Preparation method of phenolic resin-based porous carbon based on synergistic activation of water vapor and carbon dioxide

Abstract

This invention relates to the field of porous carbon materials technology, and discloses a method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide. The focus of this invention is on constructing a "ZIF-8@Ni-MOF derived bifunctional material with pore formation – nitrogen / nickel co-doping + dynamic pressure – dual-gas synergistic etching + Ti3C2T" process. x The "MXene gradient modification" multi-dimensional process utilizes MOF-derived materials to provide well-defined initial pores and active sites. Combined with complementary dual-gas properties and dynamic pressure control, precise customization of pore sizes from 0.7 to 50 nm is achieved. MXene modification simultaneously enhances conductivity and interfacial adhesion. The resulting material exhibits superior performance, with a microporosity ≥88% and a specific surface area ≥2200 m². 2 / g, total pore volume ≥1.3cm³ 3 / g, the process produces no chemical waste pollution. When applied to silicon-carbon anodes in lithium batteries, it maintains a capacity retention rate of ≥85% after 500 cycles, demonstrating high industrialization value.

Description

Technical Field

[0001] This invention relates to the field of porous carbon materials technology, and more specifically, to a method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide. Background Technology

[0002] Lithium-ion batteries are the primary power batteries for new energy vehicles and portable electronic devices, and improving their energy density has always been a key research focus. Silicon materials, with a theoretical specific capacity as high as 4200 mAh / g, are considered the most promising candidate to replace traditional graphite anode materials. However, silicon materials undergo significant volume expansion during charge and discharge, leading to electrode material pulverization and detachment, severely impacting battery cycle life and safety performance. Currently, vapor deposition (VCD) is considered an effective way to solve the volume expansion problem of silicon anode materials. This method utilizes porous carbon as a silicon source carrier, introducing silane gas into the pores of the porous carbon under high-temperature conditions, causing the silicon source to deposit within the channels of the porous carbon to form a silicon-carbon composite material. The porous structure of the porous carbon provides a buffer space for silicon expansion, effectively suppressing silicon particle pulverization. However, existing methods such as physical activation and alkaline activation inevitably result in the formation of ultra-micropores (pore size < 0.7 nm) in porous carbon materials. This ultra-micropore structure affects lithium-ion insertion and extraction, reducing the battery's initial coulombic efficiency and rate performance. Furthermore, existing porous carbon materials have poor conductivity, low surface activity, and weak interfacial bonding with silicon sources / electrolytes, making it difficult to achieve both cycle stability and rate performance of silicon-carbon anodes.

[0003] Therefore, developing a resin-based self-activated porous carbon material with customizable pore size and avoiding the formation of ultra-microporous structures to overcome the defect of poor conductivity is of great significance for improving the electrochemical performance of porous silicon-carbon anode materials. Summary of the Invention

[0004] In view of this, the present invention proposes a method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide, aiming to solve the problems of porous carbon materials in the current technology being prone to forming ultra-microporous structures and having poor electrical conductivity.

[0005] This invention proposes a method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide, comprising the following steps:

[0006] Step 1): Phenolic resin and ZIF-8@Ni-MOF-derived bifunctional material are mixed at a mass ratio of 10:3 to 10:6, followed by the addition of PVP binder and deionized water, and stirred to obtain a slurry; the slurry is then spray-granulated to obtain spherical precursors.

[0007] Step 2): The spherical precursor is placed in an inert gas atmosphere for high-temperature carbonization, and after cooling to room temperature, a phenolic resin-based carbonized material is obtained.

[0008] Step 3): The phenolic resin-based carbonized material is subjected to plasma treatment by introducing an argon-oxygen mixed gas, controlling the power at 80~150W and the pressure at 0.08~0.12MPa, and treating for 15~40min to obtain the pre-activated carbonized material.

[0009] Step 4): Activate the pre-activated carbonized material by introducing inert gas to replace the air at a flow rate of 18-28 L / min. Then, raise the temperature to 850-1000℃ at a rate of 5-10℃ / min, while simultaneously increasing the pressure from atmospheric pressure to 0.2-0.35 MPa. After reaching the set temperature and pressure, introduce a mixed activation gas of water vapor and carbon dioxide at a flow rate of 2-30 L / min, while simultaneously performing dynamic pressure regulation. Maintain the temperature for activation for 2-10 hours.

[0010] The volume ratio of water vapor to carbon dioxide in the mixed activation gas is 1:7 to 7:1; the dynamic pressure control cycle is 1.5 hours, and the pressure change is ±0.06 MPa.

[0011] Step 5): After activation, cool to 250~350℃ and introduce a solution containing 5~12 vol% Ti3C2T. x Nitrogen gas was applied to the MXene dispersion at a flow rate of 10-15 L / min, and the mixture was kept at this temperature for 1.5-3 h to obtain phenolic resin-based porous carbon.

[0012] Step 6): Stop the ventilation and instead introduce inert gas to cool to room temperature, and wash and dry the phenolic resin-based porous carbon.

[0013] Preferably, the ZIF-8@Ni-MOF-derived bifunctional material is prepared by mixing ZIF-8 and Ni-MOF at a mass ratio of 2:1 and then pyrolyzing the mixture at 700°C for 2 hours under a nitrogen atmosphere.

[0014] Preferably, in step 1), the amount of PVP adhesive added is 5% to 8% of the mass of phenolic resin;

[0015] Preferably, in step 1), the ratio of the mass of deionized water added to the mass of solids in the system is 1:2.

[0016] Preferably, the stirring time in step 1) is 30-60 minutes and the stirring speed is 2500-3500 rpm.

[0017] Preferably, in step 1), the inlet air temperature of the spray granulation is 120~150℃ and the outlet air temperature is 60~80℃.

[0018] Preferably, the particle size of the spherical precursor obtained in step 1) is 100~200μm.

[0019] Preferably, the inert atmosphere in step 2) is a nitrogen atmosphere or an argon atmosphere; the conditions for high-temperature carbonization in step 2) are: heating to 700~850℃ at a heating rate of 4~9℃ / min and holding at that temperature for 3~5h.

[0020] Preferably, the phenolic resin-based carbonized material obtained in step 2) needs to be ground to a particle size of 40~80μm.

[0021] Preferably, the volume ratio of argon to oxygen in the argon-oxygen mixture in step 3) is 9:1.

