CN112125295B - Phenolic resin/sucrose-based hard carbon microsphere material, preparation method thereof and sodium ion battery - Google Patents

Phenolic resin/sucrose-based hard carbon microsphere material, preparation method thereof and sodium ion battery Download PDF

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CN112125295B
CN112125295B CN202011029115.5A CN202011029115A CN112125295B CN 112125295 B CN112125295 B CN 112125295B CN 202011029115 A CN202011029115 A CN 202011029115A CN 112125295 B CN112125295 B CN 112125295B
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phenolic resin
sucrose
hard carbon
based hard
carbon microsphere
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CN112125295A (en
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徐斌
徐冉
孙宁
常夏青
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the technical field of sodium ion batteries, and provides a preparation method of a phenolic resin/sucrose-based hard carbon microsphere material. According to the invention, phenolic resin, sucrose and a solvent are mixed for solvothermal reaction, rich functional groups of the sucrose and the phenolic resin are utilized, in the solvothermal reaction process, the long chain structure of the phenolic resin is rearranged, the hydroxyl in the sucrose and the unsaturated group in the phenolic resin are subjected to cross-linking reaction, the product is slowly crystallized to obtain spherical particles with smooth surfaces, and then the spherical particles are subjected to high-temperature carbonization treatment to obtain the hard carbon material with the spherical structure. Experimental results show that the hard carbon material provided by the invention is used as a cathode of a sodium ion battery, so that the high initial coulombic efficiency and the high cycling stability are maintained, and meanwhile, the reversible capacity is high.

Description

Phenolic resin/sucrose-based hard carbon microsphere material, preparation method thereof and sodium ion battery
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a phenolic resin/sucrose-based hard carbon microsphere material, a preparation method thereof and a sodium ion battery.
Background
The sodium element has the advantages of similar properties with the lithium element, abundant reserves, low cost and potential high safety, so the sodium ion battery has great development prospect in large-scale energy storage application. The hard carbon material has a macroscopic non-graphite structure, large interlayer spacing and disordered microstructure, and is not easy to graphitize. The hard carbon precursor has rich sources, including resin (epoxy resin, phenolic resin and the like), high molecular polymer, biomass and the like, has higher low-voltage platform capacity as an electrode material of the sodium ion battery, and is one of the most promising negative electrode materials of the sodium ion battery.
Sucrose and phenolic resin are two common hard carbon precursors, the hard carbon material prepared by direct pyrolysis is used for the cathode of the sodium ion battery,the capacity attenuation is fast, the first coulombic efficiency is low, and the practical application cannot be met. This is mainly due to the formation of SEI and irreversible intercalation of sodium ions in the material over a large specific surface area, which is closely related to the material structure determined by the synthesis method. Researchers have carried out many researches around the modification treatment of sucrose and phenolic resin pyrolytic hard carbon, and Ji et al (ACSAppl. Mater. interfaces,2015,7,4) have doped relatively expensive graphene oxide in the process of preparing hard carbon by taking sucrose as a precursor, so that the specific surface area of sucrose-based hard carbon is reduced, and when the modified hard carbon is used as a sodium ion battery cathode material, the reversible capacity is 233mAh g-1The coulomb efficiency is improved to 83% for the first time; although patent "a method for preparing a negative electrode material for a composite hard carbon sodium ion battery" (application No. 201610727767.3) discloses a method for preparing graphene oxide, which has a relatively simple process and does not require the use of expensive materials: mixing boron-doped hard carbon and starch microspheres, ball-milling, and then carrying out high-temperature treatment to prepare composite hard carbon, wherein the boron-doped hard carbon is prepared by dispersing thermoplastic phenolic resin in absolute ethyl alcohol, adding boric acid and a curing agent, gradually heating and carbonizing, and grinding; the obtained composite hard carbon has a core-shell structure which takes boron-doped hard carbon as a core and is coated with a layer of amorphous carbon on the surface, and shows good circulation stability when used as a sodium-electricity negative electrode material, but the specific capacity is only 200mAh g-1Left and right.
