A resin, a method for producing the same, and a porous carbon and silicon-carbon negative electrode material

Abstract

This invention discloses a resin, its preparation method, and porous carbon and silicon-carbon anode materials. The resin comprises an in-situ bonded polymeric resin and a cyclic oligomer. The cyclic oligomer is distributed within the polymeric resin as a rigid framework. At least one of the following interactions exists between the polymeric resin and the cyclic oligomer: intermolecular hydrogen bonding, intermolecular π-π stacking, and covalent bonding. By introducing a cyclic resin oligomer with high structural rigidity as a molecular-scale supporting unit, it is in-situ bonded to linear or branched polymeric resin chains during polymerization or curing, forming a composite resin system with a stable rigid framework. During subsequent carbonization, this rigid structure effectively inhibits resin shrinkage, maintains morphological stability, and promotes the escape of volatiles during pyrolysis, forming interconnected channels. This allows for the controllable construction of a pore structure from micropores to mesopores without relying on any external template.

Description

Technical Field

[0001] This invention relates to the field of lithium-ion battery anode material technology, and more specifically, to a resin and its preparation method, as well as porous carbon and silicon-carbon anode materials. Background Technology

[0002] Porous carbon materials, due to their unique pore structure and excellent physicochemical properties, show broad application prospects in the field of energy storage. As a key component of silicon-carbon anodes in lithium-ion batteries, the pore structure characteristics of porous carbon directly affect the loading capacity and electrochemical performance of silicon materials. Studies have shown that a hierarchical pore structure dominated by mesopores and assisted by micropores can effectively alleviate the volume effect during the charging and discharging process of silicon materials, while providing efficient electron transport paths and ion diffusion channels.

[0003] Phenolic resins, due to their highly designable molecular structure and high carbonization yield, have become ideal precursors for preparing porous carbon materials. In existing technologies, the template method is a commonly used approach for constructing phenolic resin-based porous carbon structures, including two main process routes: the hard template method and the soft template method. The hard template method typically uses inorganic materials such as zinc oxide and silica as pore-forming agents, preparing porous carbon through steps such as impregnation, carbonization, and acid washing; the soft template method utilizes the self-assembly of organic molecules such as surfactants to form mesoscopic structures. Patent literature shows that by optimizing the type of template agent and process parameters, a specific surface area exceeding 2000 m² can be obtained. 2 / g porous carbon material.

[0004] However, the template-based preparation process has inherent limitations: on the one hand, the structure of the template agent itself restricts the controllability of the pore morphology, resulting in materials that are predominantly microporous with a mesoporous ratio generally below 30%; on the other hand, the template removal process increases the complexity and production cost. More importantly, the network structure formed by methylene bridges in phenolic resin molecules is prone to bond breakage during high-temperature carbonization, leading to the collapse of the mesoporous structure. This structural instability makes it difficult for the final product to maintain the initially designed mesoporous ratio, severely restricting the material's application in high-performance silicon-carbon anodes.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a resin and its preparation method, as well as porous carbon and silicon-carbon anode materials, thereby improving the above-mentioned technical problems.

[0007] This invention is implemented as follows: In a first aspect, the present invention provides a resin comprising an in-situ bonded polymeric resin and a cyclic oligomer, wherein the cyclic oligomer is distributed within the polymeric resin as a rigid framework, and at least one of the following interactions exists between the polymeric resin and the cyclic oligomer: intermolecular hydrogen bonds, intermolecular π-π stacking, and covalent bonds.

[0008] In an optional embodiment, the mass ratio of the cyclic oligomer to the polymeric resin is 1:5 to 1:1000.

[0009] In an optional embodiment, the polymer resin has at least one of the following characteristics: a. The polymer resin is a linear polymer with a number-average molecular weight (NUMBER). M n The value ranges from 10,000 to 1,000,000 Da, with a dispersion ( The number average molecular weight is 1.0~4.0, or the polymer resin is a network polymer with a number average molecular weight (NUMBER). M n The value ranges from 10,000 to 1,000,000 Da, with a dispersion ( The value ranges from 2.0 to 5.0. b. The polymer resin chain contains at least one of the following reactive sites: aromatic hydrocarbon, hydroxymethyl, carboxylic acid, or aldehyde group; c. The monomers used to prepare the polymer resin include at least one of phenols, aromatic hydrocarbons, aryl carboxylic acids, aldehydes, and alcohols; d. The polymer resin is synthesized via a Friedel-Crafts reaction mechanism.

