Carbon composite stannic phosphide material, preparation and application thereof
Carbon composite tin phosphide materials were prepared by hydrothermal-chemical vapor deposition, which solved the pulverization problem of tin phosphide materials during charge and discharge, improved the conductivity and cycle stability of the materials, and achieved high-efficiency sodium-ion battery anode performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2023-08-24
- Publication Date
- 2026-07-21
AI Technical Summary
Existing tin phosphide materials are prone to pulverization during charge-discharge cycles, resulting in reduced cycle life and poor conductivity, which affects the rate cycling performance of the material.
Carbon-composite tin phosphide materials with particle sizes of 30–100 nm were prepared by hydrothermal-chemical vapor deposition. By adding inexpensive materials such as sodium tartrate, sodium alginate, sodium citrate, tin tetrachloride, stannous chloride, acetylene black, and activated carbon, a carbon composite structure was formed, which improved the conductivity and stability of the material.
The prepared carbon composite tin phosphide material exhibits excellent electrochemical performance. When used as a negative electrode material for sodium-ion batteries, it achieves a discharge specific capacity of 143 mAh g-1 at a current density of 2 A g-1, and has good cycle stability and conductivity, making it suitable for large-scale production.
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Figure CN119503762B_ABST
Abstract
Description
Technical Field
[0001] This application relates to a novel carbon composite tin phosphide material and its application, belonging to the field of inorganic material preparation and electrochemical technology. Background Technology
[0002] Tin phosphide (Sn4P3) is a layered semiconductor material composed of alternating layers of phosphorus and tin atoms. It exhibits good electrochemical activity towards sodium ions, and is particularly beneficial to Li. + Na + Plasma ion intercalation / deintercalation. This material possesses high theoretical specific capacity and good cycle reversibility, thus attracting considerable attention from researchers recently. Furthermore, the precursor is inexpensive and the preparation process is relatively simple, which is particularly beneficial for large-scale production. However, in practical applications, this material is prone to volume expansion and pulverization during charge-discharge cycling, leading to a reduced cycle life; simultaneously, its poor conductivity results in poor rate cycling performance. To address this issue, most researchers have focused on coating the material surface with carbon materials or compounding it with other materials, such as graphene. However, this not only increases the material's preparation cost, but the additional coating or compounding components also reduce the material's specific capacity. Summary of the Invention
[0003] The purpose of this application is to provide a novel carbon composite tin phosphide material to avoid the shortcomings of the prior art.
[0004] According to one aspect of this application, a method for preparing a novel carbon-composite tin phosphide material is provided. The novel carbon-composite tin phosphide material has a particle structure with a particle size of 30–100 nm.
[0005] The novel carbon-composite tin phosphide material was prepared by a hydrothermal-chemical vapor deposition method. The specific preparation method is as follows:
[0006] At least one of sodium tartrate, sodium alginate, and sodium citrate is dissolved in deionized water. Then, at least one of tin tetrachloride and stannous dichloride is added and stirred until completely dissolved to form a solution. Next, at least one of acetylene black and activated carbon is added and stirred evenly. Subsequently, sodium hydroxide is added, and after stirring for 10–30 minutes, the mixed solution is transferred to a reaction vessel lined with polytetrafluoroethylene. The reaction is carried out at 120–180 °C for 6–12 hours. Afterward, the temperature is allowed to drop to room temperature, and the white precipitate is collected using a centrifuge. The obtained product is then washed 3–4 times with deionized water using a centrifuge, and the precipitate is collected and dried at 60–80 °C for 6–12 hours to obtain the precursor. The obtained precursor material is placed in a crucible and then placed in a tube furnace. Using at least one of sodium hypophosphite and red phosphorus as the phosphorus source, the precursor material is phosphated and carbonized using chemical vapor deposition.
[0007] The concentrations of sodium tartrate, sodium alginate, and sodium citrate in the solution are 1 mg / mL. -1 ~50mg / mL -1 ;
[0008] The concentrations of tin tetrachloride and stannous dichloride in the solution are 1 mg / mL. -1 ~100mg / mL -1 ;
[0009] The concentrations of acetylene black and activated carbon in the solution were 0.01 mg / mL. -1 ~10mg / mL -1 .
[0010] The mass ratio of sodium hypophosphite, red phosphorus, and the precursor body after hydrothermal reaction is 0.1:1 to 10:1.
[0011] The chemical vapor deposition method is performed at a temperature of 300-400℃ for 2-4 hours.
