A phenolic resin, pitch and silicon mesoporous silicon-carbon composite material and a preparation method thereof
Patent Information
- Application Number
- CN202610538206.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-22
- Publication Date
- 2026-08-04
AI Technical Summary
这类材料导电性能优异，但其碳骨架在高温处理或长期循环过程中易发生收缩、坍塌或重组，结构稳定性不足，影响其使用寿命和性能保持率
[0023] The beneficial effects of this invention are as follows: This invention overcomes the performance defects of a single precursor mesoporous carbon by combining the structural stability of hard carbon precursors and the conductivity advantages of soft carbon precursors; by introducing rigid silicate components, it effectively suppresses the skeleton shrinkage during high-temperature carbonization to obtain high-performance mesoporous silicon-carbon composite materials; the preparation process is simple and low-cost, and no template removal step is required, making it suitable for fields such as energy storage devices, fuel cells, catalyst supports, and environmental remediation.
Smart Images
Figure CN122501844A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of nanocomposite materials technology, specifically relating to a mesoporous silicon-carbon composite material of phenolic resin, pitch and silicon, and its preparation method. Background Technology
[0002] Mesoporous carbon materials, due to their high specific surface area, tunable pore structure, and good physicochemical stability, have shown great application potential in energy storage and conversion, catalysis, adsorption, and environmental remediation. However, mesoporous carbon prepared from traditional single carbon precursors often has inherent performance limitations, which restricts their practical application and large-scale development.
[0003] Currently, common mesoporous carbons are mainly divided into two categories: one is mesoporous carbon prepared from hard carbon precursors, represented by phenolic resins. These materials exhibit strong framework rigidity and good structural stability after carbonization, but their low degree of graphitization results in generally poor conductivity, making it difficult to meet the requirements of high-power-density energy storage or efficient electrocatalysis. The other category is mesoporous carbon prepared from soft carbon precursors, represented by pitch. These materials have excellent conductivity, but their carbon framework is prone to shrinkage, collapse, or reorganization during high-temperature treatment or long-term cycling, resulting in insufficient structural stability and affecting their service life and performance retention.
[0004] Therefore, developing a novel method for preparing mesoporous carbon composite materials that is simple, low-cost, and simultaneously achieves structural stability and high electrical conductivity has become a key technical problem urgently needing to be solved in this field. This will not only expand the application range of mesoporous carbon materials under harsh conditions but also provide a practical technical path for their industrialization and promotion. Summary of the Invention
[0005] Based on the above-mentioned technical problems, the purpose of this invention is to provide a phenolic resin, asphalt and silica mesoporous silicon carbon composite material and a method for preparing the same.
[0006] This invention provides a method for preparing a composite material of phenolic resin, bitumen, and mesoporous silica-carbon, comprising the following steps:
[0007] (1) Phenolic resin, asphalt, tetraethyl orthosilicate and acid catalyst are mixed and reacted;
[0008] (2) The mixture in step (1) is induced to self-assemble by solvent evaporation, and then subjected to heat treatment to crosslink and condense the phenolic resin and tetraethyl orthosilicate to obtain a cured precursor.
[0009] (3) The cured precursor is calcined at 500-1500°C for 1-5 hours in an inert atmosphere to obtain the mesoporous silicon-carbon composite material.
[0010] In some embodiments, a surfactant is also added in step (1), the surfactant being selected from (a) PEO-PPO-PEO type nonionic block copolymers, including F127, P123, F108, P105, and L64;
[0011] (b) Hydrophobic-hydrophilic block copolymers, including PS-b-PEO, PS-b-PAA, PS-b-PMMA, PS-b-P2VP, and PCS-b-PMMA;
[0012] (c) Ionic surfactants, including CTAB, CTAC, DTAB, SDS, SDBS, and AOT;
[0013] Furthermore, the surfactant is selected from F127, PS-b-PEO and CTAB.
[0014] In some embodiments, the surfactant / structure directing agent is used to form an ordered mesoporous structure, regulate pore size and pore connectivity, improve the dispersion compatibility of asphalt and silicon source, and can further achieve pore size enlargement and structure optimization by cooperating with pore size regulating agents. When using ionic surfactants (such as CTAB, CTAC), the solvent can be an alcohol / water system or a mixture of alcohol / water and tetrahydrofuran to improve its solubility and self-assembly effect.
