CN116621153A - Sodium ion battery biomass hard carbon anode material and preparation method and application thereof - Google Patents
Sodium ion battery biomass hard carbon anode material and preparation method and application thereof Download PDFInfo
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- CN116621153A CN116621153A CN202310603891.9A CN202310603891A CN116621153A CN 116621153 A CN116621153 A CN 116621153A CN 202310603891 A CN202310603891 A CN 202310603891A CN 116621153 A CN116621153 A CN 116621153A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 94
- 239000002028 Biomass Substances 0.000 title claims abstract description 45
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 33
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 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 50
- 239000007833 carbon precursor Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 20
- 229920005610 lignin Polymers 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000005416 organic matter Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 27
- 125000005842 heteroatom Chemical group 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical compound [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 claims description 3
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- WUQVMHPQRIQJMG-UHFFFAOYSA-L iron(2+);6-methylheptanoate Chemical compound [Fe+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O WUQVMHPQRIQJMG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 claims description 2
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 claims description 2
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical compound [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- QEEPNARXASYKDD-UHFFFAOYSA-J tris(7,7-dimethyloctanoyloxy)stannyl 7,7-dimethyloctanoate Chemical compound [Sn+4].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O QEEPNARXASYKDD-UHFFFAOYSA-J 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 25
- 239000002131 composite material Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 238000009656 pre-carbonization Methods 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- -1 magnesium-cobaltocene Chemical compound 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PEAGOPNMLBSBFY-UHFFFAOYSA-N [CH-]1C=CC=C1.[CH-]1C=CC=C1.[Co+2].[Ni] Chemical compound [CH-]1C=CC=C1.[CH-]1C=CC=C1.[Co+2].[Ni] PEAGOPNMLBSBFY-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 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
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007740 vapor deposition Methods 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
- H01M10/052—Li-accumulators
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of batteries, in particular to a sodium ion battery biomass hard carbon anode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, preparing a pre-oxidized hard carbon precursor material by utilizing sodium lignin; s2, uniformly mixing a catalyst, a metal organic matter and a pre-oxidized hard carbon precursor to prepare a porous metal doped hard carbon precursor material; s3, transferring the porous metal doped hard carbon precursor material into a tube furnace, and introducing carbon source mixed gas for carbonization to obtain the biomass hard carbon anode material. The pre-oxidized hard carbon precursor material is obtained by oxidizing sodium lignin, and chemical reaction is carried out between the pre-oxidized hard carbon precursor material and metal organic matters to improve the electronic conductivity and the structural stability of the material.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a biomass hard carbon anode material of a sodium ion battery, a preparation method and application thereof.
Background
Sodium ion batteries are considered as an important choice for next generation secondary batteries due to the abundant sodium content in the crust and their higher energy density. For the negative electrode, due to the larger radius of sodium ions, graphite commonly used in the traditional lithium ion battery is not suitable for being used as a negative electrode material of the sodium ion battery due to the narrow interlayer spacing. Hard carbon has a large interlayer spacing, which is favorable for the deintercalation of sodium ions, however, a large number of disordered structures in the hard carbon can cause a large number of side reactions and reduce the initial coulombic efficiency of the battery. Soft carbon limited active sites and small interlayer spacing also do not favor sodium storage. The biomass-derived carbon material retains the structural characteristics of the biomass precursor, and has the advantages of controllable structure and wide market prospect, and is paid attention to. However, compared with hard carbon derived from organic polymers such as phenolic resin, the hard carbon (lignin) structure of biomass is more irregular, and the problems of large irreversible capacity, poor power performance and the like exist, so that the application is greatly limited.
Disclosure of Invention
In order to improve the power performance of the hard carbon material, the composite material provided by the invention provides more active sites by utilizing N, B, P heteroatom doping, improves the specific capacity of the hard carbon material and the amorphous carbon on the vapor deposition surface, and reduces the surface defects to improve the primary efficiency.
The first aspect of the invention provides a preparation method of a sodium ion battery biomass hard carbon anode material, which comprises the following steps:
s1, preparing a pre-oxidized hard carbon precursor material by utilizing sodium lignin;
s2, uniformly mixing a catalyst, a metal organic matter and a pre-oxidized hard carbon precursor to prepare a porous metal doped hard carbon precursor material;
s3, transferring the porous metal doped hard carbon precursor material into a tube furnace, and introducing carbon source mixed gas for carbonization to obtain the biomass hard carbon anode material.
