A deposition apparatus, system, and method for preparing phosphorus-carbon composite anode materials.

Abstract

This invention discloses a deposition apparatus and system for preparing phosphorus-carbon composite anode materials, relating to the field of lithium battery material technology. Specifically, it includes: a reactor body, a transition chamber, and first and second sealing assemblies; the reactor body and transition chamber are fixedly and sealed together, and each sealing assembly is equipped with a high-temperature valve. The transition chamber is filled with phosphorus-capturing active material. The supporting system includes a high-temperature roller kiln with preheating, high-temperature, and cooling temperature zones. This invention effectively solves the risks of white phosphorus leakage and spontaneous combustion during high-temperature deposition through the rigid seal between the reactor body and the transition chamber, and the physical adsorption and chemical passivation of active copper powder within the transition chamber. This apparatus and system achieve stable kilogram-level production in a single batch, increasing capacity by more than 100 times, reducing unit production costs by more than 60%, and controlling product consistency deviation within 5%, aiming to meet the large-scale mass production needs of power batteries for high-capacity, high-stability anode materials.

Description

Technical Field

[0001] This invention relates to the field of battery materials technology, and in particular to a deposition apparatus, system and method for preparing phosphorus-carbon composite anode materials. Background Technology

[0002] Phosphorus-based electrode materials have a theoretical capacity of up to With abundant reserves and low cost, phosphorus has become a highly promising candidate material for lithium-ion battery anodes. However, phosphorus materials have inherent drawbacks such as poor conductivity and significant volume expansion during charge and discharge, resulting in extremely rapid capacity decay and short cycle life in practical applications. To improve these shortcomings, the industry currently mainly prepares phosphorus-carbon composite anode materials through deposition methods, but most existing preparation processes are still at the gram-level experimental stage and cannot meet the market's demand for mass production of phosphorus-carbon anode materials. In addition, the risk of white phosphorus vapor leakage and the sealing failure of the reactor under vibration conditions during high-temperature deposition have been difficult to effectively solve.

[0003] Therefore, how to achieve stable kilogram-level mass production and ensure the sealing reliability and safety during the deposition process has become an urgent technical challenge. Summary of the Invention

[0004] The main objective of this invention is to provide a deposition apparatus, system, and method for preparing phosphorus-carbon composite anode materials, aiming to achieve stable kilogram-level mass production and ensure the sealing reliability and safety during the deposition process.

[0005] To achieve the above objectives, the present invention provides a deposition apparatus for preparing phosphorus-carbon composite anode materials, comprising: The vessel body, the transition chamber, and a first sealing assembly and a second sealing assembly for sealing the vessel body and the transition chamber respectively; the vessel body and the transition chamber are fixedly sealed together, and both the first sealing assembly and the second sealing assembly are equipped with high-temperature valves; the interior of the transition chamber is filled with phosphorus capture active material.

[0006] Preferably, the material of the high-temperature valve is... , or titanium alloy Any one of them.

[0007] Preferably, the first sealing assembly includes a first cover that covers the top of the vessel body, a first gasket disposed between the vessel body and the first cover, and a first flange for locking the first cover onto the vessel body; the high-temperature valve includes a first high-temperature needle valve installed at the center of the first cover.

[0008] Preferably, the phosphorus capture active material is active copper powder.

[0009] Preferably, the active copper powder is used to adsorb white phosphorus and reacts with the white phosphorus to form a copper phosphide passivation layer on the surface of the white phosphorus, wherein the molecular formula of the copper phosphide is [insert molecular formula here]. .

[0010] Preferably, the second sealing assembly includes a second cover covering the top of the transition chamber, a second gasket disposed between the transition chamber and the second cover, and a first flange for locking the transition chamber and the second cover; the high-temperature valve further includes a second high-temperature needle valve installed on the second cover.

[0011] Preferably, the vessel body is a container with a seamless bottom connection to the bottom and an open top.

