CN111994895B - Phenolic resin carbon microsphere and preparation method and application thereof - Google Patents
Phenolic resin carbon microsphere and preparation method and application thereof Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention relates to the field of chemical synthetic resin carbon microspheres, in particular to phenolic resin carbon microspheres and a preparation method and application thereof. A preparation method of phenolic resin carbon microspheres comprises the following steps: dissolving thermoplastic phenolic resin in an alkaline solution to obtain a system I; adding phenol, aldehyde and a catalyst into a reaction kettle, and heating for reaction to obtain a system II; uniformly mixing the system I and the system II, adjusting the pH value of the system to 6.5-10.5, heating for reaction, separating and drying to obtain phenolic resin microspheres; and carbonizing the phenolic resin microspheres to obtain the carbon microspheres. The invention has the following remarkable advantages: the method for preparing the carbon microsphere has the advantages of rich raw materials, low preparation cost, simple process, high yield, no need of adding auxiliary agents such as a surfactant, an emulsifier and the like in the preparation process, mild reaction conditions, suitability for large-scale industrial production and the like. The prepared carbon microsphere has the advantages of uniform particle size, controllable sphere diameter and specific surface area, high compression strength and excellent electrochemical performance.
Description
Technical Field
The invention relates to the field of chemical synthetic resin carbon microspheres, in particular to phenolic resin carbon microspheres and a preparation method and application thereof.
Background
The new energy is a green energy, and has been widely noticed and researched in recent years, the use of the new energy is most important in the storage and release of the energy, and the research and development of the lithium ion battery, the super capacitor and the like as a new high-energy storage battery which is widely used in recent years have made a great progress, and are cross projects relating to multiple subjects of chemistry, physics, materials, energy, electronics and the like, and many problems still exist in the research and development. The cathode material is used as a main component of an energy storage device and has obvious influence on the performance of the energy storage device, and the cathode material which is commercially used at present mainly comprises graphite, activated carbon and the like, but is not an optimal cathode material and still has the defects of low energy density, low cycling stability and the like.
The carbon microsphere is a novel functional material, has the advantages of high specific surface area, adjustable particle size and pore structure and the like, can be used as a high-performance lithium ion battery cathode material, and is increasingly valued by researchers in various countries around the world. The phenolic resin carbon microsphere has the advantages of easily obtained source of the phenolic resin, low cost, high carbon residue and easy activation and pore formation, so the phenolic resin carbon microsphere is a carbon material with good application value, is widely applied to the field of gas adsorption and storage, and has huge potential application prospects in the aspects of super capacitor materials, lithium ion batteries, catalysis and the like. At present, the method for preparing the phenolic resin carbon microspheres mainly comprises the steps of preparing the microspheres by a suspension method, an emulsion polymerization method, a spray drying method, a high-pressure hydrothermal method and the like, and then carbonizing to prepare the carbon microspheres. However, the prepared carbon microspheres are smooth in surface and cannot be regulated in surface structure, and meanwhile, in the method for preparing the microspheres, auxiliary agents such as a surfactant and an emulsifier are required to be added, or conditions such as high temperature and high pressure are required, so that the operation is complex, and large-scale preparation is difficult to realize.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the phenolic resin carbon microsphere and the preparation method and application thereof are provided, and the problems that the operation of the preparation method of the phenolic resin carbon microsphere in the prior art is complex, the prepared carbon microsphere has a smooth surface, and the surface structure cannot be regulated and controlled are solved.
In order to solve the technical problems, the invention adopts the technical scheme that:
the phenolic resin carbon microsphere is prepared by carbonizing phenolic resin microsphere, the surface of the carbon microsphere is of a coarse structure, the particle size is 20-1000nm, and the surface specific surface area is 40-100m2The carbon is used as a main component, and the content of the carbon is more than or equal to 80 percent.
The invention also provides a preparation method of the phenolic resin carbon microspheres, which at least comprises the following steps:
1) dissolving thermoplastic phenolic resin in an alkaline solution to obtain a system I;
2) adding phenol, aldehyde and a catalyst into a reaction kettle, and heating for reaction to obtain a system II;
3) and uniformly mixing the system I and the system II, adjusting the pH value of the system to 6.5-10.5, heating for reaction, separating and drying to obtain the phenolic resin microspheres.