In some embodiments, S1 comprises ultrasonically washing, drying, and heating sodium lignin to obtain a pre-oxidized hard carbon precursor material.
Further, the step S1 comprises the steps of placing sodium lignin in an ultrasonic cleaner for ultrasonic washing, performing suction filtration and drying to obtain a biomass precursor, and transferring the biomass precursor into a tube furnace for infrared heating to obtain the pre-oxidized hard carbon precursor material.
In some embodiments, the step S2 comprises preparing an N-methyl pyrrolidone solution with a mass concentration of 1-10% of the catalyst, adding a metal organic substance and a pre-oxidized hard carbon precursor material, uniformly mixing, transferring the mixture into a high-pressure reaction kettle, reacting at a temperature of 80-120 ℃ and a pressure of 1-5Mpa for 1-6h, filtering, and freeze-drying at a temperature of-40 ℃ for 24h to obtain the porous metal doped hard carbon precursor material.
The applicant finds in the research that the catalyst and the metal organic compound can be added simultaneously to increase sodium storage promoted by the holes of the material and improve specific capacity, and the metal compound can improve the electronic conductivity and power performance of the material, and further, the mass ratio of the catalyst to the metal organic compound to the pre-oxidized hard carbon precursor is (1-10): 100, when the mass ratio of the three is controlled, the energy density and the power performance can be considered, the energy density is reduced due to the excessive content of metal organic matters, and the power performance is improved to a limited extent due to the insufficient content of metal organic matters.
In some embodiments, the catalyst comprises at least one of ferrocene, cobaltocene, nickel-cobaltocene, titanocene, zirconocene, magnesium-cobaltocene.
In some embodiments, the metal-organic comprises at least one of iron isooctanoate, tin isooctanoate, chromium isooctanoate, bismuth neodecanoate, tin neodecanoate, dibutyl tin dilaurate. The applicant finds that adding the above metal organic compound improves the processing and the compatibility with electrolyte by containing amorphous carbon after the organic metal compound is carbonized by itself compared with the existing metal powder or inorganic metal compound for doping, and the organic metal compound contains carboxyl groups, which is beneficial to the pore-forming of the material to improve the specific capacity.
In some embodiments, the step S3 comprises transferring the porous metal doped hard carbon precursor material into a tube furnace, exhausting air in the tube by inert gas, introducing carbon source mixed gas, heating to 300-500 ℃ at a heating rate of 1-10 ℃/min, preserving heat for 1-6h, heating to 700-1200 ℃ at a heating rate of 1-10 ℃/min, preserving heat for 1-6h, and naturally cooling to room temperature to obtain the hard carbon composite material.
Further, the carbon source mixed gas is a mixture of a carbon source gas and a heteroatom gas.
In some embodiments, the volume ratio of carbon source gas to heteroatom gas is 10: (1-5).
In some embodiments, the heteroatom gas comprises at least one of ammonia, diborane, phosphine.
The applicant has also found that the addition of a heteroatom gas can improve the specific capacity of the material and its power performance, in particular the volume ratio of carbon source gas to heteroatom gas is 10: in the process (1-5), the impedance of the material coating layer can be effectively reduced, and too much heteroatom gas can cause loosening of the surface structure of the material to reduce tap density and structural stability, and too little heteroatom gas can not obviously improve the power performance of the material.
The second aspect of the invention provides a biomass hard carbon anode material of a sodium ion battery, which has a core-shell structure, wherein the core is made of a metal doped hard carbon material, and the shell is made of heteroatom doped amorphous carbon.
The third aspect of the invention provides the preparation method or the application of the sodium ion battery biomass hard carbon anode material in preparation of secondary batteries.
Compared with the prior art, the invention has the following beneficial effects:
1) The pre-oxidized hard carbon precursor material is obtained by oxidizing sodium lignin, and chemical reaction is carried out between the pre-oxidized hard carbon precursor material and metal organic matters to improve the electronic conductivity and the structural stability of the material.
2) The electron conductivity of the material is improved by the heteroatom gas, and the rate performance is improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are some embodiments of the invention and that other drawings may be obtained from these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of the biomass hard carbon negative electrode material of the sodium ion battery 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.
