CN114436237A - 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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- CN114436237A CN114436237A CN202111575195.9A CN202111575195A CN114436237A CN 114436237 A CN114436237 A CN 114436237A CN 202111575195 A CN202111575195 A CN 202111575195A CN 114436237 A CN114436237 A CN 114436237A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 70
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 35
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 21
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007833 carbon precursor Substances 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000005011 phenolic resin Substances 0.000 claims description 17
- 229920001568 phenolic resin Polymers 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 229920002472 Starch Polymers 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 235000019698 starch Nutrition 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 239000011734 sodium Substances 0.000 abstract description 8
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000007773 negative electrode material Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229910021384 soft carbon Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a hard carbon material, which comprises the following steps: s100, pre-oxidizing a hard carbon precursor; s200, grinding the pre-oxidized hard carbon precursor into powder; s300, performing microwave treatment on the powder; and S400, calcining the powder obtained in the step S300 to obtain the hard carbon material. A hard carbon material is prepared by the preparation method. The hard carbon material prepared by the preparation method is applied to the cathode of a sodium ion battery. The effect is as follows: the hard carbon material prepared by the invention is used as a sodium ion battery cathode material to be assembled into a sodium half battery, the cycling stability is good within the voltage range of 0-2V, the initial reversible capacity is up to 370mAh/g, the capacity retention rate is up to 95.9 percent after 50 cycles under the current density of 20mA/g, and compared with the traditional preparation method, the hard carbon specific capacity is obviously improved.
Description
Technical Field
The invention relates to the technical field of negative electrode materials of sodium-ion batteries, in particular to a hard carbon material and a preparation method and application thereof.
Background
The development of sodium ion battery technology is a national strategic demand and also a marketing demand:
on one hand, the lithium ion battery technology breaks through continuously, the proportion of lithium batteries in global electrochemical energy storage is as high as 86%, however, the lithium ion battery used in the field of large-scale energy storage is limited by lithium resource shortage, the global lithium resource distribution China only accounts for 22.9% of the total amount of the world, and the annual lithium resource consumption accounts for 40% of the world, so that the lithium ion battery has to be imported from abroad in large quantity;
on the other hand, in the application field of large-scale energy storage, the cost is the most important concern, and the most outstanding advantage of the sodium ion battery compared with the lithium ion battery is the low price.
In the field of sodium ion batteries, carbon-based negative electrodes are classified into graphite, soft carbon, hard carbon, and the like according to the degree of graphitization. The sodium storage of graphite cathode materials widely used in lithium batteries requires solvation co-intercalation, which causes the reduction of the cycling stability of the materials. The non-graphitized soft carbon has certain sodium storage performance, but the first coulombic efficiency is not high; the soft carbon after graphitization has reduced sodium storage capacity and higher average potential of sodium storage. Among the carbon-based sodium-storage negative electrode materials, the hard carbon material is the most ideal negative electrode material and the most promising negative electrode material for realizing the industrialized sodium-ion battery. Since 2000, researchers have studied a lot of hard carbon synthesis methods of various carbon sources, the specific capacity of the obtained hard carbon material is mostly distributed in 150-350 mAh/g, and the preparation of the hard carbon material with high capacity and stable circulation by using a simple and easy method is urgent to solve in the industrialization of sodium ion batteries.
Therefore, based on the urgent need of large-scale energy storage, the development and design of a sodium ion battery with hard carbon as a negative electrode have important scientific significance and practical application value.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a hard carbon material, a preparation method and an application thereof, so as to overcome the defects in the prior art.
The technical scheme for solving the technical problems is as follows: a preparation method of a hard carbon material comprises the following steps:
s100, pre-oxidizing a hard carbon precursor;
s200, grinding the pre-oxidized hard carbon precursor into powder;
s300, performing microwave treatment on the powder;
and S400, calcining the powder obtained in the step S300 to obtain the hard carbon material.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the pre-oxidizing the hard carbon precursor in S100 specifically comprises:
s110, grinding the hard carbon precursor into fine powder;
and S120, pre-oxidizing the powder obtained in the S110 at a low temperature for a preset time.
Further, in S110, the hard carbon precursor is ground by dry hand until it is in a fine powder state, and the contact area with air is increased.
Further, in S120, the hard carbon precursor may be placed in the crucible during pre-oxidation, and the crucible is not covered during pre-oxidation, so that the hard carbon precursor is exposed to the air.
Further, the hard carbon precursor is a biomass derivative carbon source or a high molecular organic matter.
Further, the biomass derivative carbon source is starch, cellulose or sugar;
the high molecular organic matter is phenolic resin or PAN.
