A device for large-scale continuous preparation of black phosphorus crystals

Abstract

This application discloses a large-scale continuous preparation device for black phosphorus crystals, relating to the field of elemental phosphorus material preparation technology. It solves the problem that existing black phosphorus crystal growth processes can only produce gram-level batches, making large-scale mass production impossible. The device includes a traction motor, a chain drive mechanism, a box furnace, and multiple reaction vessels; the reaction vessels contain the raw materials to be reacted; the chain drive mechanism includes a traction chain, a drive sprocket, and a transmission sprocket; the traction chain is tensioned between the drive sprocket and the transmission sprocket; the output end of the traction motor is connected to the drive sprocket; the traction motor can drive the traction chain at a uniform speed; multiple reaction vessels are equidistantly arranged along the extension direction of the traction chain; the traction chain passes through the box furnace from left to right; the box furnace has a heating zone, a holding zone, and a cooling zone arranged sequentially from left to right. This application aims to improve the performance of black phosphorus crystal preparation devices.

Description

Technical Field

[0001] This application relates to the field of elemental phosphorus material preparation technology, and in particular to a device for large-scale continuous preparation of black phosphorus crystals. Background Technology

[0002] With the development of science and technology and the improvement of people's living standards, modern society has an increasing demand for portable electronic devices, electric vehicles, and renewable energy storage systems. These applications place higher demands on the energy density and charging speed of lithium-ion batteries. Black phosphorus has high conductivity (3S / cm), a low lithium-ion diffusion barrier (0.08eV, compared to 0.58eV for Si), and a very high theoretical specific capacity (2596mAh / g), thus showing potential as a high-energy-density and high-rate anode material. Since research began in 2007, phosphorus-carbon anode materials have achieved high-rate (13A / g) and long-cycle (2000 cycles) performance.

[0003] With ongoing research, breakthroughs have been made in black phosphorus crystal growth technology. The development from the initial high-pressure white phosphorus conversion method and mercury catalysis method to the relatively mature vacuum chemical vapor deposition method has been a long process. Chinese patent "A Method for Preparing Orthorhombic Black Phosphorus Single Crystals" (Publication No.: CN105133009A) discloses a method for preparing orthorhombic black phosphorus single crystals. This method divides the reactor into two interconnected regions. Red phosphorus raw material, metallic tin, and iodine are placed in the first region, while the second region is used to generate and collect orthorhombic black phosphorus single crystals. The temperatures of the first and second regions are precisely controlled at 550-800℃ and 400-700℃, respectively, with the temperature of the first region required to be 80-150℃ higher than that of the second region. Orthorhombic black phosphorus is then obtained through programmed heating and cooling, but the yield is only in the 1g range. Chinese patent "A Method for Preparing High-Purity Black Phosphorus" (Publication No.: CN108059138A) discloses a method for preparing high-purity black phosphorus. The method involves encapsulating a red phosphorus precursor and a small amount of black phosphorus seed crystals on both sides of a vacuum tube. The tube furnace is first heated to 500-650°C, and then the red phosphorus end of the quartz tube is quickly placed in the high-temperature zone of the tube furnace and kept at that temperature for 2-200 hours. Subsequently, the temperature is lowered to 200°C and allowed to cool naturally to room temperature, thus producing large blocks of high-purity black phosphorus.

[0004] The aforementioned publicly disclosed black phosphorus crystal growth process only produces gram-level yields per batch, resulting in high production costs and low capacity. This severely limits its application in fast-charging phosphorus-carbon anode materials, and there are currently no reports of large-scale black phosphorus crystal production. Therefore, developing a process that enables large-scale black phosphorus crystal growth, achieving ton-level and thousand-ton-level production per batch, is of great significance for reducing the production cost of black phosphorus crystals, increasing the global production capacity of high-purity black phosphorus, and accelerating the marketization of fast-charging phosphorus-carbon anode materials. Summary of the Invention

[0005] The embodiments of this application provide a large-scale continuous preparation device for black phosphorus crystals, which solves the problem that the existing black phosphorus crystal growth process can only produce gram-level quantities per batch and cannot be mass-produced.

