Method for producing phosphorus-doped silicon composite anode material and the product and its use

Abstract

The present invention relates to a method for producing a phosphorus-doped silicon-based composite negative electrode material, comprising: step (1) of sufficiently mixing a gas of a phosphorus source and a gas of a carbon source with a gas of a silicon source at room temperature in an inert atmosphere to obtain a mixed gas, wherein in the mixed gas, taking the total volume as 100%, the volume ratio of the gas of the phosphorus source is 0.1 to 3.0%, the volume ratio of the gas of the carbon source is 15 to 28%, and the remainder is the gas of the silicon source; step (2) of flowing the mixed gas into a deposition furnace in which a substrate is placed, and obtaining an intermediate product after thermal deposition; and step (3) of performing carbon coating treatment on the intermediate product and then obtaining a phosphorus-doped silicon-based composite negative electrode material through post-treatment. The present invention discloses a method for manufacturing a phosphorus-doped silicon-based composite negative electrode material. A lithium-ion battery assembled with the manufactured negative electrode material has excellent cycle stability and high reversible specific capacity and first Coulomb efficiency at the same time.

Description

Technical Field

[0001] The present invention relates to the technical field of negative electrode materials for lithium batteries, and particularly relates to a method for manufacturing a phosphorus-doped silicon-based composite negative electrode material, its products, and their uses.

Background Art

[0002] Silicon is considered the most promising candidate to replace graphite. It is the second most abundant element in the earth's crust, environmentally friendly, and has an extremely high theoretical capacity (4200 mAh / g). However, the drastic volume change during the lithium insertion / extraction process has a significant adverse effect, resulting in very low cycle stability. The silicon monoxide material has a significantly lower volume expansion during the lithium insertion process than elemental silicon and also has a relatively high theoretical specific capacity (>2,000 mAh / g). However, the first Coulombic efficiency of silicon monoxide is too low (lower than 76%), so its wider applications are limited. On the other hand, commercially available silicon-carbon products have high initial efficiency and capacity characteristics compared to silicon monoxide, but their cycle performance is significantly lower than that of silicon monoxide. Therefore, manufacturing a silicon-based negative electrode material with high capacity, high initial efficiency, and high cycle performance is an urgent problem to be solved.

[0003] A Chinese patent document with publication number CN107623118A discloses a "method for producing phosphorus-doped porous carbon anode material with improved initial Coulombic efficiency." The method involves using elemental red phosphorus as the phosphorus source, dispersing an organic carbon source in water to form a slurry, uniformly mixing it with the red phosphorus, drying it, firing it in a sealed tank filled with a protective atmosphere, and then firing it again in a tubular furnace with an inert atmosphere to produce a phosphorus-doped porous carbon anode material. This invention claims that using phosphorus as a doping element improves the reversible ratio capacity of the carbon material, significantly improving the initial Coulombic efficiency of the material. While the manufacturing method disclosed in this invention is simple, the use of liquid-solid phase mixing makes it difficult to guarantee doping uniformity, thus affecting the consistency of the manufacturing method. Furthermore, the highest initial Coulombic efficiency of the material obtained by this method is only 71%, which does not meet market demand.

[0004] A Chinese patent document with publication number CN113809311A discloses "Silicon-based lithium-ion anode material coated with phosphorus-doped soft carbon, method for producing the same, and use thereof." A phosphorus-containing gas source or a high-boiling-point phosphorus-containing compound is used as the doping material, and a phosphorus-doped silicon monoxide material is obtained by gas-phase mixing reaction of the vapor of the doping material and the vapor of a preheated silicon source at 1200-1700°C for 1-24 hours. However, the vapor of the silicon source is a mixed gas of silicon vapor and silicon oxide vapor. The phosphorus-doped silicon monoxide material is cooled to room temperature and discharged, crushed and sieved, the sieved material is analyzed and measured, and the material whose doping uniformity meets the predetermined conditions is coated with carbon to obtain a phosphorus-doped silicon-based lithium-ion anode material. This proposed technology involves a gas-phase mixing reaction between a phosphorus-containing material and silicon vapor and silicon oxide vapor, ensuring sufficient contact between the reactants to obtain a lithium-ion battery anode material with uniform bulk phase doping. The resulting material exhibits higher cycle stability and superior material consistency. However, the phosphorus-doped silicon anode material obtained by this method only achieves a maximum initial Coulomb efficiency of 80.6%, lacking any significant product advantages. Furthermore, this technology consumes very high energy. Preheating silicon and silicon oxide to form vapor requires temperatures reaching at least 1350°C, the gas-phase mixing reaction is carried out at a high temperature of 1200-1200°C, and the subsequent carbon coating is also carried out at a high temperature of 800-1000°C. Therefore, this technology is not suitable for large-scale industrial production. [Overview of the project] [Problems that the invention aims to solve]

