CN116724411A - Method for preparing hard carbon anode material by using fiber biomass, product and application thereof - Google Patents
Method for preparing hard carbon anode material by using fiber biomass, product and application thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000010405 anode material Substances 0.000 title claims abstract description 47
- 239000002028 Biomass Substances 0.000 title claims abstract description 45
- 239000000835 fiber Substances 0.000 title claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000003763 carbonization Methods 0.000 claims abstract description 20
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 21
- 239000007773 negative electrode material Substances 0.000 claims description 20
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 10
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 10
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 10
- 239000011425 bamboo Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 7
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 229920005596 polymer binder Polymers 0.000 claims description 6
- 239000002491 polymer binding agent Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 244000183278 Nephelium litchi Species 0.000 claims description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 2
- 241000018646 Pinus brutia Species 0.000 claims description 2
- 235000011613 Pinus brutia Nutrition 0.000 claims description 2
- 241000183024 Populus tremula Species 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 239000011148 porous material Substances 0.000 abstract description 17
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 241001330002 Bambuseae Species 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 240000001008 Dimocarpus longan Species 0.000 description 3
- 235000000235 Euphoria longan Nutrition 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000005539 carbonized material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 235000015742 Nephelium litchi Nutrition 0.000 description 1
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010796 biological waste Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 210000000744 eyelid Anatomy 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a method for preparing a hard carbon anode material by using fibrous biomass, a product and application thereof, wherein the method comprises the following steps: (1) Placing the fiber biomass in an inert atmosphere, performing low-temperature sintering treatment at 250-350 ℃ to obtain a precursor, and adjusting the granularity of the precursor; (2) Placing the precursor obtained in the step (1) in an inert atmosphere, heating, and then performing medium-temperature sintering treatment at 700-1000 ℃; (3) And (3) heating the precursor obtained in the step (2) in catalytic gas, and then performing high-temperature carbonization treatment to obtain the hard carbon anode material. The method provided by the application combines low-temperature sintering, medium-temperature sintering and catalytic carbonization, so that abundant pore structures can be left in the treated fiber biomass material, and the method is simple in preparation process, free of waste water generation and very wide in applicability, thus the method has practical significance for subsequent industrial application of the hard carbon negative electrode.
Description
Technical Field
The application relates to the field of sodium ion battery materials, in particular to a method for preparing a hard carbon anode material by using fiber biomass, a product and application thereof.
Background
With the wide use of lithium ion batteries, the demand for lithium resources is increasing, but lithium resources are limited on the earth, so that the phenomenon of shortage of lithium resources is generated, and the secondary battery system in the related electrochemical system is hardly suitable for large-scale energy storage application, so that the development of the energy storage battery system with excellent comprehensive performance of the next generation is urgently needed.
The new generation of energy storage battery system needs to have the characteristics of rich resources, low price, environmental friendliness, electrochemical performance similar to that of lithium and the like. Sodium and lithium belong to the same group element, have similar physicochemical properties as lithium, are rich in resources, are environment-friendly, are low in price, and have more stable electrochemical performance and safety performance. But the ionic radius (r=0.113 nm) of sodium ions is at least 35% larger than that of lithium ions (r=0.076 nm), so that sodium ions are relatively stable in rigid lattices, almost no sodium intercalation capacity exists in regular graphite structures and carbon mesophase microspheres graphitized at high temperature, the irreversible capacity of hard carbon sodium intercalation can be realized by optimizing the structure, the specific surface area is reduced, the first coulomb efficiency of a sodium ion battery is improved, and the problem that sodium ions cannot be intercalated between graphite layers can be solved.
CN114709408A provides a method for preparing sodium ion hard carbon negative electrode material, 1) mixing asphalt and high molecular material; 2) Placing the mixture into a reaction kettle, reacting for 0.5-15h at 300-500 ℃ in an inert atmosphere or an air atmosphere, and cooling to obtain a pretreated sample; 3) Heating the sample prepared in the step 2) to 900-1700 ℃ in an inert atmosphere, preserving heat for 0.5-15h, and cooling to obtain a synthetic product. The application has the advantages that: the yield of the prepared synthetic material is 65-80%, the method is simple, the cost is low, and the commercial application is easy.
