CN117691090A - Hard carbon composite material with high first efficiency and preparation method thereof - Google Patents
Hard carbon composite material with high first efficiency and preparation method thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 9
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- 239000011734 sodium Substances 0.000 claims abstract description 24
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 14
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 10
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- 238000000151 deposition Methods 0.000 claims abstract description 5
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- 238000000034 method Methods 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 9
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- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000007740 vapor deposition Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
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- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001431 2-methylbenzaldehyde Substances 0.000 claims description 4
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
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- 239000008103 glucose Substances 0.000 claims description 3
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- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 2
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 claims description 2
- JRHHJNMASOIRDS-UHFFFAOYSA-N 4-ethoxybenzaldehyde Chemical compound CCOC1=CC=C(C=O)C=C1 JRHHJNMASOIRDS-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
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- 238000000498 ball milling Methods 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 239000011257 shell material Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
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- 239000000843 powder Substances 0.000 abstract description 8
- 238000000227 grinding Methods 0.000 abstract description 4
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- 230000008018 melting Effects 0.000 abstract description 4
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- 230000002427 irreversible effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- -1 polyoxypropylene Polymers 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
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- 239000002994 raw material Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
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- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
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- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of secondary battery materials, and discloses a hard carbon composite material with high first efficiency and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a porous hard carbon precursor, uniformly grinding the hard carbon precursor and sodium powder in an inert atmosphere by a ball mill, melting sodium into hard carbon pores by treatment, vapor depositing heteroatom carbon source gas, and heating for carbonization to obtain the hard carbon composite material. According to the invention, sodium powder is used for pre-sodium treatment of the porous hard carbon, so that the irreversible capacity of the material is reduced, and the first efficiency and the cycle performance are improved; and simultaneously, the heteroatom amorphous carbon is deposited on the outer layer of the material, so that the electronic conductivity of the material is improved, and the rate capability is improved.
Description
Technical Field
The invention relates to the technical field of secondary battery materials, in particular to a hard carbon composite material with high first efficiency and a preparation method thereof.
Background
Compared with a lithium ion battery, the sodium ion battery is characterized in that: the method has obvious advantages in the aspects of raw material sources, low-temperature performance, safety performance and cost, but the energy density of the materials is low due to the low specific capacity and compaction density of the anode and cathode materials used for the sodium ion battery, so that the cost of the sodium ion battery is influenced. The negative electrode is a key material affecting the fast charge performance and cost of the sodium ion battery. The current anode materials used in market mainly comprise biomass raw materials, coal-based raw materials and asphalt-based raw materials, but the problems of low first efficiency and the like exist, so that the exertion of the gram capacity of the anode of the sodium ion battery is low, and the energy density of the battery is influenced.
At present, the first efficiency of improving the hard carbon is mainly to reduce the defects of the surface of the material, reshape the material and reasonably distribute the pore diameter of the material, and doping and coating of the material are the most effective measures, but the specific capacity of the material is reduced after coating, and the dynamic performance of the material is reduced after doping. For example, patent publication No. CN114639816a discloses a hard carbon composite material with high first efficiency and a preparation method thereof, the composite material has a core-shell structure, the inner core is a hard carbon material, the middle layer is a lithium carbonate composite layer coating the inner core, the outer shell is an amorphous carbon layer coating the middle layer, the first efficiency of the material applied to a lithium ion battery is improved, but the middle layer can block the intercalation and deintercalation of lithium ions in the charge and discharge process, and the rate performance of the material is reduced; meanwhile, the intermediate layer coated with the core hard carbon is not obvious in improving the first efficiency of the material.
Disclosure of Invention
The invention solves the technical problems that:
the method is used for solving the problem that an interlayer in the hard carbon composite material in the prior art can obstruct the intercalation and deintercalation of lithium ions in the charge and discharge process, and the rate capability of the interlayer is reduced, so that the first efficiency is not obvious.
The invention adopts the technical scheme that:
aiming at the technical problems, the invention aims to provide a hard carbon composite material with high primary efficiency and a preparation method thereof, wherein metal sodium is doped in porous hard carbon, and amorphous carbon is coated on the porous hard carbon, so that the defect degree of the porous hard carbon is reduced, the primary efficiency is improved, and the impedance is reduced.
