CN112225194B - Hard carbon material and preparation method and application thereof - Google Patents
Hard carbon material and preparation method and application thereof Download PDFInfo
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- CN112225194B CN112225194B CN202011018024.1A CN202011018024A CN112225194B CN 112225194 B CN112225194 B CN 112225194B CN 202011018024 A CN202011018024 A CN 202011018024A CN 112225194 B CN112225194 B CN 112225194B
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- 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
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- 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
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- 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
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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- 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 a hard carbon material and a preparation method and application thereof. The method is characterized in that a conductive additive is introduced into the hard carbon material precursor to improve the conductivity of the obtained material, and a large number of oxygen-containing functional groups are introduced in combination with variable-speed heating pre-oxidation, so that the crosslinking degree of a material framework is increased, the strength of the material is improved, and the sodium storage specific capacity, the first-turn coulombic efficiency and the rate capability are obviously improved. The hard carbon material used for the sodium ion battery has the advantages of high reversible capacity, high first-turn coulombic efficiency, good cycle stability and the like. The material has the characteristics of simple preparation method and cheap and easily-obtained raw materials, and provides more choices for the cathode of the sodium-ion battery.
Description
Technical Field
The invention relates to the field of batteries, in particular to a preparation method of a hard carbon material and application of the hard carbon material in a negative electrode of a sodium-ion battery.
Background
Due to shortage of petroleum resources and aggravation of environmental pollution, the vigorous development of clean energy is increasingly important. Lithium ion batteries have the outstanding advantages of no pollution, long service life, rapid charge and discharge, and the like, and have been widely used in portable electronic devices and electric vehicles. However, with the continuous expansion of application fields and the rapid increase of usage amount, the price of the lithium ion battery is higher due to the limited and uneven distribution of metal lithium resources. The sodium resource which is in the same main group with lithium and is similar to lithium in physical chemistry is very rich, the price of the raw material is low, the sodium is distributed all over the world, is not limited by resources and regions, and has a larger cost advantage in the application of a large-scale energy storage system. Meanwhile, the sodium ion battery and the lithium ion battery have similar electrochemical de-intercalation mechanisms, so the sodium ion battery is expected to become a substitute of the lithium ion battery in large-scale energy storage.
For sodium ion negative electrode materials, the specific capacity of the carbon material commonly used at present is less than 300mAh/g, and the first-turn coulombic efficiency is low (< 70%), so that the development of a high-capacity and high-coulombic efficiency sodium ion battery as the negative electrode material is a key point and a hotspot in the current research and development. The phenolic resin is an organic polymer, and can be used as one of the choices of the negative electrode of the sodium-ion battery because the phenolic resin has higher carbon yield and has a more stable structure after hard carbon is formed. But the material is soft, the crosslinking degree is low after direct carbonization, and the material serving as the negative electrode material of the sodium-ion battery has the problems of poor cycle and rate performance, so that the application of the material in the sodium battery is limited to a great extent.
Disclosure of Invention
… the invention provides a hard carbon material prepared by taking phenolic resin as a raw material and carbonizing the phenolic resin after preoxidation, which overcomes the defects of low coulombic efficiency of the first ring, low reversible specific capacity and poor cycling stability of the prior sodium battery cathode material. Meanwhile, the preparation method of the hard carbon material with easily available raw materials and simple production process and the application of the hard carbon material as the cathode material of the sodium-ion battery are provided. The negative electrode material is prepared from phenolic resin, wherein the average particle size of the phenolic resin is 10-50 mu m, and the specific surface area is 2-10m2/g。
The invention provides a preparation method of a hard carbon material, which comprises the following steps:
1) phenolic resin pretreatment: dissolving phenolic resin in an organic solvent, adding a conductive additive, and drying to obtain a treated phenolic resin compound;
2) pre-oxidation: heating in an atmosphere containing oxygen to obtain pre-oxidized particles;
3) and (3) cooling: cooling the pre-oxidized particles, and grinding to obtain powder;
4) high-temperature carbonization: and (4) carbonizing the powder in the step (3) at high temperature in an inert atmosphere, and performing ball milling to obtain the hard carbon material.
The atmosphere containing oxygen is not particularly limited, and may be an atmosphere having an oxygen content of more than 20%, for example, air.
Preferably, the step of heating for pre-oxidation means that the treated phenolic resin is subjected to rapid temperature rise, medium temperature rise and slow temperature rise in sequence.