[0010] In an optional embodiment, the cyclic oligomer has at least one of the following characteristics: a. The number of aromatic ring monomer units in the cyclic oligomer is 5 to 10; b. The diameter of the cyclic oligomer is 0.9~4.0 nm; c. The cyclic oligomer contains at least one of the following reactive sites: aromatic hydrocarbon, hydroxymethyl, carboxylic acid, or aldehyde group; d. The monomers used to prepare the cyclic oligomers include at least one of phenols, aromatic hydrocarbons, aryl carboxylic acids, aldehydes, and alcohols; e. The cyclic oligomer is synthesized via a Friedel-Crafts reaction mechanism.

[0011] In an optional embodiment, the intermolecular hydrogen bond is an intermolecular hydrogen bond formed by phenolic structural units; the intermolecular π-π stacking is an intermolecular π-π stacking formed by aromatic ring structural units; and the covalent bond is a covalent bond formed between the reactive sites on the polymer resin and the cyclic oligomer.

[0012] In a second aspect, the present invention provides a method for preparing a resin as described in any of the foregoing embodiments, comprising: The first monomer is subjected to an oligomerization reaction with the first crosslinking agent to form the cyclic oligomer; The polymer resin is prepared by adding a second monomer and a second crosslinking agent to the reaction system and then performing a polymerization reaction. After heating the reaction system, the polymer resin and the cyclic oligomer undergo cross-linking and curing.

[0013] In an optional implementation, at least one of the first monomer and the second monomer is of the same monomer type; preferably, at least one of the first monomer and the second monomer has the same monomer structure.

[0014] In an optional implementation, the oligomerization reaction takes 1 h to 5 h.

[0015] Thirdly, the present invention provides a porous carbon, which is obtained by carbonizing and activating the resin described in any of the foregoing embodiments. Preferably, the carbonization process is as follows: under the protection of an inert atmosphere, the final carbonization temperature is controlled at 620~670 °C, the heating rate is 0.5~1.5 °C / min, and the temperature is maintained at the final temperature for 1.5~2.5 h; the activation process is as follows: using water vapor as the activation reagent, the air flow rate is 1.5~2.5 mL / min, and the temperature is treated at 750~800 °C for 1.5~2.5 h.

[0016] Fourthly, the present invention provides a silicon-carbon anode material, which is obtained by silicon deposition of porous carbon as described in the foregoing embodiments via vapor deposition.

[0017] The present invention has the following beneficial effects: 1. Innovation of green, efficient, and scalable preparation pathways This invention overcomes the limitations of traditional template methods in terms of process complexity, energy consumption, and environmental impact. Compared with traditional processes, it significantly simplifies the preparation process: traditional methods require multiple key steps, including template agent synthesis, dispersion and compounding, high-temperature carbonization, chemical etching to remove the template, and post-processing, each of which presents challenges in process control and environmental impact. Its core innovation lies in molecularizing the "pore-forming template" function. By introducing specific rigid cyclic oligomers, a stable three-dimensional support network is constructed in situ during the resin curing stage. Subsequent carbonization only requires a single step to simultaneously achieve the triple goals of resin pyrolysis, pore formation, and framework shaping, thus simplifying the process. This technology not only significantly reduces equipment investment, energy consumption, and time costs, but also fundamentally eliminates the problem of treating corrosive wastewater generated by strong acid / alkali etching steps in traditional processes, making the production process both safe and environmentally friendly, while also facilitating continuous and large-scale production.

