CN118289737A - Heteroatom doped porous hard carbon anode material and preparation method and application thereof - Google Patents
Heteroatom doped porous hard carbon anode material and preparation method and application thereof Download PDFInfo
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- CN118289737A CN118289737A CN202410439503.2A CN202410439503A CN118289737A CN 118289737 A CN118289737 A CN 118289737A CN 202410439503 A CN202410439503 A CN 202410439503A CN 118289737 A CN118289737 A CN 118289737A
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- hard carbon
- asphalt
- anode material
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- 239000010405 anode material Substances 0.000 title claims abstract description 46
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 42
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- 238000000034 method Methods 0.000 claims abstract description 33
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
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- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 7
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of alkali metal ion battery anode materials, in particular to a heteroatom doped porous hard carbon anode material, a preparation method and application thereof. The preparation method comprises the following steps: performing low-temperature heat treatment on the original asphalt in an oxygen-containing atmosphere to obtain pre-oxidized asphalt; dispersing pre-oxidized asphalt, a functional auxiliary agent and a hard carbon precursor in a solvent, and removing the solvent to obtain a precursor compound; wherein the functional auxiliary agent is a functional auxiliary agent integrating crosslinking, pore-forming and heteroatom source; and carrying out high-temperature heat treatment on the precursor compound in a protective atmosphere to obtain the heteroatom doped porous hard carbon anode material. The heteroatom doped porous hard carbon anode material prepared by the method can remarkably improve the sodium storage specific capacity and the first-circle coulomb efficiency of the material, and has excellent cycle stability and rate capability.
Description
Technical Field
The invention relates to the field of alkali metal ion battery anode materials, in particular to a heteroatom doped porous hard carbon anode material, a preparation method and application thereof.
Background
With the rapid development of portable electronic equipment and new energy electric vehicles and the continuous increase of energy storage demands in various fields of society, the production and manufacture of lithium ion batteries reach unprecedented scales. However, lithium resources are low in abundance and unevenly distributed in the crust, so that 80% of lithium resources in China are dependent on import at present. Therefore, development and commercialization of Sodium Ion Batteries (SIBs) with low cost, excellent environmental protection characteristics and moderate energy density have attracted great attention from the country. The negative electrode material is used as a sodium storage main body of the SIB, and realizes intercalation and deintercalation of sodium ions in the charging and discharging process, so that the overall electrochemical performance of the SIB is directly determined. Currently, amorphous hard and soft carbons are considered to be the most potential commercial SIB anode materials.
The hard carbon has the advantages of low sodium intercalation platform, high capacity and the like, but the further development of the hard carbon is restricted by lower first-circle coulomb efficiency, poorer cycle stability and higher preparation cost. The microstructure of hard carbon directly affects its sodium storage capacity, which in turn depends to a large extent on the choice of precursor material. Wherein, the larger interlayer spacing and porous structure can provide more channels for sodium ion transmission, and simultaneously provide more active sites and sodium storage spaces for ion intercalation and deintercalation. The stable heterostructure coupling heteroatom doping (such as N, S, P, O, B and the like) can be constructed, the surface defects, pore channel structures, layer spacing and heterogeneous interface ion transmission impedance of the hard carbon can be accurately regulated, and the sodium ion anode material with performance advantages and economic benefits can be obtained.
Currently, hard carbon precursors are mainly biomass-based, resin-based, pitch, and the like. The biomass-based hard carbon has the defects of poor product consistency, low carbon yield, easiness in seasonal influence and the like, and the hard carbon material prepared by the resin matrix has good sodium storage performance, but the raw material cost is higher. Asphalt is used as a byproduct in the petroleum industry, has low cost and high carbon yield, and is an ideal precursor for preparing carbon materials. However, most of the asphalt-based hard carbon materials are complex in preparation process at present, such as: the preparation process of the spherical asphalt-based derived hard carbon material disclosed in the patent CN109037603A relates to the processes of crosslinking oxidation preparation, spray granulation, carbonization, coating, graphitization and the like; patent CN114477130a discloses that the preparation process of porous hard carbon involves briquetting and pickling processes, and in addition, asphalt is easily graphitized to form a highly ordered soft carbon material in the high-temperature carbonization process; patent CN115676804a discloses that the preparation process of an asphalt-based porous carbon anode material not only involves links such as spray drying and multiple acid treatments, the sodium storage behavior is a typical soft carbon structure, but also has a capacity retention rate of about 67% after 100 charge and discharge cycles, which indicates that the material has poor cycle stability.