Therefore, at present, a simple, efficient and low-cost preparation method of a hard carbon material is urgently needed to be developed, so that the prepared hard carbon material has high reversible capacity and can keep higher first coulombic efficiency and cycle stability when being used as a negative electrode material of a sodium ion battery.
Disclosure of Invention
In view of the above, the present invention aims to provide a phenolic resin/sucrose-based hard carbon microsphere material, and a preparation method and an application thereof. The raw materials used by the preparation method provided by the invention are phenolic resin and sucrose, the resource is rich, the cost is low, the preparation method is green and pollution-free, and when the prepared phenolic resin/sucrose-based hard carbon microspheres are used for the negative electrode of a sodium ion battery, the prepared phenolic resin/sucrose-based hard carbon microspheres show higher capacity, first coulombic efficiency and cycling stability, the whole preparation process is simple, and meanwhile, graphene oxide with relatively high price is not required.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a phenolic resin/sucrose-based hard carbon microsphere material comprises the following steps:
(1) mixing phenolic resin, cane sugar and a solvent to carry out solvothermal reaction to obtain a cross-linked product;
(2) and (2) carrying out high-temperature carbonization treatment on the cross-linked product obtained in the step (1) to obtain the phenolic resin/sucrose-based hard carbon microsphere material.
Preferably, the mass ratio of the phenolic resin to the sucrose in the step (1) is 1: 10-10: 1.
Preferably, the phenolic resin in the step (1) is an alcohol-soluble thermoplastic phenolic resin.
Preferably, the temperature of the solvothermal reaction in the step (1) is 150-190 ℃, and the time of the solvothermal reaction is 6-24 h.
Preferably, the atmosphere of the high-temperature carbonization treatment in the step (2) is an inert atmosphere.
Preferably, the inert atmosphere comprises at least one of argon, nitrogen, helium and neon.
Preferably, the temperature of the high-temperature carbonization treatment in the step (2) is 800-1600 ℃, and the time of the high-temperature carbonization treatment is 1-10 h.
Preferably, the temperature rise rate of the high-temperature carbonization treatment in the step (2) is 2-10 ℃/min.
The invention also provides the phenolic resin/sucrose-based hard carbon microsphere material prepared by the preparation method.
The invention also provides a sodium ion battery prepared from the phenolic resin/sucrose-based hard carbon microsphere material in the technical scheme, wherein the phenolic resin/sucrose-based hard carbon microsphere material is used as a negative electrode material.
The invention provides a preparation method of a phenolic resin/sucrose-based hard carbon microsphere material, which comprises the following steps: firstly, mixing phenolic resin, cane sugar and a solvent to carry out solvothermal reaction to obtain a cross-linked product; then the obtained cross-linkingAnd (4) carrying out high-temperature carbonization treatment on the combined product to obtain the phenolic resin/sucrose-based hard carbon microsphere material. The invention takes sucrose and phenolic resin with rich functional groups as raw materials, and the hard carbon material with a spherical structure is prepared by the way of carrying out the thermal reaction of a solvent to fully carry out the cross-linking reaction and then carrying out the high-temperature carbonization treatment. Because the reactant dispersed in the solvent has higher reaction activity under the solvent thermal critical condition, in the solvent thermal reaction process, the long chain structure of the phenolic resin is rearranged, the hydroxyl in the sucrose reacts with the unsaturated group in the phenolic resin, the product is slowly crystallized to obtain spherical particles with smooth surfaces, and the finally obtained spherical hard carbon material has the advantage of shorter ion diffusion path and larger interlayer distance, and is beneficial to the embedding/stripping and rapid migration of ions, thereby obtaining excellent electrochemical sodium storage performance; the hard carbon material is used as a negative electrode of a sodium ion battery, and has high first coulombic efficiency and cycle stability, and high reversible capacity. Experimental results show that when the phenolic resin/sucrose-based hard carbon microspheres prepared by the preparation method provided by the invention are used for the negative electrode of a sodium ion battery, 327.2mAh g is shown-1The first coulombic efficiency of the high reversible capacity can reach 86.55%, and after 50 cycles, the discharge capacity and the charge capacity of the battery are 306.7 mAh g and 302.8mAh g respectively-1The coulombic efficiency is 98.73%, and the capacity fading is small. Compared with the prior art, the method is simple to operate, the application of expensive graphene oxide is avoided, and the obtained hard carbon material keeps higher first coulombic efficiency and circulation stability when being used as a sodium-ion battery cathode material.
