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CN119841303B - A modified phenolic resin-based hard carbon material and its preparation method and application - Google Patents

A modified phenolic resin-based hard carbon material and its preparation method and application

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Publication number
CN119841303B
CN119841303B CN202510057523.8A CN202510057523A CN119841303B CN 119841303 B CN119841303 B CN 119841303B CN 202510057523 A CN202510057523 A CN 202510057523A CN 119841303 B CN119841303 B CN 119841303B
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phenolic resin
hard carbon
carbon material
based hard
modified phenolic
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CN119841303A (en
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潘安强
周双
王哲
李航
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Central South University
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/05Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28Chemically modified polycondensates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a modified phenolic resin-based hard carbon material, and a preparation method and application thereof, and belongs to the technical field of phenolic resin-based hard carbon materials. The invention creatively uses formaldehyde containing aldehyde groups and oxygen-enriched glucurolactone to replace formaldehyde in the traditional method, adopts 1,2, 4-benzene triphenol containing three phenolic hydroxyl groups and simultaneously having two phenolic hydroxyl groups at ortho positions to replace phenol in the traditional method, provides a method for easily preparing thermosetting phenolic resin, has the advantages of low cost, no toxicity and no pollution, the prepared modified phenolic resin-based hard carbon material has proper specific surface area, abundant micropores and larger graphitized interlayer spacing, the specific surface area of the modified phenolic resin-based hard carbon material is 451.51m 2/g, the micropore volume is 0.217cm 3/g, the prepared modified phenolic resin-based hard carbon material is used as a sodium ion battery anode material, has 86.44% of first coulomb efficiency, has 232.8mAh/g of platform capacity under the current density of 0.05A/g, and still has 83.71% of capacity retention rate after stabilizing 1000 circles with the coulomb efficiency of 99.97% under the current density of 1A/g.

Description

Modified phenolic resin-based hard carbon material and preparation method and application thereof
Technical Field
The invention relates to the technical field of phenolic resin-based hard carbon materials, in particular to a modified phenolic resin-based hard carbon material, and a preparation method and application thereof.
Background
Phenolic resin has better high temperature resistance, chemical resistance, bonding strength and the like, has wide application, and is regarded as a high-quality carbon precursor for a long time due to the advantages of simple preparation process, high carbon residue rate, easy structure regulation and the like. The thermoplastic phenolic resin (oxygen-enriched and oxygen-deficient) is easy to graphitize at the temperature of more than 1000 ℃ to form a soft carbon material, and the thermosetting phenolic resin (oxygen-enriched and hydrogen-deficient) is difficult to graphitize at the temperature of more than 1000 ℃ to form a hard carbon material due to a large amount of oxygen, so that the thermosetting phenolic resin can be used as a negative electrode material of a sodium ion battery.
The traditional phenolic resin is formed by phenol and formaldehyde through phenolic polycondensation under the catalysis of acidity or alkalinity, but the phenol cost is higher, 3 types of cancerogenic substances published by the international cancer research institute of the world health organization are provided, and formaldehyde is 1 type of cancerogenic substances published by the international cancer research institute of the world health organization, so that the life health safety of human beings is threatened greatly in the production process.
Sodium ion batteries are considered to be effective supplements of lithium ion batteries due to the similar working principle as lithium ion batteries, and hard carbon materials are considered to be the most promising negative electrode materials of sodium ion batteries due to good low-voltage platforms and sodium storage capacity, but the problems of low specific capacity, low coulombic efficiency and poor cycle stability still exist at present, and although some technologies are improved, the problems cannot be considered.
Disclosure of Invention
The invention aims to provide a modified phenolic resin-based hard carbon material, and a preparation method and application thereof, so as to solve the problems that the preparation cost of the phenolic resin-based hard carbon material is high, the life health safety of workers is greatly threatened in the preparation process, and the specific capacity, the coulomb efficiency and the cycle stability are low when the phenolic resin-based hard carbon material prepared at present is used as a battery anode material.