Example 1
The first aspect of the embodiment provides a preparation method of a biomass hard carbon anode material of a sodium ion battery, which comprises the following steps:
step S1, placing sodium lignin in deionized water, ultrasonically washing the sodium lignin in an ultrasonic cleaner, filtering, performing suction filtration, drying to obtain a biomass precursor, transferring the biomass precursor into a tube furnace, and performing infrared heating (at the temperature of 200 ℃ for 3 hours) to obtain a pre-carbonization treatment to obtain a pre-oxidized hard carbon precursor material;
step S2, adding 5g of catalyst into 100g of N-methyl pyrrolidone to prepare a solution with the mass concentration of 5%, adding 5g of metal organic matters and 100g of pre-oxidized hard carbon precursor materials, uniformly mixing, transferring the mixture into a high-pressure reaction kettle, reacting for 3 hours at the temperature of 100 ℃ and the pressure of 3Mpa, filtering, and freeze-drying for 24 hours at the temperature of-40 ℃ to obtain the porous metal doped hard carbon precursor material; the catalyst is ferrocene, and the metal organic matter is iron isooctanoate;
step S3, transferring the porous metal doped hard carbon precursor material into a tube furnace, introducing argon inert gas to remove air in the tube, introducing carbon source mixed gas, heating to 400 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, and naturally cooling to room temperature (25 ℃), thus obtaining the hard carbon composite material; the carbon source mixed gas is methane: ammonia = 10:3 (V/V).
The second aspect of the embodiment provides a biomass hard carbon anode material of a sodium ion battery, wherein the material has a core-shell structure, a core is made of a metal doped hard carbon material, and a shell is made of heteroatom doped amorphous carbon.
The third aspect of the embodiment provides an application of the sodium ion battery biomass hard carbon anode material in preparation of a secondary battery.
Example 2
The first aspect of the embodiment provides a preparation method of a biomass hard carbon anode material of a sodium ion battery, which comprises the following steps:
step S1, placing sodium lignin in deionized water, ultrasonically washing the sodium lignin in an ultrasonic cleaner, filtering, performing suction filtration, drying to obtain a biomass precursor, transferring the biomass precursor into a tube furnace, and performing infrared heating (at the temperature of 200 ℃ for 3 hours) to obtain a pre-carbonization treatment to obtain a pre-oxidized hard carbon precursor material;
step S2, adding 1g of catalyst into 100g of N-methyl pyrrolidone to prepare a solution with the mass concentration of 1%, adding 1g of metal organic matters and 100g of pre-oxidized hard carbon precursor materials, uniformly mixing, transferring the mixture into a high-pressure reaction kettle, reacting for 6 hours at the temperature of 80 ℃ and the pressure of 5Mpa, filtering, and freeze-drying for 24 hours at the temperature of-40 ℃ to obtain the porous metal doped hard carbon precursor material; the catalyst is cobaltocene, and the metal organic matter is tin isooctanoate;
step S3, transferring the porous metal doped hard carbon precursor material into a tube furnace, introducing argon inert gas to remove air in the tube, introducing carbon source mixed gas, heating to 300 ℃ at a heating rate of 1 ℃/min for 6 hours, heating to 700 ℃ at a heating rate of 1 ℃/min for 3 hours, and naturally cooling to room temperature (25 ℃) to obtain a hard carbon composite material; the carbon source mixed gas is acetylene: diborane = 10:1 (V/V).
The second aspect of the present embodiment provides a biomass hard carbon anode material for a sodium ion battery, and the specific embodiment is the same as that of example 1.
The third aspect of the embodiment provides an application of the sodium ion battery biomass hard carbon anode material in preparation of a secondary battery.