[0018] 2. Performance Breakthrough: Synergistic Optimization of Precisely Controllable Hierarchical Porous Structure and Mechanical Properties This invention, through innovative design at the molecular level, effectively resolves the inherent contradiction between pore structure and mechanical strength in porous materials. Its technical advantages are reflected in: (1) Pore structure can be precisely controlled: By systematically adjusting the type, molecular size and addition ratio of cyclic oligomers (such as cyclic phenolic resins, cyclic aromatic ether ketones, etc.), the escape path of volatile components and the distribution of shrinkage stress during pyrolysis can be precisely controlled, thereby orderly constructing interconnected mesopores and even macropores in the microporous matrix, forming an ideal hierarchical pore structure. This special structure provides ample space for the uniform distribution of high loading of silicon particles, and also constructs an efficient three-dimensional channel network for electrolyte wetting and rapid lithium-ion transport.

[0019] (2) Significantly enhanced mechanical properties: Cyclic oligomers are uniformly distributed in the carbon matrix as nanoscale reinforcing phases, which can greatly improve the intrinsic mechanical strength and structural toughness of the material. The resulting porous carbon material exhibits excellent anti-pulverization ability during the repeated expansion / contraction of silicon particles, providing a key material guarantee for the development of silicon-carbon anode materials with high cycle stability and excellent rate performance.

[0020] 3. Outstanding economic benefits and industrialization advantages The technological advantages of this invention translate into significant economic benefits and industrialization potential: (1) Increased carbon yield: Since the template removal process is completely avoided (in traditional processes, the template usually accounts for 20% to 50% of the composite material mass), the carbon yield is increased by more than 15% compared with traditional methods, directly reducing the unit cost of materials.

[0021] (2) Strong process stability: The prepared porous carbon materials have excellent batch consistency and structural uniformity, and the performance regulation does not depend on high-cost complex template agents, with obvious raw material cost advantages.

[0022] (3) Good industrial compatibility: This method is highly compatible with existing resin-based carbon material production processes (including impregnation, coating, curing, etc.), and can achieve technological upgrades without modifying core production equipment, which greatly reduces the technical threshold and transformation cost of industrialization transformation.

[0023] In summary, this invention, through its original design concept of "intramolecular self-support," successfully transforms the complex physical pore-forming process into a controllable chemical structure evolution process. This technology not only represents a breakthrough innovation over traditional template methods in principle, but also simultaneously achieves four major goals in practical applications: greening the process, designable structure, enhanced performance, and cost advantage. These breakthroughs provide solid technical support and leading process solutions for the research and commercial application of next-generation high-performance, long-life silicon-carbon anode materials. Attached Figure Description

[0024] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 This is a schematic diagram of the supporting effect of cyclic oligomers on linear polymer resins. In the figure, 001 represents linear polymer resin, 002 represents cyclic oligomer, 003 represents the π-π stacking force between cyclic oligomer and polymer resin, 004 represents the hydrogen bonding force between cyclic oligomer and polymer resin, and 005 represents the covalent bond force between cyclic oligomer and polymer resin. Figure 2 This is a schematic diagram showing the supporting effect of cyclic oligomers on network polymer resins. In the diagram, 006 represents the network polymer resin and 007 represents the cyclic oligomer. Figure 3 The nitrogen adsorption curve of resin 1 obtained in Example 1 is shown below. Figure 4 The GPC curve of resin 1 obtained in Example 1; Figure 5 The GPC curve of resin 2 obtained in Example 2; Figure 6 The GPC curve of resin 3 obtained in Example 3; Figure 7 The GPC curve of resin 4 obtained in Example 4; Figure 8 The GPC curve of resin 5 obtained in Example 5 is shown below. Figure 9 The GPC curve of resin 6 obtained in Example 6; Figure 10 The GPC curve of resin 1 obtained in Comparative Example 1 is shown. Figure 11 The image shows the GPC curve of resin 2 obtained in Comparative Example 2. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0027] Various embodiments of the present invention may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible subranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the range referred to.

[0028] In the description of this invention, the terms "comprising," "including," etc., mean "including but not limited to." In this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. In this document, "and / or" describes the relationship between related objects, indicating that three relationships may exist; for example, A and / or B can represent: A alone, A and B simultaneously, or B alone. A and B can be singular or plural. In this document, "at least one" means one or more, and "more than one" means two or more. "At least one," "at least one of the following," or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be a single or multiple.

