Preparation method and application of organic-inorganic hybrid perovskite-derived carbon composite material
By preparing organic-inorganic hybrid perovskite-derived carbon composite materials, the problem of uniform mixing of tin and carbon materials in tin-carbon composite materials was solved, which improved the capacity and cycle stability of sodium-ion batteries and simplified the preparation process.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUILIN UNIV OF ELECTRONIC TECH
- Filing Date
- 2023-06-01
- Publication Date
- 2026-05-19
AI Technical Summary
Existing technologies make it difficult to achieve uniform mixing of tin and carbon materials in tin-carbon composites, resulting in volume expansion and slow kinetic performance issues in tin-based materials in sodium-ion batteries, which affect the conductivity and stability of the electrodes.
An organic-inorganic hybrid perovskite-derived carbon composite material was prepared by mixing an inorganic tin source and an organic carbon source in an organic solvent to form a perovskite precursor solution, which was then uniformly mixed with pitch and calcined under an inert atmosphere to produce a composite material in which tin nanoparticles were uniformly embedded between carbon layers.
The process achieves uniform mixing of tin-carbon composite materials, improves the capacity and cycle stability of sodium-ion batteries, simplifies the preparation process, and facilitates industrial production.
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Figure CN116581268B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of energy storage battery materials technology. Specifically, it relates to the preparation method and application of organic-inorganic hybrid perovskite-derived carbon composite materials. Background Technology
[0002] Sodium-ion batteries, due to their low cost, high sodium abundance, and good safety performance, are considered an ideal choice for large-scale energy storage devices and have received widespread research and attention in recent years. However, commercial graphite has failed to meet the needs of sodium-ion batteries, thus necessitating the development of novel anode materials. Tin-based materials possess high theoretical capacity and a suitable voltage plateau, making them highly promising for use as anodes in sodium-ion batteries. However, the significant volume expansion and slow kinetic properties of tin-based materials remain a challenge.
[0003] Tin-carbon composite materials can effectively address the problems associated with tin-based materials because carbon acts as a matrix to mitigate the volume expansion of tin-based materials, effectively preventing tin agglomeration and pulverization. Simultaneously, the addition of carbon further improves the conductivity of the electrode and prevents electrolyte corrosion of the electrode material. However, the preparation of a uniformly mixed tin-carbon composite material remains unsolved, thus limiting its performance. Summary of the Invention
[0004] Therefore, the technical problem to be solved by the present invention is to provide a method for preparing and applying an organic-inorganic hybrid perovskite-derived carbon composite material. The preparation method is simple and can achieve ultra-uniform mixing of tin and carbon materials, which exhibits high capacity and cycle stability in sodium-ion batteries.
[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution:
[0006] A method for preparing organic-inorganic hybrid perovskite-derived carbon composite materials includes the following steps:
[0007] S1: Add the inorganic tin source and the organic carbon source to the organic solvent and mix thoroughly to obtain a perovskite precursor solution;
[0008] S2: Dry the solvent in the perovskite precursor solution to obtain the perovskite material;
[0009] S3: After the perovskite material is mixed evenly with asphalt, it is calcined and carbonized under an inert gas protective atmosphere. After the calcination and carbonization are completed, an organic-inorganic hybrid perovskite-derived carbon composite material is obtained.
[0010] In the preparation method of the above-mentioned organic-inorganic hybrid perovskite-derived carbon composite material, in step S1, the molar ratio of inorganic tin source to organic carbon source is 1:(1-5); the concentration of organic carbon source in the perovskite precursor solution is 0.1-0.5 mol / L. Tin in this invention can enhance the sodium storage capacity of perovskite materials. If the amount of inorganic tin source is too low, the final sodium-ion battery capacity will be low; if the amount is too high, it will be difficult to form the perovskite compound.
[0011] In the above-mentioned method for preparing organic-inorganic hybrid perovskite-derived carbon composite material, in step S1, the molar ratio of inorganic tin source to organic carbon source is 1:(1-2); the concentration of organic carbon source in the perovskite precursor solution is 0.4 mol / L.