4) And carbonizing the phenolic resin microspheres to obtain the carbon microspheres.
The invention has the beneficial effects that: the phenolic resin carbon microsphere is prepared by carbonizing phenolic resin, has a rough structure on the surface, mainly contains carbon with the carbon content of more than or equal to 80 percent, can be used as an electrode material for preparing a new energy storage device, endows the material with unique surface characteristics, can endow electrolyte ions with good attachment space as the electrode material, and improves the electrochemical performance of the material. The method for preparing the carbon microsphere has the advantages of rich raw materials, low preparation cost, simple process, high yield, no need of adding auxiliary agents such as a surfactant, an emulsifier and the like in the preparation process, mild reaction conditions, suitability for large-scale industrial production and the like. The prepared carbon microsphere has the advantages of uniform particle size, controllable sphere diameter and specific surface area, high compression strength and excellent electrochemical performance. Can be applied to the cathode material of a lithium ion battery or a sodium ion battery, so that the battery has high capacity and stable cycle performance.
Drawings
FIG. 1 is a TEM image of carbon microspheres of example 1 according to an embodiment of the present invention.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
The invention provides phenolic resin carbon microspheres, which are prepared by carbonizing phenolic resin microspheres, wherein the surfaces of the carbon microspheres are of rough structures, the particle sizes of the carbon microspheres are 20-1000nm, and the surface specific surface areas of the carbon microspheres are 40-100m2The carbon is used as a main component, and the content of the carbon is more than or equal to 80 percent.
The phenolic resin carbon microspheres provided by the embodiment of the invention are prepared by carbonizing phenolic resin. The phenolic resin is the earliest synthetic resin for realizing industrial production, has the advantages of wide raw material source and simple production process, has good thermal stability, is used for preparing the carbon microspheres, and has the advantages of high carbonization yield, easy pore formation and the like.
The invention provides a preparation method of phenolic resin carbon microspheres, which at least comprises the following steps:
1) dissolving thermoplastic phenolic resin in an alkaline solution to obtain a system I;
2) adding phenol, aldehyde and a catalyst into a reaction kettle, and heating for reaction to obtain a system II;
3) and uniformly mixing the system I and the system II, adjusting the pH value of the system to 6.5-10.5, heating for reaction, separating and drying to obtain the phenolic resin microspheres.
4) And carbonizing the phenolic resin microspheres to obtain the carbon microspheres.
The main mechanism of the method is that the main component in the alkaline solution is linear long-chain phenolic resin, the linear long-chain phenolic resin has good solubility and stability in the alkaline solution, the main component in the acidic solution is low-molecular resin and unreacted phenol and aldehyde, when the acidic solution and the alkaline solution are mixed, the pH value of the system is changed, the stability of the long-chain resin in the thermoplastic phenolic resin alkaline solution is influenced, liquid drop cores are separated out and formed in a dilute solution system, and the low-molecular resin, the phenol and the aldehyde can be used as reaction raw materials or a cross-linking agent to further react with the thermoplastic phenolic resin, so that the cores are further increased, and finally the granular resin microspheres are formed. Meanwhile, the resin formed by the reaction of the thermoplastic phenolic resin and the phenol, aldehyde and soluble micromolecule resin in the phenolic resin acidic wastewater is attached to the core, so that a concave-convex rough structure is created.
