CN117199288A - Heteroatom doped porous hard carbon composite anode material and preparation method and application thereof - Google Patents
Heteroatom doped porous hard carbon composite anode material and preparation method and application thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 82
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000010405 anode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000011734 sodium Substances 0.000 claims abstract description 40
- 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 claims abstract description 38
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 38
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000007833 carbon precursor Substances 0.000 claims abstract description 16
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229920005610 lignin Polymers 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910003481 amorphous carbon Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- -1 polyethylene Polymers 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000531897 Loma Species 0.000 description 1
- 229910021260 NaFe Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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Classifications
-
- 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 invention relates to the field of secondary battery materials, in particular to a heteroatom doped porous hard carbon composite anode material, a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, adding passivated sodium metal into naphthalene solution, and uniformly dispersing to obtain sodium metal solution; s2, adding porous hard carbon into a metal sodium solution, soaking in vacuum, and drying to obtain a sodium doped hard carbon precursor material; s3, transferring the sodium-doped hard carbon precursor material into a tube furnace, and introducing heteroatom mixed gas to obtain the heteroatom-doped porous hard carbon composite anode material. According to the invention, the sodium solution is doped in the porous hard carbon, so that the surface defect of the material is obviously reduced, the first efficiency is improved, and the liquid phase doped metal sodium has the advantages of good doping uniformity, obvious first efficiency improvement and the like.
Description
Technical Field
The invention relates to the field of secondary battery materials, in particular to a heteroatom doped porous hard carbon composite anode material, a preparation method and application thereof.
Background
Hard carbon is considered as the sodium ion battery negative electrode material with the most commercialized prospect due to higher disorder degree, large interlayer spacing and rich sodium storage nano-pores, however, other defects such as oxygen-containing functional groups growing along carbon edges or carbon layers in the hard carbon cause extremely large irreversible sodium ion trapping, the first efficiency of the hard carbon is low, and the high-temperature storage performance is poor. In the prior art, a plurality of methods for improving the first efficiency of hard carbon are provided, such as amorphous carbon coating, reducing defects on the surface of the material, improving active points of the material by doping atoms such as nitrogen, phosphorus, boron and the like, improving sodium storage performance of the material, selecting carbon-based raw materials with good isotropy, such as high polymer materials such as resin, starch and the like, and improving specific capacity and compaction density of the material, but the method has limited first efficiency of the material, and cannot fundamentally improve the first efficiency of the material.
Patent application number CN201910039808.3 discloses a hard carbon composite material and a preparation method thereof, the preparation method is as follows: phenolic resin is used as a carbon source, mixed with hydrogen peroxide and graphene oxide, subjected to hydrothermal reaction and freeze drying to obtain a porous hard carbon precursor; then doping cobalt source and boric acid in the porous structure of the hard carbon precursor, so as to improve the specific capacity and conductivity of the material; meanwhile, the surface of the doped hard carbon material is modified by a vapor deposition method, so that the defect degree of the material is reduced, and the hard carbon composite material is prepared, but the first efficiency is low, and the dynamic performance of the material is reduced and the charging multiplying power is reduced by depositing amorphous carbon on the surface of the hard carbon composite material.
Disclosure of Invention
In order to solve the problems of low first coulombic efficiency, low rate capability deviation and the like of the existing hard carbon, the first aspect of the invention provides a preparation method of a heteroatom doped porous hard carbon composite anode material, which comprises the following steps:
s1, adding passivated sodium metal into naphthalene solution, and uniformly dispersing to obtain sodium metal solution;
s2, adding porous hard carbon into a metal sodium solution, soaking in vacuum, and drying to obtain a sodium doped hard carbon precursor material;
s3, transferring the sodium-doped hard carbon precursor material into a tube furnace, and introducing heteroatom mixed gas to obtain the heteroatom-doped porous hard carbon composite anode material.
In some embodiments, the mass ratio of the passivated metallic sodium to the naphthalene solution is (1-10): 100.
further, the passivated sodium metal is from the company of sodium metal Mo Ji, loma.
Preparing metal sodium into solution, and supplementing sodium to form Na 6 And C, improving the first efficiency.
In some embodiments, the mass ratio of porous hard carbon to passivated sodium metal is 100: (1-10).
The doped metal sodium mainly forms Na with carbon 6 And C, improving the first efficiency, wherein if the content of the passivated metal sodium is too high, sodium precipitation of the material is caused, and if the content is too low, the first efficiency of improving the material is limited.
In some embodiments, the method of preparing porous hard carbon comprises: calcining the pretreated lignin at 1000-1200 ℃ in inert gas atmosphere, removing impurities, washing and drying to obtain the porous hard carbon.
In some embodiments, the method of pretreating lignin comprises: mixing lignin with potassium carbonate solution, and drying.
