CN117003226A - Hard carbon composite material, preparation method and application thereof - Google Patents
Hard carbon composite material, preparation method and application thereof Download PDFInfo
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- CN117003226A CN117003226A CN202311271547.0A CN202311271547A CN117003226A CN 117003226 A CN117003226 A CN 117003226A CN 202311271547 A CN202311271547 A CN 202311271547A CN 117003226 A CN117003226 A CN 117003226A
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- hard carbon
- resin
- carbon composite
- composite material
- carbon precursor
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000007833 carbon precursor Substances 0.000 claims abstract description 25
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010426 asphalt Substances 0.000 claims abstract description 17
- 238000010000 carbonizing Methods 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 13
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- 229920005749 polyurethane resin Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 238000009656 pre-carbonization Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 40
- 230000007547 defect Effects 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 5
- -1 polyoxypropylene Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- MSYLJRIXVZCQHW-UHFFFAOYSA-N formaldehyde;6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound O=C.NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 MSYLJRIXVZCQHW-UHFFFAOYSA-N 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021260 NaFe Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The embodiment of the invention discloses a hard carbon composite material, which comprises the following preparation method: and mixing the pre-carbonized resin with sodium peroxide, heating to 400-600 ℃ in the presence of steam in an inert atmosphere to react to obtain a hard carbon precursor, mixing and infiltrating the hard carbon precursor with asphalt, and carbonizing to obtain the hard carbon composite material. According to the invention, the water vapor is introduced into the mixture of the resin and the sodium peroxide, wherein the sodium peroxide reacts with the water vapor to generate oxygen, and the resin is crosslinked and hole-formed at the temperature of 400-600 ℃, so that the inner part and the surface of the material are hole-formed at the same time, the consistency of the material is improved, and the specific capacity of the material is improved. Asphalt is coated on the outer layer of the hard carbon precursor, so that more surface defects caused by excessive oxidization on the surface of the material are reduced, the surface defect degree of the material is reduced, and the first efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and relates to a secondary battery material, in particular to a hard carbon composite material for a sodium ion battery.
Background
The anode material used in the sodium ion battery in the market at present mainly uses hard carbon material, which has the defects of poor consistency, low specific capacity, low compaction density, poor electronic conductivity and the like, while one of the measures for improving the specific capacity of the material in the market at present is to add a cross-linking agent to enable the material to form a hole structure to form a micron-nano hole structure, thereby improving the sodium storage function of the material and improving the specific capacity, but the size and distribution of micropores also have important influence on the sodium storage of the material. While the specific capacity of the material can be improved by directly forming a cross-linked structure on the surface of the material through oxygen oxidation, the defects of less inner core cross-linked compounds, more outer cross-linked compounds and the like exist, so that the consistency of the material is poor, the process controllability is poor, and therefore, the problems are needed to be solved, and the specific capacity of the material is improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a hard carbon material, which is used for internally forming holes and realizing uniform hole distribution of the material, wherein sodium peroxide is doped in a hard carbon precursor and reacts under the action of water vapor to generate oxygen, so that the hard carbon is crosslinked and hole-formed, the purposes of hole formation and crosslinking reaction in the material are achieved, the specific surface area and structural consistency of the material are increased, and the specific capacity of the material is improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the technical object of the first aspect of the present invention is to provide a method for preparing a hard carbon composite material, comprising:
pre-carbonizing resin, mixing with sodium peroxide, heating to 400-600 ℃ in inert atmosphere, introducing steam for reaction, washing and drying the product to obtain a hard carbon precursor;
and uniformly mixing the hard carbon precursor with asphalt, soaking, and carbonizing to obtain the hard carbon composite material.
Further, the weight ratio of the resin to the sodium peroxide is 100: 1-5.
Further, the reaction time of the introduced water vapor is 0.5-6h, and the flow rate of the water vapor is 100-500mL/min.
Further, the temperature of the resin pre-carbonization is 350-500 ℃.
Further, the resin is an amino resin, and the amino resin is a polyurethane resin and/or a benzoguanamine formaldehyde resin.
Further, the inert atmosphere is at least one selected from the group consisting of nitrogen, helium, neon, argon, krypton, and xenon.
Further, the weight ratio of the hard carbon precursor to the pitch is 100: 1-5.
Further, the soaking is performed at the temperature of 200-300 ℃ for 10-36h.
Further, the carbonization temperature is 1200-1500 ℃ and the carbonization time is 1-6h.
Further, the asphalt is at least one of petroleum asphalt, coal asphalt and natural asphalt, and the softening point is 100-200 ℃.