[0005] This invention discloses a method for manufacturing a phosphorus-doped silicon composite anode material that addresses the problems of the prior art by having low energy consumption for production and high uniformity of the produced product. Furthermore, the lithium-ion battery obtained by assembling the fabricated anode material has excellent cycle stability and possesses both high reversible ratio capacity and initial Coulomb efficiency. [Means for solving the problem]

[0006] The specific technical proposals are as follows: A method for producing a phosphorus-doped silicon composite anode material, A mixture gas is obtained by thoroughly mixing a phosphorus-source gas and a carbon-source gas with a silicon-source gas at room temperature in an inert atmosphere.

[0007] However, in the aforementioned mixed gas, step (1) is defined as having a total volume of 100%, with the volume proportion of the phosphorus source gas being 0.1-3.0%, the volume proportion of the carbon source gas being 15-28%, and the remainder being the silicon source gas. Step (2) involves flowing the mixed gas through a deposition furnace on which the substrate is placed, and obtaining an intermediate product after thermal deposition.

[0008] A method for producing a phosphorus-doped silicon composite anode material, comprising the steps of (3) performing a carbon coating treatment on the intermediate product and then obtaining the phosphorus-doped silicon composite anode material through post-treatment.

[0009] The present invention discloses a method for producing a phosphorus-doped silicon composite anode material, in which a phosphine in a gaseous state at room temperature is used as a silicon source, a carbon source in a gaseous state is introduced separately and mixed with the silicon source in a gaseous state at room temperature to obtain a mixed gas, carbon and phosphorus are bonded to the silicon source material in a gas phase deposition reaction process, dehydrogenation is performed by thermal decomposition, and finally, a phosphorus-doped silicon composite anode material is produced by carbon coating treatment.

[0010] As demonstrated by the tests, this fabrication method significantly reduces the average particle size of primary silicon particles through phosphorus doping. The introduction of a gaseous carbon source works in conjunction with the doped phosphorus atoms to aid in the decomposition of the phosphorus source gas and promote phosphorus doping. The phosphorus-doped silicon composite anode material finally fabricated by simultaneously mixing both with the silicon source gas and going through the above series of steps possesses excellent cycle stability, reversible ratio capacity, and initial Coulomb efficiency.

[0011] As the tests show, using only a combination of phosphorus-source gas and silicon-source gas, or only a combination of carbon-source gas and silicon-source gas, does not yield the aforementioned synergistic effect.

[0012] Further testing reveals that even when employing combinations of three gases—phosphorus-source gas, carbon-source gas, and silicon-source gas—it is not possible to produce lithium-ion batteries with excellent cycle stability, high reversible specific capacity, and initial Coulomb efficiency if their volume ratios are not within the aforementioned limited range.

[0013] In step (1), The gas of the phosphorus source is selected from phosphine, The carbon source gas is selected from alkane gases that can be decomposed at 400-800°C, and is preferably selected from ethylene, propylene, acetylene, and the like. The gas of the silicon source is selected from one or more of silane, dichlorosilane, trichlorosilane, and silicon tetrachloride. In step (2), The total flow rate of the mixed gas is 0.1 to 50 L / min, preferably 20 to 50 L / min, and more preferably 25 to 30 L / min.

[0014] The substrate is selected from one or more of the following: hard carbon, conductive carbon black, carbon nanotubes, and graphene, and the mass of the added substrate accounts for 0.1 to 20.0 wt% of the total mass of the final product. Preferably, the D50 of the substrate is less than 200 nm. The temperature of the thermal deposition is 400-800°C. In step (3), The aforementioned intermediate product undergoes grinding, classification, and demagnetization treatment, followed by a carbon coating treatment.