[0012] Optionally, the concentrations of sodium tartrate, sodium alginate, and sodium citrate in the solution are selected from 1 mg / mL. -1 5mg mL -1 12mg mL -1 20mg / mL -1 35mg / mL -1 45mg mL -1 50mg / mL -1 Any value in the range or any two points mentioned above.
[0013] Optionally, the concentrations of tin tetrachloride and stannous dichloride in the solution are selected from 1 mg / mL. -1 20mg / mL -1 50mg / mL -1 80mg / mL -1 100mg / mL -1 Any value in the range or any two points mentioned above.
[0014] Optionally, the concentrations of acetylene black and activated carbon in the solution are selected from 0.01 mg / mL. -1 0.1 mg mL -1 0.5 mg / mL -1 1 mg mL -1 2mg mL -1 6mg mL -1 10mg mL -1 Any value in the range or any two points mentioned above.
[0015] Optionally, the mass ratio of sodium hypophosphite, red phosphorus, and the precursor body after hydrothermal reaction is selected from any value among 0.1:1, 1:1, 3:1, 5:1, 8:1, 10:1, or any range between any two of the above points.
[0016] According to another aspect of this application, the material prepared in this application is used as a negative electrode material for sodium-ion batteries, and a method for preparing an electrode using this material as the negative electrode active material is provided. The specific preparation method is as follows:
[0017] A certain amount of the prepared carbon composite tin phosphide material was weighed and mixed with conductive carbon black and polyvinylidene fluoride in a mass ratio of 8:1:1 to 7:1.5:1.5. After thorough grinding, an appropriate amount of N-methyl-2-pyrrolidone was added dropwise, and the mixture was stirred thoroughly to form a paste. The mixed electrode material was then coated onto carbon-coated aluminum foil and dried in a forced-air drying oven at 60–80°C for 4–6 hours. The electrode was then used to assemble a sodium-ion battery. The electrochemical performance of the prepared battery was then tested using a LAND-CT2001A battery testing system.
[0018] Test results show that batteries using carbon-composite tin phosphide as the negative electrode active material exhibit excellent electrochemical performance. When used as the negative electrode material in sodium-ion batteries, 2A g... -1 The battery's discharge specific capacity remains as high as 143 mAh g at current density. -1 Its excellent electrochemical performance indicates its great application potential. Furthermore, the preparation process is simple and controllable, requiring only basic equipment, making it an easy method for large-scale production.
[0019] The superior electrochemical performance of the novel carbon-composite tin phosphide material in this application demonstrates its significant potential as a negative electrode material for sodium-ion batteries. Furthermore, the preparation process of this novel carbon-composite tin phosphide material is simple and controllable, requiring only basic equipment, making it an easy method for large-scale production.
[0020] The beneficial effects that this application can produce include:
[0021] 1) The raw materials used in this invention are inexpensive materials such as sodium alginate, tin tetrachloride, and acetylene black. The materials are widely available, green and safe, and have low cost.
[0022] 2) The preparation method of this invention is simple and can be mass-produced.
[0023] 3) The novel carbon composite tin phosphide material obtained by this invention has broad application prospects and can be used as a negative electrode material for sodium-ion batteries with excellent electrochemical performance. Attached Figure Description
[0024] Figure 1This is a SEM image of the carbon-composite tin phosphide material of this application.
[0025] Figure 2 When the carbon composite tin phosphide material prepared in this application is used as the negative electrode of a sodium-ion battery, it achieves a speed of 0.1 A g. -1 The discharge voltage plateau diagram under the current density.
[0026] Figure 3 The rate cycling curve of the carbon composite tin phosphide material prepared in this application as the negative electrode of a sodium-ion battery. Detailed Implementation
[0027] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0028] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.
[0029] The carbon-composite tin phosphide material was scanned using a JSM-7800F scanning electron microscope.
[0030] Electrochemical performance was tested using the Blue Battery Testing System.
[0031] This invention relates to a method for preparing a carbon-composite tin phosphide material, comprising the following steps:
[0032] At least one of sodium tartrate, sodium alginate, and sodium citrate is dissolved in deionized water. Then, at least one of tin tetrachloride and stannous dichloride is added and stirred until completely dissolved to form a solution. Next, at least one of acetylene black and activated carbon is added and stirred evenly. Subsequently, sodium hydroxide is added, and after stirring for 10–30 minutes, the mixed solution is transferred to a reaction vessel lined with polytetrafluoroethylene. The reaction is carried out at 120–180 °C for 6–12 hours. Afterward, the temperature is allowed to drop to room temperature, and the white precipitate is collected using a centrifuge. The obtained product is then washed 3–4 times with deionized water using a centrifuge, and the precipitate is collected and dried at 60–80 °C for 6–12 hours to obtain the precursor. The obtained precursor material is placed in a crucible and then placed in a tube furnace. Using at least one of sodium hypophosphite and red phosphorus as the phosphorus source, the precursor material is phosphated and carbonized using chemical vapor deposition.