Drawings
FIG. 1 is a constant current charge and discharge curve diagram of the phenolic resin/sucrose-based hard carbon microsphere electrode material prepared in example 1;
FIG. 2 is an X-ray diffraction (XRD) pattern of the phenolic resin/sucrose-based hard carbon microsphere material prepared in example 2;
FIG. 3 is an SEM image of a phenolic resin/sucrose-based hard carbon microsphere material prepared in example 2;
FIG. 4 is an infrared spectrum of the phenolic resin/sucrose-based hard carbon microsphere material prepared in example 2;
FIG. 5 is a constant current charge-discharge curve diagram of the phenolic resin/sucrose-based hard carbon microsphere electrode material prepared in example 2;
FIG. 6 is a cycle plot of the phenolic resin/sucrose-based hard carbon microsphere electrode material prepared in example 2;
FIG. 7 is an X-ray diffraction (XRD) pattern of the phenolic resin/sucrose-based hard carbon microsphere material prepared in example 3;
FIG. 8 is a constant current charge-discharge curve diagram of the phenolic resin/sucrose-based hard carbon microsphere electrode material prepared in example 3;
fig. 9 is a constant current charge and discharge curve diagram of the phenolic resin/sucrose-based hard carbon microsphere electrode material prepared in example 4.
Detailed Description
The invention provides a preparation method of a phenolic resin/sucrose-based hard carbon microsphere material, which comprises the following steps:
(1) mixing phenolic resin, cane sugar and a solvent to carry out solvothermal reaction to obtain a cross-linked product;
(2) and (2) carrying out high-temperature carbonization treatment on the cross-linked product obtained in the step (1) to obtain the phenolic resin/sucrose-based hard carbon microsphere material.
The invention mixes phenolic resin, cane sugar and solvent to carry out solvent thermal reaction to obtain a cross-linked product.
In the present invention, the phenol resin is preferably an alcohol-soluble thermoplastic phenol resin, and more preferably at least one of a phenol-formaldehyde resin, a resorcinol-formaldehyde resin, a hydroquinone-formaldehyde resin, and a phenol-furfural resin. In the invention, the common alcohol-soluble thermoplastic phenolic resin is used as a hard carbon precursor for preparing the cathode of the sodium-ion battery, and the obtained battery has good electrochemical performance.
In the present invention, the solvent preferably includes alcohol and water. In the present invention, the alcohol preferably includes at least one of absolute ethanol, ethylene glycol, isopropanol, and n-butanol, and more preferably absolute ethanol. In the present invention, the water is preferably deionized water. In the present invention, the solvent is used to dissolve the raw materials of phenolic resin and sucrose, while providing the solvent required for the solvothermal reaction.
In the present invention, the mixture of the phenolic resin, sucrose and solvent is preferably: mixing phenolic resin and alcohol to obtain phenolic resin alcohol solution; mixing sucrose and water to obtain a sucrose aqueous solution; the phenolic resin alcoholic solution and the sucrose aqueous solution are then mixed. In the invention, the alcohol and the water are respectively used as solvents of the phenolic resin and the sucrose to promote the dissolution of the phenolic resin and the sucrose in the solvents, and simultaneously, the mutual solubility of the alcohol and the water improves the dispersibility between the phenolic resin and the sucrose, thereby improving the electrochemical performance of the finally obtained hard carbon material.
In the invention, the mass ratio of the phenolic resin to the sucrose is preferably 1: 10-10: 1, and more preferably 3: 7-1: 1. In the invention, the concentration of the phenolic resin alcoholic solution is preferably 0.1-1 g/mL. In the invention, the concentration of the sucrose aqueous solution is preferably 0.1-1 g/mL. In the invention, the hard carbon material obtained by controlling the dosage relation of the phenolic resin, the sucrose and the water within the range has better electrochemical performance.