The specific contents are as follows:
first, the present invention provides a high first efficiency hard carbon composite material comprising:
the inner core is sodium doped hard carbon;
a housing, which is amorphous carbon;
the shell accounts for 1-5 wt% of the mass of the composite material.
Secondly, the invention provides a preparation method of the hard carbon composite material with high first efficiency, which comprises the following steps:
s1, blending the precursor, sodium carbonate and an organic crosslinking agent, and performing carbonization treatment and post-treatment to obtain a hard carbon intermediate. The specific contents are as follows:
the mass ratio of the precursor to the sodium carbonate to the organic crosslinking agent is 100:1-5:10-30;
the precursor comprises at least one of apricot shell, coconut shell, straw, starch, glucose, sucrose, lignin, cellulose and hemicellulose;
the organic crosslinking agent comprises at least one of benzaldehyde, m-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-ethoxybenzaldehyde, alpha-dimethylbenzaldehyde, p-dimethylaminobenzaldehyde, 4-methylbenzaldehyde, 3-phenylpropionaldehyde, 3-phenyl-2-propenal and 4-methylbenzaldehyde.
Carbonization: carbonizing for 1-6 h at 300-500 ℃ in inert atmosphere;
post-treatment: washing with dilute hydrochloric acid and deionized water, and vacuum drying to obtain hard carbon intermediate.
S2, the metal sodium is in a molten state and enters into pores of the hard carbon intermediate, and then the hard carbon composite material is obtained through the processes of amorphous carbon deposition and two carbonization. The specific contents are as follows:
ball milling the hard carbon intermediate and metal sodium in inert atmosphere, heating to 100-200 ℃ and preserving heat for 30-300 min;
deposition of amorphous carbon: heating to 700-1000 ℃ to perform vapor deposition on the mixed carbon source gas; the mixed carbon source gas includes a heteroatom gas and a carbon source gas; the ratio of the heteroatom gas to the carbon source gas is 1-5:10 by volume ratio; the flow rate of the mixed carbon source gas is 50-200 ml/min, and the time is 60-240 min. The heteroatom gas includes at least one of ammonia, hydrogen sulfide, phosphine, and borane. The carbon source gas includes at least one of methane, ethane, ethylene, and acetylene.
And (2) carbonization: heating to 1200-1400 deg.c and carbonizing for 1-6 hr.
The invention achieves the technical effects that:
(1) According to the invention, the molten metal sodium is ball-milled in the porous hard carbon intermediate by a hot melting method, so that the defect degree of a hard carbon kernel material is reduced, the first efficiency is improved, and meanwhile, the metal sodium is doped in holes to form NaC with carbon in the first charge and discharge of the metal sodium 6 The compound improves the intercalation and deintercalation rate of sodium ions and improves the rate capability;
(2) According to the invention, the carbon source gas is mixed by a vapor deposition method, so that defects on the surface of the material are reduced, the storage and the cycle performance of the material are improved, and the heteroatom doped amorphous carbon has the characteristic of high electronic conductivity, and the rate performance is improved.
Drawings
Fig. 1 is an SEM image of the hard carbon composite material prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
< example >
Implementation of the embodimentsExample 1
The embodiment provides a hard carbon composite material, which comprises the following steps:
step S1, uniformly mixing 100g of coconut shells, 3g of sodium carbonate and 20g of benzaldehyde, transferring into a tube furnace, carbonizing for 3 hours at 400 ℃ under an inert argon atmosphere, washing with dilute hydrochloric acid and deionized water, and vacuum drying at 80 ℃ for 24 hours to obtain a porous hard carbon intermediate;
and S2, uniformly grinding 100g of porous hard carbon intermediate and 5g of sodium powder in an inert argon atmosphere by a ball mill, firstly heating to 150 ℃ and preserving heat for 120min to enable sodium to be molten into hard carbon pores, then heating to 900 ℃, introducing heteroatom carbon source gas (ammonia: methane=3:10, flow 100ml/min,90 min) into the pores, performing vapor deposition on the heteroatom carbon source gas, and then heating to 1300 ℃ and carbonizing for 3h to obtain the hard carbon composite material.