The technical object of the second aspect of the present invention is to provide a hard carbon composite material prepared by the above method.
The technical purpose of the third aspect of the invention is to provide the application of the hard carbon composite material as a negative electrode material of a sodium ion battery.
The implementation of the technical scheme of the invention has the following beneficial effects:
(1) The invention is characterized in that steam is introduced into a mixture of resin and sodium peroxide, wherein the sodium peroxide reacts as follows: 2Na 2 O 2 +2H 2 O=4NaOH+O 2 Oxygen is generated, and the resin is crosslinked and subjected to pore-forming at the temperature of 400-600 ℃, so that pores can be formed in the material and on the surface simultaneously, the consistency of the material is improved, and the specific capacity of the material is improved.
(2) According to the invention, asphalt is coated on the outer layer of the hard carbon precursor, so that more surface defects caused by excessive oxidization on the surface of the material are reduced, the surface defect degree of the material is reduced, and the infiltration at the temperature of 200-300 ℃ is preferably adopted, so that the defect degree is reduced, and the first efficiency is improved.
Drawings
Fig. 1 is an SEM image of the hard carbon composite material prepared in example 1.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Step S1: carbonizing 100g of polyurethane resin at 400 ℃ for 3 hours, uniformly mixing the obtained material with 3g of sodium peroxide, transferring the mixture into a tube furnace, heating to 500 ℃ under the protection of argon inert gas, introducing steam (with the flow of 300 mL/min) for pre-carbonizing treatment for 90 minutes, cooling to room temperature, washing, and drying at 80 ℃ for 24 hours to obtain a hard carbon precursor;
step S2: 100g of hard carbon precursor and 3g of petroleum asphalt are uniformly mixed, the temperature is 250 ℃ for Wen Jinrun hours, and then the temperature is raised to 1400 ℃ for carbonization for 3 hours, so that the hard carbon composite material is obtained.
Example 2
Step S1: carbonizing 100g of polyurethane resin at 350 ℃ for 6 hours, uniformly mixing with 1g of sodium peroxide, transferring into a tube furnace, heating to 400 ℃ under the protection of argon inert gas, introducing steam (with the flow of 100 mL/min) for pre-carbonizing for 300 minutes, cooling to room temperature, washing, and vacuum drying at 80 ℃ for 24 hours to obtain a hard carbon precursor;
step S2: 100g of hard carbon precursor and 1g of coal pitch are uniformly mixed, the temperature is 200 ℃ for Wen Jinrun hours, and then the temperature is raised to 1200 ℃ for carbonization for 6 hours, so that the hard carbon composite material is obtained.
Example 3
Step S1: carbonizing 100g of benzoguanamine formaldehyde resin at 500 ℃ for 1h, uniformly mixing the obtained material with 5g of sodium peroxide, transferring the mixture into a tube furnace, heating to 600 ℃ under the protection of argon inert gas, introducing steam (with the flow of 500 mL/min) for pre-carbonizing treatment for 1h, cooling to room temperature, washing, and vacuum drying at 80 ℃ for 24h to obtain a hard carbon precursor;
step S2: 100g of hard carbon precursor and 5g of natural asphalt are uniformly mixed, and subjected to high Wen Jinrun h at 300 ℃, and then heated to 1500 ℃ for carbonization for 1h, so that the hard carbon composite material is obtained.
Comparative example 1
Unlike example 1, sodium peroxide was not added and water vapor was not introduced, and the procedure was otherwise the same as example 1, except that:
step S1: carbonizing 100g of polyurethane resin at 400 ℃ for 3 hours, heating the obtained material to 500 ℃ under the protection of argon inert gas for 90 minutes, cooling to room temperature, washing, and drying at 80 ℃ for 24 hours to obtain a hard carbon precursor;
step S2: 100g of hard carbon precursor and 3g of petroleum asphalt are uniformly mixed, the temperature is 250 ℃ for Wen Jinrun hours, and then the temperature is raised to 1400 ℃ for carbonization for 3 hours, so that the hard carbon composite material is obtained.
Comparative example 2
Unlike example 1, no steam was introduced into S1, and the specific procedure was as in example 1:
step S1: carbonizing 100g of polyurethane resin at 400 ℃ for 3 hours, uniformly mixing the obtained material with 3g of sodium peroxide, transferring the mixture into a tube furnace, heating to 500 ℃ under the protection of argon inert gas, carrying out pre-carbonization treatment for 90 minutes, cooling to room temperature, washing, and drying at 80 ℃ for 24 hours to obtain a hard carbon precursor;
step S2: 100g of hard carbon precursor and 3g of petroleum asphalt are uniformly mixed, the temperature is 250 ℃ for Wen Jinrun hours, and then the temperature is raised to 1400 ℃ for carbonization for 3 hours, so that the hard carbon composite material is obtained.