[0029] The following is a detailed description of a resin and its preparation method, as well as porous carbon and silicon-carbon anode materials provided by the present invention.

[0030] Some embodiments of the present invention provide a resin comprising an in-situ bonded polymeric resin and a cyclic oligomer, wherein the cyclic oligomer is distributed within the polymeric resin as a rigid framework, and at least one of the following interactions exists between the polymeric resin and the cyclic oligomer: intermolecular hydrogen bonds, intermolecular π-π stacking, and covalent bonds.

[0031] By employing structurally rigid cyclic resin oligomers as molecular support units and in-situ bonding with polymer resin chains during curing, a composite resin system with a stable internal rigid framework was successfully constructed. During subsequent carbonization, this rigid framework structure exhibited multiple functional advantages: on the one hand, it effectively suppressed material shrinkage and maintained structural stability; on the other hand, it guided the directional escape of pyrolysis volatiles, thereby spontaneously forming a continuous hierarchical porous structure. This innovative design achieves controllable pore construction from micropores (<2 nm) to mesopores (2~50 nm) without relying on external template agents, providing a new approach for the preparation of porous materials.

[0032] In some implementations, intermolecular hydrogen bonds, intermolecular π-π stacking, and covalent bonds coexist simultaneously between the polymer resin and the cyclic oligomer. The synergistic effect of these multi-level interactions brings significant advantages to the system: 1) Formation of a robust interpenetrating network structure: Strong hydrogen bonds and π-π stacking enable uniform mixing and pre-assembly of the two before curing, laying the spatial foundation for the formation of covalent bonds; the covalent bonds act as permanent anchor points, ultimately "locking" the cyclic oligomer within the resin network, forming a uniformly dispersed and stably supported rigid framework at the nanoscale. This structure fundamentally avoids phase separation during carbonization, ensuring the uniformity of the pore structure. 2) Achievement of more precise pore control: The type, density, and intensity of the three interaction forces can be designed by adjusting the number and distribution of phenolic / aromatic ring structural units and the number of active sites. This is equivalent to providing a fine "control handle" at the molecular level for the pyrolysis behavior (such as decomposition paths and shrinkage stress) during carbonization, thereby enabling more precise control over the pore size distribution, specific surface area, and pore connectivity of the final porous carbon. 3) Imparting excellent structural stability to the material: Multilevel interactions, especially the covalent bond network, can effectively transfer and disperse thermal stress during carbonization, significantly suppressing the disordered shrinkage and collapse of the resin matrix. This not only helps maintain the predetermined porous morphology, but also gives the resulting carbon skeleton higher mechanical strength and thermal stability, providing a solid structural foundation for withstanding silicon loads and volume changes during charge and discharge processes.

[0033] Specifically, in some embodiments, the intermolecular hydrogen bonds are intermolecular hydrogen bonds formed by phenolic structural units; the intermolecular π-π stacking is intermolecular π-π stacking formed by aromatic ring structural units; and the covalent bonds are covalent bonds formed between reactive sites on polymeric resins and cyclic oligomers.

[0034] It should be noted that the pore size of polymer resins can be adjusted in at least one of the following ways: (1) Adjustment is made by measuring the diameter of the ring-shaped oligomer; (2) The proportion of the cyclic oligomer in the resin is adjusted; (3) The structure of the monomers in the polymer resin and the cyclic oligomer is adjusted.

[0035] Specifically, the mass ratio of the cyclic oligomer to the polymer resin is 1:5 to 1:1000, such as 1:200 to 1:600, 1:400 to 1:800, 1:100 to 1:600, etc., preferably 1:100 to 1:300, and most preferably 1:150 to 1:250.

[0036] Furthermore, the polymer resin has at least one of the following characteristics: a. The polymer resin is a linear polymer with a number-average molecular weight (NUMBER). M n The value ranges from 10,000 to 1,000,000 Da, with a dispersion ( The number average molecular weight is 1.0~4.0, or the polymer resin is a network polymer with a molecular weight of ( ). M n The value ranges from 10,000 to 1,000,000 Da, with a dispersion ( The value ranges from 2.0 to 5.0.