Further, during pre-oxidation, the hard carbon precursor should be primarily carbonized and have uniform color.
Furthermore, the low-temperature pre-oxidation temperature is 200-400 ℃, the pre-oxidation time is 1-4 h, and the temperature rise speed is 3 ℃/min.
Further, in S300, the microwave treatment of the powder is performed in an oxygen-containing atmosphere for 2 to 60 min.
Further, in S400, the calcining temperature is 1000-1500 ℃, the heat preservation time is 1-4 h, and the temperature rise speed is 2-5 ℃/min.
Further, in S400, the atmosphere in which the powder is calcined is under a protective gas atmosphere.
Further, the shielding gas is argon or nitrogen.
Further, the calcination is carried out in a high temperature tube furnace.
A hard carbon material is prepared by the preparation method.
The hard carbon material prepared by the preparation method is applied to the cathode of the sodium-ion battery.
The invention has the beneficial effects that: .
1) Through the pre-oxidation process, oxygen-containing functional groups such as carbonyl and the like are introduced to the surface of the hard carbon precursor, and preliminary carbonization can be realized during pre-oxidation so as to introduce more defects in the carbonization process, thereby inhibiting the growth and orientation of a carbon layer, increasing the interlayer spacing of graphite microcrystals and being beneficial to the intercalation and extraction of sodium ions;
2) by adjusting the pre-oxidation mode and process and matching with microwave treatment in the process of introducing oxygen-containing functional groups, the cross-linking degree of substances is increased, the structure is stabilized, and the separation of small molecular substances in the sintering process is reduced, so that the carbon yield is improved, the cost is reduced, and the tail gas emission is reduced;
3) the control of the carbon layer spacing and the defects under the same high-temperature pyrolysis process can be realized to a certain extent by controlling the temperature, the heat preservation time and the heating rate of the low-temperature pre-oxidation, so that different hard carbon precursor pre-oxidation processes can be designed to obtain hard carbon materials suitable for sodium storage;
4) the hard carbon material prepared by the invention is used as a negative electrode material of a sodium ion battery to be assembled into a sodium half battery, has better circulation stability in a voltage range of 0-2V than a battery assembled by only using a carbonized (calcined) hard carbon material as the negative electrode material of the sodium ion battery, has initial reversible capacity as high as 370mAh/g, circulates for 50 circles under a current density of 20mA/g, has a capacity retention rate of 95.9 percent, and has good market application prospect;
5) the method adopted by the invention is simple and easy to implement, has low production process cost and good batch stability, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is an SEM photograph of a phenolic resin obtained in example 1 of the present invention after pre-oxidation;
FIG. 2 is an SEM photograph of a hard carbon material prepared from the phenolic resin of example 1 of the present invention;
FIG. 3 is a graph showing the comparison of 0-2V cycle performance between a battery assembled by using a hard carbon material made of phenolic resin as a negative electrode material of a sodium ion battery and a battery assembled by using only carbonized phenolic resin as a negative electrode material of a sodium ion battery in example 1 of the present invention;
FIG. 4 is an SEM photograph of a hard carbon material prepared from a commercial precursor in example 2 of the present invention;
FIG. 5 is a charging/discharging curve of the sodium ion battery made of the hard carbon material made of starch in example 3.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1
A preparation method of a hard carbon material comprises the following steps:
s100, weighing 3.00g of phenolic resin, placing the phenolic resin in a mortar, grinding for 5-10 min until the phenolic resin is ground into fine powder, then placing the ground fine powder of the phenolic resin in a crucible, not covering the crucible, heating to 300 ℃ at the heating rate of 3 ℃/min, preserving the heat for 2h, and taking out after naturally cooling;
s200, grinding the pre-oxidized phenolic resin in the S100 into powder;
s300, performing microwave treatment on the powder in the S200 for 20 min;
s400, placing the powder obtained in the step S300 in a high-temperature tube furnace, introducing protective gas such as argon, heating to 1300 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and naturally cooling along with the furnace to obtain the hard carbon material.
As shown in fig. 1, the hard carbon material obtained in this example has a regular and uniform spherical morphology, and as shown in fig. 2, compared with the phenolic resin that is carbonized (calcined), it is seen that the surface is relatively rough and has more surface defects.