[0022] Preferably, the Ti3C2T in step 5) x The concentration of MXene dispersion was 5 mg / mL, and the dispersion medium was ethanol.

[0023] Preferably, the thickness of the MXene coating formed in step 5) is 5~15nm.

[0024] Another objective of this invention is to provide a phenolic resin-based porous carbon prepared by the aforementioned method of preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide.

[0025] Another object of the present invention is to provide the application of the phenolic resin-based porous carbon in lithium battery silicon-carbon anode carriers, high-efficiency adsorption materials for volatile organic compounds, supercapacitor electrode materials, or noble metal catalyst carriers.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0027] This invention constructs a "ZIF-8@Ni-MOF derived bifunctional material with integrated pore formation, nitrogen / nickel co-doping, dynamic pressure-dual gas synergistic etching, and Ti3C2T" x The multi-dimensional process system of "MXene gradient interface modification" represents a breakthrough upgrade to traditional porous carbon preparation technology. It solves the core problems of excessive micropores, wide pore size distribution, poor conductivity, and weak interfacial bonding associated with traditional physically activated carbon. Furthermore, through the synergistic effect of the well-defined initial channels provided by MOFs, the complementary dual-gas properties, and dynamic pressure control, it precisely customizes pore sizes from 0.7 to 50 nm, resulting in products without micropores and with a microporosity ≥88%, coupled with a high specific surface area (≥2200 nm). 2 / g), high total pore volume (≥1.3cm) 3 / g) The material exhibits synergistic performance advantages, while leveraging MXene modification and co-doping to optimize interface stability and electron transport efficiency. This not only allows the material to maintain a capacity retention rate of ≥85% after 500 cycles when applied to silicon-carbon anodes in lithium batteries, effectively buffering the volume expansion of silicon particles, but also adapts to the needs of multiple scenarios such as VOCs adsorption, supercapacitors, and catalyst carriers. Furthermore, the process employs physical activation without chemical waste pollution, integrating a unified "pore formation-doping-modification" process and supporting flexible control of activation time and gas flow rate. It balances production efficiency and scalability, forming multiple advantages in technological innovation, comprehensive performance, application adaptability, and environmental and economic benefits, resulting in significant industrialization value. Detailed Implementation

[0028] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the present invention.

[0029] Furthermore, regarding the numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included within this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0030] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0031] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This specification and embodiments are merely exemplary.

[0032] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0033] This invention proposes a method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide, comprising the following steps:

[0034] Step 1): Phenolic resin and ZIF-8@Ni-MOF-derived bifunctional material are mixed at a mass ratio of 10:3 to 10:6, followed by the addition of PVP binder and deionized water, and stirred to obtain a slurry; the slurry is then spray-granulated to obtain spherical precursors.

[0035] Step 2): The spherical precursor is placed in an inert gas atmosphere for high-temperature carbonization, and after cooling to room temperature, a phenolic resin-based carbonized material is obtained.

[0036] Step 3): The phenolic resin-based carbonized material is subjected to plasma treatment by introducing an argon-oxygen mixed gas, controlling the power at 80~150W and the pressure at 0.08~0.12MPa, and treating for 15~40min to obtain the pre-activated carbonized material.

[0037] Step 4): Activate the pre-activated carbonized material by introducing inert gas to replace the air at a flow rate of 18-28 L / min. Then, raise the temperature to 850-1000℃ at a rate of 5-10℃ / min, while simultaneously increasing the pressure from atmospheric pressure to 0.2-0.35 MPa. After reaching the set temperature and pressure, introduce a mixed activation gas of water vapor and carbon dioxide at a flow rate of 2-30 L / min, while simultaneously performing dynamic pressure regulation. Maintain the temperature for activation for 2-10 hours.

[0038] The volume ratio of water vapor to carbon dioxide in the mixed activation gas is 1:7 to 7:1; the dynamic pressure control cycle is 1.5 hours, and the pressure change is ±0.06 MPa.

[0039] Step 5): After activation, cool to 250~350℃ and introduce a solution containing 5~12 vol% Ti3C2T. x Nitrogen gas was applied to the MXene dispersion at a flow rate of 10-15 L / min, and the mixture was kept at this temperature for 1.5-3 h to obtain phenolic resin-based porous carbon.

[0040] Step 6): Stop the ventilation and instead introduce inert gas to cool to room temperature, and wash and dry the phenolic resin-based porous carbon.

[0041] In this invention, the ZIF-8@Ni-MOF-derived bifunctional material is preferably prepared by mixing ZIF-8 and Ni-MOF at a mass ratio of 2:1 and then pyrolyzing the mixture at 700°C for 2 hours under a nitrogen atmosphere.

[0042] In this invention, the amount of PVP adhesive added in step 1) is preferably 5% to 8% of the mass of phenolic resin, more preferably 6% to 7%.

[0043] In this invention, the ratio of the mass of deionized water added in step 1) to the mass of solids in the system is preferably 1:2.

[0044] In this invention, the stirring time in step 1) is preferably 30-60 min, more preferably 40-50 min; the stirring speed is preferably 2500-3500 rpm, more preferably 2800-3200 rpm.

[0045] In this invention, the inlet air temperature of spray granulation in step 1) is preferably 120~150℃, more preferably 130~140℃; the outlet air temperature is preferably 60~80℃, more preferably 65~75℃.

[0046] In this invention, the particle size of the spherical precursor obtained in step 1) is preferably 100~200μm, more preferably 120~160μm.

[0047] In step 2) of this invention, the preferred conditions for high-temperature carbonization are to raise the temperature to 700-850°C at a heating rate of 4-9°C / min and hold for 3-5 hours; more preferably, to raise the temperature to 750-800°C at a heating rate of 5-8°C / min and hold for 3.5-4 hours.

[0048] In this invention, the phenolic resin-based carbonized material obtained in step 2) needs to be ground, and the particle size is preferably 40~80μm, more preferably 50~70μm.

[0049] In this invention, the volume ratio of argon to oxygen in the argon-oxygen mixture in step 3) is preferably 9:1.

[0050] In this invention, Ti3C2T in step 5) x The concentration of the MXene dispersion is preferably 5 mg / mL, and the dispersion medium is preferably ethanol.