Pretreatment by crosslinking treatment and pre-oxidation method is an effective method for inhibiting graphitization of asphalt during high temperature carbonization. The patent CN113735095A and the patent CN113800496A use the oxidized asphalt as a carbon source, respectively use calcium carbonate and magnesium chloride as pore formers and cross-linking agents to obtain the honeycomb porous hard carbon material, but the first circle coulomb efficiency of the material is only 75% and 78%, respectively, and still have larger lifting space, and the whole energy density of the battery is seriously affected. The patent CN116835566A and the patent CN117228670A use inorganic salts as pore-forming oxidants and templates to obtain the porous hard carbon anode material, and show good sodium storage performance. However, reports on organic pore formers and cross-linking agents are very limited. Recently, the patent CN117276497A uses the imidazole organic cross-linking agent and the organic sodium salt simultaneously, so that the comprehensive performance of sodium storage of hard carbon is effectively improved. However, the method not only involves crosslinking solidification, soaking, filtration and secondary carbonization, but also has the ratio of asphalt to resin-based hard carbon precursor in the precursor material of 5:100, and has high preparation cost and is not beneficial to industrial production.
Disclosure of Invention
In view of the existing problems, the invention aims to provide a heteroatom doped porous hard carbon anode material with both performance and cost advantages, and a preparation method and application thereof. According to the invention, the functional auxiliary agent is utilized to regulate and control the interfacial chemical interaction between the pre-oxidized asphalt and the hard carbon precursor through a special design, and the porous hard carbon anode material is obtained through one-step heat treatment. The preparation method disclosed by the invention is simple in process, easy to popularize in other systems and capable of meeting the requirements of practical application. In addition, the heteroatom doped porous hard carbon anode material prepared by the method can remarkably improve the sodium storage specific capacity and the first-circle coulomb efficiency of the material, and has excellent cycle stability and rate capability.
In a first aspect, the invention provides a method for preparing a heteroatom doped porous hard carbon anode material, comprising the following steps:
performing low-temperature heat treatment on the original asphalt in an oxygen-containing atmosphere to obtain pre-oxidized asphalt;
Dispersing pre-oxidized asphalt, a functional auxiliary agent and a hard carbon precursor in a solvent, and removing the solvent to obtain a precursor compound; wherein the functional auxiliary agent is a functional auxiliary agent integrating crosslinking, pore-forming and heteroatom source;
And carrying out high-temperature heat treatment on the precursor compound in a protective atmosphere to obtain the porous hard carbon anode material.
Preferably, the original asphalt is any one or the combination of more than two of natural asphalt, coal-based asphalt, petroleum-based asphalt and mesophase asphalt; the oxygen-containing atmosphere is oxygen and air; or the oxygen-containing atmosphere is a mixed gas of any one of oxygen and air and inert gas; preferably, the inert gas is any one or a combination of two or more of nitrogen, helium, neon, argon, krypton and radon.
Preferably, the temperature of the low-temperature heat treatment is 100-500 ℃ and the time is 0.5-10 h.
Preferably, the mass ratio of the pre-oxidized asphalt to the functional auxiliary agent to the hard carbon precursor is 100:1:1-1:100:100, preferably 1: (0.1-10): (0.1-10).
Preferably, the functional auxiliary agent is any one or the combination of more than two of urea, thiourea, cyanamide, dicyandiamide, melamine and cyanuric acid.
Preferably, the solvent is any one or a combination of more than two of water, ethanol, diethyl ether, toluene, acetonitrile, dichloromethane, chloroform, N' N-dimethylformamide, dimethyl sulfoxide, carbon tetrachloride, xylene, quinoline and pyridine.
Preferably, the protective atmosphere is an inert gas, preferably any one or a combination of two or more of nitrogen, helium, neon, argon, krypton and radon.
Preferably, the temperature of the high-temperature heat treatment is 1000-1600 ℃ and the time is 1-6 h.