In the invention, the temperature of the solvothermal reaction is preferably 150-190 ℃, and more preferably 160-180 ℃; the solvothermal reaction time is preferably 6-24 hours, and more preferably 8-10 hours. In the invention, the hydrothermal reaction temperature and time are adopted, so that the crosslinking reaction can be fully generated between the phenolic resin and the sucrose, and the electrochemical performance of the obtained hard carbon material is improved.
After the solvothermal reaction is completed, the product of the solvothermal reaction is preferably washed and dried in sequence to obtain a crosslinked product.
In the present invention, the washing agent preferably includes alcohol and water. The washing mode is not specially specified in the invention, and unreacted raw materials and impurities in the crosslinking product can be removed by using the solvent in a washing mode well known to those skilled in the art, so that the influence of the raw materials and the impurities on the performance of the product is avoided.
In the invention, the drying temperature is preferably 80-120 ℃, and more preferably 90-100 ℃; the drying time is preferably 4-14 h, and more preferably 8-12 h. The drying mode is not specially specified in the invention, and the solvent in the crosslinked product is removed by adopting the drying mode which is well known to a person skilled in the art, so that the next carbonization operation is facilitated.
After obtaining the cross-linked product, the invention carries out high-temperature carbonization treatment on the cross-linked product to obtain the phenolic resin/sucrose-based hard carbon microsphere material.
In the invention, the temperature of the high-temperature carbonization treatment is preferably 800-1600 ℃, more preferably 1000-1500 ℃, and most preferably 1200-1400 ℃; the time of the high-temperature carbonization treatment is preferably 1.5-5 hours, and more preferably 2-3 hours. In the invention, the heating rate of the high-temperature carbonization treatment is preferably 2-10 ℃/min, and more preferably 5-8 ℃/min. In the invention, the obtained hard carbon material has good carbonization effect by adopting the temperature rise rate, the carbonization temperature and the carbonization time, thereby improving the electrochemical performance of the material.
In the present invention, the atmosphere of the high-temperature carbonization treatment is preferably an inert atmosphere. In the present invention, the inert atmosphere preferably includes at least one of argon, nitrogen, helium, and neon, and more preferably argon. In the invention, the solid powder is carbonized in an inert atmosphere, so that the solid powder is prevented from being oxidized by oxygen in the air, and the electrochemical performance of the material is reduced.
The invention also provides the phenolic resin/sucrose-based hard carbon microsphere material prepared by the preparation method.
In the invention, the preferred particle size of the phenolic resin/sucrose-based hard carbon microsphere material is 0.5-2 μm, the shape of the microsphere shortens the path of ion migration, and the capacity and the cycle stability are favorably improved. In the invention, the interlayer spacing of the (002) crystal face of the phenolic resin/sucrose-based hard carbon microsphere material is preferably 0.37-0.42 nm, and more preferably 0.38-0.40 nm. In the invention, the structural characteristics of the phenolic resin/sucrose-based hard carbon microsphere material are preferably a microstructure with short-range order and long-range disorder. In the invention, the phenolic resin/sucrose-based hard carbon microsphere material has the characteristics and has better electrochemical performance.
The invention also provides a sodium ion battery, and the phenolic resin/sucrose-based hard carbon microsphere material in the technical scheme is used as a negative electrode material.
The structure of the sodium ion battery is not particularly limited, and the phenolic resin/sucrose-based hard carbon microsphere material can be used as the negative electrode material of the sodium ion battery by adopting the sodium ion battery structure well known to the technical personnel in the field.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in the examples are: phenol-formaldehyde resin (alcohol-soluble thermoplastic phenolic resin), sucrose, absolute ethanol and deionized water.