CN111847418A provides a preparation method of biomass hard carbon for sodium ion battery anode material, comprising the following steps: providing a raw material longan shell, soaking the longan shell in hot water and an acidic solution, and drying the longan shell to obtain a precursor; introducing protective gas, preheating the precursor, cooling and grinding to obtain an intermediate product; and (3) carbonizing the intermediate product, and cooling to obtain the biomass hard carbon. The application uses the biological waste material of the eyelid as the raw material, is environment-friendly and has low cost; the carbonization treatment is adopted, so that the obtained biomass hard carbon forms a partially graphitized carbon structure, sodium ion storage is facilitated, specific capacity is improved, and the biomass hard carbon has excellent low-temperature performance.
The method for preparing the hard carbon is complicated, and the prepared material has general performance, so that a method which has simple preparation process and is more beneficial to sodium ion embedding of the finally obtained material is required to be developed to meet the application requirements.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
Aiming at the defects of the related technology, the application aims to provide a method for preparing a hard carbon anode material by using fiber biomass, and a product and application thereof.
In order to achieve the purpose, the application adopts the following technical scheme:
in a first aspect, embodiments of the present application provide a method for preparing a hard carbon anode material using fibrous biomass, the method comprising the steps of:
(1) Placing fiber biomass in inert atmosphere, performing low temperature sintering at 250-350deg.C (such as 260 deg.C, 270 deg.C, 280 deg.C, 290 deg.C, 300 deg.C, 310 deg.C, 320 deg.C, 330 deg.C or 340 deg.C, etc.), to obtain precursor, and adjusting precursor granularity;
(2) Placing the precursor obtained in the step (1) in an inert atmosphere, heating, and performing medium-temperature sintering treatment at 700-1000 ℃ (such as 750 ℃, 800 ℃, 850 ℃, 900 ℃ or 950 ℃);
(3) And (3) heating the precursor obtained in the step (2) in catalytic gas, and then carbonizing to obtain the hard carbon anode material.
The method provided by the embodiment of the application combines low-temperature sintering, medium-temperature sintering and catalytic carbonization, so that abundant pore structures are left in the treated fiber biomass material, and the material is more favorable for embedding/extracting sodium ions. According to the embodiment of the application, hemicellulose and part of cellulose in the fibrous biomass can be decomposed in a pyrolysis process through low-temperature sintering, so that a pore structure is left in the material; during medium-temperature sintering, the structure in the material is rearranged rapidly, so that a large number of pores and defects are further exposed; during the catalytic carbonization treatment, impurity elements can be removed due to the existence of catalytic gas, and the material is continuously retracted due to the rising of temperature and the stress of the material, so that a self-repairing effect is achieved, pores on the surface are repaired, and the formation of an internal pore structure is not influenced. The method provided by the embodiment of the application has the advantages of simple preparation process, no wastewater generation and very wide applicability, and thus has practical significance for the subsequent industrial application of the hard carbon negative electrode.
In one embodiment, the fibrous biomass of step (1) comprises any one or a combination of at least two of aspen, pine, lychee, coconut shell, bamboo, cotton.
In terms of raw material components, the main carbon source of the hard carbon is lignin and part of cellulose, and the raw material is fiber biomass, because the fiber biomass consists of hemicellulose, cellulose, lignin and various impurities, the hemicellulose and part of cellulose can be decomposed into tar, water and organic gas volatile matters in the pyrolysis process, and further, a richer pore structure is left in the material, so that sodium ion embedding/extraction is facilitated.
In one embodiment, the inert gas of step (1) is any one or a combination of at least two of nitrogen, argon or helium.
In one embodiment, the low temperature sintering treatment time of step (1) is 15-48h, for example, 16h, 18h, 20h, 25h, 30h, 35h, 40h, 45h, etc.
In one embodiment, the oxygen concentration during the low temperature sintering process of step (1) is less than 200ppm.
In one embodiment, the precursor obtained in step (1) is cooled to a temperature of 50 ℃ or lower, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ or the like, and then the particle size is adjusted.
