually shaken to obtain a solution dispersion of one-dimensional Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb. 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 nanofibers;

[0065] Step 6: The product obtained in step 5 is centrifuged, washed, and vacuum dried to obtain Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Tax Cl8 nanoparticle powder sample.

[0066] Example 6

[0067] The first step involves growing layered Nb3I8, Nb3SeI7, and Nb crystals with a Kagome lattice structure using a chemical vapor transport method. 3-x Ta x SeI7, Nb3Se 1-x Te x I7 and Nb 3-x Ta x I8 single crystal sample;

[0068] The second step is to prepare a 0.1 mol / L electrolyte solution by mixing tetrabutylammonium chloride and dimethyl sulfoxide.

[0069] The third step is to use Nb3I8, Nb3SeI7, and Nb respectively. 3-x Ta x SeI7, Nb3Se 1-x Te x I7 and Nb 3-x Ta x An electrochemical anode intercalation device was constructed by using an I8 single crystal as the working electrode and immersing it in an electrolyte solution, with a platinum electrode as the counter electrode.

[0070] Fourth step: Apply a voltage of -2.5V to all working electrodes and maintain it for 5 hours. This process is used for Nb3I8, Nb3SeI7, and Nb... 3-x Ta x SeI7, Nb3Se 1-x Te x I7 and Nb 3-x Ta x I8 single crystals completely expand, curl, and detach;

[0071] Fifth step: The system obtained in the third step is manually shaken to obtain a solution dispersion of one-dimensional Nb3I8, Nb3SeI7, and Nb. 3- x Ta x SeI7, Nb3Se 1-x Te x I7 and Nb 3-x Ta x I8 nanometer roll;

[0072] Step 6: Centrifuge, wash, and vacuum dry the product obtained in step 5 to obtain Nb3I8, Nb3SeI7, and Nb 3- x Ta x SeI7, Nb3Se 1-x Te xI7 and Nb 3-x Ta x I8 nanoparticle powder sample.

[0073] Comparative Example 1

[0074] The first step involves growing layered Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb crystals with Kagome lattice structures using existing chemical vapor transport methods. 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystal sample;

[0075] The second step is to prepare a 0.01 mol / L electrolyte solution by mixing tetrabutylammonium chloride and propylene carbonate.

[0076] The third step involves using Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb... 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals were used as the working electrode and immersed in an electrolyte solution, with a platinum electrode as the counter electrode to construct an electrochemical anode intercalation device.

[0077] Fourth step: Apply a voltage of -0.5V to the working electrode and maintain it for 2 hours. Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, Nb 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals do not expand, curl, or detach, making it impossible to obtain nanocrystals.

[0078] Comparative Example 2

[0079] The first step involves growing layered Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb crystals with Kagome lattice structures using existing chemical vapor transport methods. 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystal sample;

[0080] The second step is to prepare a 0.05 mol / L electrolyte solution using LiCl and N,N-dimethylformamide;

[0081] The third step involves using Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb... 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals were used as the working electrode and immersed in an electrolyte solution, with a platinum electrode as the counter electrode to construct an electrochemical anode intercalation device.

[0082] Fourth step: Apply a -5V voltage to the working electrode and maintain it for 1 hour. Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, Nb 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals do not expand.

[0083] Comparative Example 3

[0084] The first step involves growing layered Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb crystals with Kagome lattice structures using existing chemical vapor transport methods. 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystal sample;

[0085] The second step is to prepare a 0.0001 mol / L electrolyte solution by mixing tetrabutylammonium chloride and propylene carbonate.

[0086] The third step involves using Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb... 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals were used as the working electrode and immersed in an electrolyte solution, with a platinum electrode as the counter electrode to construct an electrochemical anode intercalation device.

[0087] The fourth step involves applying a -7V voltage to the working electrode and maintaining it for 5 hours. This process yields Nb3Cl8, Nb3I8, Nb3Br8, Nb3SeI7, Nb3TeI7, Ta3TeI7, and Nb... 3-x Ta x SeI7, Nb3Se 1-x Te x I7、Nb 3-x Ta x I8 and Nb 3-x Ta x Cl8 single crystals undergo slight expansion, curling, and shedding to obtain a small amount of nanorolls.

Claims

1. A method for the preparation of an anode intercalation-mediated transition metal halide nanorolls, characterized by, The method comprises the following steps: (1) preparing a transition metal halide single crystal material; the transition metal halide single crystal material is a layered M3X8 and M3QX7 with Kagome lattice; (2) preparing an electrochemical anode intercalation electrolyte, and constructing an electrochemical anode intercalation device by taking the M3X8 and M3QX7 single crystal sample as a working electrode and taking an inert electrode that does not react with the electrolyte as a counter electrode; the electrolyte of the anode intercalation electrolyte is a soluble tetraalkylammonium salt and / or an inorganic metal salt; (3) applying a working voltage, and intercalating cations in the electrolyte into the M3X8 and M3QX7 single crystals to cause swelling, curling and peeling off; after shaking, one-dimensional M3X8 and M3QX7 nanorolls dispersed in a solution are obtained; the voltage of the working electrode is-2.5~-7 V; (4) centrifuging, washing and drying the dispersion obtained in step (3) to obtain a M3X8 and M3QX7 nanoroll powder sample.

2. The method for the preparation of anode intercalation layer based transition metal halide nanorolls according to claim 1, wherein, The M3X8 includes Nb3Cl8, Nb3Br8, Nb3I8, and alloys Nb 3-x Ta x I8, Nb 3-x Ta x Cl8.

3. The method for the preparation of anode intercalation layer based transition metal halide nanorolls according to claim 1, wherein, The M3QX7 includes Nb3SeI7, Nb3TeI7, Ta3TeI7, and alloys Nb 3-x Ta x SeI7, Nb3Se 1-x Te x I7.

4. The method for the preparation of anode intercalation layer based transition metal halide nanorolls according to claim 1, wherein, In step (2), the electrolyte of the anode intercalation electrolyte comprises at least one of tetrabutylammonium chloride / bromide, tetrahexylammonium chloride / bromide, tetraoctylammonium chloride / bromide, tetradecylammonium chloride / bromide, tetraheptylammonium chloride / bromide, tetrapentylammonium chloride / bromide and tetrapropylammonium chloride / bromide.

5. The method for the preparation of anode intercalation layer based transition metal halide nanorolls according to claim 1, wherein, The concentration of the salt in the electrolyte of the anode intercalation electrolyte is 0.001~0.1 mol / L.

6. The method for the preparation of anode intercalation layer based transition metal halide nanorolls according to claim 1, wherein, In step (2), the solvent of the anode intercalation electrolyte is at least one of propylene carbonate, N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile and N-methyl pyrrolidone.

7. The method for the preparation of anode intercalation layer based transition metal halide nanorolls according to claim 1, wherein, In step (3), the intercalation swelling time of the M3X8 and M3QX7 single crystals is 0.5~5 h.

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