Assembling the battery: the negative electrode active material is the hard carbon material obtained in the embodiment of the invention, and is used as a positive electrode in a half-cell, the conductive agent is conductive carbon black (Super P, Timcal Ltd.), the binder is polyvinylidene fluoride (PVDF, HSV5130, Arkema), the dispersant is N-methyl-2-pyrrolidone (NMP), and the weight ratio of the conductive carbon material to the dispersant is as follows: super P: mixing and grinding PVDF (polyvinylidene fluoride) in a mass ratio of 8:1:1, coating the PVDF on a copper foil, drying, rolling, punching to prepare an electrode plate, and controlling the active substance on the surface of the electrode to be 1-2 mg/cm2Then, after chargingA button cell is manufactured in a glove box filled with argon, the negative electrode is a sodium sheet, the glass fiber membrane is a diaphragm, and 1mol/L NaClO is added4PC (volume ratio 1:1) is used as electrolyte, and the CR2032 button cell is assembled.
As shown in FIG. 3, the assembled battery has a first reversible specific capacity of 370mAh/g under 20mA/g in a voltage range of 0-2V, and then the battery is circulated for 50 circles under the current density, so that the capacity retention rate is 95.9%.
Example 2
A preparation method of a hard carbon material comprises the following steps:
s100, weighing 3.00g of a commercial precursor, placing the commercial precursor in a mortar, grinding for 5-10 min until the commercial precursor is ground into fine powder, taking the precursor purchased by Shandong Ziboyi company as a carbon source, then placing the ground fine powder of the commercial precursor in a crucible, heating to 200 ℃ at a heating rate of 3 ℃/min without covering the crucible, preserving the temperature for 2h, and taking out after naturally cooling;
s200, grinding the pre-oxidized commercial precursor in the S100 into powder;
s300, performing microwave treatment on the powder in the S200 for 60 min;
s400, placing the powder obtained in the step S300 in a high-temperature tube furnace, introducing protective gas such as argon, heating to 1300 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and naturally cooling along with the furnace to obtain the hard carbon material.
As shown in fig. 4, the hard carbon material obtained by the embodiment of the present invention has a regular and uniform spherical morphology.
Assembling the battery: the same as in example 1.
Through detection, the content and the cycling stability of the battery assembled by using the hard carbon material obtained in the embodiment as the negative electrode of the sodium-ion battery are improved in a voltage range of 0-2V compared with the battery assembled by using only a carbonized (calcined) commercial precursor as the negative electrode of the sodium-ion battery.
Example 3
A preparation method of a hard carbon material comprises the following steps:
s100, weighing 3.00g of starch, placing the starch in a mortar, grinding for 5-10 min until the starch is ground into fine powder, then placing the ground fine powder of the starch in a crucible, raising the temperature to 200 ℃ at a heating rate of 3 ℃/min without covering the crucible, preserving the temperature for 4h, and taking out the starch after naturally cooling, wherein the starch can be corn starch;
s200, grinding the starch preoxidized in the S100 into powder;
s300, performing microwave treatment on the powder in the S200 for 10 min;
s400, placing the powder obtained in the step S300 in a high-temperature tube furnace, introducing protective gas such as argon, heating to 1300 ℃ at a heating rate of 2 ℃/min, preserving heat for 2h, and naturally cooling along with the furnace to obtain the hard carbon material.
Through detection, the hard carbon material obtained by the embodiment of the invention keeps the original appearance of the corn starch and has high compaction density.
Assembling the battery: the same as in example 1.
Through detection, the battery assembled by taking the hard carbon material as the sodium ion battery cathode is improved in content and cycling stability in a voltage range of 0-2V compared with the battery assembled by taking only carbonized (calcined) starch as the sodium ion battery cathode, as shown in fig. 5, the first reversible specific capacity of the assembled battery reaches 360mAh/g under 20mA/g in the voltage range of 0-2V, and the performance of the assembled battery is greatly improved compared with that of an untreated control material.
Comparative example 1
The preparation method which takes phenolic resin as a precursor and does not undergo preoxidation and microwave treatment comprises the following steps:
s100, weighing 3.00g of phenolic resin, placing the phenolic resin in a mortar, and grinding for 5-10 min until the phenolic resin is ground into fine powder;
s200, placing the phenolic resin powder in a high-temperature tube furnace, introducing argon, heating to 1300 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and naturally cooling along with the furnace to obtain the hard carbon material.
Assembling the battery: in the same way as in example 1, as shown in fig. 3, the first reversible specific capacity of the assembled battery is 327mAh/g under the voltage range of 0-2V and the ionization density of 20mA/g, and the capacity retention rate is only 92.9% after the battery is cycled for 50 cycles under the ionization density.
In conclusion, the invention prepares a series of hard carbon materials with high specific volume and good cycle performance by a simple and easy method.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of a hard carbon material is characterized by comprising the following steps:
s100, pre-oxidizing a hard carbon precursor;
s200, grinding the pre-oxidized hard carbon precursor into powder;
s300, performing microwave treatment on the powder;
and S400, calcining the powder obtained in the step S300 to obtain the hard carbon material.