In a second aspect, the present invention provides a heteroatom doped porous hard carbon anode material obtained according to the preparation method of any one of the above. The heteroatom doped porous hard carbon anode material has a multi-level pore structure containing macropores, mesopores and micropores; preferably, the pore diameter of the macropores is 50-5000 nm, the pore diameter of the mesopores is 2-50 nm, and the pore diameter of the micropores is 0.5-1.8 nm.
In a third aspect, the invention provides the use of a heteroatom doped porous hard carbon anode material obtained according to any one of the preparation methods described above in an alkali metal ion battery anode material. The alkali metal ion battery includes, but is not limited to, sodium ion battery, potassium ion battery, and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention prepares the heteroatom doped porous hard carbon anode material by simple and effective process, which is beneficial to industrialized production.
2. The invention controls the interfacial chemical interaction between the pre-oxidized asphalt and the hard carbon precursor through the special design functional auxiliary agent, provides rich sodium storage active sites and a hierarchical pore structure, can keep higher first-circle coulomb efficiency, and has excellent sodium storage performance.
3. The heteroatom doped porous hard carbon anode material provided by the invention has good cycle stability and rate capability, and widens the application field of asphalt in alkali metal ion batteries.
In summary, the heteroatom doped porous hard carbon anode material prepared by the method has excellent sodium storage performance, economic advantage and huge practical application prospect.
Drawings
FIG. 1 is an SEM image of a heteroatom doped porous hard carbon anode material prepared in accordance with the present invention;
FIG. 2 is a graph of the first charge-discharge cycle of the heteroatom-doped porous hard carbon negative electrode material prepared in example 1 of the present invention;
FIG. 3 is a graph showing the long cycle performance of the heteroatom doped porous hard carbon negative electrode material prepared in example 1 of the present invention;
Fig. 4 is a graph showing the rate performance of the heteroatom-doped porous hard carbon anode material prepared in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
The heteroatom doped porous hard carbon anode material is obtained by heat treatment of a precursor compound consisting of pre-oxidized asphalt, a special functional auxiliary agent and a hard carbon precursor. The preparation method of the porous hard carbon anode material is simple, is beneficial to realizing industrial production, can improve the first-circle coulomb efficiency and sodium storage capacity of the material, and has excellent cycle stability and rate capability. The following illustrates a method for preparing the heteroatom doped porous hard carbon anode material of the present invention.
The original asphalt is subjected to low-temperature heat treatment in an oxygen-containing atmosphere to obtain pre-oxidized asphalt. The raw asphalt can be any one or more than two of natural asphalt, coal-based asphalt, petroleum-based asphalt and mesophase asphalt. The oxygen-containing atmosphere is oxygen and air. Or the oxygen-containing atmosphere is a mixed gas of any one of oxygen and air and inert gas. The volume ratio of oxygen or air in the mixed gas may be in the range of 5-100%. Preferably, the inert gas is any one or a combination of two or more of nitrogen, helium, neon, argon, krypton and radon. The temperature of the low-temperature heat treatment can be 100-500 ℃ and the time can be 0.5-10 h. The low temperature heat treatment can realize the pre-oxidation of the asphalt surface.
The pre-oxidized asphalt can be prepared and obtained according to the following method: and (3) weighing the raw asphalt in a crucible, and heating the raw asphalt from room temperature to 100-500 ℃ at a speed of 0.5-20 ℃/min in an oxygen-containing atmosphere, and preserving heat for 0.5-10 h to obtain the pre-oxidized asphalt. After the pre-oxidized asphalt is naturally cooled, grinding can be carried out by an agate mortar, and the ground powder is collected.
And dispersing the pre-oxidized asphalt, the special functional auxiliary agent and the hard carbon precursor in a solvent according to a certain proportion, and removing the solvent to obtain a precursor compound. The solvent may be removed by means of heating. For example, heated until the solvent is completely volatilized.
The mass ratio of the pre-oxidized asphalt, the special functional auxiliary agent and the hard carbon precursor can be in the range of 100:1:1-1:100:100. Preferably, the mass ratio of the pre-oxidized asphalt to the special functional auxiliary agent to the hard carbon precursor is 1: (0.1-10): (0.1-10). The mass ratio of the pre-oxidized asphalt, the special functional auxiliary agent and the hard carbon precursor is controlled in the range, so that the pore channel structure and the circulation stability of the hard carbon can be effectively regulated and controlled. If the mass ratio of the pre-oxidized asphalt, the special functional auxiliary agent and the hard carbon precursor exceeds the above range, the sodium storage capacity is reduced, the cycle performance is deteriorated and the rate capability is poor. More preferably, the mass ratio of the pre-oxidized asphalt, the special functional auxiliary agent and the hard carbon precursor is 1: (0.1-5): (0.1-5).