[0015] Preferably, the intermediate product obtained after grinding, classification, and demagnetization has a particle size concentration (SPAN value) ≤ 1.5 and an average particle size ≤ 10 μm, and more preferably, a SPAN value ≤ 1.2. In step (3), The carbon coating treatment is selected from one or more types of gas-phase carbon coating, liquid-phase carbon coating, and solid-phase carbon coating.

[0016] The carbon source used in the aforementioned gas-phase carbon coating is a hydrocarbon gas such as ethylene, propylene, or acetylene, and the specific carbon coating process employs conventional techniques in this field.

[0017] The carbon source used in the aforementioned liquid-phase carbon coating is a carbon-containing polymer such as liquid epoxy resin, petroleum slag oil, or liquid asphalt, and the specific carbon coating process employs conventional methods in this field. The carbon source used in the solid-phase carbon coating is asphalt, and the specific carbon coating process employs conventional methods in this field. The temperature of the carbon coating treatment is selected from 600 to 1000°C and is adaptively adjusted according to the type of carbon source used.

[0018] In step (3), The aforementioned post-processing includes dispersion and sieving, and the specific operations are all standard technical methods in this field. For example, spiral dispersion is employed as the dispersion method. Preferably, the number of meshes used in the sieving process is 100 to 800 meshes. Based on the above process and raw materials, preferably,

[0019] In step (3), the volume proportion of the phosphorus source gas in the mixed gas is 0.5-3.0%, the volume proportion of the carbon source gas is 15-25%, and the remainder is the silicon source gas. More preferably, In the mixed gas, the volume ratio of the phosphorus source gas is 0.5 to 1.5%, the volume ratio of the carbon source gas is 15 to 25%, and the rest is the silicon source gas. More preferably, in the mixed gas, the phosphorus source gas, the carbon source gas, and the silicon source gas are sufficiently mixed at room temperature at a volume ratio of 1.5:25:73.5.

[0020] Most preferably, the silicon source is selected from trichlorosilane. As can be seen from the tests, the lithium-ion battery assembled with the phosphorus-doped silicon-based composite negative electrode material finally prepared with trichlorosilane as the silicon source at the above more preferable volume ratio has its cycle stability, reversible specific capacity, and initial Coulomb efficiency all optimally achieved. The present invention further discloses a phosphorus-doped silicon-based composite negative electrode material prepared according to the above method.

[0021] The present invention further discloses the use of a phosphorus-doped silicon-based composite negative electrode material prepared according to the above method in a lithium-ion battery. As can be seen from the tests, the lithium-ion battery assembled with this negative electrode material has excellent cycle stability and also has a high reversible specific capacity and an initial Coulomb efficiency.

Advantages of the Invention

[0022] Compared with the prior art, the present invention has the following beneficial effects. The present invention discloses a method for manufacturing a phosphorus-doped silicon-based composite negative electrode material, which uses a phosphorus source gas, a carbon source gas, and a silicon source gas as raw materials, has a simple and controllable manufacturing process, low energy consumption, and is suitable for industrial production.

[0023] The lithium-ion battery obtained by assembling the phosphorus-doped silicon composite anode material manufactured according to the present invention has excellent cycle stability, with a capacity retention rate of 80% or more after 100 cycles, reaching a maximum of 88%, and a capacity retention rate of 70% or more after 500 cycles, reaching a maximum of 75.5%, while also possessing a high reversible ratio capacity (higher than 1800 mAh / g) and an initial Coulomb efficiency (90% or more). [Brief explanation of the drawing]

[0024] [Figure 1] This is an SEM image of the intermediate product prepared in Example 1. [Figure 2] Figure 1 shows the distribution of Si, C, and P elements within the image area. [Figure 3] Figure 1 shows the distribution of Si, C, and P elements within the image area. [Figure 4] Figure 1 shows the distribution of Si, C, and P elements within the image area. [Figure 5] This is a SEM image of the phosphorus-doped silicon composite anode material fabricated in Example 1. [Figure 6] This is a TEM diagram of the phosphorus-doped silicon composite anode material fabricated in Example 1. [Modes for carrying out the invention]

[0025] The following describes specific methods for implementing the present invention with reference to examples. However, the specific methods described herein are merely for the purpose of explaining and interpreting the present invention and do not limit it.

