An apparatus and method for preparing Ti3O5 powder materials

Abstract

This application discloses an apparatus and method for preparing Ti3O5 powder materials. Belonging to the field of oxide functional powder material preparation technology, the method utilizes TiO2 powder as raw material, sodium chloride-potassium chloride-calcium chloride as electrolyte, zinc and / or tin as cathode, and a graphite rod as anode. A sandwich-type electrolysis system of "zinc-tin-TiO2 powder-chloride salt" is constructed through density differences to directly electrolyze TiO2 powder to prepare Ti3O5 powder materials. This apparatus and method significantly shorten the traditional Ti3O5 powder material preparation process, and the zinc-tin cathode and electrolyte can be reused, greatly reducing costs. The electrolysis process involves few side reactions, is environmentally friendly, and emits no harmful substances, resulting in high-purity Ti3O5 powder materials.

Description

Technical Field

[0001] This application relates to the field of oxide functional powder material preparation, and to a method and apparatus for preparing titanium pentoxide (Ti3O5) powder material using low-cost titanium dioxide (TiO2), and particularly to an apparatus and method for preparing Ti3O5 powder material. Background Technology

[0002] Ti3O5 is a metal oxide with unique phase transition properties and a melting point as high as 2180℃. As a novel phase transition material, Ti3O5 undergoes a bistable metal-semiconductor phase transition when exposed to external stimuli such as light, heat, pressure, and electric current. This phase transition process is accompanied by changes in the material's physical properties, such as electrical conductivity and magnetic properties, as well as the absorption and release of energy. In the field of data storage, this phase transition characteristic makes Ti3O5 suitable for developing high-density, fast-response data storage devices, potentially increasing data storage capacity and read / write speeds. In thermal storage, its energy absorption and release characteristics can be used to develop efficient thermal storage materials, improving energy utilization efficiency. In the field of optoelectronic devices, Ti3O5's photoelectric properties give it potential applications in photoelectric conversion and photodetection, enabling the manufacture of high-performance optoelectronic devices. Furthermore, in the field of vacuum deposition, Ti3O5 is a high-refractive-index material for visible and infrared spectroscopy, and can be used to deposit Ti3O5 thin films in optical deposition, supporting the performance improvement of optical devices.

[0003] Currently, the preparation methods for Ti3O5 have many limitations. Early methods involved preparing λ-Ti3O5 powder by high-temperature sintering and reducing nano-titanium dioxide powder; however, this method is costly, dangerous, complex, and has low yield and efficiency. For example, patent CN111217390B provides a method for preparing λ-Ti3O5 powder, including: adding tetrabutyl titanate or propyl titanate to anhydrous ethanol under heating conditions, continuously stirring until uniformly mixed to obtain a first mixture; adding polyethylene glycol to the first mixture and continuously stirring until uniformly mixed to obtain a second mixture; drying the second mixture to obtain a gel; sintering the gel at 1050℃~1100℃ for 2 hours~6 hours under an inert atmosphere, then cooling it to room temperature in air, and grinding it to obtain λ-Ti3O5 powder. This patented method involves high-temperature sintering and other operations, which are costly and dangerous. Another method for preparing λ-Ti3O5 powder is the carbothermal reduction method, but this method requires coating the surface of nano-titanium dioxide with an inorganic material, which is cumbersome and costly. Patent CN104973622B provides a method for preparing the photoinduced phase change storage material λ-Ti3O5. It uses nano-TiO2 powder with a particle size of less than 100nm, which has been pretreated with an aluminate or zirconate coupling agent, as raw material. After being evenly dispersed with a carbonaceous reducing agent in a mixed medium, the powder is dried to obtain a mixed powder. The mixed powder is then pressed into a block and reduced at a high temperature of 900-1250℃ for 0.5-6 hours under a nitrogen or argon atmosphere, and then cooled to room temperature.

[0004] These existing preparation methods are insufficient to meet the market demand for large-scale, high-quality Ti3O5 powder. On the one hand, high costs limit the widespread application of Ti3O5 powder, especially in cost-sensitive fields; on the other hand, complex processes and low yields result in unstable supply of Ti3O5 powder, making it difficult to meet the ever-growing market demand. Therefore, there is a need to find a safer, more reliable, simpler, lower-cost, and more efficient method to prepare Ti3O5 powder. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this application is to provide an apparatus and method for preparing Ti3O5 powder materials.