In order to achieve the above purpose, the invention provides a preparation method of a modified phenolic resin-based hard carbon material, which comprises the following steps:
s1, introducing metal ions into phenolic aldehyde, sequentially adding a surfactant and 25% -30% ammonia water into a solvent, uniformly mixing, adding 1,2, 4-phloroglucinol, dissolving, adding glucurolactone, stirring and reacting;
S2, preparing a modified phenolic resin-based material, placing the solution after the reaction in the step S1 into a polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining into a hydrothermal kettle for reaction, and carrying out suction filtration, washing and drying on the product to obtain the modified phenolic resin-based material;
s3, preparing a modified phenolic resin-based hard carbon material, transferring the prepared phenolic resin-based material into a corundum porcelain boat, and reacting in a high-temperature tube furnace under argon atmosphere to obtain the modified phenolic resin-based hard carbon material.
Preferably, in the step S1, the solvent is one or two of deionized water and ethanol, and the surfactant is one of polyethylene glycol and ethylene glycol.
Preferably, in the step S1, the mass volume ratio of the solvent to the surfactant to the ammonia water to the 1,2, 4-benzene-triphenol to the glucurolactone to the metal ion salt is 60mL:0.25mL:0-3mL:1.5g:3g:0.4g.
Preferably, the metal ion salt in the step S1 is one of zinc acetate, zinc chloride and zinc sulfate.
Preferably, in the step S1, metal ion salt is added and then stirred for reaction for 12 hours.
Preferably, the hydrothermal kettle reaction condition in the step S2 is 180 ℃ for 24 hours.
Preferably, the reaction condition in the step S3 under argon atmosphere is that the temperature is raised to 900 ℃ at 5 ℃ per min, the temperature is kept for 1h, and the temperature is raised to 1300 ℃ at 2 ℃ per min, and the temperature is kept for 3h.
The modified phenolic resin-based hard carbon material prepared by the preparation method of the modified phenolic resin-based hard carbon material.
The application of the modified phenolic resin-based hard carbon material in sodium ion batteries is provided, wherein the modified phenolic resin-based hard carbon material is used as a negative electrode of the sodium ion batteries.
Therefore, the modified phenolic resin-based hard carbon material, the preparation method and the application thereof provided by the invention have the following specific technical effects:
(1) The invention creatively uses the formaldehyde which contains aldehyde groups and is rich in oxygen to replace the formaldehyde in the traditional method, the thermosetting phenolic resin is easy to prepare by adopting the method provided by the invention, and the glucurolactone has the advantages of low cost, no toxicity and no pollution as a glucose metabolite;
(2) The invention adopts the 1,2, 4-benzene triphenol containing three phenolic hydroxyl groups and two phenolic hydroxyl groups at ortho positions to replace phenol in the traditional method, is favorable for forming a coordination compound with metal ions, realizes ion doping, and can reduce the harm to human bodies in the production process by adopting one of 1,2, 4-benzene triphenol which is not 3-type cancerogenic substances;
(3) The modified phenolic resin-based hard carbon material prepared by the method provided by the invention has proper specific surface area, abundant micropores and larger graphitized layer spacing, the specific surface area of the modified phenolic resin-based hard carbon material is 451.51m 2/g, and the micropore volume is 0.217cm 3/g;
(4) The modified phenolic resin-based hard carbon material prepared by the invention is used as a negative electrode material of a sodium ion battery, has the first coulomb efficiency of 86.44%, has the platform capacity of 232.8mAh/g under the current density of 0.05A/g, and still has the capacity retention rate of 83.71% after being stably circulated for 1000 circles with the coulomb efficiency of 99.97% under the current density of 1A/g.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments of the present invention will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a FTIR chart of the phenolic resin synthesized in example 1;
FIG. 2 is an XPS chart of the phenolic resin synthesized in example 1;
FIG. 3 is a TGA curve of phenolic resins synthesized in example 1, comparative example 1-1 and comparative example 1-2;
FIG. 4 is an SEM image of the phenolic resin-based hard carbon material prepared in example 1, comparative example 1-1, where part a) and part b) are SEM images of the phenolic resin-based hard carbon material prepared in comparative example 1-1, and part c) and part d) are SEM images of the phenolic resin-based hard carbon material prepared in example 1;
FIG. 5 is an XRD pattern of the phenolic resin-based hard carbon material prepared in example 1 and comparative example 1-1;
FIG. 6 is a GCD curve at a current density of 0.05A/g for the sodium ion battery prepared in example 2;
FIG. 7 is a graph of ramp capacity versus plateau capacity for a first charge curve at a current density of 0.05A/g for the sodium-ion cell prepared in example 2, comparative example 2-1;
FIG. 8 is a graph of cycle times versus specific capacity/coulombic efficiency at a current density of 1A/g for the sodium-ion batteries prepared in example 2, comparative example 2-1, and comparative example 2-2.