[0051] In this invention, the thickness of the MXene coating formed in step 5) is preferably 5~15nm, and more preferably 8~12nm.

[0052] In this invention, all inert atmospheres are either nitrogen or argon.

[0053] In this invention, the role of adding ZIF-8@Ni-MOF-derived bifunctional material is as follows: After the MOF material is pyrolyzed, it forms regular nanoscale initial channels, providing a directional "guide channel" for the subsequent activation gas, guiding water vapor and CO2 to perform orderly etching, and fundamentally avoiding the disorderly reaction of activation gas on the surface of the carbide to form micropores; if the amount of MOF material is insufficient, the number of initial channels cannot meet the guidance requirements, the diffusion of activation gas is hindered, and over-etching is likely to occur in local areas, resulting in an increase in the proportion of micropores; if the amount of MOF material is too large, it will destroy the structural continuity of the phenolic resin matrix, making the carbide appear loose, and the mechanical strength of the material after activation is insufficient, making it difficult to withstand the volume expansion stress during the charging and discharging process of silicon particles. During the pyrolysis of MOF, ZIF-8 can introduce high-quality doping sites such as pyridine nitrogen and pyrrole nitrogen, while Ni-MOF decomposes to form nanoscale metallic nickel particles. Nitrogen doping can effectively reduce the electron transport resistance of porous carbon, and nickel particles can act as a catalyst for the activation reaction, significantly improving the activation reaction efficiency. If the nickel doping component is missing, the activation reaction rate will drop significantly, and the reaction time needs to be extended to achieve the target pore structure. This not only increases energy consumption but also leads to the deterioration of the conductivity of porous carbon, which cannot meet the electron transport requirements.

[0054] In this invention, the technical solution also includes Ti3C2T x The mechanism of MXene gradient modification is as follows: Plasma pretreatment introduces oxygen-containing active groups onto the surface of the carbide. These groups can form stable CO-Ti chemical bonds with the hydroxyl groups on the surface of MXene nanosheets, significantly improving the interfacial bonding strength. Simultaneously, the high conductivity of MXene itself can significantly reduce the interfacial impedance between porous carbon and the silicon source / electrolyte. If the modification layer is too thin, a complete conductive and bonding interface cannot be formed, resulting in limited improvement in conductivity and a still high interfacial impedance. If the modification layer is too thick, it will block some micropore channels, leading to a significant decrease in the material's specific surface area and pore volume, affecting ion transport and buffer space. When using vapor deposition for MXene modification, MXene nanosheets uniformly cover the pore surface in a single layer or few layers, playing only an interfacial control role without filling the pores, ensuring that the uniformity of pore size distribution is not affected. If solution impregnation is used, MXene nanosheets are prone to agglomeration, forming large particles. These particles fill the pore interior, resulting in a significant reduction in the proportion of mesopores, failing to provide sufficient buffer space for the volume expansion of silicon particles.

[0055] In this invention, the synergistic activation mechanism of carbon dioxide and water vapor is as follows: Carbon dioxide activation characteristics: The reaction rate between CO2 and carbon is mild, and the etching effect is gentle, which can form a uniformly distributed microporous structure based on the initial channels of MOF. If the proportion of CO2 in the mixed gas is too high, it will lead to a slow activation reaction rate, a prolonged reaction cycle, and difficulty in fully developing mesopores, which cannot meet the buffering requirements of silicon particle volume expansion. Water vapor activation characteristics: Water vapor has high reactivity with carbon and has the ability to directionally expand pores, which can further expand micropores into mesopores, realizing the construction of a micropore-mesopore hierarchical structure. If the proportion of water vapor in the mixed gas is too high, it will lead to an excessively fast etching rate, uncontrolled channel expansion, a significant reduction in the proportion of micropores, poor uniformity of pore size distribution, thinning of the pore wall structure, and easy collapse, making it impossible to form a stable buffer structure. If the mixed gas lacks water vapor components, it is difficult to achieve mesopore development by relying solely on CO2, and the stress generated by the volume expansion of silicon particles cannot be effectively released, ultimately leading to electrode pulverization failure.

[0056] In this invention, the core function of dynamic pressure control is that periodic pressure fluctuations can solve the problem of uneven gas diffusion in traditional isothermal activation through a cyclical mechanism of "increasing pressure to promote deep gas penetration and ensure sufficient etching of internal pores" and "decreasing pressure to accelerate the desorption of reaction products and avoid product accumulation that hinders the reaction." Without dynamic pressure control, there will be excessive etching of surface pores and insufficient etching of internal pores, resulting in poor uniformity of pore size distribution, which affects lithium-ion transport efficiency and makes it impossible to achieve uniform buffering of silicon expansion.

[0057] In this invention, an activation temperature of 850~1000℃ is defined. Within this range, both water vapor and CO2 possess suitable reactivity, enabling sufficient expansion of the initial pores in the MOF while avoiding excessively vigorous reactions that could damage the pore walls. Simultaneously, it maintains the stability of nitrogen-doped sites and nickel particles, achieving synergistic optimization of pore structure, conductivity, and mechanical strength. If the temperature is too low, the activation gas reactivity is insufficient, resulting in a slow etching rate and requiring extended reaction time to reach the target pore volume. Furthermore, the initial pores cannot be fully expanded, leading to an insufficient micropore ratio and a limited number of ion transport channels, resulting in poor rate performance. If the temperature is too high, excessive oxidation of the carbon framework can cause pore wall collapse, reducing mechanical strength. Simultaneously, nitrogen-doped sites are easily decomposed and lost, and nickel particles agglomerate, significantly deteriorating the material's conductivity and failing to meet the electron transport requirements of silicon-carbon anodes.

[0058] In this invention, an activation time (2-10 hours) is also specified. Within this range, the activation gas and carbon framework react sufficiently to achieve complete etching and expansion of the initial pores, forming a hierarchical pore structure with sufficient pore volume and stable structure. This satisfies the silicon expansion buffering requirements while ensuring the mechanical strength of the pore walls. If the activation time is too short, the reaction between the activation gas and carbon framework is insufficient, the initial pores are not fully expanded, the pore volume to mesopore ratio is insufficient, and the volume expansion of silicon particles cannot be buffered. The silicon-carbon composite material is prone to pulverization during cycling. If the activation time is too long, it will lead to excessive etching of the pores, destruction of the microporous structure, thinning of the pore walls, and decreased mechanical stability. Although the specific surface area may be improved, the overall structural strength of the material is insufficient, and the capacity retention rate is significantly reduced during long-term cycling.