[0006] This application uses TiO2 powder as raw material, sodium chloride-potassium chloride-calcium chloride as electrolyte, and zinc and tin as cathodes. It constructs a "sandwich" electrolysis device system of "zinc-tin-TiO2 powder-chloride salt" through density differences, thereby directly electrolyzing TiO2 powder to prepare Ti3O5 powder materials. This application significantly shortens the traditional Ti3O5 powder material preparation process, and the zinc-tin and chloride salt materials can be reused, greatly reducing costs. The electrolysis process has few side reactions, is environmentally friendly, and emits no harmful substances, resulting in high-purity Ti3O5 powder materials.

[0007] This application provides the following technical solution:

[0008] The technical solution of this application provides a method for preparing Ti3O5 powder material. This method is based on a "sandwich" type electrolysis device and includes the following steps:

[0009] (a) Zinc granules and tin granules are evenly placed at the bottom of the container of the electrolysis device as a zinc-tin layer; TiO2 powder is placed above the zinc-tin layer as a raw material layer; sodium chloride, potassium chloride and calcium chloride are evenly mixed and placed above the raw material layer as a chloride salt layer, thereby obtaining a three-layer system of "zinc-tin-TiO2 powder-chloride salt";

[0010] (b) After sealing the container described in step (a) with a container lid, introduce inert gas for protection, and heat the “zinc tin-TiO2 powder-chloride salt” system to the target temperature;

[0011] (c) When the “zinc-tin-TiO2 powder-chloride” three-layer system is in a molten state, insert a graphite rod into the container through the hole in the container lid and place it in the chloride layer as the anode; insert a molybdenum wire into the zinc-tin layer through the hole in the side wall of the container and place it in the zinc-tin layer, where the zinc-tin layer serves as the cathode and the molybdenum wire is used for conduction; connect a power source between the graphite rod and the molybdenum wire, turn on the power source, apply a voltage between the cathode and the anode to perform electrolysis, and obtain the electrolysis product;

[0012] (d) Take the electrolytic product obtained in step (c) out of the container, separate the solidified chloride salt layer and zinc tin layer to obtain the raw material powder product, wash the powder product with hydrochloric acid and deionized water in sequence, and dry it to finally obtain the Ti3O5 powder material.

[0013] Furthermore, the "sandwich" type electrolysis device includes:

[0014] The container and its lid, both of which can be sealed and used for the reaction;

[0015] The air inlet and air outlet pipes are connected to the interior of the container through the container lid;

[0016] A graphite rod, a molybdenum wire, and a power supply are provided; the graphite rod serves as the anode of the electrolytic reaction, and the molybdenum wire serves as a conductive wire connecting the cathode and the anode; one end of the graphite rod and the molybdenum wire are placed inside the container, and the other end is placed outside the container, and connected to the positive and negative terminals of the power supply, respectively.

[0017] A heating wire is coiled around the perimeter of the container to heat and melt the chloride layer, raw material layer, and zinc-tin layer inside the container.

[0018] Furthermore, valves are respectively installed on the inlet pipe and the outlet pipe; the valves are kept open during the reaction to allow protective gas to flow in;

[0019] Furthermore, the container lid is provided with a hole for a graphite rod to pass through; the container sidewall is provided with a hole for a molybdenum wire to pass through; and sealing gaskets are provided at the above holes to maintain a tight seal.

[0020] Furthermore, the container is made of quartz or corundum; the shape of the container is not specifically limited, and can preferably be any one of cylindrical, cuboid or spherical, as long as various materials can fill the container after heating and melting to form a stable three-layer structure of "zinc tin-TiO2 powder-chloride".

[0021] Furthermore, the outside of the intake pipe is connected to an inert gas generator;

[0022] Furthermore, the heating wire is connected to a heating power source.

[0023] Further, in step (a), the mass fraction ratio between zinc granules and tin granules is (0-99%):(0-99%), and the sum of their mass fractions is 100%; the preferred mass fraction ratio is (1:1) to (3:1), more preferably 1:1 or 3:1; in the chloride salt layer in step (a), the mass fraction ratio between sodium chloride, potassium chloride, and calcium chloride is (0-99%):(0-99%):(0-99%), and the sum of their mass fractions is 100%.

[0024] Further, the mass fraction ratio of the three layers of materials in step (a) is (1-99%):(1-99%):(1-99%), and the sum of the mass fractions of the three is 100%.

[0025] Further, the inert gas in step (b) is preferably nitrogen or argon; the target temperature in step (b) is 550–850°C;

[0026] Further, the voltage in step (c) is 1.0 to 3.0V; the electrolysis time in step (c) is 5 to 20 hours;

[0027] Furthermore, the chloride salt layer and zinc-tin layer obtained in step (d) are used in steps (a) to (c) to achieve their recycling.