Example 1
Preparing phenolic resin/sucrose-based hard carbon microspheres:
dissolving 10g of phenol-formaldehyde resin in 80mL of absolute ethyl alcohol to form a solution with the concentration of 0.125g/mL, and stirring for 0.5 h; dissolving 10g of sucrose in 80mL of deionized water to form a solution with the concentration of 0.125g/mL, and stirring for 0.5 h; adding the sucrose solution into the phenolic resin solution, and stirring for 1h until the solution is uniform; transferring the mixture solution into a reaction kettle, and carrying out solvothermal reaction for 8 hours at 180 ℃; respectively washing the product after the solvent thermal reaction for 3 times by using deionized water and absolute ethyl alcohol, and then drying for 12 hours in an oven at the temperature of 100 ℃ to obtain solid powder; and putting the powder into a tubular furnace, introducing inert gas argon for protection, heating to 1000 ℃ at the heating rate of 5 ℃/min, and carrying out carbonization treatment for 2 hours at 1000 ℃ to obtain the phenolic resin/sucrose-based hard carbon microspheres. (the mass ratio of the phenol-formaldehyde resin to the sucrose is 1:1)
Application example 1
Mixing the prepared hard carbon material powder with sodium carboxymethylcellulose according to a ratio of 95: 5, by mass, addingGrinding with appropriate amount of water to obtain slurry, uniformly spreading the slurry on copper foil of current collector, drying, and cutting into (10 × 10) mm2The pole piece of (2). The pole piece is dried for 10 hours at 120 ℃ under the vacuum condition and then transferred to a glove box for standby. The cell was assembled in a glove box under Ar atmosphere, with sodium metal as the counter electrode and 1 mole of NaClO4And dissolving the solution of ethylene carbonate and diethyl carbonate in 1L volume ratio of 1:1 as electrolyte to assemble the CR2025 button cell.
Performance testing
The battery prepared in application example 1 was subjected to a charge and discharge performance test under the following test conditions: the charging and discharging mode is constant current; the current density is 30 mA/g; the discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V. The test results are shown in fig. 1. As can be seen from the constant current charge-discharge curve chart of FIG. 1, the reversible specific capacity is 294.5mAh g-1The first coulombic efficiency was 77.71%.
Example 2
Dissolving 10g of phenol-formaldehyde resin in 80mL of absolute ethyl alcohol to form a solution with the concentration of 0.125g/mL, and stirring for 0.5 h; dissolving 10g of sucrose in 80mL of deionized water to form a solution with the concentration of 0.125g/mL, and stirring for 0.5 h; adding the sucrose solution into the phenolic resin solution, and stirring for 1h until the solution is uniform; transferring the mixture solution into a reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 8 h; washing the product after the hydrothermal reaction respectively with deionized water and absolute ethyl alcohol for 3 times, and then drying in an oven at 100 ℃ for 12 hours to obtain solid powder; and putting the powder into a tube furnace, introducing inert gas argon for protection, heating to 1400 ℃ at the heating rate of 5 ℃/min, and carrying out carbonization treatment for 2 hours at 1400 ℃ to obtain the phenolic resin/sucrose-based hard carbon microspheres. (the mass ratio of the phenol-formaldehyde resin to the sucrose is 1:1)
The phenolic resin/sucrose-based hard carbon material prepared in example 2 was subjected to X-ray diffraction, and the test results are shown in fig. 2. It was calculated from the XRD pattern of FIG. 2 that the interlayer spacing of the (002) crystal plane was 0.40 nm.
The phenolic resin/sucrose-based hard carbon material prepared in example 2 was observed by scanning electron microscopy, and the test results are shown in fig. 3. As can be seen from the electron micrograph of FIG. 3, the obtained material is spherical and has a particle size of 1-1.5 μm.
The phenolic resin/sucrose-based hard carbon material prepared in example 2 was subjected to an infrared test, and the test results are shown in fig. 4. As can be seen from the IR spectrum of FIG. 4, the IR spectrum of sucrose is 3562.2cm-1And 1631.3cm-1The main spectral absorption corresponds to the stretching and bending vibration of-OH, while in the phenolic resin/sucrose, the stretching and bending vibration of-OH of the original sucrose disappears, which indicates that the free hydroxyl of the sucrose reacts with the phenolic resin under high temperature and high pressure. The concentration of the phenolic resin/sucrose is 3000-2700cm-1The C-H stretching vibration peak of two unsaturated bonds appears, which also indicates that the two unsaturated bonds react to generate the unsaturated bonds. The sucrose content is 990.5cm-1And 1052.5cm-1The peak value at (B) corresponds to the stretching vibration of the C-O group, and the phenolic resin is 1043.7cm-1The peak value at the position also corresponds to the stretching vibration of the C-O group, and after the C-O group and the C-O group are compounded, the stretching vibration peak of the C-O group disappears, so that the strong chemical reaction of the phenolic resin and the sucrose is further illustrated.