[0026] Example 1 (1) A mixed gas is obtained by thoroughly mixing phosphine, ethylene, and monosilane in a volume ratio of 1.5:25:73.5 at room temperature under an argon atmosphere.

[0027] (2) A mixed gas is flowed into a deposition furnace at a flow rate of 25 L / min, into which approximately 100 nm in size D50 and 100 g of hard carbon microspheres are placed, and the temperature is set to 500°C. The mixture is continuously aerated until the granular surface of the hard carbon microspheres continuously nucleates and grows, and a phosphorus-doped silicon carbon deposition layer is deposited and formed, and the aeration time is maintained for 10 hours.

[0028] (3) The deposition furnace is cooled and cooled, and the material removed from the furnace is crushed and classified to obtain uniform granules with a D50 of less than 5 μm and a SPAN value of less than 1.2, and further magnetic treatment is performed to obtain an intermediate product.

[0029] (4) In an argon atmosphere, the intermediate product is introduced into a chemical vapor deposition furnace and heated to 800°C at a rate of 5°C / min. Acetylene gas is flowed through at a rate of 1 L / min to perform vapor phase decomposition, deposition, and carbon coating. The carbon content of the carbon coating relative to the total mass of the final product is controlled to 4 wt%. After the deposition is complete, the temperature is lowered to room temperature, the material is removed, dispersed, and sieved to finally obtain a phosphorus-doped silicon composite anode material.

[0030] Figure 1 is a mapping image of the intermediate product prepared in step (3) of this embodiment. Figures 2-4 are distribution maps of Si (Figure 2), C (Figure 3), and P (Figure 4) within this image range. As can be seen from observing Figures 2-4, the intermediate product prepared in this embodiment is well doped with two types of elements, C and P, and these two types of elements are uniformly dispersed in the intermediate product.

[0031] Figure 5 is an SEM image of the final product produced in this embodiment. As can be seen from this figure, the final product produced in this embodiment has a regular spherical shape and a relatively uniform particle size distribution.

[0032] Figure 6 is a TEM diagram of the final product produced in this embodiment. As can be seen from this figure, the surface of the negative electrode material produced in this embodiment is coated with a uniform carbon layer. Example 2

[0033] The manufacturing process is largely the same as in Example 1, but the difference lies in replacing the volume ratio of phosphine, ethylene, and monosilane in step (1) with a ratio of 3:15:82. Example 3

[0034] The manufacturing process is largely the same as in Example 1, but the difference is that in step (1), the volume ratio of phosphine, ethylene, and monosilane is changed to 0.5:25:74.5. Comparative Example 1

[0035] The manufacturing process is largely the same as in Example 1, but the difference lies in replacing the volume ratio of phosphine, ethylene, and monosilane in step (1) with a ratio of 5:25:70. Comparative Example 2

[0036] The manufacturing process is largely the same as in Example 1, but the difference is that in step (1), a mixed gas is obtained by adding and mixing only ethylene and monosilane in a volume ratio of 25:75. Comparative Example 3

[0037] The manufacturing process is largely the same as in Example 1, but the difference lies in replacing the volume ratio of phosphine, ethylene, and monosilane in step (1) with a ratio of 2:30:68. Comparative Example 4

[0038] The manufacturing process is largely the same as in Example 1, but the difference lies in replacing the volume ratio of phosphine, ethylene, and monosilane in step (1) with a ratio of 2:13:85. Comparative Example 5

[0039] The manufacturing process is largely the same as in Example 1, but the difference is that in step (1), a mixed gas is obtained by adding and mixing only phosphine and monosilane in a volume ratio of 2:98. Example 4 (1) A mixed gas is obtained by thoroughly mixing phosphine, propylene, and dichlorosilane in a volume ratio of 1.5:25:73.5 at room temperature under an argon atmosphere.