[0015] In some embodiments, the mass ratio of the phenolic resin, asphalt, surfactant, and tetraethyl orthosilicate is 0.1-5: 0.1-0.5: 0.5-1:0.1-5.
[0016] In some embodiments, the phenolic resin is prepared by reacting phenol, formaldehyde, and an alkaline catalyst; the alkaline catalyst is selected from sodium hydroxide or potassium hydroxide.
[0017] In some embodiments, the acid catalyst is selected from at least one of nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, formic acid, or oxalic acid.
[0018] In some embodiments, the amount of acid catalyst added is 0.5% to 10% of the total mass of phenolic resin, pitch and tetraethyl orthosilicate.
[0019] In some implementations, the heat treatment conditions in step (2) are: first drying at room temperature for 1 to 4 hours, and then drying at 50 to 100°C for 12 to 24 hours.
[0020] In some implementations, the calcination temperature in step (3) is 600-700°C and the calcination time is 3 hours.
[0021] The present invention also provides a mesoporous silicon-carbon composite material, which is prepared by the method described above.
[0022] The present invention also provides the application of the above-mentioned mesoporous carbon composite material in energy storage devices, fuel cell catalyst supports, wastewater treatment agents or electromagnetic shielding materials.
[0023] The beneficial effects of this invention are as follows: This invention overcomes the performance defects of a single precursor mesoporous carbon by combining the structural stability of hard carbon precursors and the conductivity advantages of soft carbon precursors; by introducing rigid silicate components, it effectively suppresses the skeleton shrinkage during high-temperature carbonization to obtain high-performance mesoporous silicon-carbon composite materials; the preparation process is simple and low-cost, and no template removal step is required, making it suitable for fields such as energy storage devices, fuel cells, catalyst supports, and environmental remediation. Attached Figure Description
[0024] Figure 1 This is a transmission electron microscope image of disordered mesoporous silica carbon composite material obtained in Example 1 of the present invention, consisting of phenolic resin, asphalt, and mesoporous silica carbon.
[0025] Figure 2 This is a transmission electron microscope image of ordered mesoporous silica carbon composite material obtained in Example 2 of the present invention, consisting of phenolic resin, asphalt, and mesoporous silica carbon.
[0026] Figure 3 This is a transmission electron microscope image of ordered mesoporous silica carbon composite material obtained in Example 3 of the present invention, consisting of phenolic resin, asphalt, and mesoporous silica carbon.
[0027] Figure 4 This is a transmission electron microscope image of ordered mesoporous silica carbon composite material obtained in Example 4 of the present invention, consisting of phenolic resin, asphalt, and mesoporous silica carbon.
[0028] Figure 5 The ordered mesoporous silica-carbon nitrogen adsorption-desorption isotherm of the phenolic resin, asphalt, and mesoporous silica-carbon composite material obtained in Example 4 of this invention;
[0029] Figure 6 This is a diagram showing the ordered mesoporous silica pore size distribution of the phenolic resin, asphalt, and mesoporous silica composite material obtained in Example 4 of the present invention.
[0030] Figure 7 This is a transmission electron microscope image of disordered mesoporous silica carbon composite material obtained in Example 5 of the present invention, consisting of phenolic resin, asphalt, and mesoporous silica carbon.
[0031] Figure 8 This is a transmission electron microscope image of ordered mesoporous silica carbon composite material obtained in Example 6 of the present invention, consisting of phenolic resin, asphalt, and mesoporous silica carbon.
[0032] Figure 9 This is a transmission electron microscope image of ordered mesoporous silica carbon composite material obtained in Example 7 of the present invention, consisting of phenolic resin, asphalt, and mesoporous silica carbon.
[0033] Figure 10 This is a transmission electron microscope image of ordered mesoporous silica carbon composite material obtained in Example 8 of the present invention, consisting of phenolic resin, asphalt, and mesoporous silica carbon.