Further, the preparation method of the porous hard carbon comprises the following steps: adding 1-5 parts of lignin and 1-5 parts of potassium carbonate into 100 parts of deionized water, stirring for 2 hours at the water bath temperature of 80 ℃, and vacuum drying to obtain pretreated lignin; transferring the pretreated lignin into a tube furnace, heating to 1000-1200 ℃ at 1-10 ℃/min under argon atmosphere, calcining for 1-3h, soaking for 1-6h by using 1mol/L hydrochloric acid, removing impurities, and washing with deionized water to obtain the porous hard carbon.
Further, the step S2 includes: adding porous hard carbon into a metal sodium solution at the dew point of less than or equal to minus 60 ℃, vacuum soaking for 12-36h at the vacuum degree of minus 0.09Mpa, and drying to obtain the sodium doped hard carbon precursor material.
In some embodiments, the heteroatom mixed gas is a mixed gas of a heteroatom gas including at least one of ammonia, phosphine, borane, sulfur dioxide and a carbon source gas including at least one of methane, ethylene, acetylene.
In some embodiments, the volume ratio of the heteroatom gas to the carbon source gas is (1-5): 10. the heteroatom doping is carried out to promote the active points of the material, the specific capacity and the powder conductivity of the material are promoted; if the heteroatom content is too low, the powder conductivity amplitude of the material is not large, and if the heteroatom content is too high, the tap density of the material is reduced, so that the specific capacity and the electronic conductivity of the material can be improved by selecting a proper heteroatom proportion, and the tap density is considered.
In some embodiments, the heteroatom mixture is introduced at a temperature of 700-900 ℃ for a time of 60-300 minutes at a flow rate of 100-500mL/min.
The second aspect of the invention provides a heteroatom doped porous hard carbon composite anode material, which is prepared by the preparation method.
The third aspect of the invention provides an application of the heteroatom doped porous hard carbon composite anode material in preparing a secondary battery anode material.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the sodium solution is doped in the porous hard carbon, so that the surface defect of the material is obviously reduced, the first efficiency is improved, and the liquid phase doped metal sodium has the advantages of good doping uniformity, obvious first efficiency improvement and the like.
(2) According to the invention, through gas phase doping of hetero atoms, the active points on the surface of the hard carbon material and the specific capacity of the material are improved, and meanwhile, the gas phase doping has the advantages of good uniformity and high density, and the first efficiency and the cycle performance of the material are improved.
Drawings
Fig. 1 is an SEM image of the heteroatom-doped porous hard carbon composite anode material prepared in example 1.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but 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.
Preparation method of porous hard carbon in examples and comparative examples: adding 3g of lignin and 3g of potassium carbonate into 100g of deionized water, stirring at the water bath temperature of 80 ℃ for 2h, vacuum drying at 80 ℃ for 24h to obtain pretreated lignin, transferring the pretreated lignin into a tube furnace, heating to 1100 ℃ at 5 ℃/min under argon atmosphere, calcining for 2h, soaking for 3h by using 1mol/L hydrochloric acid, removing impurities, and washing with deionized water to obtain porous hard carbon.
Example 1
The embodiment provides a heteroatom doped porous hard carbon composite anode material, and the preparation method comprises the following steps:
s1, adding 5g of passivated metal sodium into 100g of naphthalene solution (10 wt percent, ethanol is a solvent) for uniform dispersion to obtain a metal sodium solution;
s2, adding 100g of porous hard carbon into a metal sodium solution at the dew point of-80 ℃, vacuum soaking for 24 hours under the condition that the vacuum degree is-0.09 Mpa, filtering, and vacuum drying for 24 hours at the temperature of 80 ℃ to obtain a sodium doped hard carbon precursor material;
s3, transferring the sodium doped hard carbon precursor material into a tube furnace, introducing heteroatom mixed gas (volume ratio, ammonia: methane=3:10), heating to 800 ℃, wherein the flow is 300mL/min, the introducing time is 120min, and depositing heteroatoms and amorphous carbon on the surface of the precursor material to obtain the heteroatom doped porous hard carbon composite anode material.
Example 2
The embodiment provides a heteroatom doped porous hard carbon composite anode material, and the preparation method comprises the following steps:
s1, adding 1g of passivated metal sodium into 100g of naphthalene solution (10 wt percent, ethanol is a solvent) for uniform dispersion to obtain a metal sodium solution;
s2, adding 100g of porous hard carbon into a metal sodium solution at the dew point of-80 ℃, vacuum-soaking for 12 hours under the condition that the vacuum degree is-0.09 Mpa, filtering, and vacuum-drying for 24 hours at the temperature of 80 ℃ to obtain a sodium doped hard carbon precursor material;
s3, transferring the sodium doped hard carbon precursor material into a tube furnace, introducing heteroatom mixed gas (volume ratio, phosphine: acetylene=1:10), heating to 700 ℃, wherein the flow is 100mL/min, and the introducing time is 300min, and depositing heteroatoms and amorphous carbon on the surface of the precursor material to obtain the heteroatom doped porous hard carbon composite anode material.