The phenolic resin carbon microsphere is prepared by carbonizing phenolic resin serving as a raw material, the surface of the phenolic resin carbon microsphere is of a rough structure, the particle size is 20-1000nm, and the surface specific surface area is 40-100m2The carbon is used as the main component, the content of the carbon is more than or equal to 80 percent, the carbon can be used as an electrode material for preparing a new energy storage device, the material is endowed with unique surface characteristics, and the carbon can be used as the electrode material to endow electrolyte ions with good attachment space, so that the electrochemical performance of the material is improved. As a method for preparing the microspheres, the phenolic resin microspheres are prepared by dissolving thermoplastic phenolic resin in an alkali solution to form a phenolic resin alkali solution, then reacting the phenolic resin alkali solution with phenol and aldehyde under the condition of a catalyst to form a resin acid solution, mixing the resin acid solution and the resin acid solution, and heating and stirring the mixture. The low molecular resin and unreacted phenol in the acid solution are used as reaction raw materials and a curing cross-linking agent, are further reacted and cross-linked with linear long-chain macromolecules in the alkali solution, are precipitated into microspheres by utilizing the instability under the weak acid or weak alkaline condition, and are further carbonized to obtain the carbon microspheres. The method has the advantages of rich raw materials, low preparation cost, simple process, high yield, no need of adding curing agent, surfactant, emulsifier and the like in the preparation process, suitability for large-scale industrial production and the like. The prepared carbon microsphere has the advantages of uniform particle size, controllable sphere diameter and specific surface area, high compression strength and excellent electrochemical performance. Can be applied to the cathode material of a lithium ion battery or a sodium ion battery, so that the battery has high capacity and stable cycle performance.
Further, in the structure of the phenolic resin carbon microsphere:
the specific surface area of the carbon microsphere is 100-2/g；
The pore volume of the carbon microsphere is 0.1-1.0cm3/g；
The average pore diameter of the carbon microsphere is 1-10 nm.
Furthermore, the phenolic resin carbon microspheres are different from other phenolic resin carbon microspheres, and the surfaces of the phenolic resin carbon microspheres have rough structures, so that the carbon microspheres have more apparent characteristics. The particle size of the carbon microsphere is 20-1000nm, the lower limit of the particle size can be 50nm, 100nm or 200nm, and the upper limit of the particle size can be 800nm, 600nm or 500 nm. The phenolic resin carbon microspheres have nano particle size, more specific surface area and abundant hole structures, and can be applied to the fields of electrochemical energy storage, catalysis, adsorption and the like.
Furthermore, the surface specific surface area of the phenolic resin carbon microspheres is 40-100m2A/g, preferably of 40 to 80m2(ii) g, more preferably 40 to 60m2(ii) in terms of/g. The rough surface structure enables the material to have a large surface specific surface area, provides a favorable place for the attachment of other substances, ions and electrons, and enables the electrode prepared from the material to have good electrochemical performance.
Furthermore, the specific surface area of the phenolic resin carbon microspheres is 100-2The lower limit is more preferably 600m2(ii) in terms of/g. The pore volume of the carbon microsphere is 0.1-1.0cm3Per g, more preferably 0.2 to 0.5cm3(ii) in terms of/g. The average pore diameter of the carbon microsphere is 1-10nm, the pores preferably have micropores and mesopores in a certain proportion, the micropores can provide more specific surface area and form more ion attachment spaces, and the mesopores can shorten the ion transmission distance and reduce the transmission resistance. The specific surface area, the pore volume and the pore diameter can be adjusted in the process of preparing the phenolic resin microspheres and can also be adjusted by carbonization conditions.
Further, the thermoplastic phenolic resin may be one or more of phenolic resin, such as phenol-formaldehyde resin, resorcinol-formaldehyde resin, 3-aminophenol-formaldehyde resin, bisphenol a-formaldehyde resin, cardanol modified phenolic resin, boron modified phenolic resin, silicon modified phenolic resin, or selenium modified phenolic resin.
Further, the base is an alkaline compound, including but not limited to one of sodium hydroxide, calcium hydroxide, magnesium hydroxide, or potassium hydroxide. The thermoplastic phenolic resin has good solubility and stability in alkaline solution, can form uniformly dispersed solution, and improves good foundation for forming the resin carbon microspheres with spherical structures.
Further, the solvent of the alkaline solution is one or a combination of two of water, methanol and ethanol. The size of the carbon microsphere can be accurately regulated and controlled by changing the type and the using amount of the solvent, and the preferred solvent is water, so that the use of an organic solvent can be reduced, and the method has better environmental protection benefit.