[0037] b. The polymer resin chain contains at least one of the following reactive sites: aromatic hydrocarbon, hydroxymethyl, carboxylic acid, or aldehyde.

[0038] c. The monomers used to prepare polymer resins include at least one of phenols, aromatics, aryl carboxylic acids, aldehydes, and alcohols.

[0039] like Figure 1 As shown in the figure, 001 represents linear polymer resin, 002 represents cyclic oligomer, 003 represents the π-π stacking force between the cyclic oligomer and the polymer resin, 004 represents the hydrogen bonding force between the cyclic oligomer and the polymer resin, and 005 represents the covalent bond force between the cyclic oligomer and the polymer resin. These three interaction forces enable the cyclic oligomer to provide better support for the linear polymer resin. Figure 2 As shown in the figure, 006 represents the network polymer resin and 007 represents the cyclic oligomer. The cyclic oligomer also has a better supporting effect on the network polymer resin.

[0040] Specifically, phenolic monomers include, but are not limited to, phenol, p-cresol, p-tert-butylphenol, cashew phenol, m-diphenol, o-diphenol, p-diphenol, p-fluorophenol, etc.; aromatic monomers include, but are not limited to, benzene, naphthalene, anthracene, pyrene, perylene, phenanthrene, biphenyl, etc.; aryl carboxylic acid monomers include, but are not limited to, terephthalic acid, phthalic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid, etc.; aldehyde monomers include, but are not limited to, formaldehyde, acetaldehyde, propionaldehyde, isopropionaldehyde, tert-butanal, benzaldehyde, etc.; alcohol monomers include, but are not limited to, terephthalic glycol, isophthalic glycol, o-phthalic glycol, 4,4'-dihydroxybiphenyl, etc.

[0041] d. Polymer resins are synthesized via the Friedel-Crafts reaction mechanism.

[0042] Friedel-Crafts reactions include, but are not limited to, electrophilic reactions occurring under acid catalysis between phenolic monomers and aldehyde monomers, between phenolic monomers and alcohol monomers, between aromatic monomers and aldehyde monomers, between aromatic monomers and alcohol monomers, and between aromatic monomers and arylcarboxylic acid monomers.

[0043] Furthermore, in some embodiments, the cyclic oligomer has at least one of the following characteristics: a. The number of aromatic ring monomer units in the cyclic oligomer is 5 to 10; b. The diameter of the cyclic oligomer is 0.9~4.0 nm; c. The cyclic oligomer contains at least one of the following reactive sites: aromatic hydrocarbon, hydroxymethyl, carboxylic acid, or aldehyde; d. The monomer types for preparing cyclic oligomers include at least one of phenols, aromatic hydrocarbons, aryl carboxylic acids, aldehydes, and alcohols; e. Cyclic oligomers are synthesized via the Friedel-Crafts reaction mechanism.

[0044] It should be noted that the selection of monomer types for synthesizing cyclic oligomers and the relevant Friedel-Crafts reaction can be found in the aforementioned section on synthesizing polymer resins, and will not be repeated here.

[0045] Furthermore, the preparation of cyclic oligomers needs to be carried out at low concentrations, using water as a solvent. The reaction concentration can be selected as 0.01~2 mmol / mL, 1~1.5 mmol / mL, or 0.5~1 mmol / mL. To improve the reactivity, the reaction temperature for the synthesis of cyclic oligomers can be increased to 30~50 °C, preferably 40 °C.

[0046] Some embodiments of the present invention also provide a method for preparing the resin as described in any of the foregoing embodiments, comprising: The first monomer is subjected to an oligomerization reaction with the first crosslinking agent to form the cyclic oligomer; The polymer resin is prepared by adding a second monomer and a second crosslinking agent to the reaction system and then performing a polymerization reaction. After heating the reaction system, the polymer resin and cyclic oligomer undergo cross-linking and curing.

[0047] It should be noted that the first monomer and the second monomer can be a single monomer or a mixture of two or more monomers. Similarly, the first crosslinking agent and the second crosslinking agent can be a single crosslinking agent or a compound crosslinking agent.