Comparative example 3
Unlike example 1, sodium peroxide was not added, and the specific procedure was as in example 1:
step S1: carbonizing 100g of polyurethane resin at 400 ℃ for 3 hours, heating the obtained material to 500 ℃ under the protection of argon inert gas, introducing steam (with the flow of 300 mL/min) for pre-carbonizing treatment for 90min, cooling to room temperature, washing, and drying at 80 ℃ for 24 hours to obtain a hard carbon precursor;
step S2: 100g of hard carbon precursor and 3g of petroleum asphalt are uniformly mixed, the temperature is 250 ℃ for Wen Jinrun hours, and then the temperature is raised to 1400 ℃ for carbonization for 3 hours, so that the hard carbon composite material is obtained.
Comparative example 4
Unlike example 1, the asphalt high temperature infiltration process was not performed, and the other steps were the same as in example 1, except that:
step S1: carbonizing 100g of polyurethane resin at 400 ℃ for 3 hours, uniformly mixing the obtained material with 3g of sodium peroxide, transferring the mixture into a tube furnace, heating to 500 ℃ under the protection of argon inert gas, introducing steam (with the flow of 300 mL/min) for pre-carbonizing treatment for 90 minutes, cooling to room temperature, washing, and drying at 80 ℃ for 24 hours to obtain a hard carbon precursor;
step S2: and heating 100g of hard carbon precursor to 1400 ℃ for carbonization for 3 hours to obtain the hard carbon composite material.
Properties and Properties of each of the materials in examples and comparative examples were determined:
(1) SEM test
SEM test of the hard carbon composite material prepared in example 1 shows that the hard carbon composite material prepared in example 1 has granular structure with relatively homogeneous size distribution and grain size D50 of 5-10 microns as shown in FIG. 1.
(2) Physical and chemical performance test
The hard carbon composites prepared in examples and comparative examples were tested for interlayer spacing (D002), specific surface area, tap density, powder OI value, and powder conductivity. The interlayer spacing of the materials was tested by XRD as determined in standard GBT-24533-2019, lithium ion battery graphite cathode materials. The test results are shown in Table 1.
Table 1.
| Examples | D002（nm） | Specific surface area (m) 2 /g） | Tap density (g/cm) 3 ） | Powder OI value | Powder conductivity (S/cm) |
| Example 1 | 0.388 | 7.5 | 0.83 | 6.5 | 34 |
| Example 2 | 0.387 | 6.9 | 0.82 | 6.3 | 30 |
| Example 3 | 0.385 | 7.8 | 0.86 | 6.6 | 39 |
| Comparative example 1 | 0.379 | 4.8 | 0.72 | 7.7 | 13 |
| Comparative example 2 | 0.372 | 1.4 | 0.80 | 6.9 | 28 |
| Comparative example 3 | 0.370 | 1.8 | 0.71 | 7.3 | 15 |
| Comparative example 4 | 0.372 | 5.3 | 0.74 | 7.9 | 21 |
(3) Button cell testing
The hard carbon composite materials obtained in the examples and the comparative examples are respectively used as negative electrode materials of sodium ion batteries to be assembled into button batteries, and the preparation method comprises the following steps: according to the hard carbon composite material: CMC: SBR: SP: h 2 Mixing the materials according to the mass ratio of O of 94:2.5:1.5:2:150 to prepare a negative plate; sodium flakes as counter electrode; the electrolyte adopts NaPF 6 (the solvent is EC: DEC: PC: propylene glycol polyoxypropylene ether=1:2:1:0.05, the concentration is 1.3 mol/L) is electrolyte; the diaphragm adopts a composite film of polyethylene PE, polypropylene PP and polyethylene propylene PEP. The button cell assembly was performed in an argon filled glove box. Electrochemical performance was carried out on a wuhan blue electric CT2001A type battery tester, the charge-discharge voltage range was 0.00V to 2.0V, the charge-discharge rate was 0.1C, and the first discharge capacity and first efficiency of the button cell were tested. The test results are shown in Table 2.