Further, the phenol is one or a combination of two of phenol, bisphenol A, cresol, bisphenol F, resorcinol, hydroquinone, catechol, 3-aminophenol, 2-aminophenol, 4-aminophenol or cardanol.
Further, the aldehyde is formaldehyde aqueous solution or solid formaldehyde, and the catalyst is one or a combination of two of formic acid, oxalic acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, zinc acetate or ammonia water.
Further, the molar ratio of the phenol to the aldehyde is 1:4-0.6, the dosage of the catalyst is 0.1% -1%, and the solid content of the solution A is 0.1-10%. As for preparing the phenolic resin carbon microspheres, a dilute solution system is the key of the balling, the solid content of the solution A has specific requirements, and the solid content of the solution A can be regulated and controlled by adjusting the proportion of the thermoplastic phenolic resin and the alkaline solution. The solution A has excessively high solid content and low apparent energy, and only flaky random resin can be formed by intermolecular adsorption, but the excessively low solid content can cause the carbon microsphere product to have low yield and high cost, and is not beneficial to industrial production. In the invention, the solid content of the solution A is also a main factor influencing the grain diameter of the carbon microspheres, the solid content is high, the grain diameter of the carbon microspheres is large, the lower the solid content is, the smaller the grain diameter of the carbon microspheres is, and the grain diameter is the same as the grain diameterThe surface specific surface area of the carbon microsphere is deeply influenced, and the particle size of the carbon microsphere is 20nm-1000nm and the surface specific surface area is 40-100m2Per gram of carbon microspheres, control of the solids content of solution A is a critical factor. Thus, the upper limit of the solid content of the solution a defined in the present invention is 10%, and the upper limit of the solid content of the solution a which may be further preferable is one of 8%, 5%, and 4%. The lower limit of the solid content of the solution A selected by the invention is 0.1%, and the further preferential lower limit can be one of 0.5%, 0.8% and 1.0%.
In order to further improve the homogeneity of the product, the solution a may be further subjected to separation processes to remove insoluble impurities, including but not limited to precipitation, centrifugation, filtration, and the like.
Furthermore, the pH of the adjusting system is 6.5-10.5, the preferable upper limit of the pH is 10, 9.5 or 9, and the lower limit of the pH is 7, 7.3 or 7.6.
Further, the reaction temperature for uniformly mixing the system I and the system II is 80-110 ℃, the temperature preferably has one of the upper limits of 105 and 100 and one of the lower limits of 85, 90 and 95.
Furthermore, the carbon microspheres are applied to electrode materials.
Example 1
Dissolving 2g of thermoplastic phenol-formaldehyde resin in 100ml of sodium hydroxide aqueous solution to obtain a system I; adding 0.2g of phenol, 0.53g of formaldehyde solution and 0.001g of oxalic acid into a reaction kettle, heating to 80 ℃, and reacting for 30min to obtain a system II; uniformly mixing the system I and the system II, adjusting the pH value of the system to 10, and heating to 100 ℃ for reaction for 24 hours; separating for 5min by a centrifugal machine with the speed of 5000r/min, and then drying in an oven with the temperature of 120 ℃ to obtain phenolic resin microspheres; and carbonizing the phenolic resin microspheres for 4 hours at 650 ℃ in a nitrogen atmosphere to obtain the phenolic resin carbon microspheres C1. The prepared phenolic resin carbon microspheres have the particle size of 173nm and the surface specific surface area of 56m2(iv)/g, carbon content 89.3%, BET specific surface area 657m2Per g, pore volume 0.25cm3(ii)/g, mean pore diameter 5.6nm, see FIG. 1.
The carbon microsphere is obtained according to a GB/T19587-2004 gas adsorption BET method, the surface specific surface area is calculated by a T-Plot method, the average particle size is tested by a laser particle sizer, and the carbon content is tested by an XPS method.