[0012] In the above-mentioned method for preparing organic-inorganic hybrid perovskite-derived carbon composite materials, in step S1, the organic carbon source is methylammonium bromide and / or phenylethylammonium bromide. Compared with chloride carbon sources and iodide carbon sources, the carbon composite material prepared by synthesizing perovskite materials with bromide carbon sources and carbonizing pitch can prepare sodium-ion batteries with higher capacity. The inorganic tin source is stannous bromide, stannous iodide or stannous chloride.
[0013] In the preparation method of the above-mentioned organic-inorganic hybrid perovskite-derived carbon composite material, in step S2, the drying temperature is 110-120℃ and the drying time is 10-24h. If the drying temperature is too high, the perovskite will decompose prematurely, making it difficult to form perovskite material; if the drying temperature is too low, the formed perovskite material particles will be too large, affecting the capacity and cycle stability of the final sodium-ion battery.
[0014] In the preparation method of the above-mentioned organic-inorganic hybrid perovskite-derived carbon composite material, in step S3, the mass ratio of perovskite material to pitch is 1:(1-20). Perovskite plays a catalytic cross-linking role in pitch. If the mass ratio of perovskite material to pitch is too small, the catalytic degree is small, and less tin source is introduced, resulting in a low sodium capacity of the final organic-inorganic hybrid perovskite-derived carbon composite material. If the mass ratio of perovskite material to pitch is too large, there will be too much tin source, making it difficult for tin to be dispersed evenly, which in turn leads to tin easily expanding and pulverizing when storing sodium.
[0015] In the preparation method of the above-mentioned organic-inorganic hybrid perovskite-derived carbon composite material, in step S3, the mass ratio of perovskite material to pitch is 1:4; the pitch passes through a 100-mesh sieve, and the particle size of the perovskite material is 10-100 μm. Pitch and perovskite material with this particle size are easier to mix evenly, which is more conducive to achieving the ideal carbonization effect in subsequent calcination and carbonization. If the particle size of pitch and perovskite material is too large, it will affect the mixing uniformity of the two, and thus affect the sodium storage performance of the organic-inorganic hybrid perovskite-derived carbon composite material formed after carbonization. In addition, if the particle size of perovskite material is too large, it will lead to the introduction of excessively large tin particles in the organic-inorganic hybrid perovskite-derived carbon composite material generated later, which will further affect the performance of the carbon composite material.
[0016] In the preparation method of the above-mentioned organic-inorganic hybrid perovskite-derived carbon composite material, the organic solvent is N,N-dimethylformamide (dimethyl sulfoxide DMSO, N-methyl-2-pyrrolidone NMP or γ-butyrolactone GBL can also be used as organic solvents, but the effect is not as good as N,N-dimethylformamide), and the inert protective atmosphere is nitrogen atmosphere and / or argon atmosphere.
[0017] In the preparation method of the above-mentioned organic-inorganic hybrid perovskite-derived carbon composite material, step S3 involves calcination under the following conditions: heating to 800℃ at a rate of 3–5℃ / min, followed by carbonization at 800℃ for 2 hours. If the heating rate is too rapid during carbonization, impurities in the mixed raw materials will be difficult to volatilize, affecting the performance of the final product. If the calcination temperature is too low or the carbonization time is too short, insufficient carbonization and impurities will result; if the calcination temperature is too high, the degree of graphitization will increase, which is detrimental to sodium storage.
[0018] The application of organic-inorganic hybrid perovskite-derived carbon composite materials is that the organic-inorganic hybrid perovskite-derived carbon composite materials prepared by the above-mentioned preparation method will be used as the anode material for sodium-ion batteries.
