CN110518243B - Application of lignin in preparation of lithium battery graphite negative electrode material - Google Patents
Application of lignin in preparation of lithium battery graphite negative electrode material Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 37
- 239000010439 graphite Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007773 negative electrode material Substances 0.000 title claims description 15
- 239000002028 Biomass Substances 0.000 claims abstract description 41
- 239000010406 cathode material Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 10
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
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- 239000002245 particle Substances 0.000 claims description 12
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000006184 cosolvent Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 6
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 6
- 241000018646 Pinus brutia Species 0.000 claims description 6
- 235000011613 Pinus brutia Nutrition 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 150000007517 lewis acids Chemical class 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
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- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 244000198134 Agave sisalana Species 0.000 claims description 2
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 240000000491 Corchorus aestuans Species 0.000 claims description 2
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 2
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 2
- 241000219146 Gossypium Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims description 2
- 240000000907 Musa textilis Species 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 241000209504 Poaceae Species 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012527 feed solution Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 238000005056 compaction Methods 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000002006 petroleum coke Substances 0.000 description 9
- 229910021383 artificial graphite Inorganic materials 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 239000002551 biofuel Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229940040102 levulinic acid Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 244000105624 Arachis hypogaea Species 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000010792 warming 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an application of lignin in preparation of a lithium battery graphite cathode material, which comprises the following steps: and (2) carrying out hydrolysis reaction on the biomass in an acid solution to obtain a reaction solution, namely a hydrolyzed feed solution, adding 2-10 volume times of water into the hydrolyzed feed solution, stirring, separating out solids, filtering, washing filter residues with clear water, and drying to obtain the lignin. The method can completely liquefy and hydrolyze the biomass, and then extract the lignin generated by liquefying and hydrolyzing the biomass, the lignin has high aromaticity and low sulfur content, and has better performance parameters such as first discharge specific capacity, first coulombic efficiency, powder compaction density, graphitization degree, fixed carbon content and the like when being applied to the preparation of the lithium battery graphite cathode material.
Description
Technical Field
The invention relates to application of lignin in preparation of a lithium battery graphite negative electrode material.
Background
The biomass is mainly stored in the form of agricultural and forestry wastes in a large amount in our lives, the domestic biomass wastes are derived from straws of crops such as soybean, corn and the like, and meanwhile, a furniture factory also generates a large amount of sawdust and wood shavings in the furniture manufacturing process, and the environment pollution can be caused by improper treatment. The theoretical yield of the Chinese straws in 2017 reaches 8.84 hundred million tons, and the amount of the collectable resources reaches 7 hundred million tons, wherein rice straws account for 25 percent, wheat straws account for 18.3 percent, corn straws account for 33 percent, cotton straws account for 3 percent, and rape flowers and peanuts account for 4.4 percent. Mainly distributed in 13 main food production areas such as Liaoning, Jilin, Heilongjiang and the like, and the straw resource amount accounts for more than 70 percent of the total amount.
Generally, the agricultural biomass waste has the following treatment methods: 1) the field is returned to the field by burning on the spot, but serious air pollution is caused, so the country specially produces the 'method for forbidding burning the straws and comprehensively utilizing and managing' to forbid the outdoor burning of the straws. 2) Biomass power generation, and agricultural biomass waste is directly put into a power generation boiler. Although the method solves the pollution problem caused by local incineration, the utilization rate of the biomass is low. 3) Biomass thermal cracking (e.g., chinese patent 201210048116.3, biomass is thermally cracked to produce biomass tar): the biomass is decomposed into biomass charcoal, biomass tar or pyrolysis gas by high-temperature (400-. The main fuel uses are: low calorific value biomass pyrolysis gas and biomass tar. Although the method realizes the conversion of biomass into biofuel, the added value of the biofuel product is low.
However, in the prior art, no literature report on the preparation of a high value-added graphite negative electrode material for a lithium battery by using biomass as a starting material is provided. In the prior art, petroleum coke is generally used as a raw material for preparing artificial graphite, but the petroleum coke has the following defects: 1. high content of heavy metal, 2, high sulfur content. Secondly, natural graphite is also a common material used as a negative electrode material of a lithium battery, but the natural material has more impurities, and the separation and extraction of the impurities needs to use toxic chlorine gas, thereby inevitably increasing the complexity of the process. Moreover, petroleum and natural graphite are non-renewable resources, and the large amount of petroleum coke causes problems of global warming, environmental pollution and the like.