Detailed Description
The technical scheme of the invention is further described below through the attached drawings and the embodiments.
In order to make the objects, technical solutions and advantages of the present application more clear, thorough and complete, the technical solutions of the present application will be clearly and completely described below through the accompanying drawings and examples. The following detailed description is of embodiments, and is intended to provide further details of the application. Unless defined otherwise, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
The instrumentation and reagent materials used in the examples are all commercially available.
Example 1
The preparation method of the modified phenolic resin-based hard carbon material comprises the following specific steps:
(1) To 60mL of deionized water, 0.25mL of polyethylene glycol and 0.5mL of 28% aqueous ammonia were added and stirred well, then 1.5g of 1,2, 4-benzenetriol was added, 3g of glucurolactone was added after dissolution, and stirring was continued for 2 hours at 50℃until 0.4g of zinc acetate was added after the time, and stirring was continued for 12 hours.
(2) Transferring the solution after stirring in the step (1) into a 100mL polytetrafluoroethylene lining, carrying out hydrothermal treatment at 180 ℃ for 24 hours, carrying out suction filtration on a hydrothermal product, washing with deionized water, and drying at 60 ℃ for 24 hours to obtain the phenolic resin-based material.
The obtained phenolic resin-based material was successfully synthesized by combining 1,2, 4-benzenetriol with glucurolactone as shown in the Fourier transform infrared absorption spectrum (FTIR) of the phenolic resin-based material in FIG. 1. The X-ray photoelectron spectrum (XPS) of the obtained phenolic resin-based material is shown in figure 2, and the result shows that Zn is successfully introduced into the phenolic resin by using Zn-O coordination.
(3) Transferring the obtained phenolic resin-based material into a corundum porcelain boat, heating to 900 ℃ at 5 ℃ per min in a high-temperature tube furnace under argon atmosphere, preserving heat for 1h, and heating to 1300 ℃ at 2 ℃ per min for 3h to obtain the modified phenolic resin-based hard carbon material.
Comparative examples 1 to 1
The preparation method of the phenolic resin-based hard carbon material comprises the following specific steps:
(1) To 60mL of deionized water, 0.25mL of polyethylene glycol and 0.5mL of 28% aqueous ammonia were added and stirred well, then 1.5g of 1,2, 4-benzenetriol was added, 3g of glucurolactone was added after dissolution, and stirred for 2 hours at 50 ℃.
(2) Transferring the solution after stirring in the step (1) into a 100mL polytetrafluoroethylene lining, carrying out hydrothermal treatment at 180 ℃ for 24 hours, carrying out suction filtration on a hydrothermal product, washing with deionized water, and drying at 60 ℃ for 24 hours to obtain the phenolic resin-based material.
(3) Transferring the obtained phenolic resin-based material into a corundum porcelain boat, heating to 900 ℃ at 5 ℃ per min in a high-temperature tube furnace under argon atmosphere, preserving heat for 1h, and heating to 1300 ℃ at 2 ℃ per min for 3h to obtain the phenolic resin-based hard carbon material.
Comparative examples 1 to 2
The preparation method of the glucurolactone-based hard carbon material comprises the following specific steps:
(1) To 60mL of deionized water, 0.25mL of polyethylene glycol and 0.5mL of 28% aqueous ammonia were added and stirred well, followed by addition of 3g of glucurolactone and stirring at 50℃for 2 hours.