The rapid temperature rise is carried out at a temperature rise rate of 11-15 ℃/min to 200 ℃ and 250 ℃, and the roasting is carried out for 1-2 h; the medium-speed heating is to heat to 350 ℃ at the heating rate of 8-10 ℃/min, and then to roast for 1-2 h; the slow temperature rise is carried out at the temperature rise rate of 4-7 ℃/min to 400-450 ℃, and the roasting is carried out for 0.5-1 h.
The invention creatively provides a fast-medium speed-slow speed pre-oxidation step. Firstly, rapidly heating to 250 ℃ at a heating rate of 11-15 ℃/min, removing impurities on the surface of the phenolic resin, preliminarily opening blocked micropores, partially decomposing hydrocarbons on the surface under the condition of rapid heating, forming unstable defect sites on carbon chains, rapidly introducing oxygen-containing functional groups, and improving the crosslinking degree; then, the temperature is raised to 350 ℃ at the temperature rise rate of 8-10 ℃/min through medium-speed temperature rise, a molecular chain is further formed to be converted into a net-like structure which is more favorable for fixing oxygen and carbon, unstable defect points are enabled to mutually form an amorphous structure, a cross-linking structure is stabilized, and the improvement of the sodium ion electronic conductivity and the sodium storage specific capacity of the battery cathode material is facilitated; finally, the temperature is raised to 400-450 ℃ through stable slow temperature rise at the temperature rise rate of 4-7 ℃/min, the micropore stabilizing effect is further realized under the condition of ensuring that the main carbon chain is not broken, and the specific surface area of the carbonized product is slightly increased, so that the charge and discharge capacity of the battery is improved. According to the specific different heating rates and different temperatures of the staged pre-oxidation step, a large number of oxygen-containing functional groups can be introduced, the crosslinking degree of the material framework is increased, the sodium storage specific capacity and the first coulomb efficiency are obviously improved, so that the organic carbon chain initially forms an annular net structure, the cracking of the organic carbon chain in the subsequent carbonization process is avoided, and the determination of the pre-oxidation temperature, time and heating rate has certain influence on the pore structure, the specific surface area, the interaction, the morphology and the crystal form of the subsequent hard carbon material.
In a preferred embodiment of the present invention, the method for preparing the hard carbon material comprises the steps of:
1) pretreatment of phenolic resin: adding a conductive additive into the phenolic resin solution, and drying to obtain the treated phenolic resin;
2) step-by-step pre-oxidation:
rapidly heating the treated phenolic resin to 250 ℃ at the heating rate of 11-15 ℃/min in the air atmosphere, roasting for 1-2h, then heating to 350 ℃ at the heating rate of 8-10 ℃/min, roasting for 1-2h, finally heating to 450 ℃ at the heating rate of 4-7 ℃/min, and roasting for 0.5-1h to obtain pre-oxidized particles;
3) and (3) cooling: rapidly cooling the particles obtained in the step 2), naturally cooling, and finally grinding;
4) carbonizing: carbonizing the powder obtained in the step 3) at high temperature in an inert atmosphere, and performing ball milling to obtain the hard carbon material.
Wherein in step 1), the organic solvent is preferably at least one selected from ethanol, acetone, toluene, chloroform, and dimethyl sulfoxide (DMSO); the conductive additive is at least one selected from crystalline flake graphite, conductive carbon black, graphene and carbon nano tubes; more preferably, the conductive additive is added in an amount of 2 to 5 wt% of the phenolic resin.
Wherein, in the step 3), as a preferred scheme, the rapid cooling is to cool the temperature to 150-; the natural cooling is to naturally cool the temperature to 20-30 ℃; the milling is ball milling to a powder with an average particle size of 0.5-20 μm.
Wherein in the step 4), the carbonization temperature is 1000-1600 ℃, more preferably 1200-1400 ℃, the carbonization time is 4-10h, and the temperature rise rate is 5-10 ℃/min.
The inert atmosphere is not particularly limited, and the oxygen content may be less than 0.1%. In one embodiment of the invention, the inert atmosphere is a mixed atmosphere of Ar/N2, wherein the volume percentage of argon is 20-30%.