[0006] To achieve the above objectives, embodiments of this application provide a large-scale continuous preparation apparatus for black phosphorus crystals, including a traction motor, a chain drive mechanism, a box furnace, and multiple reaction vessels; the reaction vessels contain raw materials to be reacted; the chain drive mechanism includes a traction chain, a drive sprocket, and a transmission sprocket; the traction chain is tensioned between the drive sprocket and the transmission sprocket; the output end of the traction motor is connected to the drive sprocket; the traction motor can drive the traction chain to transmit at a uniform speed; the multiple reaction vessels are equidistantly arranged along the extension direction of the traction chain; the traction chain passes through the box furnace from left to right; the box furnace is provided with a heating zone, a heat preservation zone, and a cooling zone from left to right.

[0007] Furthermore, the reactor is fastened to the traction chain by snap-fit.

[0008] Furthermore, the reactor is a cylindrical sealed reactor with a diameter of 50-100cm and a length of 50-200cm; the distance between two adjacent reactors is 40cm.

[0009] Furthermore, the length of the heating zone is equal to the length of the cooling zone; the lengths of the heating zone and the cooling zone are less than the length of the insulation zone.

[0010] Furthermore, the insulation zone includes a first side and a second side; the second side is located close to the cooling zone; the temperature of the first side is higher than the temperature of the second side.

[0011] Furthermore, both the first side and the second side of the insulation zone are set to constant temperature.

[0012] Furthermore, the temperature gradient of the heating zone is set to 1-100℃ / m; the temperature gradient of the cooling zone is set to 10-50℃ / m; the temperature on the first side of the insulation zone is set to 500-550℃; and the temperature on the second side of the insulation zone is set to 460-530℃.

[0013] Furthermore, both the box furnace and the reactor are horizontal; the first side of the insulation zone is located to the left of the second side of the insulation zone; or, both the box furnace and the reactor are vertical; the first side of the insulation zone is located below the second side of the insulation zone; or, both the box furnace and the reactor are horizontal-vertical hybrid types with an L-shaped structure; the first side of the insulation zone is located to the left of the second side of the insulation zone.

[0014] Furthermore, the stepping speed of the traction chain is 0.5-6 m / h.

[0015] Furthermore, the raw material to be reacted is positioned near one end of the reactor.

[0016] This application has the following advantages over the prior art:

[0017] The large-scale continuous preparation device for black phosphorus crystals in this application arranges multiple reaction vessels sequentially on a traction chain driven at a uniform speed. Each reaction vessel is then conveyed to a box furnace via the traction chain. The raw materials to be reacted in the reaction vessels pass through a heating zone, a holding zone, and a cooling zone in the box furnace. That is, the raw materials undergo heating-holding-cooling in the box furnace. After the reaction is completed, the reaction vessel containing the reaction products is output. Thus, it is possible to process kilogram-level raw materials from a single reaction vessel, and the daily output of black phosphorus can reach the ton level, realizing the large-scale production of black phosphorus and reducing the production cost of black phosphorus in the market. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0019] Figure 1 This is a schematic diagram of the structure of the black phosphorus crystal large-scale continuous preparation device according to an embodiment of this application;

[0020] Figure 2 This is a schematic diagram of the temperature zones of the box furnace used in the apparatus for the large-scale continuous preparation of black phosphorus crystals according to this application.

[0021] Figure 3 This is a schematic cross-sectional view showing the arrangement of a horizontal box furnace and a horizontal reactor;

[0022] Figure 4 This is a schematic cross-sectional view showing the arrangement of a vertical box furnace and a vertical reactor;

[0023] Figure 5 This is a schematic cross-sectional view showing the arrangement of a horizontal-vertical mixing box furnace and a horizontal-vertical mixing reactor. Detailed Implementation

[0024] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0025] In the description of this application, it should be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this application.

[0026] In the description of this application, it should be noted that, unless otherwise expressly specified and limited, the terms "installation", "connection" and "joining" should be interpreted broadly, for example, they can refer to fixed connections, detachable connections, or integral connections; those skilled in the art can understand the specific meaning of the above terms in this application based on the specific circumstances.