The special functional auxiliary agent is characterized in that: the crosslinked network structure can be accurately designed and regulated, and has various functional groups, such as: amino, hydroxyl, carboxyl and the like can be used as a cross-linking agent and a pore-forming agent, and can also realize the functions of doping hetero atoms and the like. Therefore, the functional auxiliary agent is a functional auxiliary agent integrating crosslinking, pore-forming and heteroatom source. For example, the functional auxiliary agent is any one or a combination of two or more of urea, thiourea, cyanamide, dicyandiamide, melamine (trimer) and cyanuric acid.
For example, the functional auxiliary agent is urea. Urea has rich amino groups, can realize the sufficient cross-linking of a heterogeneous interface between asphalt and a hard carbon precursor, can generate volatile gases such as ammonia gas and the like at high temperature, and is favorable for the generation of a porous structure. In addition, urea can be used as a nitrogen source, so that in-situ co-doping of nitrogen is realized, and the interlayer spacing, electronic structure and the like of the carbon material can be adjusted.
Salt oxides, such as permanganate, ferrate, persulfate, percarbonate or carbonate, etc., although they can perform pore-forming and oxidation, have no crosslinking effect. The functional auxiliary agent with the structure is selected, so that the purpose of pore forming can be realized, and a crosslinked network with rich functional groups can be formed by thermal polymerization in the heat treatment process, so that a stable heterogeneous interface is formed in a precursor compound through chemical crosslinking. In contrast, inorganic salt oxides cannot achieve the above functions due to lack of abundant functional groups.
Similarly, imidazole crosslinking agents or thiazole crosslinking agents, such as 4-methylimidazole, dimet imidazole, 2-n-butyl-4-chloro-5-formylimidazole, 2-n-propyl-4-methyl-6-carboxybenzimidazole, 1,2' -bis (2-chlorophenyl) -tetraphenylbiimidazole, biimidazole, and oxaimidazole, have a crosslinking effect, but have limited pore-forming functions because only a small amount of volatile gas escapes during a high temperature process due to limited nitrogen content, and are disadvantageous in improvement of rate performance.
Therefore, the introduction of the functional auxiliary agent crosslinking agent has multiple functions: (1) The interaction between asphalt molecules can be enhanced, the graphitization process of the asphalt molecules at high temperature is inhibited, and the interlayer spacing of hard carbon microcrystals is increased; (2) A stable heterogeneous interface can be obtained, so that the cycling stability of the hard carbon material is improved; (3) Can also be used as a pore-forming agent and introduces hetero atoms, which is beneficial to the generation of a multi-level pore structure and the introduction of rich sodium storage active sites.
The hard carbon precursor is a carbon material having oxygen-containing groups. For example, the hard carbon precursor includes, but is not limited to, any one or a combination of two or more of glucose, sucrose, fructose, polyacrylonitrile, phenolic resin, epoxy resin, polyethylene terephthalate, polyfurfuryl alcohol, lignin, and cellulose.
It is noted herein that although the prior art mentions the use of melamine resins as hard carbon precursors, the melamine resins do not function to aggregate crosslinking, pore-forming, and heteroatom incorporation.
The solvent is any one or the combination of two or more of water, ethanol, diethyl ether, toluene, acetonitrile, dichloromethane, chloroform, N' N-dimethylformamide, dimethyl sulfoxide, carbon tetrachloride, xylene, quinoline and pyridine. Preferably, the solvent is a mixture of a volatile solvent such as water, ethanol, diethyl ether, acetonitrile, etc., and a non-volatile solvent such as toluene, methylene chloride, chloroform, N' N-dimethylformamide, dimethyl sulfoxide, carbon tetrachloride, xylene, quinoline, pyridine, etc. More preferably, the volatile solvent accounts for 20 to 80% of the volume of the mixed solution. The organic solvents such as N' N-dimethylformamide, dimethylsulfoxide, carbon tetrachloride, xylene, quinoline, pyridine and the like can be volatilized along with the volatile solvents such as water, ethanol, diethyl ether and the like under the condition of small usage amount.