[0028] Compared with the prior art, this application has the following features and advantages:

[0029] 1. This application employs a unique "zinc-tin-TiO2 powder-chloride salt" sandwich-type electrolysis device structure. By constructing a three-layer electrolysis reaction system through density differences, it differs from traditional complex preparation processes, providing a completely new approach and method for the preparation of Ti3O5 powder materials. This specific structural design facilitates effective reactions between substances during electrolysis, improving reaction efficiency and targeting.

[0030] 2. Using TiO2 powder as raw material, sodium chloride-potassium chloride-calcium chloride as electrolyte, and zinc and tin as cathode, this carefully designed combination of raw materials and electrolyte can fully utilize the characteristics of each substance to achieve efficient conversion of TiO2 powder to Ti3O5 powder material during electrolysis. The process is simple, the flow is short, the product morphology is controllable, and the added value is high, making it suitable for industrial production.

[0031] 3. The device provided in this application has an externally connected cathode, which facilitates the disassembly and assembly of the structure and avoids direct contact between the cathode and the two layers of material above it. In the prior art, some devices use several stacked containers to hold materials, which is relatively complex. This application simplifies the structure by using an externally connected cathode. Attached Figure Description

[0032] Figure 1 This application provides a schematic diagram of an apparatus for preparing Ti3O5 powder material in Example 1;

[0033] Figure 2 X-ray diffraction pattern of Ti3O5 powder material prepared in Example 1 of this application;

[0034] Figure 3 SEM images of fibrous Ti3O5 powder material prepared in Example 2 of this application;

[0035] Figure 4 Macroscopic photographs of the Ti3O5 powder material prepared in Example 3 of this application;

[0036] Figure label:

[0037] 1. Container, 2. Container lid, 3. Inlet pipe, 4. Outlet pipe, 5. Graphite rod, 6. Heating wire, 7. Molybdenum wire, 8. Chloride layer, 9. Raw material layer, 10. Zinc-tin layer, 11. Power supply. Detailed Implementation

[0038] To enable those skilled in the art to better understand the technical solutions of this application, the following detailed description is provided in conjunction with specific embodiments. It should be noted that the following embodiments will help those skilled in the art to further understand this application, but do not limit this application in any way. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of this application. These all fall within the protection scope of this application.

[0039] All raw materials used in this application are not subject to any particular restriction on their source; they may be purchased from the market or prepared using conventional methods known to those skilled in the art.

[0040] The following embodiments are all based on a "sandwich" type electrolysis device, which is a sealed electrolysis device. The main body consists of a container 1 and a container cover 2, which are sealed together and used for reaction. During the reaction, the material inside the container 1 forms a stable three-layer structure of "zinc tin-TiO2 powder-chloride salt" from bottom to top, namely zinc tin layer 10-raw material layer 9-chloride salt layer 8, and is in a molten state.

[0041] The container lid 2 has three holes for connecting the inlet pipe 3, the outlet pipe 4, and the graphite rod 5, respectively. The side wall of the container 1 has one hole for connecting the molybdenum wire 7. One end of the graphite rod 5 is inserted into the chloride layer 8, and one end of the molybdenum wire 7 is inserted into the zinc-tin layer 10. The other ends of the graphite rod 5 and the molybdenum wire 7 are located outside the container 1 and connected to the positive and negative terminals of the power supply 11, respectively. In the reaction system, the chloride layer 8 serves as the electrolyte, the graphite rod 5 as the anode, and the zinc-tin layer 10 as the cathode.

[0042] Heating wire 6 is coiled around the periphery of the container 1 and connected to a heating power source to heat and melt the chloride salt layer 8, raw material layer 9, and zinc-tin layer 10 inside the container 1.

[0043] Example 1:

[0044] (a) Using a quartz crucible with an inner diameter of 6 cm as container 1, place 100 g of zinc granules and 100 g of tin granules at the bottom of the quartz crucible, add 50 g of TiO2 powder, and then add a mixed salt of sodium chloride (50 g), potassium chloride (50 g), and calcium chloride (550 g).

[0045] (b) Turn on the heating power to activate heating wire 6, and introduce high-purity nitrogen gas to raise the temperature to 750°C for protection. Due to the density effect of each component, a distinct three-layer structure of "zinc-tin-TiO2 powder-chloride salt" will be formed, such as... Figure 1 As shown.

[0046] (c) A graphite rod 5 is inserted into molten sodium chloride-potassium chloride-calcium chloride as an anode, and a molybdenum wire 7 is connected to a liquid zinc-tin layer 10 outside the crucible as a cathode. A constant voltage of 2.0V is applied to the anode and cathode for 10 hours to electrolyze and obtain the electrolysis product.