2. The method for preparing a hard carbon material according to claim 1, wherein:
the pre-oxidation of the hard carbon precursor in the S100 specifically comprises the following steps:
s110, grinding the hard carbon precursor into fine powder;
and S120, pre-oxidizing the powder obtained in the S110 at a low temperature for a preset time.
3. A method for preparing a hard carbon material according to claim 1 or 2, wherein: the hard carbon precursor is a biomass derivative carbon source or a high molecular organic matter.
4. A method for preparing a hard carbon material according to claim 1, 2 or 3, wherein:
the biomass derivative carbon source is starch, cellulose or saccharides;
the high molecular organic matter is phenolic resin or PAN.
5. A method for preparing a hard carbon material according to claim 2, wherein:
the low-temperature pre-oxidation temperature is 200-400 ℃, the pre-oxidation time is 1-4 h, and the heating rate is 3 ℃/min.
6. The method for preparing a hard carbon material according to claim 1, wherein:
in S300, the microwave treatment of the powder is carried out in an oxygen-containing atmosphere, and the treatment time is 2-60 min.
7. The method for preparing a hard carbon material according to claim 1, wherein:
in the S400, the calcining temperature is 1000-1500 ℃, the heat preservation time is 1-4 h, and the heating rate is 2-5 ℃/min.
8. The method for preparing a hard carbon material according to claim 7, wherein:
in S400, the environment for calcining the powder is in a protective gas atmosphere.
9. A hard carbon material characterized by: the product is prepared by the preparation method of any one of claims 1 to 8.
10. An application of the hard carbon material prepared by the preparation method of any one of claims 1 to 9 in a negative electrode of a sodium ion battery.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114988391A (en) * | 2022-06-29 | 2022-09-02 | 宜昌邦普循环科技有限公司 | Preparation method and application of hard carbon negative electrode material |
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| CN115504449A (en) * | 2022-06-10 | 2022-12-23 | 四川大学 | Method and material for F-doped modified phenolic resin base |
| CN115504449B (en) * | 2022-06-10 | 2023-11-03 | 四川大学 | F-doped modified phenolic resin based method and material |
| CN114988391B (en) * | 2022-06-29 | 2023-04-11 | 宜昌邦普循环科技有限公司 | Preparation method and application of hard carbon negative electrode material |
| CN114988391A (en) * | 2022-06-29 | 2022-09-02 | 宜昌邦普循环科技有限公司 | Preparation method and application of hard carbon negative electrode material |
| WO2024000817A1 (en) * | 2022-06-29 | 2024-01-04 | 宜昌邦普循环科技有限公司 | Preparation method for hard carbon negative electrode material, and use of preparation method |
| GB2623150A (en) * | 2022-06-29 | 2024-04-10 | Yichang Brunp Recycling Tech Co Ltd | Preparation method for hard carbon negative electrode material, and use of preparation method |
| CN115259132B (en) * | 2022-07-29 | 2023-08-29 | 广东容钠新能源科技有限公司 | Preparation method and application of ultra-high first-effect hard carbon anode material |
| CN115259132A (en) * | 2022-07-29 | 2022-11-01 | 华南理工大学 | Preparation method and application of ultrahigh first-effect hard carbon negative electrode material |
| WO2024148678A1 (en) * | 2023-01-10 | 2024-07-18 | 广东邦普循环科技有限公司 | Sodium-ion battery hard carbon negative electrode material, preparation method therefor, and use thereof |
| CN116692858A (en) * | 2023-04-17 | 2023-09-05 | 湖北万润新能源科技股份有限公司 | Preparation method and application of sodium ion battery biomass hard carbon anode material |
| CN116692858B (en) * | 2023-04-17 | 2024-03-15 | 湖北万润新能源科技股份有限公司 | Preparation method and application of sodium ion battery biomass hard carbon anode material |
| CN117293312A (en) * | 2023-11-24 | 2023-12-26 | 深圳市贝特瑞新能源技术研究院有限公司 | Hard carbon material, preparation method and application thereof, and sodium ion battery |
| CN117293312B (en) * | 2023-11-24 | 2024-03-12 | 深圳市贝特瑞新能源技术研究院有限公司 | Hard carbon material, preparation method and application thereof, and sodium ion battery |
| CN117594794A (en) * | 2024-01-18 | 2024-02-23 | 武汉天钠科技有限公司 | Hard carbon material, preparation method thereof, negative electrode material and sodium ion battery |
| CN117594794B (en) * | 2024-01-18 | 2024-05-10 | 武汉天钠科技有限公司 | Hard carbon material, preparation method thereof, negative electrode material and sodium ion battery |
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