At present, atmosphere and temperature in the phenolic resin carbonization process have certain influence on the conductivity of a subsequent carbon electrode material, and the single nitrogen or argon carbonization has the defects of low carbonization degree, high residual carbon and high impurities, so that the carbon electrode material has the defects of low utilization rate and low charge and discharge capacity. In order to maintain the good structure and performance of the hard carbon material, organic matter macromolecules are generally required to be pre-oxidized before carbonization, so that linear molecular chains are promoted to be converted, the effects of fixing oxygen and carbon are achieved, and the linear molecules are prevented from being cracked due to high-temperature pyrolysis. If the carbon is directly carbonized without being subjected to pre-oxidation, a polymer such as a resin is broken by high-temperature pyrolysis to generate resin carbon.
The inventor finds that the strength and the conductivity of the phenolic resin material can be improved by adding the conductive additive into the phenolic resin firstly, and then the conductive additive can be better dispersed and attached to the hard carbon material formed by the phenolic resin in the pre-oxidation stage through proper pre-oxidation conditions, so that the electrical property of the final negative electrode material is better. The inventors have unexpectedly discovered that the use of specific staged pre-oxidation conditions results in a final hard carbon material having superior overall properties. By setting different programmed heating rates, the pre-oxidation is subjected to sectional pre-oxidation at three variable heating rates of fast, medium and slow, and the pretreated phenolic resin is subjected to multiple activation, so that the prepared hard carbon material not only meets good mechanical strength, but also can improve the electrochemical performance of the hard carbon cathode material.
Further, in the cooling process before carbonization, the performance of the obtained hard carbon material is further improved by adopting a mode of combining quick cooling and natural cooling, and the method comprises the following steps: rapidly cooling, namely rapidly cooling the defect sites formed in the rapid heating process to rapidly fix the molecular chains with the porous structures and stable amorphous shapes, and reducing the formation of crystalline states and impurities; keeping 20-30s for facilitating the interaction in molecular chains to reach an equilibrium state; and after the rapid cooling, the precursor of the hard carbon material is naturally cooled, so that the precursor of the hard carbon material has a proper specific surface area and a stable structure, the subsequent carbonization step is facilitated, the charge and discharge capacity of the battery material is improved, and the strength of the hard carbon material is improved.
The variable-speed pre-oxidation provided by the invention can also solve the problems that the crystal form is difficult to control in the inert atmosphere roasting process, the converted impurities are high, the main carbon chain is easy to break, the short-chain carbon crystal form is unstable, the strength is poor, and the conductivity is poor due to too large specific surface area.
According to the invention, through pre-oxidation and introduction of oxygen functional groups, the oxygen content and the polymer crosslinking degree are increased, and the diffusion and transportation of sodium ions are facilitated, so that the reversible specific capacity is improved. The pre-oxidation can increase the specific surface area of the carbon material, thereby sacrificing the electrical property of the carbon material, and the invention adopts the specific pre-oxidation process as follows: the negative influence of the electrical performance reduction caused by the increase of the specific surface area can be reduced by the step-by-step heating and variable-speed cooling, the increase amplitude of the specific surface area is effectively reduced, the specific surface area of the carbon material is maintained in a proper range, and the excellent electrical performance is maintained.
The invention also provides application of the hard carbon material as a negative electrode material of a sodium-ion battery.
Preparing electrode slurry from a hard carbon material, a conductive additive, a binder and a corresponding solvent; uniformly coating the prepared electrode slurry on a carbon-coated aluminum foil, and drying to obtain an electrode slice; the conductive additive is selected from acetylene black, Super P carbon black and Ketjen black; the binder and the corresponding solvent are polyvinylidene fluoride (PVDF) and N-methyl pyrrolidone (NMP) solutions.
More specifically, the preparation method of the battery anode material using the hard carbon material comprises the following steps:
1) and (3) mixing the obtained hard carbon material, the conductive additive and PVDF according to the mass ratio of 80-90: 5-10: 5-10, adding a proper amount of NMP for pulping to obtain uniformly mixed electrode slurry;
2) and uniformly coating the prepared electrode slurry on a carbon-coated aluminum foil, drying at 70-80 ℃, and then putting into a vacuum oven for drying at 100-110 ℃ for 12h to obtain the electrode slice.
The invention has the advantages of
1. The invention provides a preparation method of a hard carbon cathode material, the synthesis process is simple, the conditions are mild and controllable, the prepared hard carbon cathode material has good electrochemical performance, the reversible capacity under the current density of 20mA/g reaches more than 280mAh/g, the best reversible capacity can reach 310mAh/g, and the first-turn coulombic efficiency reaches 90.3%.