[0019] The technical solution of the present invention achieves the following beneficial technical effects:
[0020] The method for preparing the organic-inorganic hybrid perovskite-derived carbon composite material of this invention is simple and easy to industrialize, overcoming the problem of uniform dispersion of metallic tin in the traditional ball milling preparation of tin-carbon composite materials; and the carbon composite material prepared has a special tin-carbon composite structure, that is, tin nanoparticles are uniformly embedded between carbon layers, and the outer layer is coated with a dense carbon shell, which greatly improves the stability of the composite material; when used as a sodium-ion battery anode, it exhibits high capacity and cycle stability. Attached Figure Description
[0021] Figure 1XRD pattern of the organic-inorganic hybrid perovskite-derived carbon composite material of Example 1 of the present invention;
[0022] Figure 2 XRD pattern of the organic-inorganic hybrid perovskite-derived carbon composite material of Example 2 of the present invention;
[0023] Figure 3 XRD pattern of the organic-inorganic hybrid perovskite-derived carbon composite material of Example 3 of the present invention;
[0024] Figure 4 XRD pattern of the carbon composite material of Comparative Example 1 of the present invention;
[0025] Figure 5 The batteries using carbon materials as the negative electrode in Examples 1-3 and the Comparative Examples of this invention have a capacity of 100 mAh g. -1 Comparison of cycling performance under current;
[0026] Figure 6 In Example 3 of this invention, the organic-inorganic hybrid perovskite-derived carbon composite material used as the negative electrode in a battery with a capacity of 100 mAh g -1 Charge and discharge diagrams under current;
[0027] Figure 7 The cyclic voltammogram of the organic-inorganic hybrid perovskite-derived carbon composite material used as the negative electrode in Example 3 of this invention;
[0028] Figure 8a SEM image of the organic-inorganic hybrid perovskite-derived carbon composite material in Example 3 of this invention;
[0029] Figure 8b Mapping diagram of the organic-inorganic hybrid perovskite-derived carbon composite material of Example 3 of this invention;
[0030] Figure 9 SEM image of the carbon composite material in Comparative Example 1 of this invention;
[0031] Figure 10 Charge-discharge curves of the battery assembled in Embodiment 1 of the present invention;
[0032] Figure 11 Charge and discharge curves of the battery assembled in Embodiment 2 of the present invention. Detailed Implementation
[0033] Example 1
[0034] The preparation method of the organic-inorganic hybrid perovskite-derived carbon composite material in this embodiment is as follows:
[0035] S1: Add the inorganic tin source stannous bromide and the organic carbon source methylamine bromide to the organic solvent N,N-dimethylformamide (DMF) in a 1:1 molar ratio and mix thoroughly to obtain a uniform and transparent perovskite precursor solution; the concentration of the organic carbon source in the perovskite precursor solution is 0.4 mol / L.
[0036] S2: Place the perovskite precursor solution in a drying oven and keep it at 120℃ for 10 hours to evaporate the solvent and obtain the perovskite material; the particle size of the perovskite material is 10-100μm.
[0037] S3: After uniformly mixing the perovskite material with pitch powder that has passed through a 100-mesh sieve at a mass ratio of 1:4, the mixture is placed in a tube furnace and calcined and carbonized under a nitrogen atmosphere. The calcination conditions are: heating to 800℃ at a heating rate of 5℃ / min, and then calcining and carbonizing at 800℃ for 2 hours; after the calcination and carbonization are completed, the mixture is cooled to room temperature to obtain the organic-inorganic hybrid perovskite-derived carbon composite material.