(2) Transferring the stirred solution obtained in the step (1) into a 100mL polytetrafluoroethylene lining, carrying out hydrothermal treatment at 180 ℃ for 24 hours, carrying out suction filtration on a hydrothermal product, washing with deionized water, and drying at 60 ℃ for 24 hours to obtain the glucurolactone material.
(3) Transferring the obtained glucurolactone material into a corundum porcelain boat, heating to 900 ℃ at 5 ℃ per min in a high-temperature tube furnace under argon atmosphere, preserving heat for 1h, and heating to 1300 ℃ at 2 ℃ per min, and preserving heat for 3h to obtain the glucurolactone-based hard carbon material.
Thermogravimetric analysis (TGA) of the material (carbonized precursor material) obtained in step (2) of example 1, step (2) of comparative example 1-1, step (2) and step (2) of comparative example 1-2, the results are shown in fig. 3, and the results show that the carbon yields of example 1 and comparative example 1-1 are improved, further indicate that the polymerization reaction of glucurolactone and 1,2, 4-benzenetriol occurs to form phenolic resin material.
Scanning Electron Microscope (SEM) pictures of the phenolic resin-based hard carbon materials obtained in example 1 and comparative example 1-1 are shown in FIG. 4, wherein part a) and part b) are SEM pictures of the phenolic resin-based hard carbon materials prepared in comparative example 1-1, and part c) and part d) are SEM pictures of the phenolic resin-based hard carbon materials prepared in example 1. From the comparison of the part a) and the part c), and the part b) and the part d), zn introduced by utilizing Zn-O coordination plays a role in pore forming in the carbonization process, so that the porosity is improved, the specific surface area is increased, and more active sites are exposed.
X-ray diffraction (XRD) analysis of the phenolic resin-based hard carbon materials obtained in example 1 and comparative example 1-1 shows that the phenolic resin-based hard carbon materials prepared in example 1 and comparative example 1-1 all show typical hard carbon characteristics, and compared with the typical hard carbon characteristics, the left shift of the peak position of the broad peak indicates that Zn introduced by Zn-O coordination improves graphitization interlayer spacing in carbonization process, thereby facilitating better diffusion kinetics.
Example 2
The modified phenolic resin-based hard carbon material prepared in example 1 is assembled into a sodium ion battery, and the energy storage potential and the cycle stability are tested, and specifically, the modified phenolic resin-based hard carbon material prepared in example 1 is used as an active material of an anode, a sodium sheet is used as a cathode, an electrolyte is 1MNaF 6 of diethylene glycol dimethyl ether (DIGLYME) solution, and the battery is assembled in a glove box protected by argon by using a model 2032 button battery, so that the sodium ion battery is obtained.
The prepared sodium ion battery is tested under the current density of 0.05A/g, the GCD curve of the sodium ion battery is shown as figure 6, and the modified phenolic resin has the first coulombic efficiency of 86.44% as the negative electrode material of the sodium ion battery under the proper specific surface area. The ramp capacity versus plateau capacity versus histogram for the first charge cycle is shown in fig. 7 and the cycle number versus specific capacity/coulombic efficiency curve at a current density of 1A/g is shown in fig. 8.
Comparative example 2-1
The phenolic resin-based hard carbon material prepared in comparative example 1-1 was used as an active material of the positive electrode, a sodium sheet was used as the negative electrode, and an electrolyte was 1M diethylene glycol dimethyl ether (DIGLYME) solution of NaF 6, and battery assembly was performed in an argon-protected glove box using a model 2032 coin cell. The ramp capacity and plateau capacity versus plateau for the first charge curve is shown in FIG. 7 for a test at a current density of 0.05A/g and the cycle number versus specific capacity/coulombic efficiency curve at a current density of 1A/g is shown in FIG. 8.
As can be seen from fig. 7, the phenolic resin-based hard carbon material prepared in example 2 has more sodium storage sites due to the larger porosity generated by pore-forming, which is beneficial to generating more sodium storage capacity.