2. According to the invention, through pre-oxidation and introduction of oxygen functional groups, the oxygen content and the polymer crosslinking degree are increased, and the diffusion and transportation of sodium ions are facilitated, so that the reversible specific capacity is improved. The pre-oxidation can increase the specific surface area of the carbon material, thereby sacrificing the electrical property of the carbon material, and the invention adopts the specific pre-oxidation process as follows: the negative influence of the electrical performance reduction caused by the increase of the specific surface area can be reduced by the step-by-step heating and variable-speed cooling, the increase amplitude of the specific surface area is effectively reduced, the specific surface area of the carbon material is maintained in a proper range, and the excellent electrical performance is maintained.
3. The inventor also creatively introduces three stages of variable speed pre-oxidation of fast, medium and slow, increases the oxygen content, increases the crosslinking degree of the material framework, and improves the material strength and the ion diffusion speed, thereby further improving the reversible specific capacity; the problems that in the inert atmosphere roasting process, the crystal form is difficult to control, the converted impurities are high, the residual carbon content is high, the main carbon chain is easy to break, the short-chain carbon crystal form is unstable, the strength is poor, the specific surface area is too large, and the conductive capacity is poor are solved, and the reversible specific capacity and the first-turn coulombic efficiency are improved.
4. According to the invention, the conductive additive is introduced into the hard carbon precursor, so that on one hand, the resin strength is improved, on the other hand, the conductive additive can be better dispersed and attached to the hard carbon material formed by the phenolic resin in the pre-oxidation stage, and the conductive additive and the hard carbon material interact with each other, so that the conductivity of the carbonized phenolic resin material is improved, and the sodium storage capacity, the rate capability and the first-turn coulombic efficiency are improved.
5. The variable-speed cooling mode combining rapid cooling and natural cooling is adopted, so that the defect sites formed by pre-oxidation are stable, the carbon material has a proper specific surface area and a more proper pore structure, and the retention rate of the battery is favorably improved.
6. The carbon chain is carbonized under the inert atmosphere combining argon and nitrogen to form certain inert competition, the defects that impurities are increased, residual carbon is low and the utilization rate is low after the carbon chain is broken due to the single inert atmosphere are reduced, and the battery maintenance efficiency is improved.
Drawings
FIG. 1 is a scanning electron micrograph of a hard carbon material obtained in example 1;
fig. 2 is a first charge-discharge curve of the hard carbon anode material obtained in example 1;
fig. 3 is an X-ray photoelectron spectrum of the hard carbon negative electrode material obtained in example 1 and comparative example 1.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
(1) Phenolic resin pretreatment: taking 10g of phenolic resin (specific surface area 2 m)2And/g) completely dissolving in absolute ethyl alcohol, adding conductive carbon black with the weight percent of 5 percent of phenolic resin, stirring for 2 hours, and then putting into a 70 ℃ oven for 12 hours to obtain the treated phenolic resin.
(2) Pre-oxidation treatment: heating 5g of the treated phenolic resin to 200 ℃ at a heating rate of 12 ℃/min in the air atmosphere, roasting for 1h, then heating to 300 ℃ at a heating rate of 8 ℃/min, roasting for 1h, finally heating to 400 ℃ at a heating rate of 5 ℃/min, and roasting for 0.5 h.
(3) And (3) cooling: the pre-oxidized particles are rapidly cooled to 150 ℃ at a speed of 20 ℃/min, kept for 20S and then naturally cooled to 30 ℃.
(4) Carbonizing: taking out the particles, ball-milling the particles into powder, putting the obtained powder into a tube furnace, carbonizing the powder for 6 hours at 1250 ℃ in the atmosphere of 20% Ar/N2 at the heating rate of 5 ℃/min, cooling, taking out the powder, and ball-milling the powder to obtain the hard carbon material.
The preparation and test method of the negative electrode material comprises the following steps: the hard carbon material, Super P and PVDF are mixed according to the mass ratio of 90: 5: 5, mixing, adding a proper amount of NMP, and pulping to obtain uniformly mixed electrode slurry; uniformly coating the prepared electrode slurry on an aluminum foil, drying at 80 ℃, and then putting into a vacuum oven to dry at 100 ℃ for 12 hours to prepare an electrode slice; a button cell is assembled in an argon-protected glove box by taking a metal sodium sheet as a counter electrode, glass fiber as a diaphragm and 1mol/L NaPF6 (a solvent is ethylene carbonate and diethyl carbonate with a volume ratio of 1: 1) as an electrolyte. Constant current charge and discharge test is carried out, the current density is 20mA/g, the charge and discharge voltage interval is 0.001-2.0V, and the test results are shown in Table 1.