[0034] Figure 11 A price comparison chart of phenolic resin and asphalt used in the implementation of this invention;
[0035] Figure 12 The sodium electrical properties of the ordered mesoporous silica-carbon composite material obtained by implementing the present invention are described. Detailed Implementation
[0036] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0037] Example 1
[0038] A phenolic resin prepolymer was obtained by mixing and heating a phenol, formaldehyde, and sodium hydroxide solution. 0.3 g of this prepolymer was dissolved in tetrahydrofuran. 0.1 g of asphalt with a softening temperature of 150°C was dissolved in tetrahydrofuran. 70 g of surfactant F12 was dissolved in tetrahydrofuran. These three solutions were mixed, and 0.1 g of concentrated nitric acid (~67%) was added. The mixture was then dried at room temperature for 1–4 h using a solvent evaporation-induced self-assembly method, placed in a 50°C oven for 24 h, followed by a 100°C oven for 24 h, and finally calcined at 650°C in an inert atmosphere for 3 h to obtain a disordered mesoporous material (e.g., ...). Figure 1 ).
[0039] Example 2
[0040] A phenolic resin prepolymer was obtained by heating a mixture of phenol, formaldehyde solution, and sodium hydroxide solution. 0.3g of this prepolymer was dissolved in tetrahydrofuran. 0.1g of asphalt at a softening temperature of 150°C was dissolved in tetrahydrofuran. 0.6g of surfactant F127 was dissolved in tetrahydrofuran. 0.4g of tetraethyl orthosilicate was also dissolved in tetrahydrofuran. These four solutions were mixed, and 0.1g of concentrated nitric acid (~67%) was added. The mixture was then dried at room temperature for 1-4 hours using a solvent evaporation-induced self-assembly method. It was then placed in a 50°C oven for 24 hours, followed by a 100°C oven for 24 hours. Finally, the material was calcined at 650°C in an inert atmosphere for 3 hours to obtain an ordered mesoporous material (e.g., ...). Figure 2 ).
[0041] Example 3
[0042] A phenolic resin prepolymer was obtained by mixing and heating a phenol, formaldehyde, and sodium hydroxide solution. 0.3g of this prepolymer was dissolved in tetrahydrofuran. 0.1g of asphalt at a softening temperature of 150°C was dissolved in tetrahydrofuran. 0.6g of a surfactant, PS-b-PEO, was dissolved in tetrahydrofuran. 0.4g of tetraethyl orthosilicate was also dissolved. These four solutions were mixed, and 0.1g of concentrated nitric acid (~67%) was added. The mixture was then dried at room temperature for 1-4 hours using a solvent evaporation-induced self-assembly method. It was then placed in a 50°C oven for 24 hours, followed by a 100°C oven for 24 hours. Finally, the material was calcined at 650°C in an inert atmosphere for 3 hours to obtain an ordered mesoporous material (e.g., ...). Figure 3 ).
[0043] Example 4
[0044] A phenolic resin prepolymer was obtained by heating a mixture of phenol, formaldehyde solution, and sodium hydroxide solution. 0.3 g of this prepolymer was dissolved in tetrahydrofuran. 0.1 g of asphalt with a softening temperature of 150°C was dissolved in tetrahydrofuran. 0.6 g of surfactant CTAB and 0.4 g of tetraethyl orthosilicate were dissolved in tetrahydrofuran. These four solutions were mixed, and 0.1 g of concentrated nitric acid (~67%) was added. The mixture was then dried at room temperature for 1–4 h using a solvent evaporation-induced self-assembly method, placed in a 50°C oven for 24 h, followed by a 100°C oven for 24 h, and finally calcined at 650°C in an inert atmosphere for 3 h to obtain an ordered mesoporous material (e.g., ...). Figure 4 BET has a specific surface area of 509 m². 2 / g, pore size 3.7 nm (e.g.) Figure 5 ,6).