[0048] In some embodiments, at least one of the first monomer and the second monomer is of the same type; preferably, at least one of the first monomer and the second monomer has the same structure. At least one of the first crosslinking agent and the second crosslinking agent is of the same type; preferably, at least one of the first crosslinking agent and the second crosslinking agent has the same structure. Synthesis via the same reaction mechanism in 1-2 steps, i.e., through a "one-pot one-step" or "one-pot two-step" method, reduces the process flow and minimizes the introduction of more side-reacting substances between different reactions.

[0049] Different monomer structures exhibit significant differences in carbon yield during carbonization: polycyclic aromatic hydrocarbon monomers show higher carbon yields, while monomers containing alkane structures show lower carbon yields. This characteristic indicates that the structural stability of polymer resins during carbonization can be effectively adjusted by controlling the monomer molecular structure. Specifically, when alkyl aldehyde monomers are used, the carbonization process easily leads to material structure collapse and the formation of shrinkage cavities; conversely, if easily graphitized polycyclic aromatic hydrocarbons are used to synthesize cyclic oligomers as precursors, the structural strength of the carbonized products can be significantly improved, thereby effectively inhibiting the formation of microporous structures.

[0050] In some implementations, the proportion of cyclic oligomers can be adjusted by the oligomerization reaction time and the amount of the first monomer. The oligomerization reaction time is 1 h to 5 h, such as 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h or 5 h, etc. The specific reaction time needs to be determined according to the selected monomer.

[0051] Some embodiments of the present invention also provide a porous carbon, which is obtained by carbonizing and activating the resin described in any of the foregoing embodiments.

[0052] Specifically, in some embodiments, the carbonization process is as follows: under the protection of an inert atmosphere, the final carbonization temperature is controlled at 620~670 °C, the heating rate is 0.5~1.5 °C / min, and the final temperature is maintained for 1.5~2.5 h; the activation process is as follows: water vapor is used as the activation reagent, the gas flow rate is 1.5~2.5 mL / min, and the treatment is carried out at 750~800 °C for 1.5~2.5 h.

[0053] This carbonization and activation process can produce porous carbon with better pore size distribution, specific surface area, pore volume and framework stability.

[0054] Some embodiments of the present invention also provide a silicon-carbon anode material, which is obtained by silicon deposition of porous carbon as described in the foregoing embodiments via vapor deposition.

[0055] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0056] Example 1 This embodiment provides a resin, the preparation process of which is as follows: In step S1, using acetic acid as a catalyst (1 mol%), 1 mol of diphenyl ether and 1.1 mol of formaldehyde were reacted in 50 mL of deionized water at 60 °C for 2 hours to obtain cyclic oligomers. Step S2: Add 15 mol of diphenyl ether and 15.1 mol of formaldehyde to the reaction system, and add 100 mL of deionized water and 0.1 mol of acetic acid. Continue the polymerization reaction at 40 °C for 4 hours. Step S3, finally, raise the system temperature to 80 °C and react for 1 hour to cure and crosslink to obtain resin 1.

[0057] Figure 3 The nitrogen adsorption curve of resin 1 was obtained by testing according to the GB / T 19587-2017 standard.

[0058] Figure 4 The GPC curve of resin 1 obtained in Example 1 is shown below. M n =31.8 kDa, =1.8.

[0059] Example 2 This embodiment provides a resin whose preparation steps are the same as those in Example 1, except that in step S2, the dimethyl ether is replaced with phenol monomer to obtain resin 2.

[0060] Figure 5 The GPC curve of resin 2 obtained in Example 2 is shown below. M n =19.6KDa, =1.6; Example 3 This embodiment provides a resin whose preparation steps are the same as those in Example 2, except that the synthesis time of the cyclic oligomer in step S1 is extended from 2 hours to 4 hours to obtain resin 3.

[0061] Figure 6 The GPC curve of resin 3 obtained in Example 3 is shown. M n = 34.9 kDa, =1.9.

[0062] Example 4 (Increasing the proportion of cyclic oligomers) This embodiment provides a resin whose preparation steps are the same as those in Example 2, except that the molar amounts of phenol monomer and formaldehyde in step S2 are reduced to 7 mol and 8.1 mol, respectively, to obtain resin 4.