In one embodiment, the adjusting of the precursor particle size of step (1) to 4-10 μm may be, for example, 5 μm, 6 μm, 7 μm, 8 μm or 9 μm, etc.
In one embodiment, the method of adjusting the particle size of the precursor in step (1) is to subject the precursor to three-stage crushing.
In one embodiment, the three-stage crushing is performed by crushing the precursor to centimeter-level, then to millimeter-level, and finally to micrometer-level.
In one embodiment, the inert gas of step (2) is any one or a combination of at least two of nitrogen, argon or helium.
In one embodiment, the heating rate of step (2) is 20-50deg.C/min, which may be, for example, 25deg.C/min, 30deg.C/min, 35deg.C/min, 40deg.C/min, 45deg.C/min, etc.
The temperature rising rate in the medium temperature treatment is 20-50 ℃/min, the internal structure of the material can be rearranged rapidly through rapid temperature rising, and the connection between the structures is disordered gradually due to rapid temperature change and rapid molecular weight movement, so that a large number of pores and defects can be exposed.
In one embodiment, the intermediate temperature sintering treatment time is 6-12h, for example, 7h, 8h, 9h, 10h, 11h, or the like.
In one embodiment, the oxygen concentration during the medium temperature sintering process is less than 200ppm.
In one embodiment, the catalytic gas of step (3) comprises chlorine.
In one embodiment, the heating rate of step (3) is 1-3 ℃/min, which may be, for example, 1.2 ℃/min, 1.5 ℃/min, 1.8 ℃/min, 2 ℃/min, 2.2 ℃/min, 2.5 ℃/min, 2.8 ℃/min, or the like.
The heating rate in carbonization treatment is 1-3 ℃/min, and the heating rate is slow, so that impurity elements can be better removed under the catalysis gas, and the self-repairing effect of the material is better.
In one embodiment, the carbonization treatment is performed at a temperature of 1600-1800 ℃ (e.g., 1650 ℃, 1700 ℃, 1720 ℃, 1750 ℃, 1780 ℃, etc.), and the treatment is performed for 3-20 hours (e.g., 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, etc.).
Specific point values within the above numerical ranges are all selectable, and will not be described in detail herein.
In a second aspect, an embodiment of the present application provides a hard carbon anode material, where the hard carbon anode material is prepared by using the method as described in the first aspect.
In one embodiment, the content of the impurity element in the hard carbon negative electrode material is less than 50ppm, and may be, for example, 10ppm, 15ppm, 20ppm, 25ppm, 30ppm, 35ppm, 40ppm, 45ppm, or the like.
In one embodiment, the pore size of the hard carbon anode material is 0.5-20nm, for example, 1nm, 3nm, 5nm, 7nm, 10nm, 12nm, 15nm, 17nm or 19nm, etc.
In one embodiment, the hard carbon anode material has a true density of 1.3-2.0g/cm 3 For example, it may be 1.4g/cm 3 、1.5g/cm 3 、1.6g/cm 3 、1.7g/cm 3 、1.8g/cm 3 Or 1.9g/cm 3 Etc.
In one embodiment, the specific surface area of the hard carbon anode material is less than 5m 2 /g, for example, may be 1m 2 /g、2m 2 /g、3m 2 /g or 4m 2 /g, etc.
Specific point values within the above numerical ranges are all selectable, and will not be described in detail herein.
In a third aspect, an embodiment of the present application provides a negative electrode sheet, where the preparation raw materials of the negative electrode sheet include the hard carbon negative electrode material, sodium carboxymethyl cellulose, super P conductive agent, and polymer binder as described in the second aspect.
In one embodiment, the mass ratio of the hard carbon anode material, the sodium carboxymethyl cellulose, the super P conductive agent and the polymer binder is (90-100): 1-3): 0.5-2): 1-3.
Wherein "90-100" may be 91, 92, 93, 94, 95, 96, 97, 98 or 99, etc.;
the first "1-3" may be 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, etc.;
"0.5-2" may be 0.8, 1, 1.2, 1.4, 1.5, 1.7, 1.9, etc.;
the second "1-3" may be 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, etc.