Comparative examples 2 to 2
The glucurolactone-based hard carbon prepared in comparative examples 1-2 was used as an active material of a positive electrode, a sodium sheet was used as a negative electrode, and an electrolyte was 1M solution of NaF 6 in diethylene glycol dimethyl ether (DIGLYME), and battery assembly was performed in an argon-protected glove box using a model 2032 coin cell. The cycle number-specific capacity/coulombic efficiency curve at a current density of 1A/g is shown in FIG. 8, tested at a current density of 0.05A/g.
As can be seen from comparison of FIG. 8, the cycle number of example 2 and comparative example 2-1 can reach 1000 cycles at a current density of 1A/g, and comparative example 2-2 only has nearly 800 cycles, which means that the phenolic resin synthesized in example 2 and comparative example 2-1 has a stable crosslinked structure and remains after hard carbon is formed to form a stable carbon skeleton, and at the same time, example 2 has a higher cycle specific capacity after pore formation and still has a specific capacity of 83.71%232mAh/g after 1000 cycles.
The modified phenolic resin-based hard carbon material has the advantages of proper specific surface area, abundant micropores and larger graphitized layer spacing, the specific surface area of the modified phenolic resin-based hard carbon material is 451.51m 2/g, the micropore volume is 0.217cm 3/g, the modified phenolic resin-based hard carbon material prepared by the method is used as a negative electrode material of a sodium ion battery, the first coulombic efficiency of 86.44 percent, the platform capacity of 232.8mAh/g under the current density of 0.05A/g, and the capacity retention rate of 83.71 percent after the modified phenolic resin-based hard carbon material is stably circulated for 1000 circles under the current density of 1A/g at the coulombic efficiency of 99.97 percent.
It should be noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted by the same, and the modified or substituted technical solution may not deviate from the spirit and scope of the technical solution of the present invention.

Claims (4)

1. The preparation method of the modified phenolic resin-based hard carbon material is characterized by comprising the following steps of:
s1, introducing metal ions into phenolic aldehyde, sequentially adding a surfactant and 25-30% ammonia water into a solvent, uniformly mixing, adding 1,2, 4-benzene-triphenol, dissolving, adding glucurolactone, stirring and reacting;
S2, preparing a modified phenolic resin-based material, placing the solution after the reaction in the step S1 into a polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining into a hydrothermal kettle for reaction, and carrying out suction filtration, washing and drying on the product to obtain the modified phenolic resin-based material;
S3, preparing a modified phenolic resin-based hard carbon material, transferring the prepared phenolic resin-based material into a corundum porcelain boat, and reacting in a high-temperature tube furnace under argon atmosphere to obtain the modified phenolic resin-based hard carbon material;
in the step S1, the solvent comprises a surfactant, ammonia water, 1,2, 4-benzene triphenol, glucurolactone and metal ion salt, wherein the mass volume ratio of the metal ion salt to the ammonia water to the glucurolactone is 60mL to 0.25mL to 0-3mL to 1.5g to 3g to 0.4g, and the metal ion salt is added and stirred for reaction for 12 hours;
the hydrothermal kettle reaction condition in the step S2 is 180 ℃ for 24 hours;
the reaction condition in the step S3 under the argon atmosphere is that the temperature is raised to 900 ℃ at 5 ℃ per min, the heat is preserved for 1h, and the temperature is raised to 1300 ℃ at 2 ℃ per min, and the heat is preserved for 3h.
2. The method of claim 1, wherein the solvent in the step S1 is one or both of deionized water and ethanol, and the surfactant is one of polyethylene glycol and ethylene glycol.
3. A modified phenolic resin-based hard carbon material prepared by the method for preparing a modified phenolic resin-based hard carbon material according to claim 1 or 2.
4. The application of the modified phenolic resin-based hard carbon material in sodium ion batteries as claimed in claim 3, wherein the modified phenolic resin-based hard carbon material is used as a negative electrode of the sodium ion batteries.
CN202510057523.8A 2025-01-14 2025-01-14 A modified phenolic resin-based hard carbon material and its preparation method and application Active CN119841303B (en)

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