Example 2
Dissolving 2g of thermoplastic phenol-formaldehyde resin in 50ml of sodium hydroxide aqueous solution to obtain a system I; adding 0.2g of phenol, 0.53g of formaldehyde solution and 0.001g of oxalic acid into a reaction kettle, heating to 80 ℃, and reacting for 30min to obtain a system II; uniformly mixing the system I and the system II, adjusting the pH value of the system to 10, and heating to 100 ℃ for reaction for 24 hours; separating for 5min by a centrifugal machine with the speed of 5000r/min, and then drying in an oven with the temperature of 120 ℃ to obtain phenolic resin microspheres; and carbonizing the phenolic resin microspheres for 4 hours at 650 ℃ in a nitrogen atmosphere to obtain the phenolic resin carbon microspheres C2. The prepared phenolic resin carbon microspheres have the particle size of 253nm and the surface specific surface area of 51m2(ii)/g, carbon content 91.1%, BET specific surface area 552m2Per g, pore volume 0.23cm3G, average pore diameter of 7 nm.
Example 3
Dissolving 2g of thermoplastic phenol-formaldehyde resin in 100ml of sodium hydroxide aqueous solution to obtain a system I; adding 0.2g of phenol, 0.53g of formaldehyde solution and 0.001g of oxalic acid into a reaction kettle, heating to 80 ℃, and reacting for 30min to obtain a system II; uniformly mixing the system I and the system II, adjusting the pH of the system to 8.5, and heating to 100 ℃ for reaction for 24 hours; separating for 5min by a centrifugal machine with the speed of 5000r/min, and then drying in an oven with the temperature of 120 ℃ to obtain phenolic resin microspheres; and carbonizing the phenolic resin microspheres for 4 hours at 650 ℃ in a nitrogen atmosphere to obtain the phenolic resin carbon microspheres C3. The prepared phenolic resin carbon microspheres have the particle size of 325nm and the surface specific surface area of 42m2(ii)/g, carbon content 90.3%, BET specific surface area 506m2Per g, pore volume 0.21cm3In terms of/g, the mean pore diameter is 6.2 nm.
Example 4
Dissolving 2g of thermoplastic phenol-formaldehyde resin in 100ml of sodium hydroxide aqueous solution to obtain a system I; adding 0.2g of phenol, 0.53g of formaldehyde solution and 0.001g of oxalic acid into a reaction kettle, heating to 80 ℃, and reacting for 30min to obtain a system II; mixing system I and system II, and blendingThe pH value of the joint system is 10, and the joint system is heated to 100 ℃ to react for 24 hours; separating for 5min by a centrifugal machine with the speed of 5000r/min, and then drying in an oven with the temperature of 120 ℃ to obtain phenolic resin microspheres; and carbonizing the phenolic resin microspheres for 4 hours at 850 ℃ in a nitrogen atmosphere to obtain the phenolic resin carbon microspheres C4. The prepared phenolic resin carbon microspheres have the particle size of 160nm and the surface specific surface area of 52m2(ii)/g, carbon content 92.3%, BET specific surface area 738m2Per g, pore volume 0.28cm3In terms of/g, the mean pore diameter is 6.3 nm.
Further, the phenolic resin carbon microspheres prepared in the examples were tested for electrochemical performance. The method comprises the following steps:
weighing carbon microspheres, acetylene black and a 3% SBR-CMC mixture, uniformly mixing the mixture according to a mass ratio of 8:1:1 to prepare slurry (active substance), coating the active substance slurry on the rough part of the long-strip graphite paper, and putting the graphite paper into a vacuum oven to dry for 5 hours at 100 ℃.
And (3) testing conditions are as follows: a three-electrode system is adopted, an electrode prepared from active substances is a working electrode, a Pt sheet is a counter electrode, and a saturated calomel electrode is a reference electrode. Electrolyte is 1M H2SO4Solution, scanning window: -0.2-0.8V, and the test results are shown in Table 1.
Table 1 electrical property test results
As can be seen from the table, the battery prepared by using the phenolic resin carbon microspheres obtained by the invention as the material has high capacity and capacity retention rate, and the comparison shows that the carbon microspheres with large specific surface area have better electrical storage performance.