[0033] A certain amount of the prepared carbon composite tin phosphide material was weighed and mixed with conductive carbon black and polyvinylidene fluoride in a mass ratio of 8:1:1 to 7:1.5:1.5. After thorough grinding, an appropriate amount of N-methyl-2-pyrrolidone was added dropwise, and the mixture was stirred thoroughly to form a paste. The mixed electrode material was then coated onto nickel foam and dried in a forced-air drying oven at 60–80°C for 4–6 hours. Sodium-ion batteries were then assembled using this electrode. The electrochemical performance of the prepared batteries was then tested using a LAND-CT2001A battery testing system.
[0034] Preparation Example 1
[0035] Weigh 0.1g of the prepared carbon composite tin phosphide material, mix it with conductive carbon black and polyvinylidene fluoride in a mass ratio of 8:1:1, and grind it thoroughly. Then, add 2mL of N-methyl-2-pyrrolidone dropwise using a dropper, and stir thoroughly to form a paste. Coat the mixed electrode material onto nickel foam with a loading of 1-3mg cm⁻¹. -2 (Here it is 2.6mg cm) -2 The electrode was a circular disc with a diameter of 1.6 cm and a thickness of approximately 70-100 micrometers (92 micrometers in this case). It was then dried in a forced-air drying oven at 60-80℃ (70℃ in this case) for 4-6 hours (5 hours in this case). This electrode was then used to assemble sodium-ion batteries, with a sodium disc as the counter electrode, a glass fiber membrane as the separator, and a 1M NaClO4 / DC (diethyl carbonate):EC (ethylene carbonate):DMC (dimethyl carbonate) = 1:1:1 electrolyte. The prepared batteries were then subjected to electrochemical performance testing using a LAND-CT2001A battery testing system, including constant current and rate charge / discharge tests at current densities of 0.1 A g. -1 ; 0.1, 0.2, 0.3, 0.5, 1, 2 and 0.03A g -1 .
[0036] Example 1
[0037] 0.1 g of sodium alginate was dissolved in 50 mL of deionized water, followed by the addition of 0.71 g of tin tetrachloride, and the mixture was stirred until completely dissolved. Then, 0.1 g of acetylene black was added and stirred until homogeneous. Next, 0.16 g of sodium hydroxide was added, and the mixture was stirred for 20 minutes before being transferred to a reaction vessel lined with polytetrafluoroethylene (PTFE). The reaction was carried out at 150 °C for 8 hours. After cooling to room temperature, the white precipitate was collected using a centrifuge. The resulting product was then washed three times with deionized water using a centrifuge, and the precipitate was collected and dried at 60 °C for 8 hours to obtain the precursor.
[0038] The obtained precursor material was placed in a crucible and then placed in a tube furnace. Sodium hypophosphite was used as the phosphorus source and placed in front of the precursor material (in the direction of nitrogen flow, nitrogen flows through the phosphorus source and the precursor material in sequence). The precursor material was phosphated and carbonized by chemical vapor deposition under a nitrogen atmosphere at 350°C for 4 hours.
[0039] Using the carbon-composite tin phosphide material prepared according to the above steps as the active material and the electrode prepared according to the process of Preparation Example 1 as the negative electrode, a sodium-ion battery was assembled. The prepared battery was then subjected to electrochemical performance testing using a Blue Battery Testing System.
[0040] Figure 1 The image shows a SEM image of the prepared carbon-composite tin phosphide material. The image reveals that the material has a particle structure with a diameter of 30–100 nm and exhibits good crystallinity.
[0041] Figure 2 When the carbon composite tin phosphide material prepared in this application is used as the negative electrode of a sodium-ion battery, it achieves a speed of 0.1 A g. -1 The discharge voltage plateau is shown in Figure 2. It is clear from Figure 2 that the battery's discharge voltage is 0.4V.