Therefore, the development of a novel method for preparing the graphite cathode material of the lithium battery is of great significance.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide the application of lignin in the preparation of the lithium battery graphite cathode material.
The application of the lignin in preparing the lithium battery graphite cathode material is characterized in that the preparation process of the lignin is as follows: and (2) carrying out hydrolysis reaction on the biomass in an acid solution to obtain a reaction solution, namely a hydrolyzed feed solution, adding 2-10 volume times of water into the hydrolyzed feed solution, stirring, separating out solids, filtering, washing filter residues with clear water, and drying to obtain the lignin.
The application of the lignin in the preparation of the lithium battery graphite cathode material is characterized in that the lignin is used as a raw material, and the preparation of the lithium battery graphite cathode material comprises the following steps:
1) mixing lignin and a stabilizer solution according to a mass ratio of 1: 2-12, standing and stabilizing at 40-70 ℃ for 3-6 hours, filtering, and drying filter residues to obtain stable lignin;
2) placing the stabilized lignin obtained in the step 1) in a rotary kiln, and calcining for 2-4 hours at 1200-1500 ℃ in a nitrogen protective atmosphere to obtain calcined lignin;
3) placing the calcined lignin obtained in the step 2) in a graphitization furnace, calcining for 3-15 hours at 2500-2800 ℃ in an argon protective atmosphere, and naturally cooling to room temperature to obtain the lithium battery graphite cathode material.
The application of the lignin in the preparation of the lithium battery graphite cathode material is characterized in that the stabilizer solution is a diammonium hydrogen phosphate aqueous solution with the mass concentration of 10-20%.
The application of the lignin in preparing the lithium battery graphite cathode material is characterized in that a reaction solution obtained by hydrolysis reaction of biomass in an acid solution is prepared according to the following processes:
s1: adding biomass particles into a reaction kettle, adding a water cosolvent in an anaerobic state, heating to 150-220 ℃ under stirring, adding Lewis acid, and performing hydrolysis reaction for 20-40 minutes to obtain a hydrolyzed biomass mixed solution;
s2: and (4) adding alkali into the biomass mixed liquid obtained in the step (S1) to neutralize and adjust the pH value to 4.5-8, cooling, and filtering to remove precipitates obtained by neutralization and ash in the biomass to obtain the reaction liquid.
The application of the lignin in the preparation of the lithium battery graphite cathode material is characterized in that in the step S1, the water content of biomass particles is less than 8%, the particle size of the particles is less than 25mm, and the biomass is any one or a mixture of several of wood, straws, paper products, pine, grasses, rice husks, bagasse, cotton, jute, flax, bamboo, sisal, abaca, straws and corncobs.
The application of the lignin in the preparation of the lithium battery graphite cathode material is characterized in that in the step S1, the mass ratio of the water cosolvent is 1: 1-1: 5 water and tetrahydrofuran.
The application of the lignin in preparing the lithium battery graphite cathode material is characterized in that in the step S1, the mass ratio of the biomass to the water cosolvent is 1: 2-7; the Lewis acid is at least one of sulfuric acid, hydrochloric acid and nitric acid, and the mass of the Lewis acid is 0.3-3% of that of the water cosolvent.
Compared with the prior art, the invention has the following beneficial effects:
1) the reaction liquid after the biomass is subjected to hydrolysis reaction in the acid solution is marked as hydrolyzed feed liquid, and the hydrolyzed feed liquid contains biomass hydrolysis products such as: sugar of C5-C6, furfural, levulinic acid, hydrolyzed lignin and the like, wherein the hydrolyzed lignin is the aromatic hydrocarbon organic matter. And adding a certain amount of water into the hydrolyzed feed liquid for mixing, so that the solubility of lignin in the hydrolyzed feed liquid can be reduced, and then the lignin is separated out (biomass hydrolysis products such as sugar, furfural and levulinic acid of C5-C6 are basically dissolved in the hydrolyzed feed liquid, and can be used as liquid fuel, plant nutrient solution and the like. After the separated lignin is cleaned and dried by clear water, the obtained lignin product has high aromaticity, and the obtained lignin has low sulfur content and ash content, and is particularly suitable for preparing downstream graphite materials with high added value.