[0012] This application also discloses a deposition system for preparing phosphorus-carbon composite anode materials, comprising: The deposition apparatus for preparing phosphorus-carbon composite anode materials as described above; and A high-temperature roller kiln includes an insulating shell, a transmission device, and preheating, high-temperature, and cooling zones arranged sequentially along the transmission direction of the transmission device; the transmission device is used to load the deposition device to pass through each of the temperature zones sequentially.

[0013] Preferably, the high-temperature roller kiln is provided with a first protective gas inlet and a first protective gas outlet, and the high-temperature roller kiln is provided with multiple first thermocouples distributed in each temperature zone.

[0014] This application also discloses a deposition method for preparing phosphorus-carbon composite anode materials, employing the deposition system for preparing phosphorus-carbon composite anode materials as described above, including the following steps: loading the reactor with a mass percentage of... red phosphorus and The carbon material; the transmission device drives the deposition device to sequentially pass through a preheating zone, a high-temperature zone, and a cooling zone; wherein, the temperature of the preheating zone is controlled at... This converts red phosphorus into white phosphorus vapor; the temperature of the high-temperature zone is controlled at... This allows white phosphorus vapor to enter the pores of the carbon material; the temperature of the cooling zone is controlled at... This causes white phosphorus molecules to revert to red phosphorus within the pores.

[0015] The above technical solution has the following advantages: This application employs a rigid sealing structure consisting of a vessel body, a transition chamber, and sealing components for sealing both, ensuring a fixed, sealed connection between the vessel body and the transition chamber. This guarantees that both components remain relatively stationary during the experiment, effectively preventing loosening of the seals due to equipment vibration. The phosphorus-capturing active material filled inside the transition chamber provides dual protection through physical barrier and chemical stabilization. It not only adsorbs the escaping white phosphorus vapor using its porous mesh structure but also generates stable phosphorus through chemical reactions. A passivation layer is applied to eliminate the risk of spontaneous combustion due to white phosphorus oxidation. Combined with high-temperature valves made of specific high-temperature and corrosion-resistant materials, this device achieves stable deposition of kilogram-level phosphorus-carbon composite anode materials in single batches, increasing production capacity by more than a hundred times compared to traditional gram-level preparation, while ensuring extremely high product consistency and safety. Attached Figure Description

[0016] The present invention will now be described in detail with reference to specific embodiments and accompanying drawings, wherein: Figure 1 This is a schematic diagram of the vessel structure of the deposition apparatus provided in an embodiment of the present invention.

[0017] Figure 2 This is a schematic diagram of the overall structure of the deposition apparatus provided in an embodiment of the present invention.

[0018] Figure 3 This is a schematic diagram of the structure of a high-temperature roller kiln provided in an embodiment of the present invention. Detailed Implementation

[0019] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only for illustration and explanation and are not intended to limit this application. Unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other.

[0020] Example 1 Phosphorus-based electrode materials have high properties With its theoretical capacity and abundant, low-cost resources, phosphorus has become a highly promising candidate material for lithium-ion battery anodes. However, phosphorus materials exhibit poor conductivity and undergo significant volume expansion during charge and discharge, directly leading to rapid capacity decay in practical applications and failing to meet commercial cycle life requirements. Although combining phosphorus with carbon-based supports via vapor deposition can effectively alleviate these problems, current industrial production of phosphorus-carbon composite materials is mostly at the gram-scale experimental stage. The sealing, safety, and production scale of the preparation equipment cannot meet the mass production needs of the power battery industry chain. In particular, the risk of white phosphorus vapor leakage during high-temperature deposition and the sealing failure of the reactor under vibration conditions have always been bottlenecks in the preparation of high-performance phosphorus-carbon anode materials.

[0021] To address the aforementioned technical problems, this embodiment provides a deposition apparatus for preparing phosphorus-carbon composite anode materials, which enables a leap from gram-level small-scale trials to kilogram-level pilot-scale trials. (Refer to...) Figure 1 and Figure 2 The core structure of the deposition apparatus includes a vessel body 1, a transition chamber 6 located on top of the vessel body 1, and a first sealing assembly and a second sealing assembly to ensure the system's airtightness. The vessel body 1 and the transition chamber 6 are connected by a fixed seal, meaning that they are in a relatively static state during the experiment. This rigid connection effectively prevents the seals from loosening due to equipment vibration.