[0042] Figure 3 The rate cycle curve of the carbon composite tin phosphide material prepared in this application as the negative electrode of a sodium-ion battery is shown. Figure 3 As can be seen, 2Ag -1 The battery discharge specific capacity can still reach 143mAh g. -1 .
[0043] Example 2
[0044] 0.1 g of sodium citrate was dissolved in 50 mL of deionized water, followed by the addition of 0.71 g of tin tetrachloride, and the mixture was stirred until completely dissolved to form a solution. Then, 0.1 g of activated carbon was added and stirred until homogeneous. Subsequently, 0.16 g of sodium hydroxide was added, and the mixture was stirred for 20 minutes before being transferred to a reaction vessel lined with polytetrafluoroethylene (PTFE). The reaction was carried out at 150 °C for 8 hours. After cooling to room temperature, the white precipitate was collected using a centrifuge. The obtained product was then washed three times with deionized water using a centrifuge, and the precipitate was collected and dried at 60 °C for 8 hours to obtain the precursor. The obtained precursor material was placed in a crucible and then placed in a tube furnace. Red phosphorus was used as the phosphorus source and placed in front of the precursor material. The precursor material was phosphorylated and carbonized using chemical vapor deposition (CVD) under a nitrogen atmosphere at 350 °C for 4 hours.
[0045] Using the carbon-composite tin phosphide material prepared according to the above steps as the active material and the electrode prepared according to the process of Preparation Example 1 as the negative electrode, a sodium-ion battery was assembled. The prepared battery was then subjected to electrochemical performance testing using a Blue Battery Testing System.
[0046] Example 2 uses essentially the same method as Example 1, except that sodium alginate is replaced with sodium citrate, acetylene black is replaced with activated carbon, and the phosphorus source is changed from sodium hypophosphite to red phosphorus. Electrochemical test results show that the carbon composite tin phosphide material prepared by this method has essentially the same properties as that in Example 1, 2Ag -1 The battery discharge specific capacity can still reach 140mAh g. -1 This is because, within a certain range, the performance of carbon-composite tin phosphide materials is independent of the types of sodium salt, carbon source, and phosphorus source.
[0047] Comparative Example 1
[0048] 0.1 g of sodium alginate was dissolved in 50 mL of deionized water, followed by the addition of 0.71 g of tin tetrachloride. The mixture was stirred until completely dissolved to form a solution. Then, 0.16 g of sodium hydroxide was added, and the mixture was stirred for 20 minutes. The solution was then transferred to a reaction vessel lined with polytetrafluoroethylene (PTFE). The reaction was carried out at 150 °C for 8 hours. After cooling to room temperature, the white precipitate was collected using a centrifuge. The resulting product was then washed three times with deionized water using a centrifuge, and the precipitate was collected and dried at 60 °C for 8 hours to obtain the precursor. The precursor material was placed in a crucible and then placed in a tube furnace. Sodium hypophosphite was used as the phosphorus source and placed in front of the precursor material. The precursor material was phosphated and carbonized using chemical vapor deposition (CVD) under a nitrogen atmosphere at 350 °C for 4 hours.
[0049] Using the carbon-composite tin phosphide material prepared according to the above steps as the active material and the electrode prepared according to the process of Preparation Example 1 as the negative electrode, a sodium-ion battery was assembled. The prepared battery was then subjected to electrochemical performance testing using a Blue Battery Testing System.
[0050] Comparative Example 1 used essentially the same method as Example 1, except that acetylene black was not added during material preparation. Electrochemical test results showed that the carbon composite tin phosphide material prepared by this method had a significantly lower rate discharge specific capacity compared to Example 1, with a capacity of 2Ag. -1 The battery discharge specific capacity is only 98mAh g. -1 This is because composite acetylene black can enhance the conductivity and cycle stability of the material, and its use or absence will significantly affect the discharge performance of the composite material.
[0051] Comparative Example 2
[0052] 0.71 g of tin tetrachloride was dissolved in 50 mL of deionized water and stirred until completely dissolved to form a solution. Then, 0.1 g of acetylene black was added and stirred until homogeneous. Subsequently, 0.16 g of sodium hydroxide was added, and after stirring for 20 minutes, the mixture was transferred to a reaction vessel lined with polytetrafluoroethylene. The reaction was carried out at 150 °C for 8 hours. Afterward, the temperature was lowered to room temperature, and the white precipitate was collected using a centrifuge. The obtained product was then washed three times with deionized water using a centrifuge, and the precipitate was collected and dried at 60 °C for 8 hours to obtain the precursor. The obtained precursor material was placed in a crucible and then placed in a tube furnace. Sodium hypophosphite was used as the phosphorus source and placed in front of the precursor material. The precursor material was phosphated and carbonized using chemical vapor deposition under a nitrogen atmosphere at 350 °C for 4 hours.