[0047] (d) The cooled crucible was then removed, and the solidified zinc-tin layer 10 and chloride layer 8 were removed to obtain the powder product. The powder product was washed with dilute hydrochloric acid and deionized water to obtain the final Ti3O5 product, the X-ray diffraction pattern of which is shown below. Figure 2 As shown, it exhibits obvious single-phase characteristic peaks of Ti3O5. This fully demonstrates that the method and apparatus proposed in this application can effectively prepare Ti3O5 powder materials.

[0048] Example 2:

[0049] (a) Using an 8 cm inner diameter corundum crucible as a container, place 150 g of zinc granules and 50 g of tin granules at the bottom of the corundum crucible, add 60 g of TiO2 powder (microscopic morphology is fibrous), and then add a mixed salt of sodium chloride (300 g), potassium chloride (50 g), and calcium chloride (250 g).

[0050] (b) Turn on the heating power supply to make the heating wire 6 work, introduce high-purity argon gas to protect the temperature to 600℃ and keep it at that temperature to form a distinct three-layer structure of “zinc tin-TiO2 powder-chloride salt”.

[0051] (c) A graphite rod 5 is inserted into molten sodium chloride-potassium chloride-calcium chloride as an anode, and a molybdenum wire 7 is connected to a liquid zinc-tin layer 10 outside the crucible as a cathode. A constant voltage of 2.2V is applied to the anode and cathode for 15 hours to electrolyze and obtain the electrolysis product.

[0052] (d) The cooled crucible was then removed, and the solidified zinc-tin layer 10 and chloride salt layer 8 were removed to obtain the powder product. The powder product was washed with dilute hydrochloric acid and deionized water to obtain the final Ti3O5 product, the microstructure of which is as follows. Figure 3 As shown, it exhibits a typical fibrous morphology, consistent with the microstructure of the raw material. This fully demonstrates that the method and apparatus proposed in this application can effectively design and prepare Ti3O5 powder materials with special morphologies.

[0053] Example 3: Repeating the melting and electrolysis process twice

[0054] (a) Using a corundum crucible with an inner diameter of 5 cm as a container, place 100 g of zinc granules and 100 g of tin granules at the bottom of the corundum crucible, add 30 g of TiO2 powder, and then add a mixed salt of sodium chloride (100 g), potassium chloride (100 g), and calcium chloride (100 g).

[0055] (b) Turn on the heating power supply to make the heating wire 6 work, introduce high-purity nitrogen gas to protect the temperature to 650°C and keep it at that temperature to form a distinct three-layer structure of “zinc tin-TiO2 powder-chloride salt”.

[0056] (c) A graphite rod 5 is inserted into molten sodium chloride-potassium chloride-calcium chloride as an anode, and a molybdenum wire 7 is connected to a liquid zinc-tin layer 10 outside the crucible as a cathode. A constant voltage of 2.5V is applied to the anode and cathode for 10 hours to electrolyze and obtain the electrolysis product.

[0057] (d) The cooled crucible was then removed, and the solidified zinc-tin layer 10 and chloride salt layer 8 were removed to obtain the powder product. The powder product was washed with dilute hydrochloric acid and deionized water to obtain the first batch of Ti3O5 product.

[0058] (e) Place the collected solidified zinc-tin layer 10 back into a corundum crucible with a diameter of 5 cm, add 30 g of TiO2 powder, and then add the collected solidified chloride salt layer 8.

[0059] (f) Turn on the heating power supply to activate heating wire 6, introduce high-purity nitrogen gas for protection, raise the temperature to 650℃ and hold, continuing the formation of the "zinc-tin-TiO2 powder-chloride salt" three-layer structure. Repeat steps (c) to (d) to obtain the second batch of Ti3O5 product.

[0060] This embodiment achieves continuous Ti3O5 production through repeated electrolysis. The macroscopic morphology of the Ti3O5 products obtained in the first and second batches is as follows: Figure 4 As shown, they all exhibit typical blue-black characteristics. This fully demonstrates that the method and apparatus proposed in this application can effectively and continuously produce Ti3O5 powder materials.

[0061] In summary, based on the significant application value of Ti3O5 powder materials and the problems existing in current preparation techniques, this application proposes a novel preparation method and apparatus, aiming to promote the research and application development of Ti3O5 powder materials. By reducing production costs, improving production efficiency and product quality, it provides strong support for the large-scale application of Ti3O5 powder.

[0062] The research findings of this application will help promote the application and development of Ti3O5 in fields such as data storage, thermal storage, optoelectronic devices, and vacuum coating, providing new impetus for technological progress and industrial upgrading in related industries. At the same time, the successful implementation of this application's technology will also provide valuable reference for the preparation of other metal oxide powders, promoting the overall development of the metal oxide materials field.