[0038] The XRD pattern of the organic-inorganic hybrid perovskite-derived carbon composite material prepared in this embodiment is as follows: Figure 1 As shown, from Figure 1 As can be seen from the image, the diffraction peak (002) shows a low-angle shift and a wider half-peak width, indicating that the addition of hybrid perovskite leads to a wider carbon interlayer spacing and finer grains, which is more conducive to the insertion and extraction of sodium ions. The organic-inorganic hybrid perovskite-derived carbon composite material prepared in this embodiment is used as the anode material for sodium-ion batteries. The preparation method of the carbon electrode is as follows:
[0039] Organic-inorganic hybrid perovskite-derived carbon composite material was ground and mixed with conductive carbon black SuperP and sodium alginate in a mass ratio of 8:1:1, and then dispersed in ultrapure water. The resulting electrode slurry was uniformly coated onto copper foil and vacuum dried at 80°C for 12 hours to obtain the negative electrode sheet. The negative electrode sheet was then pressed and shaped using a pressing machine and cut to obtain the battery negative electrode sheet. The prepared negative electrode material was assembled in the following order: positive electrode shell - active material - PP film - electrolyte - sodium sheet - gasket - spring sheet - negative electrode shell, and then placed in a button cell packaging machine for pressing. The pressed battery was placed horizontally for 24 hours before testing.
[0040] (3) Sodium storage performance test: The LAND Blue Battery Charge-Discharge Tester was used to test the sodium storage performance at a capacity of 100mAh g. -1 Charge-discharge performance was tested at current density within a voltage range of 0.01–2.0V, at a constant temperature of 25℃. The test results are shown below. Figure 10 The electrode's first-cycle discharge specific capacity is 250.7 mAh / g, and its charge specific capacity is 106.4 mAh / g. Its cycle performance is as follows: Figure 5 As shown.
[0041] Example 2
[0042] The preparation method of the organic-inorganic hybrid perovskite-derived carbon composite material in this embodiment is as follows:
[0043] S1: Add the inorganic tin source stannous bromide and the organic carbon source methylamine bromide to the organic solvent N,N-dimethylformamide (DMF) in a molar ratio of 1:2 and mix thoroughly to obtain a uniform and transparent perovskite precursor solution; the concentration of the organic carbon source in the perovskite precursor solution is 0.4 mol / L.
[0044] S2: Place the perovskite precursor solution in a drying oven and keep it at 120℃ for 10 hours to evaporate the solvent and obtain the perovskite material; the particle size of the perovskite material is 10-100μm.
[0045] S3: The perovskite material and the asphalt powder that has passed through a 100-mesh sieve are mixed evenly at a mass ratio of 1:4 and spread evenly in a corundum boat. Then, the mixture is placed in a tube furnace and calcined and carbonized under a nitrogen atmosphere. The calcination conditions are: heating to 800℃ at a heating rate of 5℃ / min, and then calcining and carbonizing at 800℃ for 2 hours. After the calcination and carbonization are completed, the mixture is cooled to room temperature to obtain the organic-inorganic hybrid perovskite-derived carbon composite material.
[0046] The XRD pattern of the organic-inorganic hybrid perovskite-derived carbon composite material prepared in this embodiment is as follows: Figure 2 As shown, from Figure 2 As can be seen from the data, similar to the effect in Example 1, the diffraction peak of (002) shows a low-angle shift and a wider half-peak width, indicating that the addition of hybrid perovskite leads to a wider interlayer spacing and finer grains in the carbon composite material, which is more conducive to the insertion and extraction of sodium ions. The organic-inorganic hybrid perovskite-derived carbon composite material prepared in this example is used as the negative electrode material for sodium-ion batteries. The preparation method of the carbon electrode is as follows:
[0047] Organic-inorganic hybrid perovskite-derived carbon composite material was ground and mixed with conductive carbon black SuperP and sodium alginate in a mass ratio of 8:1:1, and then dispersed in ultrapure water. The resulting electrode slurry was uniformly coated onto copper foil and vacuum dried at 80°C for 12 hours to obtain the negative electrode sheet. The negative electrode sheet was then pressed and shaped using a pressing machine and cut to obtain the battery negative electrode sheet. The prepared negative electrode material was assembled in the following order: positive electrode shell - active material - PP film - electrolyte - sodium sheet - gasket - spring sheet - negative electrode shell, and then placed in a button cell packaging machine for pressing. The pressed battery was placed horizontally for 24 hours before testing.