And carrying out high-temperature heat treatment on the precursor compound in a protective atmosphere to obtain the porous hard carbon anode material. The protective atmosphere is any one or the combination of more than two of nitrogen, helium, neon, argon, krypton and radon. The temperature of the high-temperature heat treatment is 1000-1600 ℃ and the time is 1-6 h.
The precursor compound can be heated from room temperature to a preset high-temperature heat treatment temperature in a protective atmosphere at a certain heating rate, and the porous hard carbon anode material is obtained after heat preservation for a plurality of hours and natural cooling. The heating rate can be in the range of 1-20 ℃/min.
The heteroatom doped porous hard carbon anode material has a multi-level pore structure and contains macropores, mesopores and micropores. Preferably, the pore diameter of the macropores is 50-5000 nm, the pore diameter of the mesopores is 2-50 nm, and the pore diameter of the micropores is 0.5-1.8 nm.
The invention also provides application of the heteroatom doped porous hard carbon anode material. In particular to application in the cathode material of alkali metal ion batteries.
In summary, the invention controls the interfacial chemical interaction between the pre-oxidized asphalt and the hard carbon precursor through the special functional auxiliary agent, can not only inhibit the graphitization process of the asphalt at high temperature and increase the interlayer spacing of hard carbon microcrystals, but also obtain stable heterogeneous interfaces, introduce hetero atoms and hierarchical pore structures, provide rich sodium storage active sites, obviously improve the sodium storage comprehensive performance of the hard carbon material and overcome the problems existing in the background technology. In addition, the invention does not need to perform the pre-sodium treatment on the material, and the obtained hard carbon material can have higher first-circle coulomb efficiency.
The present invention will be described in more detail by way of examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
The embodiment provides a heteroatom doped porous hard carbon anode material, which is prepared by the following steps:
20g of petroleum asphalt is weighed and placed in a crucible, and is heated from room temperature to 350 ℃ at a speed of 2 ℃/min in an Ar/O 2 (volume fraction of Ar 10%), the temperature is kept for 4 hours, and the pre-oxidized asphalt is obtained after cooling along with a furnace and grinding. 3g of pre-oxidized asphalt, 7g of urea and 7g of phenolic resin were weighed out respectively and dispersed ultrasonically in 100mL of a mixed solvent of ethanol and water (v: v=1:1) to obtain a uniform dispersion. And heating the dispersion liquid to 80 ℃, stirring, and obtaining the precursor compound after the solvent is completely volatilized. And then heating the precursor compound from room temperature to 1400 ℃ at a speed of 5 ℃/min under argon atmosphere, preserving heat for 2 hours, cooling along with a furnace, and grinding to obtain the heteroatom doped porous hard carbon anode material.
Fig. 1 is an SEM image of a heteroatom-doped porous hard carbon anode material obtained in example 1 of the present invention. From this figure, it can be seen that the material has a rich pore structure.
Fig. 2 is a graph of the first charge-discharge cycle of the heteroatom-doped porous hard carbon anode material obtained in example 1 of the present invention. 160mg of heteroatom doped porous hard carbon anode material, 20mg of Super P and 20mg of CMC are respectively weighed and dispersed in 2mL of water to obtain slurry, and the slurry is subjected to homogenate-coating-drying-cutting operation to prepare the sodium ion battery anode piece. Then, the sodium metal sheets are respectively used as cathodes, the obtained pole pieces are used as anodes, GF/C glass fiber is used as a diaphragm, the electrolyte is 1mol/LNaPF 4 of diethylene glycol dimethyl ether solution, and the CR2025 button type sodium ion battery is assembled in an argon glove box. And placing the assembled battery for 8 hours, discharging to 0.01V at a constant current density of 0.25g/A, placing for 5 minutes, charging to 2.5V at the same constant current density, and placing for 5 minutes to complete a constant current charging and discharging cycle. Experimental results show that the sodium storage specific capacity of the obtained heteroatom doped porous hard carbon anode material is 349mA/g, and the first-circle coulomb efficiency is 85.9%.