Example 3
The first aspect of the embodiment provides a preparation method of a biomass hard carbon anode material of a sodium ion battery, which comprises the following steps:
step S1, placing sodium lignin in deionized water, ultrasonically washing the sodium lignin in an ultrasonic cleaner, filtering, performing suction filtration, drying to obtain a biomass precursor, transferring the biomass precursor into a tube furnace, and performing infrared heating (at the temperature of 200 ℃ for 3 hours) to obtain a pre-carbonization treatment to obtain a pre-oxidized hard carbon precursor material;
step S2, adding 10g of catalyst into 100g of N-methyl pyrrolidone to prepare a solution with the mass concentration of 10%, adding 10g of metal organic matters and 100g of pre-oxidized hard carbon precursor materials, uniformly mixing, transferring the mixture into a high-pressure reaction kettle, reacting for 1h at the temperature of 120 ℃ and the pressure of 1Mpa, filtering, and freeze-drying for 24h at the temperature of-40 ℃ to obtain the porous metal doped hard carbon precursor material; the catalyst is nickel dichloride, and the metal organic matter is chromium isooctanoate;
step S3, transferring the porous metal doped hard carbon precursor material into a tube furnace, introducing argon inert gas to remove air in the tube, introducing carbon source mixed gas, heating to 500 ℃ at a heating rate of 10 ℃/min for 1h, heating to 1200 ℃ at a heating rate of 10 ℃/min for 1h, and naturally cooling to room temperature (25 ℃) to obtain a hard carbon composite material; the carbon source mixed gas is ethylene: phosphine=10: 5 (V/V).
The second aspect of the present embodiment provides a biomass hard carbon anode material for a sodium ion battery, and the specific embodiment is the same as that of example 1.
The third aspect of the embodiment provides an application of the sodium ion battery biomass hard carbon anode material in preparation of a secondary battery.
Comparative example 1
The comparative example provides a preparation method of a biomass hard carbon anode material of a sodium ion battery, and the specific implementation mode is the same as that of the example 1, wherein the carbon source mixed gas is methane.
Comparative example 2
The comparative example provides a preparation method of a biomass hard carbon anode material of a sodium ion battery, and the specific implementation mode is the same as the example 1, wherein the preparation method comprises the following steps:
step S1, placing sodium lignin in deionized water, ultrasonically washing the sodium lignin in an ultrasonic cleaner, filtering, performing suction filtration, drying to obtain a biomass precursor, transferring the biomass precursor into a tube furnace, and performing infrared heating (at the temperature of 200 ℃ for 3 hours) to obtain a pre-carbonization treatment to obtain a pre-oxidized hard carbon precursor material;
s2, transferring the pre-oxidized hard carbon precursor material into a tube furnace, introducing argon inert gas to remove air in the tube, introducing carbon source mixed gas, heating to 400 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, and naturally cooling to room temperature (25 ℃), thus obtaining the hard carbon composite material; the carbon source mixed gas is methane: ammonia = 10:3 (V/V).
Performance testing
(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 composite material exhibits a granular structure with a particle size of between 10 and 15. Mu.m.
(2) Physical and chemical properties and button cell test
The hard carbon composite materials obtained in examples 1-3 and comparative examples 1-2 were tested for conductivity, tap density, specific surface area, particle size, and powder OI values according to the test method in standard GB/T-24533-2019 "lithium ion battery graphite-based negative electrode materials". The test results are shown in Table 1.
The hard carbon composite materials prepared in examples 1 to 3 and comparative examples 1 to 2 were used as a negative electrode, and assembled with a lithium sheet, an electrolyte and a separator in a glove box having argon and water contents of less than 0.1 ppm. Wherein the membrane is cellegard 2400; the electrolyte is LiPF 6 Is a solution of (a) and (b). In the electrolyte, liPF 6 The concentration of (2) is 1mol/L, and the solvent is Ethylene Carbonate (EC) and diethyl carbonate (DMC) according to the weight ratio of 1:1 mixing the obtained mixed solution. The resulting coin cells were labeled a-1, b-1,c-1, D-1 and E-1, and then testing the performance of the button cell by adopting a blue electric tester under the following testing conditions: the charge and discharge rate of 0.2C is 0.005-2V, the cycle is stopped after 3 weeks, then the discharge capacity under the condition of 1C is tested, the rate performance of 1C/0.2C is calculated, and the cycle performance (25+/-3 ℃ C., 0.2C/0.2C,100 weeks) is calculated. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the conductivity of the hard carbon composite material prepared in examples 1-3 is significantly higher than that of comparative examples 1-2, probably because the graphite composite material prepared in examples 1-3 is doped with metal elements with high electron conductivity and elements such as nitrogen and boron, the impedance is reduced, the specific surface area is increased, and meanwhile, the electron conductivity of the material is increased by doping with outer-layer heteroatom gas, so that the rate performance and the cycle performance are improved.