[0022] The vessel body 1 is designed as a container with a seamless bottom connection to the vessel bottom and an open top. This structure improves the structural strength of the vessel body 1, enabling it to withstand pressure differentials under high vacuum conditions. Furthermore, the open design facilitates the loading of large quantities of material and the discharge of finished products. The first sealing component is used to seal the top opening of the vessel body 1, such as... Figure 1 As shown, it specifically includes a first cover 2 that covers the top of the vessel body 1, a first gasket 4 disposed between the vessel body 1 and the first cover 2, and a first flange 3 for locking the first cover 2 onto the vessel body 1. Through the first flange 3 and the bolt and nut assembly, a uniform preload force can be applied to the first gasket 4 to ensure the reliability of the vacuum inside the vessel body 1. A first high-temperature needle valve 5 is installed at the center of the first cover 2. This valve is used to connect a vacuum pump after loading is completed to extract gas from inside the vessel body 1.

[0023] The transition chamber 6 is located above the first cover 2, and its overall structure is referenced. Figure 2 The second sealing assembly seals the top of the transition chamber 6 and includes a second cover 7 that covers the top of the transition chamber 6, a second gasket 9 disposed between the transition chamber 6 and the second cover 7, and a second flange 8 for locking. A second high-temperature needle valve 10 is also installed on the second cover 7 for vacuuming the interior of the transition chamber 6. To cope with the high-temperature deposition environment, the materials of the first high-temperature needle valve 5 and the second high-temperature needle valve 10 are selected as follows: That is, nickel-chromium-iron alloy, or That is, Hastelloy, or titanium alloy. These materials possess extremely excellent high-temperature creep resistance and corrosion resistance. The sealing structure will not leak after being heated at high temperatures, and the valve stem will not deform due to high temperatures, leading to operational failure. The stable passivation film formed on the surface can effectively resist the corrosion of phosphorus vapor, greatly extending the service life of the equipment.

[0024] The innovation of this embodiment lies in the fact that the transition chamber 6 is filled with a phosphorus-capturing active material. Specifically, this phosphorus-capturing active material is active copper powder. The active copper powder forms a dual protection mechanism in the system. Firstly, it acts as a physical barrier; the copper powder particles stack within the transition chamber 6 to form a porous mesh structure, capable of adsorbing white phosphorus vapor that may escape from the first high-temperature needle valve 5. Secondly, it acts as a chemical stabilizer; the copper powder reacts chemically with the white phosphorus, generating a stable copper phosphide passivation layer on its surface. The molecular formula of copper phosphide is... This design ensures that even if a small amount of white phosphorus vapor escapes into the transition chamber 6 under extreme operating conditions, it will not cause oxidation and spontaneous combustion, significantly improving operational safety in kilogram-level production processes.

[0025] This embodiment also relates to a matching deposition system, referring to... Figure 3 The system includes the aforementioned deposition apparatus and a supporting high-temperature atmosphere roller kiln. The high-temperature atmosphere roller kiln includes an insulated outer shell 11 and an internal transmission device 12. The transmission device 12 can carry multiple deposition apparatuses sequentially through different temperature zones within the kiln along its transmission direction. For example... Figure 3 As shown, the interior of the kiln is divided into a preheating zone, a high-temperature zone, and a cooling zone along the material travel direction, and is equipped with heating rods 13 for the preheating section, 14 for the high-temperature section, and 15 for the cooling section, respectively. Multiple first thermocouples 16 are installed inside the kiln for real-time monitoring of the accurate temperature of each zone. Simultaneously, high-purity nitrogen or high-purity argon is introduced through the first protective gas inlet 17 and led out through the first protective gas outlet 18, ensuring that the oxygen content inside the kiln is less than [a certain value]. In an inert atmosphere, the risk of phosphorus combustion and explosion is completely eliminated.