[0059] In this invention, the flow rate of the mixed activation gas is also limited to 2~30 L / min. Within this range, a sufficient supply of activation gas can be ensured, which can fully penetrate into the internal channels of the carbide to participate in the reaction, and ensure that the reaction products are discharged in time, avoiding product accumulation that hinders the etching reaction and achieving uniform etching of the channels. If the gas flow rate is too low, the supply of activation gas is insufficient and cannot fully penetrate into the internal channels, resulting in incomplete etching reaction, with the pore size concentrated in the micropore range, insufficient proportion of mesopores, limited ion diffusion paths, and poor material rate performance. If the gas flow rate is too high, the residence time of the gas in the channels is too short, the probability of reaction with the carbon skeleton decreases, the activation efficiency decreases, and the high-speed gas flow will impact the carbide particles, causing particle wear and breakage, reducing product yield, and resulting in uneven etching of the channels and poor uniformity of pore size distribution.

[0060] In this invention, within the parameter range defined by the plasma pretreatment process (power 80~150W, time 15~40min), an appropriate amount of oxygen-containing active groups can be introduced onto the surface of the carbide. This satisfies the requirement for chemical bonding with MXene without causing excessive oxidation damage to the carbide surface, achieving a balance between interfacial bonding strength and intrinsic material properties. If this pretreatment step is omitted, the number of oxygen-containing active groups on the carbide surface is insufficient, and MXene can only form physical adsorption with porous carbon, resulting in weak interfacial bonding. During the volume expansion / contraction process of charge-discharge cycles, the MXene modification layer is prone to detachment, leading to an increase in interfacial impedance and a decrease in cycle stability. If the pretreatment power is too high or the time is too long, it will cause excessive oxidation of the carbide surface, damage to the carbon skeleton structure, and a reduction in specific surface area. At the same time, nitrogen and nickel doping sites are easily oxidized and lost, resulting in a simultaneous decrease in material conductivity and activation reactivity.

[0061] Another objective of this invention is to provide a phenolic resin-based porous carbon prepared by the aforementioned method of preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide.

[0062] Another object of the present invention is to provide the application of the phenolic resin-based porous carbon in lithium battery silicon-carbon anode carriers, high-efficiency adsorption materials for volatile organic compounds, supercapacitor electrode materials, or noble metal catalyst carriers.

[0063] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.

[0064] The important raw material information used in the embodiments and comparative examples of this invention is as follows:

[0065] Phenolic resin: purchased from Shanghai Mairui Biochemical Technology Co., Ltd.

[0066] PVP adhesive: purchased from Hefei Tianjian Chemical Co., Ltd.

[0067] ZIF-8: Purchased from Shanghai McLean Biochemical Technology Co., Ltd.

[0068] Ni-MOF: Purchased from Zhengzhou Aikem Chemical Co., Ltd.

[0069] Ti3C2T x MXene: Purchased from Beijing Huawirui Chemical Technology Co., Ltd., CAS: 12363-89-2

[0070] The ZIF-8@Ni-MOF-derived bifunctional materials used in the embodiments and comparative examples of this invention were prepared by mixing ZIF-8 and Ni-MOF at a mass ratio of 2:1 and then pyrolyzing them at 700°C for 2 hours under a nitrogen atmosphere.

[0071] All other materials are common commercially available materials and will not be described separately here.

[0072] Example 1

[0073] Step 1) Preparation of composite precursor: a. Phenolic resin and ZIF-8@Ni-MOF derived bifunctional material are mixed at a mass ratio of 10:4.5; b. 6% PVP binder by mass of phenolic resin is added, with a solid-liquid mass ratio of 1:2, and the mixture is stirred at a high speed of 3000 rpm for 45 min until a uniform slurry is formed; c. Spray granulation: the inlet air temperature is 135℃ and the outlet air temperature is 70℃, and granulation is performed to obtain spherical precursors with a particle size of 150μm.

[0074] Step 2) Carbonization treatment: Nitrogen atmosphere, heating rate 7℃ / min, heating to 780℃ and holding for 4h, then cooling and grinding to 60μm;

[0075] Step 3) Plasma pre-activation: Argon-oxygen mixed gas (volume ratio 9:1), power 115W, pressure 0.1MPa, treatment for 25min;

[0076] Step 4) Dynamic pressure-coordinated activation: a. Nitrogen base flow rate 23 L / min; b. Heating rate 8℃ / min, reaching 930℃, simultaneously increasing the furnace pressure to 0.28 MPa; c. Mixed activation gas (water vapor: CO2 = 3:1), flow rate 18 L / min, dynamic pressure cycle 1.5 h (±0.06 MPa), heat preservation activation 6.5 h;

[0077] Step 5) MXene gradient modification: containing 8 vol% Ti3C2T x MXene dispersion (concentration 5 mg / mL, anhydrous ethanol as medium) was heated at 300℃ for 2.2 h with nitrogen flow rate of 12 L / min to form a 10 nm thick gradient coating.

[0078] Step 6) Post-treatment: Wash three times with 0.5 mol / L hydrochloric acid, wash with deionized water until neutral, and vacuum dry at 130℃ for 7 h.