Specific point values within the above numerical ranges are all selectable, and will not be described in detail herein.
In a fourth aspect, an embodiment of the present application provides a method for preparing the negative electrode sheet according to the third aspect, where the method includes dissolving the hard carbon negative electrode material according to the second aspect, sodium carboxymethyl cellulose, super P conductive agent and polymer binder in deionized water according to a formula amount to prepare a slurry, then coating the slurry on a copper foil, and drying the slurry to obtain the negative electrode sheet.
In one embodiment, the drying temperature is 70-90 ℃ (e.g., 72 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃, 85 ℃, 88 ℃, etc.) and the time is 4-10 hours (e.g., 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, etc.).
Specific point values within the above numerical ranges are all selectable, and will not be described in detail herein.
In a fifth aspect, embodiments of the present application provide a sodium ion battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte.
The negative electrode includes a negative electrode tab according to the third aspect.
Compared with the related art, the application has the following beneficial effects:
1. the method provided by the application combines low-temperature sintering, medium-temperature sintering and catalytic carbonization, so that abundant pore structures can be left in the treated fiber biomass material, and the material is more favorable for embedding/extracting sodium ions.
2. The method disclosed by the application is simple in preparation process, does not generate waste water, and is very wide in applicability, so that the method has practical significance for subsequent industrial application of the hard carbon negative electrode.
Other aspects will become apparent upon reading and understanding the accompanying drawings and detailed description.
Drawings
The accompanying drawings are included to provide a further understanding of the technology herein, and are incorporated in and constitute a part of this specification, illustrate technology herein and together with the description serve to explain, without limitation, the technology herein.
FIG. 1 is an SEM image of a material after medium temperature treatment of example 1;
FIG. 2 is a graph showing pore size distribution of a material after the medium temperature treatment in example 1;
FIG. 3 is an SEM image of a carbonized material of example 1;
FIG. 4 is a pore size distribution diagram of a carbonized material of example 1;
fig. 5 is a charge-discharge curve of the sodium ion battery in application example 1.
Detailed Description
The technical scheme of the application is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the application and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a method for preparing a hard carbon anode material by using fibrous biomass, which comprises the following steps:
(1) The bamboo scraps are placed in a nitrogen atmosphere and treated for 24 hours at 300 ℃ to obtain a precursor, wherein the oxygen concentration in the treatment process is lower than 200ppm;
(2) Cooling the precursor obtained in the step (1) to 40 ℃ for three-stage crushing treatment until the granularity of the precursor is 6 mu m;
(3) Placing the precursor obtained in the step (2) in a nitrogen atmosphere, and heating to 800 ℃ at a speed of 30 ℃/min for medium-temperature treatment for 8 hours, wherein the oxygen concentration in the medium-temperature treatment process is lower than 200ppm;
(4) And (3) placing the precursor treated in the step (3) in chlorine, and then heating to 1700 ℃ at a speed of 2.5 ℃/min for carbonization treatment for 10 hours to obtain the hard carbon anode material.
Example 2
The embodiment provides a method for preparing a hard carbon anode material by using fibrous biomass, which comprises the following steps:
(1) The bamboo scraps are placed in a nitrogen atmosphere and treated for 20 hours at 330 ℃ to obtain a precursor, wherein the oxygen concentration in the treatment process is lower than 200ppm;
(2) Cooling the precursor obtained in the step (1) to 40 ℃ for three-stage crushing treatment until the granularity of the precursor is 4 mu m;
(3) Placing the precursor obtained in the step (2) in a nitrogen atmosphere, and heating to 900 ℃ at a speed of 25 ℃/min for carrying out medium-temperature treatment for 7 hours, wherein the oxygen concentration in the medium-temperature treatment process is lower than 200ppm;
(4) And (3) placing the precursor treated in the step (3) in chlorine, and then heating to 1600 ℃ at a speed of 1.5 ℃/min for carbonization treatment for 15 hours to obtain the hard carbon anode material.