In conclusion, the phenolic resin carbon microspheres provided by the invention are prepared by carbonizing phenolic resin serving as a raw material, the surfaces of the phenolic resin carbon microspheres are of rough structures, the particle sizes of the phenolic resin carbon microspheres are 20-1000nm, and the surface specific surface areas of the phenolic resin carbon microspheres are 40-100m2The carbon is used as the main component, the content of the carbon is more than or equal to 80 percent, the carbon can be used as an electrode material for preparing a new energy storage device, the material is endowed with unique surface characteristics, and the carbon can be used as the electrode material to be further endowed with electrolyteThe ions have good attachment space, and the electrochemical performance of the material is improved. As a method for preparing the microspheres, the phenolic resin microspheres are prepared by dissolving thermoplastic phenolic resin in an alkali solution to form a phenolic resin alkali solution, then reacting the phenolic resin alkali solution with phenol and aldehyde under the condition of a catalyst to form a resin acid solution, mixing the resin acid solution and the resin acid solution, and heating and stirring the mixture. The low molecular resin and unreacted phenol in the acid solution are used as reaction raw materials and a curing cross-linking agent, are further reacted and cross-linked with linear long-chain macromolecules in the alkali solution, are precipitated into microspheres by utilizing the instability under the weak acid or weak alkaline condition, and are further carbonized to obtain the carbon microspheres. The method has the advantages of rich raw materials, low preparation cost, simple process, high yield, no need of adding curing agent, surfactant, emulsifier and the like in the preparation process, suitability for large-scale industrial production and the like. The prepared carbon microsphere has the advantages of uniform particle size, controllable sphere diameter and specific surface area, high compression strength and excellent electrochemical performance. Can be applied to the cathode material of a lithium ion battery or a sodium ion battery, so that the battery has high capacity and stable cycle performance.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.
Claims (5)
1. The preparation method of the phenolic resin carbon microspheres is characterized by comprising the following steps:
step 1: dissolving thermoplastic phenolic resin in an alkaline solution to obtain a system I;
step 2: adding phenol, aldehyde and a catalyst into a reaction kettle, and heating for reaction to obtain a system II;
and step 3: uniformly mixing the system I and the system II, adjusting the pH value of the system to 6.5-10.5, heating for reaction, separating and drying to obtain phenolic resin microspheres; the reaction temperature of the step 3 is 80-110 ℃;
and 4, step 4: carbonizing phenolic resin microspheres to obtain carbon microspheres;
the carbon microspheresThe surface is rough structure, the particle diameter is 20-1000nm, and the surface specific surface area is 40-100m2(ii)/g, the main component is carbon, and the content of the carbon is more than or equal to 80%;
the molar ratio of the phenol to the aldehyde is 1:4-0.6, the dosage of the catalyst is 0.1% -1% of the mass of the phenol, and the solid content of the system I is 0.1% -10%.
2. The method for preparing the phenolic resin carbon microspheres of claim 1, wherein the thermoplastic phenolic resin is one or more of phenol-formaldehyde resin, resorcinol-formaldehyde resin, 3-aminophenol-formaldehyde resin, bisphenol A-formaldehyde resin, cardanol modified phenolic resin, boron modified phenolic resin, silicon modified phenolic resin or selenium modified phenolic resin.
3. The method for preparing phenolic resin carbon microspheres according to claim 1, wherein the alkali in the alkaline solution is one of sodium hydroxide, calcium hydroxide, magnesium hydroxide and potassium hydroxide, and the solvent in the alkaline solution is one or a combination of water, methanol and ethanol.
4. The method for preparing the phenolic resin carbon microspheres of claim 1, wherein the phenol is one or a combination of two of phenol, bisphenol A, cresol, bisphenol F, resorcinol, hydroquinone, catechol, 3-aminophenol, 2-aminophenol, 4-aminophenol or cardanol.
5. The method for preparing the phenolic resin carbon microspheres of claim 1, wherein the aldehyde is aqueous formaldehyde or solid formaldehyde, and the catalyst is one or a combination of two of formic acid, oxalic acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, zinc acetate or ammonia water.
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