[0045] Example 5
[0046] A phenolic resin prepolymer was obtained by heating a mixture of phenol, formaldehyde solution, and sodium hydroxide solution. 0.3g of this prepolymer was dissolved in tetrahydrofuran. 0.1g of asphalt with a softening temperature of 150°C was dissolved in tetrahydrofuran. 0.6g of surfactant F127 and 0.4g of tetraethyl orthosilicate were also dissolved in tetrahydrofuran. These four solutions were mixed and dried at room temperature for 1–4 h using a solvent evaporation-induced self-assembly method. The mixture was then placed in a 50°C oven for 24 h, followed by a 100°C oven for 24 h. Finally, the material was calcined at 650°C in an inert atmosphere for 3 h to obtain a disordered mesoporous material (e.g., ...). Figure 7 ).
[0047] Example 6
[0048] A phenolic resin prepolymer was obtained by mixing and heating a phenolic resin solution, formaldehyde solution, and sodium hydroxide solution. 0.3g of this prepolymer was dissolved in tetrahydrofuran. 0.1g of asphalt with a softening temperature of 150°C was dissolved in tetrahydrofuran. 0.6g of surfactant F127 was dissolved in tetrahydrofuran. 0.4g of tetraethyl orthosilicate was also dissolved in tetrahydrofuran. These four solutions were mixed, and 0.1g of concentrated nitric acid (~67%) was added. The mixture was then dried at room temperature for 1-4 hours using a solvent evaporation-induced self-assembly method. It was then placed in a 50°C oven for 24 hours, followed by a 100°C oven for 24 hours. Finally, the material was directly carbonized in an inert atmosphere carbonization apparatus preheated to 650°C for 3 hours to obtain an ordered mesoporous material (e.g., ...). Figure 8 ).
[0049] Example 7
[0050] A phenolic resin prepolymer was obtained by mixing and heating a phenolic resin solution, formaldehyde solution, and sodium hydroxide solution. 0.3g of this prepolymer was dissolved in tetrahydrofuran. 0.1g of asphalt at a softening temperature of 200°C was dissolved in tetrahydrofuran. 0.6g of a surfactant, PS-b-PEO, and 0.4g of tetraethyl orthosilicate were dissolved in tetrahydrofuran. These four solutions were mixed, and 0.1g of concentrated nitric acid (~67%) was added. The mixture was then dried at room temperature for 1-4 hours using a solvent evaporation-induced self-assembly method, placed in a 50°C oven for 24 hours, followed by a 100°C oven for 24 hours. Finally, the material was directly carbonized in an inert atmosphere carbonization apparatus preheated to 650°C for 3 hours to obtain an ordered mesoporous material (e.g., ...). Figure 9 ).
[0051] Example 8
[0052] A phenolic resin prepolymer was obtained by mixing and heating a phenolic resin solution, formaldehyde solution, and sodium hydroxide solution. 0.3 g of this prepolymer was dissolved in tetrahydrofuran. 0.1 g of asphalt at a softening temperature of 250°C was dissolved in tetrahydrofuran. 0.6 g of surfactant F127 was dissolved in tetrahydrofuran. 0.4 g of tetraethyl orthosilicate was also dissolved in tetrahydrofuran. These four solutions were mixed, and 0.1 g of concentrated nitric acid (~67%) was added. The mixture was then dried at room temperature for 1–4 h using a solvent evaporation-induced self-assembly method, placed in a 50°C oven for 24 h, followed by a 100°C oven for 24 h. Finally, the material was directly carbonized in an inert atmosphere carbonization apparatus preheated to 650°C for 3 h to obtain an ordered mesoporous material (e.g., ...). Figure 10 ).
[0053] From a cost perspective, the unit price of phenolic resin is approximately 1.56 yuan / gram, while that of asphalt is only about 0.012 yuan / gram (e.g., ...). Figure 11The cost difference between the two is approximately 130 times. If calculated based on the same carbon source, phenolic resin would significantly increase raw material and experimental iteration costs, and scaling up to the kilogram level would create even greater financial pressure. Asphalt, on the other hand, is widely available, has stable prices, can be purchased on a large scale, and possesses good carbon-forming properties and processability, facilitating large-scale preparation and industrial transformation. Furthermore, asphalt reduces solvent and curing steps, lowering energy consumption and process complexity, resulting in a more significant cost advantage. Therefore, under the premise of meeting performance requirements, adding asphalt is a more economical and sustainable choice.