Application example 2
Mixing the prepared hard carbon material powder with sodium carboxymethylcellulose according to a ratio of 95: 5, adding a proper amount of water, grinding to form slurry, uniformly coating the slurry on a current collector copper foil by scraping, drying, and cutting into (10 multiplied by 10) mm2The pole piece of (2). The pole piece is dried for 10 hours at 120 ℃ under the vacuum condition and then transferred to a glove box for standby. The cell was assembled in a glove box under Ar atmosphere, with sodium metal as the counter electrode and 1 mole of NaClO4And dissolving the solution of ethylene carbonate and diethyl carbonate in 1L volume ratio of 1:1 as electrolyte to assemble the CR2025 button cell.
Performance testing
The battery prepared in the application example 2 was subjected to a charge and discharge performance test under the following test conditions: the charging and discharging mode is constant current; the current density is 30 mA/g; the discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V. The test results are shown in fig. 5. As can be seen from the constant current charge-discharge curve chart of FIG. 5, the reversible specific capacity is 327.2mAh g-1The first coulombic efficiency was 86.55%.
To applicationsThe battery prepared in example 2 was subjected to cycle performance test under the following conditions: the charging and discharging mode is constant current; the current density is 30 mA/g; the discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V (please determine if the test condition is the above condition). The test results are shown in fig. 6. As can be seen from the cycle chart of FIG. 6, the charge capacity of the battery was 302.8mAh g after 50 cycles-1And the capacity retention rate is 92.5 percent, which shows that the material shows better cycle stability
Example 3
Dissolving 10g of phenol-formaldehyde resin in 80mL of absolute ethyl alcohol to form a solution with the concentration of 0.125g/mL, and stirring for 0.5 h; dissolving 10g of sucrose in 80mL of deionized water to form a solution with the concentration of 0.125g/mL, and stirring for 0.5 h; adding the sucrose solution into the phenolic resin solution, and stirring for 1h until the solution is uniform; transferring the mixture solution into a reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 8 h; washing the product after the hydrothermal reaction respectively with deionized water and absolute ethyl alcohol for 3 times, and then drying in an oven at 100 ℃ for 12 hours to obtain solid powder; and putting the powder into a tube furnace, introducing inert gas argon for protection, heating to 1400 ℃ at the heating rate of 5 ℃/min, and carrying out carbonization treatment for 2 hours at 1400 ℃ to obtain the phenolic resin/sucrose-based hard carbon microspheres. (the mass ratio of the phenol-formaldehyde resin to the sucrose is 1:1)
The phenolic resin/sucrose-based hard carbon material prepared in example 3 was subjected to X-ray diffraction, and the test results are shown in fig. 7. From the XRD pattern of FIG. 7, the interlayer spacing of the (002) crystal plane was calculated to be 0.38 nm.
Application example 3
Mixing the prepared hard carbon material powder with sodium carboxymethylcellulose according to a ratio of 95: 5, adding a proper amount of water, grinding to form slurry, uniformly coating the slurry on a current collector copper foil by scraping, drying, and cutting into (10 multiplied by 10) mm2The pole piece of (2). The pole piece is dried for 10 hours at 120 ℃ under the vacuum condition and then transferred to a glove box for standby. The cell was assembled in a glove box under Ar atmosphere, with sodium metal as the counter electrode and 1 mole of NaClO4Dissolving ethylene carbonate and diethyl carbonate solution with volume ratio of 1:1 in 1L as electrolyte, assembling into CR2025 buttonA battery is provided.