[0063] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, this application is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of this application without departing from the scope of this application should be within the protection scope of this application.

Claims

1. A method for preparing Ti3O5 powder material, characterized in that, This method is based on a "sandwich" type electrolysis device and includes the following steps: (a) Zinc granules and tin granules are evenly placed at the bottom of the container (1) of the electrolysis device as a zinc-tin layer (10); TiO2 powder is placed above the zinc-tin layer (10) as a raw material layer (9); sodium chloride, potassium chloride and calcium chloride are evenly mixed and placed above the raw material layer (9) as a chloride salt layer (8), thereby obtaining a "zinc-tin-TiO2 powder-chloride salt" three-layer system; (b) After sealing the container (1) described in step (a) with the container lid (2), introduce inert gas for protection, and heat the "zinc tin-TiO2 powder-chloride salt" system to the target temperature; (c) When the "zinc-tin-TiO2 powder-chloride" three-layer system is in a molten state, insert the graphite rod (5) into the container (1) through the hole on the container lid (2) and place it in the chloride layer (8) as the anode; insert the molybdenum wire (7) through the hole on the side wall of the container (1) and place it in the zinc-tin layer (10), where the zinc-tin layer (10) serves as the cathode and the molybdenum wire (7) is used for conduction; connect a power source between the graphite rod (5) and the molybdenum wire (7), turn on the power source, apply a voltage between the cathode and the anode to perform electrolysis, and obtain the electrolysis product; (d) Take the electrolytic product obtained in step (c) out of the container (1), separate the solidified chloride salt layer (8) and zinc tin layer (10), and obtain the powder product of the raw material layer (9). After cleaning and drying the powder product, the Ti3O5 powder material is finally obtained.

2. The method for preparing Ti3O5 powder material according to claim 1, characterized in that, The "sandwich" type electrolysis device includes the following structure: A container (1) and a container lid (2), both sealed and used for the reaction; the container (1) is made of quartz or corundum; The air inlet pipe (3) and the air outlet pipe (4) are connected to the interior of the container (1) through the container cap (2); Graphite rod (5), molybdenum wire (7), power supply (11); the graphite rod (5) serves as the anode of the electrolytic reaction, and the molybdenum wire (7) serves as the conductive wire connecting the cathode and the anode; one end of the graphite rod (5) and the molybdenum wire (7) are placed inside the container (1), and the other end is placed outside the container (1), and are respectively connected to the positive and negative terminals of the power supply (11); A heating wire (6) is coiled around the periphery of the container (1) for heating.

3. The method for preparing Ti3O5 powder material according to claim 2, characterized in that, Valves are respectively installed on the air inlet pipe (3) and the air outlet pipe (4); The container lid (2) is provided with a hole for passing through the graphite rod (5); the side wall of the container (1) is provided with a hole for passing through the molybdenum wire (7); sealing gaskets are provided at these holes to maintain a tight seal.

4. The method for preparing Ti3O5 powder material according to claim 2, characterized in that, The air inlet pipe (3) is connected to an inert gas generator; the heating wire (6) is connected to a heating power source.

5. The method for preparing Ti3O5 powder material according to claim 1, characterized in that, The mass fraction ratio between zinc granules and tin granules in step (a) is (0-99%):(0-99%), and the sum of their mass fractions is 100%.

6. The method for preparing Ti3O5 powder material according to claim 1, characterized in that, In the chloride layer (8) described in step (a), the mass fraction ratio of sodium chloride, potassium chloride and calcium chloride is (0-99%):(0-99%):(0-99%), and the sum of the mass fractions of the three is 100%.

7. The method for preparing Ti3O5 powder material according to claim 1, characterized in that, The mass fraction ratio of the three layers of materials in step (a), namely zinc-tin layer (10), raw material layer (9) and chloride salt layer (8), is (1-99%):(1-99%):(1-99%), and the sum of the mass fractions of the three is 100%.

8. The method for preparing Ti3O5 powder material according to claim 1, characterized in that, The inert gas in step (b) is nitrogen or argon; the target temperature in step (b) is 550–850°C.

9. The method for preparing Ti3O5 powder material according to claim 1, characterized in that, The voltage in step (c) is 1.0 to 3.0V; the electrolysis time in step (c) is 5 to 20 hours.

10. The method for preparing Ti3O5 powder material according to claim 1, characterized in that, The chloride layer (8) and zinc-tin layer (10) obtained in step (d) are used in steps (a) to (c) for recycling.

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