[0048] (3) Sodium storage performance test: The LAND Blue Battery Charge-Discharge Tester was used to test the sodium storage performance at a capacity of 100mAh g. -1Charge-discharge performance was tested at current density within a voltage range of 0.01–2.0V, at a constant temperature of 25℃. The test results are shown below. Figure 11 The electrode's first-cycle discharge specific capacity is 239.3 mAh / g, and its charge specific capacity is 114.2 mAh / g. Its cycle performance is as follows: Figure 5 As shown.
[0049] Example 3
[0050] The preparation method of the organic-inorganic hybrid perovskite-derived carbon composite material in this embodiment is as follows:
[0051] S1: Add the inorganic tin source stannous bromide and the organic carbon source phenylethyl ammonium bromide to the organic solvent N,N-dimethylformamide DMF in a molar ratio of 1:2 and mix thoroughly to obtain a uniform and transparent perovskite precursor solution; the concentration of the organic carbon source in the perovskite precursor solution is 4 mol / L.
[0052] S2: Place the perovskite precursor solution in a drying oven and keep it at 120℃ for 10 hours to evaporate the solvent and obtain the perovskite material; the particle size of the perovskite material is 10-100μm.
[0053] S3: The perovskite material and the asphalt powder that has passed through a 100-mesh sieve are mixed evenly at a mass ratio of 1:4 and spread evenly in a corundum boat. Then, the mixture is placed in a tube furnace and calcined and carbonized under a nitrogen atmosphere. The calcination conditions are: heating to 800℃ at a heating rate of 5℃ / min, and then calcining and carbonizing at 800℃ for 2 hours. After the calcination and carbonization are completed, the mixture is cooled to room temperature to obtain the organic-inorganic hybrid perovskite-derived carbon composite material.
[0054] The XRD pattern of the organic-inorganic hybrid perovskite-derived carbon composite material prepared in this embodiment is as follows: Figure 3 As shown, from Figure 3 It can be seen from the XRD that the peak intensity of (002) is significantly lower than that of Example 1. Figure 1 ) and Example 2 ( Figure 2 Materials prepared by ) Figure 8a and Figure 8b The images show the SEM image and mapping diagram of the carbon composite material. The images reveal that the asphalt was catalyzed by the perovskite material, resulting in a carbon composite material with a rich porous structure, which is beneficial for improving sodium storage capacity. The mapping diagram shows that tin is uniformly distributed in the carbon composite material, preventing tin agglomeration and improving the cycle stability of the battery.
[0055] The organic-inorganic hybrid perovskite-derived carbon composite material prepared in this embodiment is used as the anode material for sodium-ion batteries. The preparation method of the carbon electrode is as follows:
[0056] Organic-inorganic hybrid perovskite-derived carbon composite material was ground and mixed with conductive carbon black SuperP and sodium alginate in a mass ratio of 8:1:1, and then dispersed in ultrapure water. The resulting electrode slurry was uniformly coated onto copper foil and vacuum dried at 80°C for 12 hours to obtain the negative electrode sheet. The negative electrode sheet was then pressed and shaped using a pressing machine and cut to obtain the battery negative electrode sheet. The prepared negative electrode material was assembled in the following order: positive electrode shell - active material - PP film - electrolyte - sodium sheet - gasket - spring sheet - negative electrode shell, and then placed in a button cell packaging machine for pressing. The pressed battery was placed horizontally for 24 hours before testing.
[0057] (3) Sodium storage performance test: The LAND Blue Battery Charge-Discharge Tester was used to test the sodium storage performance at a capacity of 100mAh g. -1 Charge-discharge performance was tested at a current density of 0.01–2.0V within a constant temperature range of 25℃. The first-cycle discharge specific capacity was 264.0 mAh / g, and the first-cycle charge specific capacity was 173.2 mAh / g. Its cycle performance is as follows: Figure 5 As shown, the charge-discharge curves are as follows: Figure 6 As shown in the figure. Simultaneously, cyclic voltammetry curves were tested using a Chenhua CHI660E electrochemical workstation. The test voltage ranged from 0.01 to 2 V, and the scan rate was 0.001 V / s. The test results are shown in the figure. Figure 7 The good overlap of the CV curves indicates that the anode prepared by the organic-inorganic hybrid perovskite-carbon composite material has good structural stability.