Performance testing
The battery prepared in application example 3 was subjected to a charge and discharge performance test under the following test conditions: the charging and discharging mode is constant current; the current density is 30 mA/g; the discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V. The test results are shown in fig. 8. As can be seen from the constant current charge-discharge curve chart of FIG. 8, the reversible specific capacity is 305.7mAh g-1The first coulombic efficiency was 85.28%.
Example 4
Dissolving 3g of phenol-formaldehyde resin in 24mL of absolute ethyl alcohol to form a solution with the concentration of 0.125g/mL, and stirring for 0.5 h; dissolving 7g of sucrose in 56mL of deionized water to form a solution with the concentration of 0.125g/mL, and stirring for 0.5 h; adding the sucrose solution into the phenolic resin solution, and stirring for 1h until the solution is uniform; transferring the mixture solution into a reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 8 h; washing the product after the hydrothermal reaction respectively with deionized water and absolute ethyl alcohol for 3 times, and then drying in an oven at 100 ℃ for 12 hours to obtain solid powder; and putting the powder into a tubular furnace, introducing inert gas for protection, heating to 1200 ℃ at the heating rate of 5 ℃/min, and carrying out carbonization treatment for 2 hours at 1200 ℃ to obtain the phenolic resin/sucrose-based hard carbon microspheres. (the mass ratio of the phenol-formaldehyde resin to the sucrose is 3:7)
Application example 4
Mixing the prepared hard carbon material powder with sodium carboxymethylcellulose according to a ratio of 95: 5, adding a proper amount of water, grinding to form slurry, uniformly coating the slurry on a current collector copper foil by scraping, drying, and cutting into (10 multiplied by 10) mm2The pole piece of (2). The pole piece is dried for 10 hours at 120 ℃ under the vacuum condition and then transferred to a glove box for standby. The cell was assembled in a glove box under Ar atmosphere, with sodium metal as the counter electrode and 1 mole of NaClO4And dissolving the solution of ethylene carbonate and diethyl carbonate in 1L volume ratio of 1:1 as electrolyte to assemble the CR2025 button cell.
Performance testing
The battery prepared in the application example 4 was subjected to a charge and discharge performance test under the following test conditions: the charging and discharging mode is constant current; the current density is 30 mA-g; the discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V. The test results are shown in fig. 9. As can be seen from the constant current charge-discharge curve diagram of FIG. 9, the reversible specific capacity is 289.9mAh g-1The first coulombic efficiency was 84.66%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A preparation method of a phenolic resin/sucrose-based hard carbon microsphere material comprises the following steps:
(1) mixing phenolic resin, cane sugar and a solvent to carry out solvothermal reaction to obtain a cross-linked product;
(2) carrying out high-temperature carbonization treatment on the cross-linked product obtained in the step (1) to obtain a phenolic resin/sucrose-based hard carbon microsphere material;
the temperature of the solvothermal reaction in the step (1) is 180 ℃, and the solvothermal reaction time is 8 hours;
the solvent in the step (1) is alcohol and water;
the mass ratio of the phenolic resin to the sucrose in the step (1) is 1: 1;
the phenolic resin in the step (1) is alcohol-soluble thermoplastic phenolic resin.
2. The production method according to claim 1, wherein an atmosphere of the high-temperature carbonization treatment in the step (2) is an inert atmosphere.
3. The method of claim 2, wherein the inert atmosphere comprises at least one of argon, nitrogen, helium, and neon.
4. The method according to claim 1, wherein the temperature of the high-temperature carbonization treatment in the step (2) is 800 to 1600 ℃ and the time of the high-temperature carbonization treatment is 1 to 10 hours.
5. The production method according to claim 1, wherein the temperature increase rate of the high-temperature carbonization treatment in the step (2) is 2 to 10 ℃/min.
6. The phenolic resin/sucrose-based hard carbon microsphere material prepared by the preparation method of any one of claims 1 to 5.
7. A sodium ion battery, characterized in that the phenolic resin/sucrose-based hard carbon microsphere material of claim 6 is used as a negative electrode material.
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