Example 3
The embodiment provides a method for preparing a hard carbon anode material by using fibrous biomass, which comprises the following steps:
(1) The bamboo scraps are placed in a nitrogen atmosphere and treated for 40 hours at the temperature of 280 ℃ to obtain a precursor, wherein the oxygen concentration in the treatment process is lower than 200ppm;
(2) Cooling the precursor obtained in the step (1) to 35 ℃ for three-stage crushing treatment until the granularity of the precursor is 8 mu m;
(3) Placing the precursor obtained in the step (2) in a nitrogen atmosphere, and heating to 700 ℃ at a speed of 40 ℃/min for carrying out intermediate temperature treatment for 10 hours, wherein the oxygen concentration in the intermediate temperature treatment process is lower than 200ppm;
(4) And (3) placing the precursor treated in the step (3) in chlorine, and then heating to 1800 ℃ at a speed of 3 ℃/min for carbonization treatment for 8 hours to obtain the hard carbon anode material.
Example 4
This example provides a method for preparing a hard carbon anode material using fibrous biomass, which differs from example 1 only in that the heating rate in step (3) is 60 ℃/min, and the remaining steps are identical to those in example 1.
Example 5
This example provides a method for preparing a hard carbon anode material using fibrous biomass, which differs from example 1 only in that the heating rate in step (3) is 10 ℃/min, and the remaining steps are identical to those in example 1.
Example 6
This example provides a method for preparing a hard carbon anode material using fibrous biomass, which differs from example 1 only in that the heating rate in step (4) is 20 ℃/min, and the remaining steps are identical to those in example 1.
Example 7
This example provides a method for preparing a hard carbon anode material using fibrous biomass, which differs from example 1 only in that the heating rate in step (4) is 0.5 ℃/min, and the remaining steps are identical to those in example 1.
Comparative example 1
This comparative example provides a method for preparing a hard carbon anode material using fibrous biomass, the method comprising:
(1) Performing three-stage crushing treatment on the bamboo scraps until the granularity is 6 mu m;
(2) And (3) placing the bamboo scraps treated in the step (1) into chlorine, and then heating to 1700 ℃ at a speed of 2.5 ℃/min for carbonization treatment for 10 hours to obtain the hard carbon anode material.
Comparative example 2
This comparative example provides a method for preparing a hard carbon anode material using fibrous biomass, the method comprising:
(1) The bamboo scraps are placed in a nitrogen atmosphere and treated for 24 hours at 300 ℃ to obtain a precursor, wherein the oxygen concentration in the treatment process is lower than 200ppm;
(2) Cooling the precursor obtained in the step (1) to 40 ℃ for three-stage crushing treatment until the granularity of the precursor is 6 mu m;
(3) And (3) placing the precursor treated in the step (2) in chlorine, and then heating to 1700 ℃ at a speed of 2.5 ℃/min for carbonization treatment for 10 hours to obtain the hard carbon anode material.
Comparative example 3
This comparative example provides a method for preparing a hard carbon anode material using fibrous biomass, the method comprising:
(1) Performing three-stage crushing treatment on the bamboo scraps until the granularity is 6 mu m;
(2) Placing the bamboo scraps obtained in the step (1) in a nitrogen atmosphere, and heating to 800 ℃ at a speed of 30 ℃/min for medium-temperature treatment for 8 hours, wherein the oxygen concentration in the medium-temperature treatment process is lower than 200ppm;
(3) And (3) placing the precursor treated in the step (2) in chlorine, and then heating to 1700 ℃ at a speed of 2.5 ℃/min for carbonization treatment for 10 hours to obtain the hard carbon anode material.
Application example 1
The application example provides a sodium ion battery, wherein a diaphragm in the battery is glass fiber, metal sodium is used as a counter electrode and a reference electrode, and electrolyte is 1mol/L sodium perchlorate (NaClO) dissolved in ethylene carbonate and propylene carbonate with the volume ratio of 1:1 4 ) The preparation method of the negative electrode comprises the following steps: dissolving the hard carbon anode material, sodium carboxymethylcellulose, super P conductive agent and resin binder obtained in the embodiment 1 with the mass ratio of 95:2:1:2 in deionized water to prepare slurry, coating the slurry on copper foil, and drying the slurry at 80 ℃ for 5 hours to obtain an anode electrode slice; the materials are pressed into button cells according to CR2032 standardThe construction was assembled in a high purity argon filled glove box to yield a sodium ion battery.