[0079] Performance test results: Pore size distribution 0.7~48nm (adjustment deviation ±1.8nm), micropore ratio 89%, specific surface area 2350m² 2 / g, total pore volume 1.42cm³ 3 / g, The silicon-carbon anode exhibited a capacity retention of 87.3% after 500 cycles, an initial coulombic efficiency of 84.1%, and a capacity retention of 68.5% at a rate of 10 A / g. Example 2

[0080] Step 1) Preparation of composite precursor: a. Phenolic resin and ZIF-8@Ni-MOF derived bifunctional material are mixed at a mass ratio of 10:3; b. 5% PVP binder by mass of phenolic resin is added, with a solid-liquid mass ratio of 1:2, and the mixture is stirred at a high speed of 2500 rpm for 30 min; c. Spray granulation: inlet air temperature 120℃, outlet air temperature 60℃, spherical precursor with a particle size of 100μm;

[0081] Step 2) Carbonization treatment: Argon atmosphere, heating rate 4℃ / min, 700℃ for 3h, grinding to 40μm;

[0082] Step 3) Plasma pre-activation: Argon-Oxygen (9:1), power 80W, pressure 0.08MPa, treatment for 15min;

[0083] Step 4) Dynamic pressure synergistic activation: a. Argon basic flow rate 18 L / min; b. Heating rate 5℃ / min, 850℃, pressure 0.2 MPa; c. Mixed activation gas (water vapor: CO2 = 1:5), flow rate 8 L / min, dynamic pressure cycle 1.5 h (±0.06 MPa), activation for 4 h;

[0084] Step 5) MXene gradient modification: 5 vol% Ti3C2T x MXene dispersion, nitrogen flow rate 10 L / min, heat treatment at 250℃ for 1.5 h, coating thickness 5 nm;

[0085] Step 6) Post-treatment: Wash twice with 0.5 mol / L hydrochloric acid, wash with deionized water until neutral, and vacuum dry at 120℃ for 6 h.

[0086] Performance test results: Pore size distribution 0.7~42nm (deviation ±1.9nm), micropore ratio 91%, specific surface area 2205m² 2 / g, total pore volume 1.31cm³ 3 / g, resistivity The silicon-carbon anode maintained a capacity of 85.1% after 500 cycles, with an initial coulombic efficiency of 82.3% and a capacity retention of 65.2% at a rate of 10 A / g.

[0087] Example 3

[0088] Step 1) Preparation of composite precursor: a. Phenolic resin and ZIF-8@Ni-MOF derived bifunctional material are mixed at a mass ratio of 10:6; b. 8% PVP binder by mass of phenolic resin is added, with a solid-liquid mass ratio of 1:2, and the mixture is stirred at a high speed of 3500 rpm for 60 min; c. Spray granulation: inlet air temperature 150℃, outlet air temperature 80℃, spherical precursor with a particle size of 200μm;

[0089] Step 2) Carbonization treatment: Nitrogen atmosphere, heating rate 9℃ / min, 850℃ for 5h, grinding to 80μm;

[0090] Step 3) Plasma pre-activation: Argon-Oxygen (9:1), power 150W, pressure 0.12MPa, treatment for 40min;

[0091] Step 4) Dynamic pressure synergistic activation: a. Nitrogen base flow rate 28 L / min; b. Heating rate 10℃ / min, 1000℃, pressure 0.35 MPa; c. Mixed activation gas (water vapor: CO2 = 5:1), flow rate 30 L / min, dynamic pressure cycle 1.5 h (±0.06 MPa), activation for 10 h;

[0092] Step 5) MXene gradient modification: 12 vol% Ti3C2Tx MXene dispersion, nitrogen flow rate 15 L / min, heat treatment at 350℃ for 3 h, coating thickness 15 nm;

[0093] Step 6) Post-treatment: Wash 3 times with 0.5mol / L hydrochloric acid, wash with deionized water until neutral, and vacuum dry at 140℃ for 8h.

[0094] Performance test results: Pore size distribution 0.7~50nm (deviation ±2.0nm), micropore ratio 88%, specific surface area 2420m² 2 / g, total pore volume 1.53cm³ 3 / g, resistivity 2.9 cm; The silicon-carbon anode retains 88.5% capacity after 500 cycles, with an initial coulombic efficiency of 85.7% and a capacity retention of 70.3% at a rate of 10 A / g.

[0095] Example 4

[0096] Step 1) Preparation of composite precursor: a. Phenolic resin and ZIF-8@Ni-MOF derived bifunctional material are mixed at a mass ratio of 10:3.5; b. 5.5% PVP binder by mass of phenolic resin is added, with a solid-liquid mass ratio of 1:2, and the mixture is stirred at a high speed of 2800 rpm for 35 min; c. Spray granulation: inlet air temperature 125℃, outlet air temperature 65℃, spherical precursor with a particle size of 120μm;

[0097] Step 2) Carbonization treatment: Argon atmosphere, heating rate 6℃ / min, 750℃ for 3.5h, grinding to 50μm;

[0098] Step 3) Plasma pre-activation: Argon-Oxygen (9:1), power 100W, pressure 0.09MPa, treatment for 20min;

[0099] Step 4) Dynamic pressure synergistic activation: a. Argon basic flow rate 20 L / min; b. Heating rate 7℃ / min, 890℃, pressure 0.25 MPa; c. Mixed activation gas (water vapor: CO2 = 1:7), flow rate 12 L / min, dynamic pressure cycle 1.5 h (±0.06 MPa), activation for 5 h;

[0100] Step 5) MXene gradient modification: 7 vol% Ti3C2T x MXene dispersion, nitrogen flow rate 11 L / min, heat treatment at 280℃ for 2 h, coating thickness 8 nm;

[0101] Step 6) Post-treatment: Wash twice with 0.5 mol / L hydrochloric acid, wash with deionized water until neutral, and vacuum dry at 125℃ for 6.5 h.

[0102] Performance test results: Pore size distribution 0.7~45nm (deviation ±1.6nm), micropore ratio 90%, specific surface area 2260m² 2 / g, total pore volume 1.36cm³ 3 / g, resistivity 4.2 cm; The silicon-carbon anode retains 86.4% capacity after 500 cycles, with an initial coulombic efficiency of 83.5% and a capacity retention of 67.1% at a rate of 10 A / g.

[0103] Example 5

[0104] Step 1) Preparation of composite precursor: a. Phenolic resin and ZIF-8@Ni-MOF derived bifunctional material are mixed at a mass ratio of 10:5.5; b. 7% PVP binder by mass of phenolic resin is added, with a solid-liquid mass ratio of 1:2, and the mixture is stirred at a high speed of 3200 rpm for 50 min; c. Spray granulation: inlet air temperature 140℃, outlet air temperature 75℃, spherical precursor with a particle size of 180μm;

[0105] Step 2) Carbonization treatment: Nitrogen atmosphere, heating rate 8℃ / min, holding at 820℃ for 4.5h, grinding to 70μm;

[0106] Step 3) Plasma pre-activation: Argon-Oxygen (9:1), power 130W, pressure 0.11MPa, treatment for 30min;

[0107] Step 4) Dynamic pressure synergistic activation: a. Nitrogen base flow rate 25 L / min; b. Heating rate 9℃ / min, 970℃, pressure 0.32 MPa; c. Mixed activation gas (water vapor: CO2 = 7:1), flow rate 25 L / min, dynamic pressure cycle 1.5 h (±0.06 MPa), activation for 8 h;

[0108] Step 5) MXene gradient modification: 10 vol% Ti3C2T x MXene dispersion, nitrogen flow rate 13 L / min, heat treatment at 320℃ for 2.5 h, coating thickness 12 nm;

[0109] Step 6) Post-treatment: Wash three times with 0.5 mol / L hydrochloric acid, wash with deionized water until neutral, and vacuum dry at 135℃ for 7.5 h.