Example 2
The embodiment provides a hard carbon composite material, which comprises the following steps:
step S1, uniformly mixing 100g of glucose, 1g of sodium carbonate and 10g of m-hydroxybenzaldehyde, transferring into a tube furnace, carbonizing for 6 hours at 300 ℃ under the inert atmosphere of argon, washing with dilute hydrochloric acid and deionized water, and vacuum drying at 80 ℃ for 24 hours to obtain a porous hard carbon intermediate;
and S2, uniformly grinding 100g of hard carbon intermediate and 1g of sodium powder in an inert argon atmosphere by a ball mill, firstly heating to 100 ℃ and preserving heat for 300min to enable sodium to be molten into hard carbon pores, then heating to 700 ℃, introducing heteroatom carbon source gas (volume ratio, hydrogen sulfide: acetylene=1:10, flow rate of 50ml/min,240 min) to perform vapor deposition on heteroatom carbon source gas, and then heating to 1200 ℃ and carbonizing for 6h to obtain the hard carbon composite material.
Example 3
The embodiment provides a hard carbon composite material, which comprises the following steps:
step S1, uniformly mixing 100g of lignin, 5g of sodium carbonate and 30g of 3-hydroxybenzaldehyde, transferring into a tube furnace, heating to 500 ℃ under an inert argon atmosphere, carbonizing for 1h, washing with dilute hydrochloric acid and deionized water, and vacuum drying at 80 ℃ for 24h to obtain a porous hard carbon intermediate;
and S2, uniformly grinding 100g of porous hard carbon intermediate and 10g of sodium powder in an inert argon atmosphere by a ball mill, firstly heating to 200 ℃, preserving heat for 30min, melting sodium into hard carbon pores, then heating to 1000 ℃, introducing heteroatom carbon source gas (volume ratio: borane: ethylene=5:10, flow rate of 200ml/min,60 min) into the mixture, and then heating to 1400 ℃ for carbonization for 1h to obtain the hard carbon composite material.
Comparative example
Comparative example 1
The difference between this comparative example and example 1 is that: sodium carbonate and benzaldehyde were not added, and the same as in example 1 was repeated.
Comparative example 2
This comparative example is different from example 1 in that no sodium powder was added, and the other is the same as example 1.
< test example >
(1) SEM test
The hard carbon composite material prepared in example 1 was subjected to SEM test, and the results are shown in fig. 1. As can be seen from FIG. 1, the hard carbon composite material prepared in example 1 exhibits a granular structure with a particle size D50 of between (5-10) μm.
(2) Physical and chemical properties and button cell testing
The hard carbon composites prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to measurement of interlayer spacing (D002), specific surface area, tap density, particle size D50, and powder conductivity. The testing method is tested according to the method of the national standard GBT-24533-2019 lithium ion battery graphite anode material. The test results are shown in Table 1.
The hard carbon composite materials in examples 1-3 and comparative examples 1-2 are used as negative electrode materials of lithium ion batteries to be assembled into button batteries, and the specific preparation method of the negative electrode materials is as follows: 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 tablet asIs a 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 1.
TABLE 1
As can be seen from table 1, the hard carbon composites prepared in examples 1 to 3 are superior to comparative examples 1 to 2 in specific capacity and first efficiency, because: the hot melting method ball-mills molten metal sodium in porous hard carbon, reduces the defect degree of the hard carbon kernel material, improves the first efficiency, and simultaneously, the metal sodium is doped in holes to form NaC6 compounds with carbon in the first charge and discharge process, thereby improving the electric conductivity of the powder.
(3) Soft package battery test
The hard carbon composite materials in examples 1-3 and comparative examples 1-2 were slurried and coated to prepare a negative electrode sheet, which was prepared by using a layered oxide as a positive electrode and NaPF 6 (the solvent is EC: DEC: PC: propylene glycol polyoxypropylene ether=1:2:1:0.05, and the concentration is 1.3 mol/L) as an electrolyte to prepare a 5Ah soft package battery.
Testing the cycle performance: the charge and discharge current is 1.0C/1.0C, the voltage range is 1-4.0V, and the cycle number is 500.
Testing rate performance: and testing the constant current ratio of the soft package battery under the initial cycle DCR and 2C charging conditions.
The test results are shown in Table 2.