Example 2
(1) Phenolic resin pretreatment: taking 10g of phenolic resin (specific surface area 2 m)2/g) completely dissolving in absolute ethyl alcohol, adding conductive carbon black with 5 wt% of phenolic resin, stirring for 2h, and drying at 70 DEG CAnd (5) in a box for 12h to obtain the treated phenolic resin.
(2) Pre-oxidation treatment: heating 5g of the treated phenolic resin to 250 ℃ at a heating rate of 15 ℃/min in air atmosphere, roasting for 2h, then heating to 350 ℃ at a heating rate of 10 ℃/min, roasting for 2h, finally heating to 450 ℃ at a heating rate of 7 ℃/min, and roasting for 1 h.
(3) And (3) cooling: the pre-oxidized particles are rapidly cooled to 150 ℃ at a speed of 20 ℃/min, kept for 20S and then naturally cooled to 30 ℃.
(4) Carbonizing: taking out the particles, ball-milling the particles into powder, putting the powder into a tube furnace, carbonizing the powder at 1200 ℃ for 6h in the atmosphere of 20% Ar/N2 at the heating rate of 5 ℃/min, taking out the powder, and ball-milling the powder to obtain the hard carbon material.
The preparation and test methods of the negative electrode material are the same as those of example 1, and the test results are shown in table 1.
Example 3
(1) Phenolic resin pretreatment: taking 10g of phenolic resin (specific surface area 2 m)2And/g) completely dissolving in absolute ethyl alcohol, adding conductive carbon black with the weight percent of 5 percent of phenolic resin, stirring for 2 hours, and then putting into a 70 ℃ oven for 12 hours to obtain the treated phenolic resin.
(2) Pre-oxidation treatment: heating 5g of the treated phenolic resin to 200 ℃ at a heating rate of 11 ℃/min in the air atmosphere, roasting for 1h, then heating to 300 ℃ at a heating rate of 9 ℃/min, roasting for 2h, finally heating to 400 ℃ at a heating rate of 5 ℃/min, and roasting for 1 h.
(3) And (3) cooling: the pre-oxidized particles are rapidly cooled to 150 ℃ at a speed of 20 ℃/min, kept for 20S and then naturally cooled to 30 ℃.
(4) Carbonizing: taking out the particles, ball-milling the particles into powder, putting the powder into a tube furnace, carbonizing the powder at 1300 ℃ for 6h in the atmosphere of 20% Ar/N2 at the heating rate of 5 ℃/min, cooling, taking out the powder, and ball-milling the powder to obtain the hard carbon material.
The preparation and test methods of the negative electrode material are the same as those of example 1, and the test results are shown in table 1.
Example 4
The other steps and conditions are the same as those in example 1, except that in the pre-oxidation treatment in step (2), the temperature of the treated phenolic resin is raised to 450 ℃ at a temperature raising rate of 8 ℃/min in an air atmosphere, and the phenolic resin is roasted for 2.5 hours.
Example 5
The other steps and conditions are the same as those in example 1, except that in the pre-oxidation treatment in step (2), 5g of the treated phenolic resin is heated to 200 ℃ at a heating rate of 12 ℃/min in an air atmosphere and then is calcined for 1h, and then is heated to 400 ℃ at a heating rate of 5 ℃/min and then is calcined for 1 h.
Example 6
The other steps are the same as those in example 1 except that in the cooling step of step (3), the pre-oxidized pellets are naturally cooled to 30 ℃.
Example 7
The other steps are the same as those of example 1, except that in the step (4) of carbonization, the obtained powder is put into a tube furnace, carbonized at 1250 ℃ for 6 hours at a heating rate of 5 ℃/min in an atmosphere of N2, cooled, taken out and ball-milled into powder to obtain the hard carbon material.
Example 8
The other steps are the same as those of the example 1, except that in the step (4) of carbonizing, the obtained powder is put into a tube furnace, is carbonized at 1250 ℃ for 6 hours at the temperature rising rate of 5 ℃/min in the Ar atmosphere, is cooled and taken out, and is ball-milled into powder, so that the hard carbon material is obtained.