[0058] Comparative Example 1
[0059] (1) Preparation of carbon materials: First, the raw asphalt was ground through a 100-mesh sieve. 5g of asphalt was evenly spread and placed in a corundum boat. The material was placed in a tube furnace and heated to 800℃ in a nitrogen atmosphere at a heating rate of 5℃ / min for carbonization. The temperature was held for 2 hours, and after cooling, the asphalt carbon material was obtained. Its XRD is as follows: Figure 4 As shown, SEM Figure 9 As shown; from Figure 4 The XRD pattern shows that the (002) diffraction peak is located at around 25.5° with a half-maximum width of 6.6°. The higher diffraction peak indicates the formation of soft carbon with narrower interlayer spacing, and the smaller half-maximum width indicates a larger grain size, both of which are unfavorable for sodium ion insertion / extraction. Figure 9 As can be seen from the comparison, the carbon material prepared in Comparative Example 1 has a smooth surface and large particles, which is not conducive to the storage of sodium ions.
[0060] (2) The preparation and testing of the carbon electrode were the same as in Example 1. The first discharge specific capacity of the electrode was 158.2 mAh / g, and the charging specific capacity was 91.6 mAh / g, showing excellent sodium storage performance.
[0061] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of the claims of this patent application.
Claims
1. A method for preparing organic-inorganic hybrid perovskite-derived carbon composite materials, characterized in that, Includes the following steps: S1: Inorganic tin source and organic carbon source are added to an organic solvent and mixed thoroughly to obtain a perovskite precursor solution; the molar ratio of inorganic tin source to organic carbon source is 1:(1-5); the concentration of organic carbon source in the perovskite precursor solution is 0.1-0.5 mol / L; the organic carbon source is methylammonium bromide and / or phenylethylammonium bromide; the inorganic tin source is stannous bromide, stannous iodide or stannous chloride; S2: Dry the solvent in the perovskite precursor solution to obtain the perovskite material; the drying temperature is 110-120℃ and the drying time is 10-24h. S3: After the perovskite material and asphalt are mixed evenly, the mass ratio of the perovskite material to the asphalt is 1:(1~20). The mixture is then calcined and carbonized under an inert gas protective atmosphere. After the calcination and carbonization are completed, an organic-inorganic hybrid perovskite-derived carbon composite material is obtained.
2. The method for preparing the organic-inorganic hybrid perovskite-derived carbon composite material according to claim 1, characterized in that, In step S1, the molar ratio of inorganic tin source to organic carbon source is 1:(1-2); the concentration of organic carbon source in perovskite precursor solution is 0.4 mol / L.
3. The method for preparing the organic-inorganic hybrid perovskite-derived carbon composite material according to claim 1, characterized in that, In step S3, the mass ratio of perovskite material to asphalt is 1:4; the asphalt passes through a 100-mesh sieve, and the particle size of the perovskite material is 10-100 μm.
4. The method for preparing the organic-inorganic hybrid perovskite-derived carbon composite material according to claim 1, characterized in that, The organic solvent in step S1 is N,N-dimethylformamide, and the inert protective atmosphere in step S3 is a nitrogen atmosphere and / or an argon atmosphere.
5. The method for preparing the organic-inorganic hybrid perovskite-derived carbon composite material according to claim 1, characterized in that, In step S3, the calcination conditions are as follows: the temperature is increased to 800℃ at a heating rate of 3-5℃ / min, and then calcined and carbonized at 800℃ for 2 hours.
6. The application of organic-inorganic hybrid perovskite-derived carbon composite materials, characterized in that, The organic-inorganic hybrid perovskite-derived carbon composite material prepared by the method described in claim 1 is used as a negative electrode material for sodium-ion batteries.