[0027] The terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" can explicitly or implicitly include one or more of that feature. In the description of this application, unless otherwise stated, "a plurality of" means two or more.

[0028] Example 1:

[0029] Reference Figures 1 to 3 This application provides an apparatus for the large-scale continuous preparation of black phosphorus crystals, including a traction motor 1, a chain drive mechanism 2, multiple reaction vessels 3, and a box furnace 4. The box furnace 4 is a horizontal box furnace, and the reaction vessels 3 are horizontal reaction vessels.

[0030] The chain drive mechanism 2 includes a traction chain 21, a drive sprocket (not shown in the figure), and a transmission sprocket (not shown in the figure). The traction chain 21 is tensioned between the drive sprocket and the transmission sprocket. The output end of the traction motor 3 is connected to the drive sprocket, and the fixed end of the traction motor 1 is fixed to the ground or a mounting platform. The shafts of both the drive sprocket and the transmission sprocket are supported on the ground or a mounting platform. The left side of the traction chain 21 is the loading area 211, and the right side is the unloading area 212. It should be noted that the traction chain 21 has a longitudinal section on the left side. The inclined part in the figure is only schematic to indicate that the chain has a bend from the longitudinal to the transverse direction. A smooth line can also be used to represent the bend here.

[0031] Multiple reactors 3 are fastened to the traction chain 21 by snap-fit, and are arranged along the extension direction of the traction chain 21. The distance between two adjacent reactors 3 is 40cm, ensuring that there is one reactor 3 per meter. In the feeding area 211, a total of 50 kg of red phosphorus and catalyst is added to each reactor 3 according to the specified ratio. The raw materials to be reacted are fed into one end of the reactor 3.

[0032] Reactor 3 is made of stainless steel. It is a cylindrical, sealed reactor with a diameter of 60cm and a length of 120cm. After the traction motor 1 starts, it drives the traction chain 21 at a constant speed of 2m / h. Therefore, reactor 3 will not experience significant vibration during the entire transport process.

[0033] Reference Figure 2 The box furnace 4 is mounted on the traction chain 21, which passes through the box furnace 4 from left to right. The length of the box furnace 4 is 72m. It should be noted that the portion of the traction chain 2 that transmits power from left to right is inside the box furnace 4, while the portion that transmits power from right to left is outside the box furnace 4.

[0034] The furnace 4 contains, from left to right, a heating zone 41, a heat preservation zone 42, and a cooling zone 43. The heat preservation zone 42 includes a first side 421 and a second side 422. The first side 421 and the second side 422 are separated by the reactor 3. The first side 421 is located to the left of the second side 422. Both the first side 421 and the second side 422 are kept at a constant temperature, with the temperature of the first side 421 being higher than that of the second side 422.

[0035] Specifically, the temperature gradient of the heating zone 41 is set to 12℃ / m, the temperature gradient of the cooling zone 43 is set to 15℃ / m, the temperature of the first side 421 of the insulation zone is set to 500℃, and the temperature of the second side 422 of the insulation zone is set to 480℃.

[0036] Since the heating and cooling times required in the preparation process are equal, and the holding time is relatively long, the length of the heating zone 41 is equal to the length of the cooling zone 43. The lengths of the heating zone 41 and the cooling zone 43 are less than the length of the holding zone 42. Specifically, the lengths of the heating zone 41 and the cooling zone 43 are both 12m, and the length of the holding zone 42 is 48m.

[0037] The working process of the black phosphorus crystal large-scale continuous preparation device in this embodiment is as follows:

[0038] The reactor 3 is embedded in the traction chain 21 by a snap fastener. In the feeding area 211, red phosphorus and catalyst are added to one side of each reactor 3 according to the ratio.

[0039] Turn on the box furnace 4 and set the temperature gradient of the heating zone 41, the temperature of the first side of the insulation zone 421, the temperature of the second side of the insulation zone 422, and the temperature gradient of the cooling zone 43 respectively.