[0026] In actual production, 50% to 70% by mass of red phosphorus and 30% to 50% carbon material, such as porous carbon, graphite, hard carbon, or carbon nanotubes, are first loaded into the vessel 1. The vessel 1 and the transition chamber 6 are then evacuated to a vacuum state. Subsequently, the deposition device is driven into the kiln via the transmission device 12. The temperature of the preheating zone is precisely controlled at... to Within this temperature range, the solid red phosphorus inside vessel 1 begins to sublimate and transform into white phosphorus vapor. When the apparatus enters the high-temperature zone, the temperature is controlled at... to The high temperature increases the kinetic energy of the white phosphorus vapor, allowing it to fully and uniformly penetrate into the micron- or nano-sized pores of the carbon material, achieving atomic-level loading. Finally, the device enters the cooling zone, where the temperature is controlled at... to During this process, white phosphorus molecules are cooled and slowly revert to chemically more stable red phosphorus within the pores of the carbon material, ultimately forming a high-performance phosphorus-carbon composite anode material. The operating speed of the transmission device 12 is controlled at... to Between these points, to ensure the adequacy of the deposition process.

[0027] Using the apparatus and system described in this embodiment, stable production of kilogram-level phosphorus-carbon composite anode materials can be achieved in a single batch, increasing production capacity by more than 100 times compared to traditional gram-level laboratory equipment. Due to the precise control of temperature and vacuum during the vapor deposition process, product consistency deviation can be controlled within 5%. In large-scale production, the production cost per unit mass of phosphorus-carbon composite material is reduced by more than 60%, and the overall energy consumption is reduced by more than 20% compared to the industry average. Experimental characterization shows that the prepared phosphorus-carbon composite anode material has a stable initial discharge specific capacity of [missing information]. The above, in After 100 cycles at high rate, the capacity retention is greater than or equal to 95%, demonstrating excellent electrochemical stability and promising prospects for industrial application.

[0028] Example 2 Building upon Example 1, this example further defines the proportions of each component in the phosphorus-carbon composite anode material and the microstructural parameters of the carbon material to achieve an optimal balance between energy density and cycle performance through precise material control. In the preparation of high-performance phosphorus-carbon composite anode materials, the choice of carbon support plays a decisive role in suppressing volume expansion of the final product. In this example, the carbon material loaded in the reactor 1 can be flexibly replaced according to requirements, such as graphite, carbon nanotubes, porous carbon, or fibrous carbon, to meet the diverse needs of high capacity, high rate, or long cycle life in different application scenarios.

[0029] When porous carbon is selected as the support, in order to ensure that phosphorus vapor can be fully deposited and form a stable supported structure, the average particle size of the porous carbon is as follows: Preferred calculation to Furthermore, to provide sufficient space for the volume expansion of phosphorus during charging and discharging, the microporosity of the porous carbon was set between 60% and 90%, and the average pore size of the porous carbon was controlled within a certain range. to Its specific surface area is controlled at to This embodiment modulates the particle size distribution law of porous carbon. ,Right now Equals expression The value of is kept between 0.1 and 2 to ensure the consistency of the carbon carrier particles, thereby making the phosphorus distribution more uniform after deposition. During the loading stage, the mass ratio of red phosphorus to carbon material is not limited to that described in Example 1. In some high-capacity demand scenarios, the mass ratio of red phosphorus can be adjusted to 10% to 80%, while the remaining components consist of carbon material and possible conductive additives.