[0110] Performance test results: Pore size distribution 0.7~49nm (deviation ±1.7nm), micropore ratio 86%, specific surface area 2380m² 2 / g, total pore volume 1.48cm³ 3 / g, resistivity 3.0 cm; The silicon-carbon anode retains 87.8% capacity after 500 cycles, with an initial coulombic efficiency of 84.9% and a capacity retention of 69.7% at a rate of 10 A / g.

[0111] Example 6

[0112] Step 1) Preparation of composite precursor: a. Phenolic resin and ZIF-8@Ni-MOF derived bifunctional material are mixed at a mass ratio of 10:5; b. 6% PVP binder by mass of phenolic resin is added, with a solid-liquid mass ratio of 1:2, and the mixture is stirred at a high speed of 3000 rpm for 40 min until a uniform slurry is formed; c. Spray granulation: the inlet air temperature is 130℃ and the outlet air temperature is 68℃, and spherical precursors with a particle size of 140μm are obtained by granulation.

[0113] Step 2) Carbonization treatment: Nitrogen atmosphere, heating rate 7℃ / min, heating to 790℃ and holding for 4h, then cooling and grinding to 55μm;

[0114] Step 3) Plasma pre-activation: Argon-oxygen mixed gas (volume ratio 9:1), power 120W, pressure 0.1MPa, treatment for 25min;

[0115] Step 4) Dynamic pressure synergistic activation: a. Nitrogen base flow rate 22 L / min; b. Heating rate 8℃ / min, reaching 940℃, simultaneously increasing the furnace pressure to 0.29 MPa; c. Mixed activation gas (water vapor: CO2 = 2:1), flow rate 2 L / min, dynamic pressure cycle 1.5 h (±0.06 MPa), holding activation for 2 h;

[0116] Step 5) MXene gradient modification: containing 8 vol% Ti3C2T x MXene dispersion (concentration 5 mg / mL, anhydrous ethanol as medium), nitrogen flow rate 12 L / min, heat at 300℃ for 2 h to form a 10 nm thick gradient coating; Step 6) Post-treatment: wash 3 times with 0.5 mol / L hydrochloric acid, wash with deionized water until neutral, and vacuum dry at 130℃ for 7 h.

[0117] Performance test results: Pore size distribution 0.7~46nm (adjustment deviation ±1.9nm), micropore ratio 90%, specific surface area 2280m² 2 / g, total pore volume 1.35cm³ 3 / g, resistivity 3.5 cm; The silicon-carbon anode retains 85.6% capacity after 500 cycles, with an initial coulombic efficiency of 83.8% and a capacity retention of 66.7% at a rate of 10 A / g.

[0118] Comparative Example 1

[0119] Compared with Example 1, the only difference is that ZIF-8@Ni-MOF-derived bifunctional materials were not added in step 1a, and only phenolic resin and PVP were mixed and granulated. Other conditions were the same as in Example 1.

[0120] Performance test results: Ultrapores (<0.7nm) accounted for 12%, pore size distribution was 0.5~40nm (deviation ±6.3nm), micropores accounted for 72%, and specific surface area was 1750m². 2 / g, total pore volume 0.85cm³ 3 / g, resistivity cm; The silicon-carbon anode retains 62.1% capacity after 500 cycles, with an initial coulombic efficiency of 71.3% and a capacity retention of 45.8% at a rate of 10 A / g.

[0121] Comparative Example 2

[0122] Compared with Example 1, step 5, MXene gradient modification, is omitted, while other conditions remain the same as in Example 1;

[0123] Performance test results: Pore size distribution 0.7~47nm (deviation ±2.1nm), micropore ratio 88%, specific surface area 2320m² 2 / g, total pore volume 1.38cm³ 3 / g, resistivity The silicon-carbon anode maintained a capacity of 73.5% after 500 cycles, with an initial coulombic efficiency of 79.2% and a capacity retention of 52.3% at a rate of 10 A / g.

[0124] Comparative Example 3

[0125] Compared with Example 1, in step 4c, the temperature and pressure (0.28MPa) were kept constant, there were no periodic pressure fluctuations, and other conditions were the same as in Example 1;

[0126] Performance test results: 9% ultramicropores, pore size distribution 0.7~55nm (deviation ±8.2nm), 78% micropores, specific surface area 2010m². 2 / g, total pore volume 1.12cm³ 3 / g, resistivity The silicon-carbon anode maintained a capacity of 76.8% after 500 cycles, with an initial coulombic efficiency of 81.5% and a capacity retention of 58.7% at a rate of 10 A / g.

[0127] Comparative Example 4

[0128] Compared with Example 1, the high-speed stirring rate in step 1b is 2000 rpm, and other conditions are the same as in Example 1;

[0129] Performance test results: The MOF-derived material aggregates have a particle size > 8 μm, a spherical precursor breakage rate of 35%, a pore size distribution of 0.7~52 nm (deviation ± 4.2 nm), an ultramicropore ratio of 7%, and a specific surface area of ​​2050 m². 2 / g, total pore volume 1.15cm³ 3 / g, resistivity The silicon-carbon anode maintained a capacity of 78.6% after 500 cycles, with an initial coulombic efficiency of 80.2% and a capacity retention of 61.3% at a rate of 10 A / g.

[0130] Comparative Example 5

[0131] Compared with Example 1, step 3, plasma pre-activation, is omitted, while other conditions are the same as in Example 1;

[0132] Performance test results: Pore size distribution 0.7~46nm (deviation ±2.0nm), micropore ratio 87%, specific surface area 2300m² 2 / g, total pore volume 1.35cm³ 3 / g, resistivity The silicon-carbon anode retains 79.8% capacity after 50 cycles, 68.7% capacity after 500 cycles, and has an initial coulombic efficiency of 83.6%.