Application examples 2 to 7
The present application example provided six sodium ion batteries differing from application example 1 only in that the hard carbon anode material in the anode preparation method was replaced with the hard carbon anode materials provided in examples 2 to 7, and the addition amount of the hard carbon anode material was kept unchanged, and the rest was identical to application example 1.
Comparative application examples 1 to 3
The present comparative application example provided three sodium ion batteries differing from application example 1 only in that the hard carbon anode material was replaced with the hard carbon anode materials provided in comparative examples 1 to 3 in the anode production method, and the addition amount of the hard carbon anode material was kept unchanged, and the rest was identical to application example 1.
Test example 1
The hard carbon anode materials obtained in examples 1 to 7 and comparative examples 1 to 3 were tested for specific surface area, impurity element content, pore diameter, and true density using a Bei Shide specific surface area tester. The specific surface area and the pore diameter are measured by a Bei Shide specific surface area tester; the impurity element was measured by an ICP spectrometer, and the true density was measured by a Bei Shide true density tester. The results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the samples prepared in examples 1-3 were smaller in specific surface area after high-temperature carbonization than comparative examples 1-2, because the materials in examples 1-3 were subjected to low-temperature treatment, medium-temperature treatment, and carbonization treatment at high temperature, and a large number of pores and defects of the samples were exposed during medium-temperature treatment, so that the materials could be continuously retracted during high-temperature carbonization to achieve a "self-repairing" effect, thereby reducing the specific surface area.
The specific surface area of the samples in examples 1-3 after the medium temperature treatment is larger than that of the high temperature carbonization treatment, but the structures in the materials are rearranged rapidly due to the rapid temperature rise to the medium temperature stage, and the connection between the structures is disordered gradually due to the rapid temperature change and the faster and faster molecular weight movement, so that a large number of pores and defects are exposed, and the specific surface area of the materials after the medium temperature treatment is larger.
Test example 2 electrochemical Performance
The sodium ion batteries obtained in application examples 1 to 7 and comparative application examples 1 to 3 were subjected to electrochemical tests, the test voltages were 0 to 2V, the current densities were 0.1A/g, and the results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the electrochemical performance of the hard carbon products prepared in examples 1-3 is better than that of comparative examples 1-3, because the method of the application combines low-temperature sintering, medium-temperature sintering and catalytic carbonization, on one hand, the impurities contained in the materials are catalytically volatilized, and on the other hand, the materials undergo structural rearrangement, so that the defects on the surfaces can be repaired by themselves, the materials form closed pores, the specific surface area is reduced, and the sodium ions forming SEI are reduced, thereby improving the capacity and initial efficiency of the materials.
The applicant states that the present application is described by way of the above examples as a method for preparing a hard carbon anode material using fibrous biomass, and products and applications thereof, but the present application is not limited to, i.e., does not mean that the present application must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present application, equivalent substitution of raw materials for the product of the present application, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present application and the scope of disclosure.
The above describes in detail the optional embodiments of the present application, but the present application is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present application within the scope of the technical concept of the present application, and these simple modifications all fall within the protection scope of the present application.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Claims (19)
1. A method for preparing a hard carbon anode material by using fibrous biomass, comprising the following steps:
(1) Placing the fiber biomass in an inert atmosphere, performing low-temperature sintering treatment at 250-350 ℃ to obtain a precursor, and adjusting the granularity of the precursor;
(2) Placing the precursor obtained in the step (1) in an inert atmosphere, heating, and then performing medium-temperature sintering treatment at 700-1000 ℃;
(3) And (3) heating the precursor obtained in the step (2) in catalytic gas, and then carbonizing to obtain the hard carbon anode material.
2. The method for preparing a hard carbon anode material using a fibrous biomass according to claim 1, wherein the fibrous biomass of step (1) comprises any one or a combination of at least two of aspen, pine, litchi, coconut shells, bamboo and cotton.