[0063] Figure 7 The GPC curve of resin 4 obtained in Example 4 is shown. M n = 30.4 kDa, =1.6.

[0064] Example 5 This embodiment provides a resin whose preparation steps are the same as those in Example 2, except that the phenol monomer in step S2 is replaced with naphthalene to obtain resin 5.

[0065] Figure 8 The GPC curve of resin 5 obtained in Example 5 is shown below. M n = 21.7 KDa, = 4.8.

[0066] Example 6 This embodiment provides a resin whose preparation steps are the same as those in Example 5, except that the formaldehyde monomer in step S2 is replaced with benzaldehyde to obtain resin 6.

[0067] Figure 9 The GPC curve of resin 6 obtained in Example 6 is shown below. M n = 23.2 kDa, = 4.1.

[0068] Comparative Example 1 Add 15 mol of diphenyl ether and 15.1 mol of formaldehyde, and stir evenly in a mixture of 150 mL of deionized water and 0.1 mol of acetic acid. React at 40 °C for 4 hours to obtain resin 7.

[0069] Figure 10 The image shows the GPC curve of resin 1 obtained in Comparative Example 1. M n = 36.3 kDa, = 3.4.

[0070] Comparative Example 2 Add 15 mol of p-naphthalene and 15.1 mol of benzaldehyde, and stir well in a mixture of 150 mL of deionized water and 0.1 mol of acetic acid. React at 40 °C for 4 hours to obtain resin 8.

[0071] Figure 11The GPC curve of resin 2 obtained in Comparative Example 2 is shown. M n =41.8 kDa, =2.5.

[0072] The resins obtained in the examples and comparative examples were characterized, and the results are shown in Table 1.

[0073] Table 1 Characterization of the resin

[0074] Example 8 This embodiment provides a porous carbon, the preparation process of which is as follows: Resin 1 is carbonized under an inert atmosphere, with the final carbonization temperature controlled at 650 °C, the heating rate at 1 °C / min, and the final temperature is maintained for 2 hours. Water vapor is used as the activating agent, the gas flow rate is 2 mL / min, and the mixture is treated at 770 °C for 2 hours to obtain porous carbon 1.

[0075] Example 9 This embodiment provides a porous carbon, the preparation process of which is the same as that in Example 8, except that resin 1 is replaced with resin 2 to obtain porous carbon 2.

[0076] Example 10 This embodiment provides a porous carbon, the preparation process of which is the same as that in Example 8, except that resin 1 is replaced with resin 3 to obtain porous carbon 3.

[0077] Example 11 This embodiment provides a porous carbon, the preparation process of which is the same as that in Example 8, except that resin 1 is replaced with resin 4 to obtain porous carbon 4.

[0078] Example 12 This embodiment provides a porous carbon, the preparation process of which is the same as that in Example 8, except that resin 1 is replaced with resin 5 to obtain porous carbon 5.

[0079] Example 13 This embodiment provides a porous carbon, the preparation process of which is the same as that of Example 8, except that resin 1 is replaced with resin 6 to obtain porous carbon 6.

[0080] Comparative Example 3 This comparative example provides a porous carbon, the preparation process of which is the same as that of Example 8, except that resin 1 is replaced with resin 7 to obtain porous carbon 7.

[0081] Comparative Example 4 This comparative example provides a porous carbon, the preparation process of which is the same as that of Example 8, except that resin 1 is replaced with resin 8 to obtain porous carbon 8.

[0082] The porous carbons of Examples 8-13 and Comparative Examples 3-4 were characterized, and the results are shown in Table 2.

[0083] First, accurately weigh the dried porous carbon raw material and record its initial mass, then load it into a CVD reactor (such as a fluidized bed reactor). Next, evacuate the reactor and introduce an inert gas for protection, then heat the material to the set deposition temperature (650 °C). Then, introduce a mixture of silane and argon in a predetermined ratio (e.g., SiH4:Ar = 1:4 to 1:10) and perform vapor deposition under a slight negative pressure (250 Pa). The amount of silicon deposited is controlled by adjusting the deposition time (e.g., 2 hours corresponds to approximately 10-15% loading, and 4 hours corresponds to approximately 20% loading). After the reaction is complete, cool the sample, remove it, weigh it again, and calculate the silicon loading using the weight gain method. If necessary, use instruments such as thermogravimetric analysis for calibration.