Example 3
The embodiment provides a heteroatom doped porous hard carbon composite anode material, and the preparation method comprises the following steps:
s1, adding 10g of passivated metal sodium into 100g of naphthalene solution (10 wt percent, ethanol is a solvent) for uniform dispersion to obtain a metal sodium solution;
s2, adding 100g of porous hard carbon into a metal sodium solution at the dew point of-80 ℃, vacuum-soaking for 36h under the condition that the vacuum degree is-0.09 Mpa, filtering, and vacuum-drying for 24h at the temperature of 80 ℃ to obtain a sodium doped hard carbon precursor material;
s3, transferring the sodium doped hard carbon precursor material into a tube furnace, introducing heteroatom mixed gas (volume ratio, borane: ethylene=5:10), heating to 900 ℃, wherein the flow is 500mL/min, the introducing time is 60min, and depositing heteroatoms and amorphous carbon on the surface of the precursor material to obtain the heteroatom doped porous hard carbon composite anode material.
Comparative example 1
The specific embodiment of the composite anode material of the present comparative example, which is a porous hard carbon doped with hetero atoms, is the same as example 3, in that the preparation method includes: transferring 100g of porous hard carbon into a tube furnace, introducing heteroatom mixed gas (volume ratio, ammonia: methane=3:10), heating to 800 ℃, wherein the flow rate is 300mL/min, the introducing time is 120min, and depositing heteroatoms and amorphous carbon on the surface of the porous hard carbon to obtain the heteroatom doped porous hard carbon composite anode material.
Comparative example 2
The specific embodiment of the heteroatom-doped porous hard carbon composite anode material in this comparative example is the same as that in example 3, and is different in that S3 is: transferring the sodium doped hard carbon precursor material into a tube furnace, introducing methane gas, heating to 800 ℃, and depositing hetero atoms and amorphous carbon on the surface of the precursor material for 120min at the flow rate of 300mL/min to obtain the hetero atom doped porous hard carbon composite anode material.
Comparative example 3
This comparative example is a heteroatom doped porous hard carbon composite anode material, specific embodiment of which is the same as example 3 except that 15g of passivated sodium metal is added to 100g of naphthalene solution.
Performance testing
1. SEM test
SEM test is carried out on the heteroatom doped porous hard carbon composite anode material prepared in example 1, and the result is shown in figure 1, and the composite material prepared in example 1 has a granular structure, uniform size distribution and particle size of 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 3 were subjected to particle size, tap density, specific surface area, OI value, powder conductivity and specific capacity thereof, and first time efficiency tests. The testing method comprises the following steps: GB/T-24533-2019 lithium ion battery graphite cathode material.
The hard carbon composites obtained in examples 1 to 3 and comparative examples 1 to 3 were assembled into button cells A1, A2, A3, B1, B2, B3, respectively; the preparation method comprises the following steps: adding binder, conductive agent and solvent into the cathode material, stirring to slurry, coating on copper foil, oven drying, and rolling. The binder used is LA132 binder, conductive agent SP, and the negative electrode material is hard carbon composite material prepared in examples 1-3 and comparative examples 1-3, the solvent is secondary distilled water, and the proportion is: negative electrode material: SP: LA132: secondary distilled water = 94g:2g:4g:220mL, and preparing a negative pole piece; the electrolyte is NaPF 6 EC+DEC (volume ratio 1:1, concentration 1.1 mol/L), sodium sheet is counter electrode, diaphragm adopts polyethylene PE, polypropylene PP or polyethylene propylene PEP composite film, simulated battery assembly is carried out in glove box filled with argon, electrochemical performance is carried out on a Wuhan blue electric CT2001A type battery tester, charging and discharging voltage range is 0.00V to 2.0V, and charging and discharging rate is 0.1C. The rate performance (1C/0.1C) and cycle performance (0.2C/0.2C, 200 times) were also tested, and the test results are shown in Table 1 below:
TABLE 1
As can be seen from table 1, compared with comparative examples 1 to 3, the first discharge capacity, first efficiency, rate capability and cycle performance of the hard carbon composite materials prepared in examples 1 to 3 are significantly improved, because in the present invention, doping heteroatoms in the composite materials improves the electronic conductivity of the materials, thereby improving the specific capacity and first efficiency, rate capability of the materials; meanwhile, the surface defect of the material is reduced by doping sodium metal in the hard carbon material, so that the first efficiency and the sodium ion intercalation and deintercalation rate in the charge and discharge process are improved, and the multiplying power and the cycle performance are improved.