[0030] Example 3 This embodiment focuses on the details of the sealing structure of the deposition apparatus and the chemical safety protection mechanism within the transition chamber 6. In the preparation of kilogram-level phosphorus-carbon materials, due to the involvement of red phosphorus sublimation and the generation of white phosphorus vapor, absolute sealing of the equipment is crucial to ensuring production safety. (Refer to...) Figure 1 and Figure 2 This embodiment employs a rigid sealing structure consisting of a vessel body 1, a transition chamber 6, and dual high-temperature needle valves. The transition chamber 6 and the vessel body 1 are rigidly connected via a first flange 3 and a first gasket 4. The bolt and nut structure of the first flange 3 has extremely high mechanical strength, enabling it to withstand high pressure differentials under vacuum conditions and ensuring that the flange sealing surface does not experience relative displacement during equipment operation.

[0031] In terms of safety, the active copper powder filling the transition chamber 6 provides dual protection through physical barrier and chemical passivation. The porous mesh structure formed by the stacked active copper powder particles effectively intercepts and adsorbs white phosphorus vapor that may leak from the first high-temperature needle valve 5. More importantly, the active copper powder can spontaneously react with the white phosphorus vapor to generate a stable copper phosphide passivation layer on the surface of the white phosphorus. The molecular formula of copper phosphide is... This passivation layer effectively inhibits further oxidation of white phosphorus. Even if a small amount of gas escapes from the first high-temperature needle valve 5, the chemical protective environment within the transition chamber 6 can prevent it from oxidizing and spontaneously combusting, thus strictly controlling the oxygen content during the production process. Inside. For ease of maintenance, the top of the vessel body 1 is designed as an open opening and is connected to the first cover body 2 via flange 3. This design not only facilitates the rapid filling of large-volume materials, but also reduces the labor intensity of disassembly and cleaning of the inner wall.

[0032] Example 4 This embodiment details the technological advantages and control parameters of the matching high-temperature atmosphere roller kiln in achieving continuous mass production. Compared to traditional intermittent box furnaces, the deposition system described in this embodiment enables automated flow of precursors, sintering, and finished products, significantly increasing production capacity and reducing energy consumption. The high-temperature atmosphere roller kiln adopts a three-stage process of continuous feeding, sintering, and cooling. The operating speed of the transmission device 12 can be specifically adjusted according to the production task. to Or to The capacity can be flexibly adjusted, and the daily production capacity of a single production line can reach [amount missing]. to .

[0033] In the process flow, the preheating temperature zone is heated by the preheating section heating rod 13, which heats the deposition unit to [temperature value missing]. to This process efficiently converts solid red phosphorus within the vessel 1 into white phosphorus vapor. Subsequently, the deposition device is fed into the high-temperature zone by the transmission device 12, where the temperature rises to [temperature value missing] under the action of the high-temperature heating rod 14. to At this point, the diffusion capacity of white phosphorus vapor reaches its peak, allowing it to fully and uniformly penetrate the deep pores of the carbon material. Finally, the device enters the cooling zone, where the temperature slowly decreases under the precise temperature control of the heating rod 15 in the cooling section. to This process transforms white phosphorus molecules within the pores of carbon materials into stable red phosphorus loading. Because the temperature fluctuation within the roller kiln is extremely small, the temperature difference can be controlled within positive and negative values. This reduces heat loss by 30% to 40% compared to batch furnaces. Furthermore, due to reduced human intervention, performance deviations between finished product batches can be controlled to within 3%, far below the industry average.

[0034] Example 5 This embodiment provides an optimized scheme for surface modification of deposited phosphorus-carbon composite materials, aiming to further improve the material's fast-charging performance and cycle stability. After completing the above-mentioned vapor deposition step, the phosphorus-carbon composite material can serve as a core, with an outer shell structure further coated on its exterior. This outer shell can be composed of coated carbon or fast ion conductors. For example, a layer with a thickness of [missing information] can be coated onto the porous carbon surface using chemical vapor deposition. to The carbon coating is used to prevent phosphorus from directly contacting the electrolyte and causing side reactions.