[0084] Table 2 Characterization of porous carbon

[0085] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A resin, characterized in that, The resin comprises an in-situ bonded polymeric resin and a cyclic oligomer. The cyclic oligomer is distributed within the polymeric resin as a rigid framework. There is at least one interaction force between the polymeric resin and the cyclic oligomer, including intermolecular hydrogen bonds, intermolecular π-π stacking, and covalent bonds.

2. The resin according to claim 1, characterized in that, The mass ratio of the cyclic oligomer to the polymeric resin is 1:5 to 1:1000.

3. The resin according to claim 1, characterized in that, The polymer resin has at least one of the following characteristics: a. The polymer resin is a linear polymer with a number-average molecular weight. M n The range is from 10,000 to 1,000,000 Da, with a dispersion. The number average molecular weight is 1.0~4.0, or the polymer resin is a network polymer with a molecular weight of 1.0~4.

0. M n The range is from 10,000 to 1,000,000 Da, with a dispersion. The value ranges from 2.0 to 5.

0. b. The polymer resin chain contains at least one of the following reactive sites: aromatic hydrocarbon, hydroxymethyl, carboxylic acid, or aldehyde group; c. The monomers used to prepare the polymer resin include at least one of phenols, aromatic hydrocarbons, aryl carboxylic acids, aldehydes, and alcohols; d. The polymer resin is synthesized via a Friedel-Crafts reaction mechanism.

4. The resin according to claim 1, characterized in that, The cyclic oligomer has at least one of the following characteristics: a. The number of aromatic ring monomer units in the cyclic oligomer is 5 to 10; b. The diameter of the cyclic oligomer is 0.9~4.0 nm; c. The cyclic oligomer contains at least one of the following reactive sites: aromatic hydrocarbon, hydroxymethyl, carboxylic acid, or aldehyde group; d. The monomers used to prepare the cyclic oligomers include at least one of phenols, aromatic hydrocarbons, aryl carboxylic acids, aldehydes, and alcohols; e. The cyclic oligomer is synthesized via a Friedel-Crafts reaction mechanism.

5. The resin according to any one of claims 1 to 4, characterized in that, The intermolecular hydrogen bonds are intermolecular hydrogen bonds formed by phenolic structural units; the intermolecular π-π stacking is intermolecular π-π stacking formed by aromatic ring structural units; the covalent bonds are covalent bonds formed between the reactive sites on the polymer resin and the cyclic oligomer.

6. A method for preparing the resin according to any one of claims 1 to 5, characterized in that, It includes: The first monomer is subjected to an oligomerization reaction with the first crosslinking agent to form the cyclic oligomer; The polymer resin is prepared by adding a second monomer and a second crosslinking agent to the reaction system and then performing a polymerization reaction. After heating the reaction system, the polymer resin and the cyclic oligomer undergo cross-linking and curing.

7. The method for preparing the resin according to claim 6, characterized in that, The first monomer and the second monomer have at least one monomer type that is the same; And / or, at least one of the first crosslinking agent and the second crosslinking agent is of the same type.

8. The method for preparing the resin according to claim 6, characterized in that, The oligomerization reaction takes 1 to 5 hours.

9. A porous carbon, characterized in that, It is obtained by carbonizing and activating the resin described in any one of claims 1 to 5. Preferably, the carbonization process is as follows: under the protection of an inert atmosphere, the final carbonization temperature is controlled at 620~670 °C, the heating rate is 0.5~1.5 °C / min, and the temperature is held at the final temperature for 1.5~2.5 h; the activation process is as follows: using water vapor as the activation reagent, the air flow rate is 1.5~2.5 mL / min, and the temperature is treated at 750~800 °C for 1.5~2.5 h.

10. A silicon-carbon anode material, characterized in that, It is obtained by silicon deposition of porous carbon as described in claim 9 via vapor deposition.

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