[0040] (2) A mixed gas is flowed into a deposition furnace at a flow rate of 30 L / min, into which approximately 100 nm in size D50 and 100 g of graphene microspheres are placed and the temperature is set to 400°C. The mixture is continuously aerated until the granular surface of the graphene microspheres continuously nucleates and grows, and a phosphorus-doped silicon-carbon deposition layer is deposited and formed, and the aeration time is maintained for 13 hours. Steps (3) and (4) are exactly the same as in Example 1. Example 5

[0041] (1) A mixed gas is obtained by thoroughly mixing phosphine, acetylene, and trichlorosilane in a volume ratio of 1.5:25:73.5 at room temperature under an argon atmosphere.

[0042] (2) Mixed gas is flowed into a deposition furnace set to a temperature of 800°C, where approximately 100 nm in size D50 and 100 g of conductive carbon black microspheres are placed, at a flow rate of 0 L / min for a total gas volume of 3. The mixture is continuously aerated until the granular surface of the conductive carbon black microspheres continuously nucleates and grows, and a phosphorus-doped silicon carbon deposition layer is deposited and formed, maintaining the aeration time for 5 hours. Steps (3) and (4) are exactly the same as in Example 1. Usage example The negative electrode materials prepared in each example and comparative example are assembled into batteries.

[0043] Under a nitrogen-protected atmosphere, the conductive agent SuperP and sodium carboxymethylcellulose CMC were thoroughly mixed and dispersed with deionized water. Then, the anode material was added and stirred at 2000 rpm for 10 minutes. Finally, the aqueous adhesive AONE (purchased from Shenzhen Yanyi New Materials Co., Ltd.) was added and stirred at 2000 rpm for another 10 minutes to obtain a anode slurry. The mass ratio of the anode material, conductive agent SuperP, sodium carboxymethylcellulose CMC, and adhesive AONE (dry weight) was 70:15:5:10, and the solid content of the slurry was 15 wt%.

[0044] The above negative electrode slurry is applied to the copper foil of the current collector, dried at 80°C for 30 minutes under a relative vacuum of -0.1 MPa, then rolled at room temperature to achieve a surface density of 9.1 mg / cm², punched, and cut into a disc with a diameter of 14 mm to create an electrode piece. The electrodes used are lithium sheet CR2016 (purchased from Shenzhen Yongxing Equipment Technology Co., Ltd.), with a diameter of 16 mm.

[0045] Assemble the button cell in a glove box under an argon protective atmosphere, ensuring that both the moisture and oxygen levels in the glove box are less than 0.01 ppm. Assemble in the following order: negative electrode case - gasket - lithium sheet - electrolyte - separator - electrolyte - electrode piece - positive electrode case. The electrolyte consists of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) (volume ratio of EC:EMC:DEC = 1:1:1) and contains 1.0 M LiPF6.

[0046] However, the electrode piece diameter is 14 mm, the lithium sheet diameter is 16 mm, the separator diameter is 19 mm, and the battery case (positive electrode case and negative electrode case) size is 20 mm. The separator is a 12 μm thick ceramic coated separator (purchased from Shanghai Enjie New Materials Technology Co., Ltd.). The assembled button battery is placed in the mold groove of a hydraulic sealing machine (purchased from Shenzhen Kejing Zhida Technology Co., Ltd.) and locked under a pressure of 500 kg / cm².2 Apply greater pressure, then unlock and remove the sealed button battery.

[0047] During battery assembly, five button batteries are prepared for each test set, and data from a total of five sets is measured. The average value of the data from these five sets is then used to determine the final performance. Performance measurement:

[0048] Phase analysis and detection are performed using Brook's XRD-D2PHASER, and the particle size of the primary silicon crystals is measured using the Scherrer formula. Morphological measurements will be performed using Thermo Fisher's Phenom Generation 5 in the United States. The carbon content is measured using a German Erte high-frequency infrared carbon-sulfur analyzer. The phosphorus content is measured using an organic elemental analyzer from Eli Monta, Germany. The CT2001A battery measurement system will be used to measure the cycle performance of the batteries. Specifically,

[0049] At 25°C, the charge-discharge cycle characteristics of the button battery are detected using the above-mentioned blue electric measurement cabinet. First, the battery is discharged to 0.005V at 0.1C, then to 0.001V at 0.08C, then to 0.001V at 0.05C, then to 0.001V at 0.02C, left for 10 minutes, and then charged to 1.5V at 0.1C, left for 10 minutes. The charge-discharge capacity after the first cycle is recorded, and the initial Coulomb efficiency is calculated. 100 cycles are performed according to the above method, the charge-discharge capacity after 100 cycles is recorded, and the capacity retention rate after 100 cycles is calculated. The measurement and calculation process for the capacity retention rate after 500 cycles is performed similarly. The measurement results are shown in Table 1 below.