3. The method for producing a hard carbon negative electrode material using a fibrous biomass according to claim 1 or 2, wherein the inert gas of step (1) is any one or a combination of at least two of nitrogen, argon or helium.
4. The method for producing a hard carbon negative electrode material using a fibrous biomass according to any one of claims 1 to 3, wherein the low-temperature sintering treatment time of step (1) is 15 to 48 hours.
5. The method for producing a hard carbon negative electrode material using a fibrous biomass according to any one of claims 1 to 4, wherein an oxygen concentration during the low-temperature sintering treatment of step (1) is less than 200ppm.
6. The method for producing a hard carbon negative electrode material using a fibrous biomass according to any one of claims 1 to 5, wherein the obtained precursor in step (1) is subjected to cooling to a temperature of 50 ℃ or lower, followed by adjusting the particle size.
7. The method for producing a hard carbon negative electrode material using a fibrous biomass according to any one of claims 1 to 6, wherein the precursor particle size is adjusted to 4 to 10 μm in step (1).
8. The method for preparing a hard carbon negative electrode material using a fibrous biomass according to any one of claims 1 to 7, wherein the method for adjusting the particle size of the precursor in the step (1) is three-stage crushing of the precursor.
9. The method for producing a hard carbon negative electrode material using a fibrous biomass according to any one of claims 1 to 8, wherein the inert gas of step (2) is any one or a combination of at least two of nitrogen, argon or helium.
10. The method for producing a hard carbon negative electrode material using a fibrous biomass according to any one of claims 1 to 9, wherein the temperature rising rate of step (2) is 20 to 50 ℃/min.
11. The method for producing a hard carbon negative electrode material using a fibrous biomass according to any one of claims 1 to 10, wherein the medium-temperature sintering treatment time of step (2) is 6 to 12 hours;
optionally, the oxygen concentration during the medium temperature treatment is less than 200ppm.
12. The method for producing a hard carbon negative electrode material using a fibrous biomass according to any one of claims 1 to 11, wherein the catalytic gas of step (3) comprises chlorine gas.
13. The method for producing a hard carbon negative electrode material using a fibrous biomass according to any one of claims 1 to 12, wherein the temperature rise rate of step (3) is 1 to 3 ℃/min;
optionally, the carbonization treatment is carried out at a temperature of 1600-1800 ℃ for 3-20 hours.
14. A hard carbon anode material prepared by the method of any one of claims 1-13.
15. The hard carbon negative electrode material according to claim 14, wherein the content of impurity elements in the hard carbon negative electrode material is less than 50ppm;
optionally, the aperture of the hard carbon anode material is 0.5-20nm;
optionally, the hard carbon anode material has a true density of 1.3-2.0g/cm 3 ；
Optionally, the specific surface area of the hard carbon anode material is less than 5m 2 /g。
16. A negative electrode sheet, the raw materials for preparing the negative electrode sheet comprise the hard carbon negative electrode material, sodium carboxymethyl cellulose, super P conductive agent and polymer binder according to claim 14 or 15.
17. The negative electrode sheet of claim 16, wherein the mass ratio of the hard carbon negative electrode material, sodium carboxymethyl cellulose, super P conductive agent, and polymer binder is (90-100): 1-3): 0.5-2): 1-3.
18. The preparation method of the negative electrode plate according to claim 16 or 17, comprising the steps of dissolving the hard carbon negative electrode material according to claim 14 or 15, sodium carboxymethyl cellulose, super P conductive agent and polymer binder in deionized water according to the formula amount to prepare slurry, coating the slurry on copper foil, and drying to obtain the negative electrode plate;
optionally, the drying temperature is 70-90 ℃ and the drying time is 4-10h.
19. A sodium ion battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte;
the negative electrode includes the negative electrode tab according to claim 16 or 17.
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| PCT/CN2023/086558 WO2024207302A1 (en) | 2023-04-06 | 2023-04-06 | Method for preparing hard carbon negative electrode material from cellulosic biomass and product thereof, and use of product |
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| CN117865127A (en) * | 2024-03-11 | 2024-04-12 | 钛科(大连)新能源有限公司 | Cotton straw-based biomass hard carbon anode material and preparation method and application thereof |
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