(3) Soft package battery test:
the hard carbon composites of examples 1 to 3 and comparative examples 1 to 3 were used as negative electrodes, and a negative electrode sheet was prepared by slurry mixing and coating to form a layered oxide (NaFe 1/3 Mn 1/3 Ni 1/3 O 2 ) As positive electrode, naPF 6 (the solvent is EC+DEC, the volume ratio is 1:1, the electrolyte concentration is 1.1 mol/L) is taken as electrolyte, and a Celgard2400 membrane is taken as a diaphragm, so that the 5Ah soft-package battery is prepared.
3.1 rate Performance test
The charge-discharge voltage ranges from 1.0V to 4.0V, the test temperature is 25+/-3.0 ℃, the charge is carried out at 1.0C, 2.0C and 3.0C, the discharge is carried out at 1.0C, the constant current ratio and the temperature of the battery in different charge modes are tested, and the results are shown in Table 2:
TABLE 2
| Multiplying power | 1C | 2C | 3C | |
| Example 1 | Constant current ratio (%) | 97.61 | 94.25 | 88.31 |
| Example 2 | Constant current ratio (%) | 97.24 | 93.56 | 87.93 |
| Example 3 | Constant current ratio (%) | 96.36 | 94.94 | 89.94 |
| Comparative example 1 | Constant current ratio (%) | 94.67 | 87.34 | 83.66 |
| Comparative example 2 | Constant current ratio (%) | 93.47 | 86.45 | 82.06 |
| Comparative example 3 | Constant current ratio (%) | 95.02 | 89.12 | 84.98 |
As can be seen from Table 2, the rate charging performance of the soft-pack batteries prepared in examples 1-3 is significantly better than that of the soft-pack batteries prepared in comparative examples 1-3, i.e. the charging time is shorter, which indicates that the composite anode material of the invention has good quick-charge performance. The reason may be that doping the example material with heteroatoms improves the electron conductivity of the material, improving the rate capability; meanwhile, the sodium ions are doped in the hard carbon to improve the intercalation and deintercalation rate of sodium ions in the charge and discharge process of the material, and the rate capability is improved.
3.2 cycle Performance test
The following experiments were performed on the pouch cells manufactured using the hard carbon composites of examples 1 to 3 and comparative examples 1 to 3: the capacity retention rate was measured by sequentially performing 100, 300 and 500 charge/discharge cycles at a charge/discharge rate of 1C/1C and a voltage ranging from 1.0 to 4.0V, and the results are shown in Table 3:
TABLE 3 Table 3
As can be seen from Table 3, the cycle performance of the lithium ion battery prepared from the hard carbon composite material prepared by the method is obviously superior to that of the comparative example in each stage, because the material has high specific surface area, the liquid retention performance of the material is improved, and meanwhile, the heteroatom compound deposited in the material core has the characteristic of strong structural stability, and the sodium ion doping of the heteroatom compound improves the quantity of sodium ions in the charge and discharge process, so that the cycle performance is improved.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the heteroatom doped porous hard carbon composite anode material is characterized by comprising the following steps of:
s1, adding passivated sodium metal into naphthalene solution, and uniformly dispersing to obtain sodium metal solution;
s2, adding porous hard carbon into a metal sodium solution, soaking in vacuum, and drying to obtain a sodium doped hard carbon precursor material;
s3, transferring the sodium-doped hard carbon precursor material into a tube furnace, and introducing heteroatom mixed gas to obtain the heteroatom-doped porous hard carbon composite anode material.
2. The preparation method according to claim 1, wherein the mass ratio of the passivated metallic sodium to the naphthalene solution is (1-10): 100.
3. the preparation method according to claim 1, wherein the mass ratio of the porous hard carbon to the passivated sodium metal is 100: (1-10).
4. The method of claim 1, wherein the method of preparing porous hard carbon comprises: calcining the pretreated lignin at 1000-1200 ℃ in inert gas atmosphere, removing impurities, washing and drying to obtain the porous hard carbon.
5. The method of preparing according to claim 4, wherein the method of pretreating lignin comprises: mixing lignin with potassium carbonate solution, and drying.
6. The method according to claim 1, wherein the heteroatom mixed gas is a mixed gas of a heteroatom gas and a carbon source gas, the heteroatom gas includes at least one of ammonia, phosphine, borane, and sulfur dioxide, and the carbon source gas includes at least one of methane, ethylene, and acetylene.
7. The method according to claim 6, wherein the volume ratio of the heteroatom gas to the carbon source gas is (1-5): 10.
8. the method according to claim 7, wherein the mixed gas of hetero atoms is introduced at a temperature of 700-900 ℃ for 60-300min at a flow rate of 100-500mL/min.
9. A heteroatom doped porous hard carbon composite anode material characterized by being obtained by the preparation method of any one of claims 1-8.
10. The use of the heteroatom-doped porous hard carbon composite anode material of claim 9 in the preparation of a secondary battery anode material.
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