[0133] Comparative Example 6

[0134] Compared with Example 1, the activation time in step 4c is 1 hour, and other conditions are the same as in Example 1;

[0135] Performance test results: Pore size distribution 0.7~38nm (deviation ±2.3nm), micropores account for 92%, mesopores account for 4%, specific surface area 2080m² 2 / g, total pore volume 1.05cm³ 3 / g, resistivity The silicon-carbon anode maintained a capacity of 69.3% after 500 cycles, with an initial coulombic efficiency of 82.1% and a capacity retention of 59.2% at a rate of 10 A / g.

[0136] Comparative Example 7

[0137] Compared with Example 1, the flow rate of the mixed activation gas in step 4c is 1 L / min, and other conditions are the same as in Example 1;

[0138] Performance test results: Pore size distribution 0.7~25nm (deviation ±2.5nm), micropores account for 93%, mesopores account for 3%, specific surface area 2020m² 2 / g, total pore volume 0.98cm³ 3 / g, resistivity The silicon-carbon anode maintained a capacity of 67.5% after 500 cycles, with an initial coulombic efficiency of 81.8% and a capacity retention of 57.6% at a rate of 10 A / g.

[0139] To provide a more intuitive comparison of the data from the embodiments and comparative examples, the performance test results of the embodiments and comparative examples are summarized in Table 1 below:

[0140] Table 1. Summary of performance test results for the examples and comparative examples

[0141]

[0142] Application Example 1

[0143] Application of phenolic resin-based porous carbon in highly efficient adsorption materials for volatile organic compounds (VOCs)

[0144] Experimental methods:

[0145] Adsorbent preparation: Take the phenolic resin-based porous carbon prepared in Example 1, grind it to a particle size of 20~50μm, and dry it for later use;

[0146] Adsorption targets: Typical VOCs pollutants were selected (toluene, initial concentration 500 ppm; formaldehyde, initial concentration 200 ppm).

[0147] Test apparatus: Dynamic adsorption apparatus (fixed bed reactor, adsorbent loading 0.5g, gas flow rate 50mL / min, temperature 25℃, relative humidity 50%).

[0148] Test indicators: saturated adsorption capacity (gravimetric method to determine the change in adsorbent mass before and after adsorption), breakthrough time (the time when the outlet pollutant concentration reaches 10% of the inlet concentration), and cycle adsorption stability (thermal desorption and regeneration, desorption temperature 120℃, desorption time 2h, 5 cycles).

[0149] Test results:

[0150] Toluene adsorption performance: saturated adsorption capacity 526 mg / g, breakthrough time 185 min, adsorption capacity retention rate after 5 cycles 92.3%;

[0151] Formaldehyde adsorption performance: saturated adsorption capacity 168 mg / g, breakthrough time 120 min, adsorption capacity retention rate 90.5% after 5 cycles;

[0152] Comparative experiment (commercial activated carbon): Toluene saturated adsorption capacity 280 mg / g, formaldehyde saturated adsorption capacity 85 mg / g, adsorption capacity retention rate 75% after 5 cycles.

[0153] Results analysis:

[0154] Porous carbon with high specific surface area (2350m²)2 / g) and high pore volume (1.42cm) 3 The MXene-modified layer provides ample adsorption sites, and the nitrogen-doped sites enhance the adsorption force for polar VOCs (such as formaldehyde). The MXene-modified layer improves the hydrophobicity of the material surface, avoiding interference from water vapor on adsorption. Therefore, the adsorption capacity and cycle stability are significantly better than commercial activated carbon, making it suitable for deep purification of low-concentration VOCs.

[0155] Application Example 2

[0156] Application of phenolic resin-based porous carbon as a supercapacitor electrode material

[0157] Experimental methods:

[0158] Electrode preparation: Phenolic resin-based porous carbon (active material), polyvinylidene fluoride (PVDF, binder), and acetylene black (conductive agent) prepared in Example 3 were mixed at a mass ratio of 85:10:5. N-methylpyrrolidone (NMP) was added to prepare a slurry, which was then coated onto a nickel foam current collector. The slurry was vacuum dried at 120°C for 12 hours and then pressed into a sheet (pressure 10 MPa) to form a working electrode (1 cm² area). 2 (thickness 0.15mm);

[0159] Electrolyte: 6 mol / L KOH aqueous solution;

[0160] Test setup: Three-electrode system (working electrode is the prepared porous carbon electrode, reference electrode is Hg / HgO electrode, counter electrode is platinum sheet);

[0161] Test parameters: Cyclic voltammetry (CV, scan rate 5~100mV / s), constant current charge-discharge (GCD, current density 0.5~20A / g), cycle stability (10,000 cycles at a current density of 10A / g).

[0162] Test results:

[0163] Specific capacitance: 328 F / g at a current density of 1 A / g, 285 F / g at 5 A / g, 236 F / g at 10 A / g, and 201 F / g at 20 A / g;

[0164] Rate performance: Specific capacitance retention of 61.3% at 20A / g and 1A / g;

[0165] Cyclic stability: After 10,000 cycles at a current density of 10 A / g, the capacity retention is 96.8%, and the equivalent series resistance increases from 0.8 Ω to 1.1 Ω;

[0166] Comparative experiment (commercial activated carbon electrode): specific capacitance of 205 F / g at 1 A / g, capacity retention of 88% after 10,000 cycles.

[0167] Results analysis:

[0168] The hierarchical pore structure (micropores + mesopores) of porous carbon ensures rapid ion transport in the electrolyte (mesopores) while providing ample charge storage sites (micropores). Nitrogen / nickel co-doping and the MXene modification layer synergistically enhance electron transport efficiency. Therefore, it possesses high specific capacitance, excellent rate performance and cycle stability, making it suitable for high power density energy storage devices.

[0169] Application Example 3

[0170] Application of phenolic resin-based porous carbon as a noble metal catalytic support (palladium-catalyzed hydrogenation of nitrobenzene to aniline)

[0171] Experimental methods:

[0172] Catalyst preparation: Palladium was supported by the equal volume impregnation method. 1 g of phenolic resin-based porous carbon prepared in Example 5 was added to a 0.05 mol / L palladium chloride aqueous solution, ultrasonically impregnated for 2 h, dried at 120 °C for 4 h, and reduced at 300 °C for 2 h under a hydrogen atmosphere to prepare a Pd / porous carbon catalyst with a Pd loading of 1 wt%.