TABLE 2
| Sample of | Cycle retention (%) | Circulation charging DCR (mΩ) | 2C constant current ratio (%) |
| Example 1 | 96.7 | 21.4 | 93.5 |
| Example 2 | 96.1 | 25.5 | 92.5 |
| Example 3 | 96.9 | 20.3 | 94.4 |
| Comparative example 1 | 89.9 | 35.1 | 88.5 |
| Comparative example 2 | 87.8 | 39.3 | 86.1 |
As is clear from Table 2, the cycle and rate performance of examples 1 to 3 are superior to those of comparative examples, in example 1 compared with comparative examplesThe analysis is as follows: in the material of the embodiment, sodium metal is doped in the holes to form NaC with carbon in the first charge and discharge of sodium metal 6 A compound, which improves the intercalation and deintercalation rate of sodium ions, improves the rate capability and reduces DCR; meanwhile, heteroatom carbon source gas is utilized by a vapor deposition method, so that defects on the surface of the material are reduced, and the cycle performance is improved.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A high first efficiency hard carbon composite, the composite comprising:
the inner core is sodium doped hard carbon;
a housing, which is amorphous carbon;
the shell accounts for 1-5 wt% of the mass of the composite material.
2. The method for preparing the high first-time efficiency hard carbon composite material according to claim 1, comprising the steps of:
s1, blending a precursor, sodium carbonate and an organic crosslinking agent, and performing carbonization treatment and post-treatment to obtain a hard carbon intermediate;
s2, the metal sodium is in a molten state and enters into pores of the hard carbon intermediate, and then the hard carbon composite material is obtained through the processes of amorphous carbon deposition and two carbonization.
3. The method of producing a high first efficiency hard carbon composite according to claim 2, wherein S1 comprises at least one of features (S1-1) to (S1-3):
(S1-1) the mass ratio of the precursor to the sodium carbonate to the organic crosslinking agent is 100:1-5:10-30;
(S1-2) the precursor comprises at least one of apricot shell, coconut shell, straw, starch, glucose, sucrose, lignin, cellulose and hemicellulose;
(S1-3) the organic crosslinking agent comprises at least one of benzaldehyde, m-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-ethoxybenzaldehyde, alpha-dimethylbenzaldehyde, p-dimethylaminobenzaldehyde, 4-methylbenzaldehyde, 3-phenylpropionaldehyde, 3-phenyl-2-propenal, and 4-methylbenzaldehyde.
4. The method of producing a high first efficiency hard carbon composite according to claim 2, wherein S1 includes at least one of features (S1-4) to (S1-5):
(S1-4) carbonization: carbonizing for 1-6 h at 300-500 ℃ in inert atmosphere;
(S1-5) post-treatment: washing with dilute hydrochloric acid and deionized water, and vacuum drying to obtain hard carbon intermediate.
5. The method for producing a high first efficiency hard carbon composite according to any one of claims 2 to 4, wherein S2 includes at least one of features (S2-1) to (S2-3):
(S2-1) ball milling the hard carbon intermediate and metallic sodium in an inert atmosphere, and then heating to 100-200 ℃ and preserving heat for 30-300 min;
(S2-2) depositing amorphous carbon: heating to 700-1000 ℃ to perform vapor deposition on the mixed carbon source gas;
(S2-3) carbonization two: heating to 1200-1400 deg.c and carbonizing for 1-6 hr.
6. The method of producing a high first efficiency hard carbon composite according to claim 5, wherein S2 comprises at least one of features (S2-2-1) to (S2-2-3):
(S2-2-1) mixing a carbon source gas including a heteroatom gas and a carbon source gas;
(S2-2-2) in a volume ratio of 1-5:10;
(S2-2-3) the flow rate of the mixed carbon source gas is 50-200 ml/min, and the time is 60-240 min.
7. The method for producing a high first-time efficiency hard carbon composite according to claim 6, wherein S2 comprises the features (S2-2-4):
(S2-2-4): the heteroatom gas includes at least one of ammonia, hydrogen sulfide, phosphine, and borane.
8. The method for producing a high first-time efficiency hard carbon composite according to claim 6, wherein S2 comprises the features (S2-2-5):
the (S2-2-5) carbon source gas includes at least one of methane, ethane, ethylene, and acetylene.
9. A composite material obtainable by the method of any one of claims 2 to 8.
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