FIG. 3 is a graph showing the long cycle performance of the heteroatom doped porous hard carbon negative electrode material prepared in example 1 of the present invention. The electrochemical test process was conducted with constant current charge and discharge cycles at a current density of 0.1 g/A. And placing the assembled battery for 8 hours, discharging to 0.01V with a constant current of 0.25g/A, placing for 5 minutes, charging to 2.5V with the same constant current, placing for 5 minutes, and performing activation treatment on the battery for 3 times in a circulating way. And (3) carrying out constant-current charge and discharge circulation on the activated sodium ion battery at a current of 0.1g/A, wherein the voltage range is 0.01-2.5V. It can be seen that the material was able to be cycled stably for 50 cycles at a current density of 0.1g/A with a reversible specific capacity of 331mA/g and a capacity retention of 99.3%, indicating that the material has good stability.
Fig. 4 is a graph showing the rate performance of the heteroatom-doped porous hard carbon anode material prepared in example 1 of the present invention. And mixing the heteroatom doped porous hard carbon material with Super P and CMC according to the mass ratio of 8:1:1, and carrying out homogenate-coating-drying-cutting operation to prepare the sodium ion battery negative electrode plate. And respectively taking a sodium metal sheet as a negative electrode, taking the obtained pole piece as a positive electrode, taking GF/C glass fiber as a diaphragm, taking 1mol/L NaPF 4 diethylene glycol dimethyl ether solution as electrolyte, and assembling the CR2025 button type sodium ion battery in an argon glove box. After the assembled battery is placed for 8 hours, the battery is discharged to 0.01V by constant current of 0.25g/A, and is charged to 2.5V by constant current of the same current after being placed for 5 minutes, and is placed for 5 minutes, and the process is circulated for 5 times. Then constant current charge and discharge cycles were performed 5 times at current densities of 0.1g/A, 0.2g/A, 0.5g/A, 1g/A, 2g/A, 5g/A, 10g/A and 1g/A, respectively. It can be seen that the obtained material has excellent rate capability, 18mA/g sodium storage capacity still exists at 10g/A current density, and when the current is adjusted back to 1A/g, the sodium storage specific capacity of the material immediately rises to 233mA/g, so that the sodium storage behavior of the material has excellent dynamics and stability.
Comparative example 1
The comparative example differs from example 1 in that the precursor composite was replaced with the original pitch.
Comparative example 2
The comparative example differs from example 1 in that a phenolic resin was used instead of the precursor composite.
Comparative example 3
The comparative example differs from example 1 in that a pre-oxidized pitch was used in place of the precursor composite.
Comparative example 4
The comparative example differs from example 1 in that the precursor compound is a mixture of pre-oxidized asphalt and urea and the mass ratio is 3:7.
Comparative example 5
The comparative example differs from example 1 in that the precursor compound is a mixture of pre-oxidized asphalt and urea in a mass ratio of 5:5.
Comparative example 6
The comparative example differs from example 1 in that the precursor compound is a mixture of pre-oxidized asphalt and urea in a mass ratio of 7:3.
Comparative example 7
The comparative example differs from example 1 in that the precursor compound is a mixture of pre-oxidized pitch and phenolic resin and the mass ratio is 3:7.
Example 2
5G of pre-oxidized asphalt, 5g of urea and 5g of phenolic resin were weighed out separately and dispersed ultrasonically in 100mL of a mixed solvent of ethanol and water (v: v=1:1) to obtain a uniform dispersion. And heating the dispersion liquid to 80 ℃, stirring, and obtaining the precursor compound after the solvent is completely volatilized.
Example 3
7G of pre-oxidized asphalt, 3g of urea and 3g of phenolic resin were weighed out respectively and dispersed ultrasonically in 100mL of a mixed solvent of ethanol and water (v: v=1:1) to obtain a uniform dispersion. And heating the dispersion liquid to 80 ℃, stirring, and obtaining the precursor compound after the solvent is completely volatilized.
The materials prepared in comparative examples 1 to 7 and examples 2 to 3 were subjected to electrochemical tests. The electrochemical test process was conducted with constant current charge and discharge cycles at a current density of 0.1 g/A. And placing the assembled battery for 8 hours, discharging to 0.01V with a constant current of 0.25g/A, placing for 5 minutes, charging to 2.5V with the same constant current, placing for 5 minutes, and performing activation treatment on the battery for 3 times in a circulating way. And (3) carrying out constant-current charge and discharge circulation on the activated sodium ion battery at a current of 0.1g/A, wherein the voltage range is 0.01-2.5V. The results are shown in Table 1.