[0173] Catalytic reaction: 100 mL of ethanol, 5 mmol of nitrobenzene, and 0.1 g of Pd / porous carbon catalyst were added to a high-pressure reactor. Hydrogen was introduced to replace the air three times. The temperature was raised to 80 °C, the hydrogen pressure was adjusted to 0.5 MPa, the stirring rate was 500 r / min, and the reaction was carried out for 2 h.

[0174] Test indicators: Gas chromatography was used to analyze the reaction products and calculate the nitrobenzene conversion rate and aniline selectivity; Cyclic stability test: After the reaction was completed, the catalyst was separated by centrifugation, washed and dried and reused 10 times.

[0175] Test results:

[0176] Catalytic performance: nitrobenzene conversion rate 99.7%, aniline selectivity 98.5%, TOF (transformation frequency) value 425 h. -1 ;

[0177] Cyclic stability: After 10 cycles, the nitrobenzene conversion was 95.3%, the aniline selectivity was 98.2%, and the Pd metal particle size increased from the initial 2.3 nm to 3.1 nm (TEM characterization).

[0178] Comparative experiment (Pd / commercial activated carbon catalyst): nitrobenzene conversion rate 92.1%, aniline selectivity 97.3%, conversion rate 85.7% after 10 cycles, Pd particle size increased to 4.8 nm.

[0179] Results analysis:

[0180] Porous carbon with high specific surface area (2380m²) 2 The nitrogen / nickel co-doping sites can effectively disperse and anchor Pd nanoparticles, preventing metal agglomeration; the hierarchical pore structure promotes the diffusion and transport of reactants and products, and the MXene modification layer improves electron transport efficiency. Therefore, the catalytic activity, selectivity and cycle stability are superior to commercial activated carbon supports, making it suitable for catalytic reaction scenarios such as hydrogenation reduction.

[0181] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the specific implementation of the present invention. Any modifications or equivalent substitutions that do not depart from the spirit and scope of the present invention should be covered within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide, characterized in that, Includes the following steps: Step 1): Phenolic resin and ZIF-8@Ni-MOF-derived bifunctional material are mixed at a mass ratio of 10:3 to 10:6, followed by the addition of PVP binder and deionized water, and stirred to obtain a slurry; the slurry is then spray-granulated to obtain spherical precursors. Step 2): The spherical precursor is placed in an inert gas atmosphere for high-temperature carbonization, and after cooling to room temperature, a phenolic resin-based carbonized material is obtained. Step 3): The phenolic resin-based carbonized material is subjected to plasma treatment by introducing an argon-oxygen mixed gas, controlling the power at 80~150W and the pressure at 0.08~0.12MPa, and treating for 15~40min to obtain the pre-activated carbonized material. Step 4): Activate the pre-activated carbonized material by introducing inert gas to replace the air at a flow rate of 18-28 L / min. Then, raise the temperature to 850-1000℃ at a rate of 5-10℃ / min, while simultaneously increasing the pressure from atmospheric pressure to 0.2-0.35 MPa. After reaching the set temperature and pressure, introduce a mixed activation gas of water vapor and carbon dioxide at a flow rate of 2-30 L / min, while simultaneously performing dynamic pressure regulation. Maintain the temperature for activation for 2-10 hours. The volume ratio of water vapor to carbon dioxide in the mixed activation gas is 1:7 to 7:1; The dynamic pressure control cycle is 1.5 hours, and the pressure change is ±0.06 MPa. Step 5): After activation is completed, the temperature is lowered to 250~350℃, and 5~12vol% Ti3C2T x The nitrogen gas of the MXene dispersion liquid is controlled at a gas flow rate of 10~15L / min, and the phenolic resin-based porous carbon is obtained after 1.5~3h of heat preservation. Step 6): Stop the ventilation and instead introduce inert gas to cool to room temperature, and wash and dry the phenolic resin-based porous carbon. The stirring time in step 1) is 30-60 minutes, and the stirring speed is 2500-3500 rpm.

2. The method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide according to claim 1, characterized in that, The ZIF-8@Ni-MOF-derived bifunctional material was prepared by mixing ZIF-8 and Ni-MOF at a mass ratio of 2:1 and then pyrolyzing the mixture at 700°C for 2 hours under a nitrogen atmosphere.

3. The method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide according to claim 1 or 2, characterized in that, In step 1), the amount of PVP adhesive added is 5% to 8% of the mass of phenolic resin; In step 1), the ratio of the mass of deionized water added to the mass of solids in the system is 1:

2.

4. The method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide according to claim 3, characterized in that, In step 1), the inlet air temperature for spray granulation is 120~150℃, and the outlet air temperature is 60~80℃. The particle size of the spherical precursor obtained in step 1) is 100~200μm.

5. The method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide according to claim 1, 2, or 4, characterized in that, The inert atmosphere in step 2) is a nitrogen atmosphere or an argon atmosphere; the conditions for high-temperature carbonization in step 2) are: heating to 700~850℃ at a heating rate of 4~9℃ / min and holding at that temperature for 3~5h.

6. The method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide according to claim 5, characterized in that, The phenolic resin-based carbonized material obtained in step 2) still needs to be ground to a particle size of 40~80μm.

7. The method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide according to claim 1, 2, 4 or 6, characterized in that, In step 3), the volume ratio of argon to oxygen in the argon-oxygen mixture is 9:

1.

8. The method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide according to claim 7, characterized in that, The Ti3C2T in step 5) x The concentration of MXene dispersion was 5 mg / mL, and the dispersion medium was ethanol; The thickness of the MXene coating formed in step 5) is 5~15nm.

9. Phenolic resin-based porous carbon prepared by the method for preparing phenolic resin-based porous carbon based on the synergistic activation of water vapor and carbon dioxide as described in any one of claims 1 to 8.

10. The application of the phenolic resin-based porous carbon of claim 9 in lithium battery silicon-carbon anode carriers, high-efficiency adsorption materials for volatile organic compounds, supercapacitor electrode materials, or noble metal catalyst carriers.

Images