Table 2.
| Examples | First discharge capacity (mAh/g) | First time efficiency (%) |
| Example 1 | 355 | 92.3 |
| Example 2 | 348 | 91.6 |
| Example 3 | 363 | 92.6 |
| Comparative example 1 | 314 | 88.6 |
| Comparative example 2 | 321 | 89.4 |
| Comparative example 3 | 318 | 89.0 |
| Comparative example 4 | 323 | 89.2 |
As can be seen from tables 1 and 2, compared with the comparative examples, the first discharge capacity and the first efficiency of the hard carbon composite materials prepared in examples 1 to 3 are superior to those of the comparative examples, because sodium peroxide is adopted and water vapor is introduced to carry out crosslinking pore-forming, pore-forming can be realized from the inside of the materials, and the uniformity of the inside and the outside of the materials is improved, so that the specific capacity of the materials is improved, and in addition, the first efficiency of the materials can be improved by coating asphalt on the outside of the materials.
(3) Soft package battery test:
the hard carbon composite materials of the examples and the comparative examples were used as a negative electrode, and a negative electrode sheet was prepared by slurry mixing and coating, using a layered oxide (NaFe 1/3 Mn 1/3 Ni 1/3 O 2 ) As positive electrode, naPF 6 The solvent is EC: DEC: PC: propylene glycol polyoxypropylene ether = 1:2:1:0.05, 1.3 mol/L) as electrolyte and cellgard 2400 as separator to prepare a 5Ah soft-pack battery.
And (3) carrying out cycle performance and multiplying power performance test on the soft package battery:
and (3) testing the cycle performance: the charge and discharge current is 1.0C/1.0C, the temperature is 25 ℃, the voltage range is 1.5-4.0V, and the cycle is 500 times.
And (3) multiplying power performance test: constant current+constant voltage charging was performed to 4.0C at a rate of 2c+0.1c, after which the constant current ratio of the battery=2c constant current capacity/(2c constant current capacity+0.1C constant voltage capacity) was calculated.
The results are shown in Table 3.
Table 3.
| Project | Cycle retention (%) | Circulation charging DCR (mΩ) | 2C constant current ratio (%) |
| Example 1 | 95.4 | 34.1 | 92.8 |
| Example 2 | 95.1 | 37.9 | 91.6 |
| Example 3 | 95.9 | 30.4 | 93.7 |
| Comparative example 1 | 92.4 | 51.8 | 86.9 |
| Comparative example 2 | 94.1 | 41.5 | 88.6 |
| Comparative example 3 | 93.6 | 45.6 | 87.1 |
| Comparative example 4 | 91.1 | 40.8 | 88.1 |
As can be seen from table 3, the constant current ratio (power performance) in examples 1 to 3 is significantly better than that in comparative examples, because of the analysis: asphalt is coated on the surface of the material in a high Wen Jinrun mode, soft carbon is obtained after carbonization, the impedance of the material can be reduced, and the power performance is improved; and meanwhile, through the actions of sodium peroxide and water vapor, the material is crosslinked and holed from the inside, the connectivity of holes is improved, the intercalation and deintercalation of sodium ions in the charge and discharge process is facilitated, the constant current ratio is improved, and the circulating DCR is reduced.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. A method of preparing a hard carbon composite comprising:
pre-carbonizing resin, wherein the resin is polyurethane resin and/or benzomelamine formaldehyde resin, mixing with sodium peroxide, heating to 400-600 ℃ in inert atmosphere, introducing steam for reaction, washing and drying the product to obtain a hard carbon precursor;
and uniformly mixing the hard carbon precursor with asphalt, soaking, and carbonizing to obtain the hard carbon composite material.
2. The preparation method according to claim 1, wherein the weight ratio of the resin to the sodium peroxide is 100: 1-5.
3. The preparation method according to claim 1, wherein the reaction time of introducing water vapor is 0.5-6h, and the flow rate of water vapor is 100-500mL/min.
4. The method of claim 1, wherein the resin pre-carbonization temperature is 350-500 ℃.
5. The method of claim 1, wherein the weight ratio of hard carbon precursor to pitch is 100:1-5, wherein the soaking is performed at the temperature of 200-300 ℃ for 10-36h.
6. The method according to claim 1, wherein the carbonization temperature is 1200 to 1500 ℃ for 1 to 6 hours.
7. A hard carbon composite material prepared by the method of any one of claims 1 to 6.
8. The use of the hard carbon composite material of claim 7 as a negative electrode material for sodium ion batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311271547.0A CN117003226A (en) | 2023-09-28 | 2023-09-28 | Hard carbon composite material, preparation method and application thereof |
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