[0050] Table 1 JPEG0007842782000001.jpg110170

[0051] 1. is the mass content of phosphorus in the intermediate product prepared in each example or comparative example. 2. is the mass content of carbon element in the intermediate product prepared in each example or comparative example. 3. is the average particle size of the primary silicon intermediate product prepared in each example or comparative example.

[0052] As can be seen by comparing the changes in phosphorus and carbon content in Table 1, the method disclosed in the present invention allows for the controllable production of phosphorus and carbon content in the product. As can be seen by comparing the average particle size of the primary silicon particles in Example 1 and Comparative Examples 2 and 3, the introduction of phosphorus can effectively reduce the average particle size of the primary silicon particles.

[0053] The present invention can be effectively implemented according to the above embodiments. Furthermore, technical solutions that, based on the above design, involve non-essential changes or modifications to the present invention to solve similar problems, are essentially the same as the present invention and therefore should also fall within the scope of protection of the present invention.

Claims

1. A method for producing a phosphorus-doped silicon composite anode material, Step (1) is to obtain a mixed gas by mixing a phosphorus source gas, a carbon source gas, and a silicon source gas at room temperature in an inert atmosphere, wherein the total volume of the mixed gas is 100%, the volume of the phosphorus source gas is 0.1 to 3.0%, the volume of the carbon source gas is 15 to 28%, and the remainder is the silicon source gas. Step (2) involves introducing the mixed gas into a deposition furnace on which the substrate is placed, and obtaining an intermediate product by thermal deposition. The process includes (3) carbon coating the intermediate product and then post-processing it to obtain a phosphorus-doped silicon composite anode material. A method for producing a phosphorus-doped silicon-based composite anode material characterized by the following features.

2. In step (1), The gas of the phosphorus source is phosphine. The carbon source gas is selected from alkane gases that can be decomposed at 400-800°C. The gas of the silicon source is selected from one or more of silane, dichlorosilane, trichlorosilane, and silicon tetrachloride. A method for producing a phosphorus-doped silicon composite anode material according to feature 1.

3. In step (2), The total flow velocity when the mixed gas is inflow is 0.1 to 50 L / min. The substrate is selected from one or more of the following: hard carbon, conductive carbon black, carbon nanotubes, and graphene. The temperature of the heat deposition is 400 to 800°C. A method for producing a phosphorus-doped silicon composite anode material according to feature 1.

4. In step (3), The aforementioned intermediate product is subjected to crushing, classification, and demagnetization, and then further subjected to carbon coating. The intermediate product after grinding, classification, and demagnetization has a particle size distribution index (SPAN value) ≤ 1.5 and an average particle size ≤ 10 μm. A method for producing a phosphorus-doped silicon composite anode material according to feature 1.

5. In step (3), The carbon coating treatment is selected from one or more types of gas-phase carbon coating, liquid-phase carbon coating, and solid-phase carbon coating. The temperature for the carbon coating treatment is 600 to 1000°C. A method for producing a phosphorus-doped silicon composite anode material according to feature 1.

6. In step (3), The aforementioned post-processing includes dispersion and sieving. A method for producing a phosphorus-doped silicon composite anode material according to feature 1.

7. In step (1), the volume of the mixed gas is 0.5 to 3.0% phosphorus source gas, 15 to 25% carbon source gas, and the remainder is silicon source gas. In step (2), the total flow velocity when the mixed gas is inflow is 20 to 50 L / min. A method for producing a phosphorus-doped silicon composite anode material according to feature 1.

8. The volume ratio of the phosphorus source gas, carbon source gas, and silicon source gas in the aforementioned mixed gas is 1.5:25:73.

5. The gas of the silicon source is trichlorosilane. A method for producing a phosphorus-doped silicon composite anode material according to feature 7.

9. A phosphorus-doped silicon composite anode material prepared by the method described in any one of claims 1 to 8.

10. Use of the phosphorus-doped silicon-based composite anode material according to claim 9 in a lithium-ion battery.

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