Table 1 comparison of sodium storage properties of carbon materials.
As can be seen from table 1, the carbon materials prepared in comparative examples 1 to 7 and examples 2 to 3 are significantly different in sodium storage performance because the ratio of the components of the precursor composite has a decisive effect on the first-ring coulombic efficiency and the specific sodium storage capacity, and especially the introduction of functional auxiliaries can enhance the interfacial interaction between the components, and precisely regulate the microstructure of the target material. The functional auxiliary agent has multiple functions: (1) The interaction between asphalt molecules can be enhanced, the graphitization process of the asphalt molecules at high temperature is inhibited, and the interlayer spacing of hard carbon microcrystals is increased; (2) A stable heterogeneous interface can be obtained, so that the cycling stability of the hard carbon material is improved; (3) Can also be used as a pore-forming agent and introduces hetero atoms, which is beneficial to the generation of a multi-level pore structure and the introduction of rich sodium storage active sites.
The detailed process equipment and process flow of the present invention are described by the above embodiments, but the present invention is not limited to, i.e., it does not mean that the present invention must be practiced depending on the detailed process equipment and process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The preparation method of the heteroatom doped porous hard carbon anode material is characterized by comprising the following steps of:
performing low-temperature heat treatment on the original asphalt in an oxygen-containing atmosphere to obtain pre-oxidized asphalt;
Dispersing pre-oxidized asphalt, a functional auxiliary agent and a hard carbon precursor in a solvent, and removing the solvent to obtain a precursor compound; wherein the functional auxiliary agent is a functional auxiliary agent integrating crosslinking, pore-forming and heteroatom source;
And carrying out high-temperature heat treatment on the precursor compound in a protective atmosphere to obtain the heteroatom doped porous hard carbon anode material.
2. The method according to claim 1, wherein the raw asphalt is one or a combination of two or more of natural asphalt, coal-based asphalt, petroleum-based asphalt, and mesophase asphalt; the oxygen-containing atmosphere is oxygen and air; or the oxygen-containing atmosphere is a mixed gas of any one of oxygen and air and inert gas; preferably, the inert gas is any one or a combination of two or more of nitrogen, helium, neon, argon, krypton and radon.
3. The preparation method according to claim 1 or 2, wherein the low-temperature heat treatment is performed at a temperature of 100 to 500 ℃ for a time of 0.5 to 10 hours.
4. A method according to any one of claims 1 to 3, wherein the mass ratio of pre-oxidized pitch, functional aid and hard carbon precursor is 100:1:1 to 1:100:100, preferably 1: (0.1-10): (0.1-10).
5. The method according to any one of claims 1 to 4, wherein the functional auxiliary agent is any one or a combination of two or more of urea, thiourea, cyanamide, dicyandiamide, melamine and cyanuric acid.
6. The production method according to any one of claims 1 to 5, wherein the solvent is any one or a combination of two or more of water, ethanol, diethyl ether, toluene, acetonitrile, methylene chloride, chloroform, N' N-dimethylformamide, dimethyl sulfoxide, carbon tetrachloride, xylene, quinoline, and pyridine.
7. The method of any one of claims 1 to 6, wherein the protective atmosphere is an inert gas, preferably any one or a combination of two or more of nitrogen, helium, neon, argon, krypton and radon.
8. The method according to any one of claims 1 to 7, wherein the high temperature heat treatment is performed at a temperature of 1000 to 1600 ℃ for a time of 1 to 6 hours.
9. The heteroatom doped porous hard carbon anode material obtained by the production method according to any one of claims 1 to 8, characterized in that the heteroatom doped porous hard carbon anode material has a multi-stage pore structure containing macropores, mesopores and micropores; preferably, the pore diameter of the macropores is 50-5000 nm, the pore diameter of the mesopores is 2-50 nm, and the pore diameter of the micropores is 0.5-1.8 nm.
10. Use of the heteroatom doped porous hard carbon anode material obtained by the preparation method according to any one of claims 1 to 8 in an alkali metal ion battery anode material.
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