[0035] Another preferred option is to coat the surface with a fast ion conductor layer, wherein the fast ion conductor can be selected from... , or Any one of the following. The shell composed of a fast-ion conductor layer and amorphous carbon can significantly improve the migration rate of sodium or lithium ions within the anode material, thereby improving the battery's rate performance and fast-charging performance. In this core-shell structure, the preferred mass ratio of phosphorus to activated carbon in the core is 80:20 to 95:5, while the mass proportion of the fast-ion conductor in the shell is 50% to 80%, and the mass proportion of amorphous carbon is 20% to 50%. Through this multi-level composite modification, the final phosphorus-carbon composite anode material is ready for use. Compare It can maintain more than 90% of its capacity even at high rate performance, and the phosphorus content deviation of the material is less than or equal to 0.2%, perfectly meeting the stringent requirements of power batteries for high energy density and long life.

[0036] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit it. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application.

Claims

1. A deposition apparatus for preparing phosphorus-carbon composite anode materials, characterized in that, include: The vessel body, the transition chamber, and a first sealing assembly and a second sealing assembly for sealing the vessel body and the transition chamber respectively; the vessel body and the transition chamber are fixedly sealed together, and both the first sealing assembly and the second sealing assembly are equipped with high-temperature valves; the interior of the transition chamber is filled with phosphorus capture active material.

2. The deposition apparatus for preparing phosphorus-carbon composite anode materials according to claim 1, characterized in that, The material of the high-temperature valve is , or titanium alloy Any one of them.

3. The deposition apparatus for preparing phosphorus-carbon composite anode materials according to claim 1, characterized in that, The first sealing assembly includes a first cover that covers the top of the vessel body, a first gasket disposed between the vessel body and the first cover, and a first flange for locking the first cover onto the vessel body; the high-temperature valve includes a first high-temperature needle valve installed at the center of the first cover.

4. The deposition apparatus for preparing phosphorus-carbon composite anode materials according to claim 1, characterized in that, The phosphorus capture active material is active copper powder.

5. The deposition apparatus for preparing phosphorus-carbon composite anode materials according to claim 4, characterized in that, The active copper powder is used to adsorb white phosphorus and reacts with the white phosphorus to form a copper phosphide passivation layer on the surface of the white phosphorus. The molecular formula of the copper phosphide is [insert molecular formula here]. .

6. The deposition apparatus for preparing phosphorus-carbon composite anode materials according to claim 3, characterized in that, The second sealing assembly includes a second cover that covers the top of the transition chamber, a second gasket disposed between the transition chamber and the second cover, and a first flange for locking the transition chamber and the second cover; the high-temperature valve also includes a second high-temperature needle valve installed on the second cover.

7. The deposition apparatus for preparing phosphorus-carbon composite anode materials according to claim 1, characterized in that, The vessel body is a container with a seamless bottom and an open top.

8. A deposition system for preparing phosphorus-carbon composite anode materials, characterized in that, include: The deposition apparatus for preparing phosphorus-carbon composite anode materials as described in claim 1; as well as A high-temperature roller kiln includes an insulating shell, a transmission device, and preheating, high-temperature, and cooling zones arranged sequentially along the transmission direction of the transmission device; the transmission device is used to load the deposition device to pass through each of the temperature zones sequentially.

9. The deposition system for preparing phosphorus-carbon composite anode materials according to claim 8, characterized in that, The atmosphere high-temperature roller kiln is provided with a first protective gas inlet and a first protective gas outlet, and the atmosphere high-temperature roller kiln is provided with multiple first thermocouples distributed in each temperature zone.

10. A deposition method for preparing phosphorus-carbon composite anode materials, characterized in that, The deposition system for preparing phosphorus-carbon composite anode materials as described in claim 8 includes the following steps: loading the reactor with a mass percentage of... red phosphorus and The carbon material; the transmission device drives the deposition device to sequentially pass through a preheating zone, a high-temperature zone, and a cooling zone; wherein, the temperature of the preheating zone is controlled at... This converts red phosphorus into white phosphorus vapor; the temperature of the high-temperature zone is controlled at... This allows white phosphorus vapor to enter the pores of the carbon material; the temperature of the cooling zone is controlled at... This causes white phosphorus molecules to revert to red phosphorus within the pores.

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