[0053] Using the carbon-composite tin phosphide material prepared according to the above steps as the active material and the electrode prepared according to the process of Preparation Example 1 as the negative electrode, a sodium-ion battery was assembled. The prepared battery was then subjected to electrochemical performance testing using a Blue Battery Testing System.
[0054] Comparative Example 2 used essentially the same method as Example 1, except that sodium alginate was not added during material preparation. Electrochemical test results showed that the carbon composite tin phosphide material prepared by this method had a significantly lower rate discharge specific capacity compared to Example 1, with a capacity of 2Ag. -1 The battery discharge specific capacity is only 110mAh g. -1 This is because the use of sodium alginate in the preparation of tin phosphide precursors can inhibit crystal growth, thereby increasing the specific surface area of the material. Furthermore, the carbonization of sodium alginate can enhance the conductivity and cycle stability of the material. Whether or not it is used will significantly affect the discharge performance of the composite material.
[0055] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A method for preparing a carbon composite tin phosphide material, characterized in that: The material was prepared by a hydrothermal-chemical vapor deposition method; the specific process is as follows: 1) Hydrothermal reaction: Dissolve at least one of sodium tartrate, sodium alginate, and sodium citrate in water, then add at least one of tin tetrachloride and stannous chloride, and stir until completely dissolved to form a solution; then add at least one of acetylene black and activated carbon and stir evenly; subsequently, add sodium hydroxide, stir for 10-30 minutes, and then transfer the mixed solution to a reaction vessel; react at 120-180 ℃ for 6-12 h; after that, after the temperature drops to room temperature, separate the solid and liquid phases and collect the precipitate; then wash the obtained precipitate with water 3-4 times, and dry it at 60-80 ℃ for 6-12 h to obtain the precursor; The concentration of at least one of sodium tartrate, sodium alginate, and sodium citrate in water is 1 mg·mL. -1 ~50mg·mL -1 ; 2) Chemical vapor deposition: The obtained precursor material is placed in a tube furnace, and at least one of sodium hypophosphite and red phosphorus is used as the phosphorus source. The precursor material is then phosphated and carbonized using chemical vapor deposition.
2. The preparation method according to claim 1, characterized in that: The concentration of at least one of sodium tartrate, sodium alginate, and sodium citrate in water in the solution is 5 mg·mL. -1 ~20mg·mL -1 ; The concentration of at least one of tin tetrachloride and stannous dichloride in the solution is 1 mg·mL. -1 ~100mg·mL -1 The concentration of at least one of acetylene black and activated carbon in the solution is 0.01 mg·mL. -1 ~10mg·mL -1 .
3. The preparation method according to claim 2, characterized in that: The concentration of at least one of tin tetrachloride and stannous dichloride in the solution is 10 mg·mL. -1 ~30mg·mL -1 ; The concentration of at least one of acetylene black and activated carbon in the solution is 1 mg·mL. -1 ~5mg·mL -1 .
4. The preparation method according to claim 1, characterized in that: The concentration of sodium hydroxide added was 0.25 mg / mL. -1 ~25mg·mL -1 .
5. The preparation method according to claim 4, characterized in that: The concentration of sodium hydroxide added is 2 mg / mL. -1 ~10mg / mL -1 .
6. The preparation method according to claim 1, characterized in that, The mass ratio of the phosphorus source to the precursor after hydrothermal reaction is 0.1:1 to 10:1, and the temperature of the chemical vapor deposition method is 300-400 ℃, and the time is 2-4 h.
7. The preparation method according to claim 1, characterized in that, The mass ratio of the phosphorus source to the precursor after hydrothermal reaction is 1:1 to 3:
1.
8. A carbon composite tin phosphide material prepared by any one of the preparation methods described in claims 1-7.
9. The carbon composite tin phosphide material according to claim 8, characterized in that, The carbon composite tin phosphide material consists of particles with a diameter of 30~100 nm.
10. The application of the carbon composite tin phosphide material according to any one of claims 8-9 as a negative electrode active material for sodium-ion batteries.
11. The application according to claim 10, characterized in that, The sodium-ion battery comprises a positive electrode, a separator, a negative electrode arranged in sequence, and a separator electrolyte filled between the positive and negative electrodes.