(3) Soft package battery performance test
The graphite composite materials of examples 1-3 and the hard carbon composite materials of comparative examples 1-2 were used as negative electrode active materials, respectively, and as a ternary material (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) The electrolyte and the separator are assembled into a soft package battery of 5 Ah. Wherein the membrane is cellegard 2400, and the electrolyte is LiPF 6 Solution (solvent is a mixed solution of EC and DEC in volume ratio of 1:1, liPF) 6 At a concentration of 1.3 mol/L). The prepared soft package batteries are respectively marked as A-2, B-2, C-2 and D-2,F-2, and the cycle and rate performance of the batteries are tested, and the test results are shown in Table 2.
3.1 cycle performance: testing the cycle performance of the battery at the temperature of 25+/-3 ℃ under the conditions that the charge-discharge multiplying power is 1C/1C and the voltage range is 2.8V-4.2V;
3.2 rate capability: the battery was charged to 100% soc in a constant current+constant voltage mode at a rate of 2C, and then a constant current ratio=constant current capacity/(constant current capacity+constant voltage capacity) was calculated.
TABLE 2
| Negative electrode material for battery | Cycle 500 times capacity retention (%) | Quick charge performance (constant current ratio) |
| Example 1 | 92.42 | 93.2％ |
| Example 2 | 93.88 | 91.5％ |
| Example 3 | 92.39 | 92.7％ |
| Comparative example 1 | 86.11 | 85.1％ |
| Comparative example 2 | 87.34 | 83.4％ |
As can be seen from Table 2, the cycling performance and the rate performance of the soft-pack battery prepared by taking the hard carbon composite materials of examples 1-3 as the negative electrode material are obviously better than those of the soft-pack battery prepared by taking the hard carbon composite materials of comparative examples 1-2. The reason for this is that the hard carbon composite material of examples 1-3 obtains a pre-oxidized hard carbon precursor material by oxidizing sodium lignin, and the pre-oxidized hard carbon precursor material and the metal organic matter undergo chemical reaction to improve the structural stability of the material and improve the cycle performance; meanwhile, the electron conductivity of the material and the OI value reduced in the embodiment are improved through the heteroatom gas, so that the rate 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 sodium ion battery biomass hard carbon anode material is characterized by comprising the following steps of:
s1, preparing a pre-oxidized hard carbon precursor material by utilizing sodium lignin;
s2, uniformly mixing a catalyst, a metal organic matter and a pre-oxidized hard carbon precursor to prepare a porous metal doped hard carbon precursor material;
s3, transferring the porous metal doped hard carbon precursor material into a tube furnace, and introducing carbon source mixed gas for carbonization to obtain the biomass hard carbon anode material.
2. The method for preparing the sodium ion battery biomass hard carbon anode material according to claim 1, wherein the step S1 comprises the steps of ultrasonic washing, drying and heating of sodium lignin to obtain a pre-oxidized hard carbon precursor material.
3. The preparation method of the sodium ion battery biomass hard carbon anode material according to claim 1, wherein the mass ratio of the catalyst to the metal organic matter to the pre-oxidized hard carbon precursor is (1-10):
(1-10):100。
4. the method for preparing the biomass hard carbon anode material of the sodium ion battery according to claim 3, wherein the catalyst comprises at least one of ferrocene, cobaltocene, nickelocene, titanocene, zirconocene and magnesium.
5. The method for preparing a biomass hard carbon negative electrode material of a sodium ion battery according to claim 3, wherein the metal organic matter comprises at least one of iron isooctanoate, tin isooctanoate, chromium isooctanoate, bismuth neodecanoate, tin neodecanoate and dibutyltin dilaurate.
6. The method for preparing the biomass hard carbon anode material of the sodium ion battery according to claim 1, wherein the carbon source mixed gas is a mixture of carbon source gas and heteroatom gas.
7. The method for preparing the biomass hard carbon anode material of the sodium ion battery according to claim 6, wherein the volume ratio of the carbon source gas to the heteroatom gas is 10: (1-5).
8. The method for preparing a biomass hard carbon anode material for a sodium ion battery according to claim 7, wherein the heteroatom gas comprises at least one of ammonia, diborane and phosphine.
9. The biomass hard carbon anode material of the sodium ion battery prepared by the method disclosed by the claim 1 is characterized by being in a core-shell structure, wherein the core is made of a metal doped hard carbon material, and the shell is made of heteroatom doped amorphous carbon.
10. Use of the preparation method of claim 1 or the sodium ion battery biomass hard carbon negative electrode material of claim 9 in the preparation of secondary batteries.
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