Comparative example 1
Taking 10g of phenolic resin (specific surface area 2 m)2And/g) completely dissolving in absolute ethyl alcohol, adding 5% of carbon black, stirring for 2 hours, and then putting into a 70 ℃ oven for 12 hours to obtain the treated phenolic resin.
Carbonizing 5g of the treated phenolic resin at 1250 ℃ for 6h in Ar atmosphere at the heating rate of 5 ℃/min, cooling, taking out and ball-milling into powder to obtain the hard carbon material directly carbonized by the phenolic resin.
Comparative example 2
The other steps and conditions were the same as in example 1 except that step (1) was omitted, i.e., the phenolic resin was not added with a conductive additive.
Comparative examples 1 and 2 negative electrode materials were prepared and tested in the same manner as in example 1, and the test results are shown in table 1.
The results of oxygen contents of the hard carbon anode materials of example 1 and comparative example 1 are shown in table 2, wherein the oxygen contents are obtained from the X-ray photoelectron spectroscopy of fig. 3.
TABLE 1
TABLE 2
The experimental data show that the conductive agent is added, the treated phenolic resin material is subjected to temperature rise and preoxidation at a fast speed, a medium speed and a slow speed, variable speed cooling is combined to obtain preoxidized particles, carbonization is performed in a composite inert atmosphere, the obtained hard carbon material has good electrochemical performance, the reversible capacity reaches 310mAh/g under the current density of 20mA/g, the first-turn coulombic efficiency reaches 90.3%, the preoxidation treatment is performed, the oxygen content is increased, the system crosslinking degree is increased, sodium ion diffusion is increased, the reversible specific capacity is improved, the specific surface area of the hard carbon material is appropriate, the oxygen content is obviously improved, the influence of other elements is small, the crosslinking degree is improved, the ion migration rate can be enhanced, and the reversible specific capacity is improved.
The above description is only a preferred embodiment of the present invention, and it should be understood that the present invention is not limited to the embodiment, and those skilled in the art can easily make various changes and modifications according to the main concept and spirit of the present invention, and therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (8)
1. A preparation method of a hard carbon material comprises the following steps:
1) phenolic resin pretreatment: dissolving phenolic resin in an organic solvent, adding a conductive additive, and drying to obtain a treated phenolic resin compound;
2) pre-oxidation: heating in an oxygen-containing atmosphere to obtain pre-oxidized particles, wherein the pre-oxidation adopts a heating process mode of step-by-step pre-oxidation: fast heating-medium speed heating-slow heating, wherein the temperature is fast raised to 250 ℃ at the speed of 11-15 ℃/min, the temperature is roasted for 1-2h, then the temperature is fast raised to 350 ℃ at the speed of 8-10 ℃/min, the temperature is roasted for 1-2h, finally the temperature is slowly raised to 450 ℃ at the speed of 4-7 ℃/min, the temperature is roasted for 0.5-1h, and pre-oxidized particles are obtained;
3) and (3) cooling: cooling the pre-oxidized particles, and grinding to obtain powder;
4) high-temperature carbonization: and (4) carbonizing the powder in the step (3) at high temperature in an inert atmosphere, and performing ball milling to obtain the hard carbon material.
2. The method according to claim 1, wherein the organic solvent in step (1) is at least one selected from the group consisting of ethanol, acetone, toluene, chloroform, and dimethyl sulfoxide (DMSO); the conductive additive is at least one selected from crystalline flake graphite, conductive carbon black, graphene and carbon nano tubes; the addition amount of the conductive additive is 2-5 wt% of the phenolic resin.
3. The method as claimed in claim 1, wherein the cooling in step 3) is performed by rapidly cooling to 150-200 ℃ for 20-30S, and then naturally cooling to room temperature of 20-30 ℃, wherein the rapid cooling rate is minus 30-minus 20 ℃/min, and the milling is performed by ball milling to obtain powder with an average particle size of 0.5-20 μm.
4. The preparation method as claimed in claim 1, wherein the carbonization temperature in step 4) is 1000-.
5. The method according to claim 1, wherein the carbonization temperature in step 4) is 1200-1400 ℃.
6. The method according to claim 1, wherein the inert atmosphere in step 4) is a mixed atmosphere of Ar/N2, wherein the volume percentage of Ar is 20%.
7. A hard carbon material produced by the method according to any one of claims 1 to 6.
8. A negative electrode material for sodium batteries, comprising the hard carbon material of claim 7, a conductive additive, a binder and a corresponding solvent.
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