[0054] In terms of energy storage, this material exhibits high and stable sodium storage capacity in sodium-ion batteries. As shown in the figure, the reversible specific capacity after the first cycle is approximately ~550 mAh g⁻¹, then slowly decreases and stabilizes in the ~535–545 mAh g⁻¹ range within the first 30–40 cycles. Afterward, it remains relatively stable with minimal fluctuations up to 100 cycles (still approximately ~535 mAh g⁻¹ at the end), indicating that after the initial SEI construction and wetting process, the electrode interface gradually stabilizes, and the sodium storage reaction exhibits good reversibility and sustainability (e.g., ...). Figure 12 Meanwhile, the coulombic efficiency remained close to and stable at ~99–100%, with almost no significant decay, indicating that side reactions were effectively suppressed and the SEI film was relatively stable. In contrast to existing technologies, commercial hard carbon, as the mainstream anode for sodium-ion batteries, typically has a reversible capacity mainly concentrated in ~250–350 mAh g⁻¹, and is susceptible to varying degrees of capacity decay due to interfacial side reactions and structural evolution during long cycles. While some modified carbon materials can improve capacity, they often come with trade-offs in rate performance or cycle stability. In contrast, the material in this work achieves stable output for 100 cycles and a coulombic efficiency close to 100% at a high capacity level of ~535 mAh g⁻¹, demonstrating its advantages in the comprehensive indicators of "high capacity—high reversibility—cycle stability". Overall, this material combines high capacity and excellent cycle stability, making it a potential candidate material for high-performance carbon-based sodium-ion battery anodes.
[0055] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A method for preparing a phenolic resin, pitch, and mesoporous silica-carbon composite material, characterized in that, Includes the following steps: (1) Phenolic resin, asphalt, tetraethyl orthosilicate and acid catalyst are mixed and reacted; (2) The mixture in step (1) is induced to self-assemble by solvent evaporation, and then subjected to heat treatment to crosslink and condense the phenolic resin and tetraethyl orthosilicate to obtain a cured precursor. (3) The cured precursor is calcined at 500-1500°C for 1-5 hours in an inert atmosphere to obtain the mesoporous silicon-carbon composite material.
2. The preparation method according to claim 1, characterized in that, The surfactant is selected from one or more of the following: (a) PEO-PPO-PEO type nonionic block copolymers, including F127, P123, F108, P105, and L64; (b) Hydrophobic-hydrophilic block copolymers, including PS-b-PEO, PS-b-PAA, PS-b-PMMA, PS-b-P2VP, and PCS-b-PMMA; (c) Ionic surfactants, including CTAB, CTAC, DTAB, SDS, SDBS, and AOT; Furthermore, the surfactant is selected from F127, PS-b-PEO and CTAB.
3. The preparation method according to claim 2, characterized in that, The mass ratio of the phenolic resin, asphalt, surfactant and tetraethyl orthosilicate is 0.1-5: 0.1-0.5: 0.5-1:0.1-5.
4. The preparation method according to claim 1 or 2, characterized in that, The phenolic resin is prepared by reacting phenol, formaldehyde and an alkaline catalyst; the alkaline catalyst is selected from sodium hydroxide or potassium hydroxide.
5. The preparation method according to claim 1, characterized in that, The acid catalyst is selected from at least one of nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, formic acid, or oxalic acid.
6. The preparation method according to claim 1, characterized in that, The amount of acid catalyst added is 0.5% to 10% of the total mass of phenolic resin, asphalt and tetraethyl orthosilicate.
7. The preparation method according to claim 1, characterized in that, The heat treatment conditions in step (2) are: first dry at room temperature for 1 to 4 hours, and then dry at 50 to 100°C for 12 to 24 hours.
8. The preparation method according to claim 1, characterized in that, The calcination temperature in step (3) is 600-700℃ and the calcination time is 3 hours.
9. A mesoporous silicon-carbon composite material, characterized in that, It is prepared by the method described in any one of claims 1 to 8.
10. The use of the mesoporous silicon-carbon composite material according to claim 9 in the preparation of energy storage devices, fuel cell catalyst supports, wastewater treatment agents or electromagnetic shielding materials.