[0040] After the temperature is set, the traction motor 1 is started. Under the action of the traction motor 1, the traction chain 21 drives the reactor 3 into the box furnace 4 at a constant speed. The material in the reactor 3 is heated, kept warm and cooled in the box furnace 4. After the reaction is completed, the reactor 3 is output from the box furnace 4 under the drive of the traction chain 21. The product of the reaction is unloaded in the unloading area 212.

[0041] Calculations show that the daily output of the black phosphorus crystal large-scale continuous production device in this application embodiment is 2.4 tons, with an annual production capacity of 720 tons based on 300 production days per year. The device provided by this invention achieves a daily black phosphorus output in the ton range, reducing the production cost of black phosphorus in the market.

[0042] Example 2:

[0043] Reference Figure 4 The only difference between Example 2 and Example 1 is that the box furnace 4 is a vertical box furnace, and the first side 421 of the insulation zone is located below the second side 422 of the insulation zone. The reactor 3 is a vertical reactor.

[0044] Example 3:

[0045] Reference Figure 5 The only difference between Example 3 and Example 1 is that the box furnace 4 is an L-shaped horizontal-vertical hybrid box furnace, with the first side 421 of the insulation zone located to the left of the second side 422 of the insulation zone. The reactor 3 is a horizontal-vertical hybrid reactor.

[0046] The above are merely specific embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions within the technical scope disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A device for large-scale continuous preparation of black phosphorus crystals, characterized in that, It includes a traction motor, a chain drive mechanism, a box furnace, and multiple reaction vessels; the reaction vessels contain raw materials to be reacted; the chain drive mechanism includes a traction chain, a drive sprocket, and a transmission sprocket; the traction chain is tensioned between the drive sprocket and the transmission sprocket; the output end of the traction motor is connected to the drive sprocket; the traction motor can drive the traction chain at a uniform speed; multiple reaction vessels are equidistantly arranged along the extension direction of the traction chain; the traction chain passes through the box furnace from left to right; the box furnace is provided with a heating zone, a heat preservation zone, and a cooling zone from left to right.

2. The apparatus for large-scale continuous preparation of black phosphorus crystals according to claim 1, characterized in that, The reactor is attached to the traction chain by snap-fit.

3. The apparatus for large-scale continuous preparation of black phosphorus crystals according to claim 1, characterized in that, The reactor is a cylindrical sealed reactor with a diameter of 50-100cm and a length of 50-200cm; the distance between two adjacent reactors is 40cm.

4. The apparatus for large-scale continuous preparation of black phosphorus crystals according to claim 1, characterized in that, The length of the heating zone is equal to the length of the cooling zone; the lengths of the heating zone and the cooling zone are less than the length of the insulation zone.

5. The apparatus for large-scale continuous preparation of black phosphorus crystals according to claim 1, characterized in that, The insulation zone includes a first side and a second side; the second side is located close to the cooling zone; the temperature of the first side is higher than the temperature of the second side.

6. The apparatus for large-scale continuous preparation of black phosphorus crystals according to claim 5, characterized in that, Both the first and second sides of the insulation zone are set to constant temperature.

7. The apparatus for large-scale continuous preparation of black phosphorus crystals according to claim 5, characterized in that, The temperature gradient of the heating zone is set to 1-100℃ / m; the temperature gradient of the cooling zone is set to 10-50℃ / m; the temperature on the first side of the insulation zone is set to 500-550℃; and the temperature on the second side of the insulation zone is set to 460-530℃.

8. The apparatus for large-scale continuous preparation of black phosphorus crystals according to claim 5, characterized in that... Both the box furnace and the reactor are horizontal; the first side of the insulation zone is located to the left of the second side of the insulation zone; or, Both the box furnace and the reactor are vertical; the first side of the insulation zone is located below the second side of the insulation zone; or, Both the box furnace and the reactor are horizontal-vertical hybrid structures with an L-shaped structure; the first side of the insulation zone is located to the left of the second side of the insulation zone.

9. The apparatus for large-scale continuous preparation of black phosphorus crystals according to claim 1, characterized in that, The stepping speed of the traction chain is 0.5-6 m / h.

10. The apparatus for large-scale continuous preparation of black phosphorus crystals according to claim 1, characterized in that, The raw material to be reacted is positioned near one end of the reactor.

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