2) When the lignin extracted by the invention is used for preparing the lithium battery graphite cathode material, the lignin has better performance parameters of specific discharge capacity for the first time, coulombic efficiency for the first time, powder compaction density, graphitization degree and fixed carbon content, and meets the use standard of the lithium battery cathode material. Secondly, the method can efficiently utilize renewable resources such as biomass straws and the like, reduces the consumption rate of the lithium battery cathode material to natural resources, reduces environmental pollution and improves economic benefits.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
the method for preparing the lithium battery graphite negative electrode material by using the lignin comprises the following steps:
1) 20 kg of pine wood particles (the water content of the pine wood particles is less than 8 percent, and the particle diameter of the pine wood particles is less than 25 mm), 20 kg of water, 60 kg of tetrahydrofuran and 600g of concentrated sulfuric acid are added into a reaction kettle and uniformly mixed (the mass concentration of the concentrated sulfuric acid is 98 percent). Stirring and heating the reaction kettle to 180 ℃ in a nitrogen atmosphere, reacting for 20 minutes, adding 1 kg of calcium hydroxide slurry with the concentration of 50% w/w to neutralize sulfuric acid in the solution after determining that cellulose, hemicellulose and lignin in pine wood particles are liquefied and hydrolyzed, and filtering to obtain 100 kg of reaction liquid;
2) mixing 100 kg of reaction liquid obtained in the step 1) with 250 kg of water, stirring uniformly, separating out solids, filtering, washing filter residues with 500 kg of water, and drying to obtain 10 kg of lignin;
3) mixing 10 kg of lignin obtained in the step 2) with 100 kg of diammonium hydrogen phosphate aqueous solution with the mass concentration of 10%, standing and stabilizing at the temperature of 60 ℃ for 4 hours, filtering, and drying filter residues to obtain 10 kg of stable lignin;
4) placing 10 kg of the stable lignin obtained in the step 3) into a rotary furnace, and calcining for 4 hours at 1400 ℃ under the protection of nitrogen to obtain 5 kg of calcined lignin;
5) and (3) placing 5 kg of calcined lignin obtained in the step 4) into a graphitization furnace, calcining for 12 hours at 2700 ℃ under the protection of argon, and naturally cooling to room temperature to obtain 3 kg of the lithium battery graphite cathode material.
The lignin obtained in step 2) of example 1 was subjected to a performance test: it has an aromaticity of 85% as determined by the ISO 21461 method, a sulfur content of 0.01% as determined by the GB/T2286 method and an ash content of 0.1% as determined by the GB/T2001 method.
In the prior art, whether a graphite negative electrode material of a lithium battery meets a standard or not is evaluated, and the following performance detection standards in 5 aspects are generally required to be met:
1 specific discharge capacity for the first time: the initial discharge specific capacity of the material is usually tested by GB/T2433s2019 standard, the initial discharge specific capacity of the high-performance natural graphite material is about 360mAh/g, the initial discharge specific capacity of petroleum coke in the artificial graphite is generally between 300 and 350mAh/g, and the initial discharge specific capacity of the lithium battery graphite cathode material cannot be too small.
2 first coulombic efficiency: the first coulombic efficiency of the graphite cathode material of the lithium battery is generally tested by adopting the GB/T2433and 2019 standard. In the process of first charging, lithium ions are inserted into the negative electrode material, when the battery discharges, the lithium ions inserted into the negative electrode material return to the positive electrode material, and because pores in the material are complicated and complicated, not all the lithium ions can be completely extracted, the method obtains the actually available capacity after the first charging, the higher the numerical value is, the higher the available volume of the negative electrode material is, and the first coulombic efficiency of petroleum coke is generally between 90 and 95 percent.
3 powder compacted density: the powder compaction density of the graphite cathode material of the lithium battery is generally tested by adopting the GB/T2433and 2019 standard. The higher the compacted density is, the higher the energy density of the lithium battery with the same volume is, and the compacted density of the petroleum coke lithium battery cathode material of the common artificial graphite is 1.0-1.4g/cm3。
4 degree of graphitization: the graphitization degree of the lithium battery graphite cathode material is generally tested by adopting the GB/T2433and 2019 standard. The higher the graphitization degree, the better the performance of the lithium battery negative electrode material. Generally, the graphitization degree of petroleum coke of the artificial graphite after graphitization is between 85% and 95%.
5, fixed carbon content: the fixed carbon content of the graphite cathode material of the lithium battery is generally tested by adopting the GB/T3521 standard. The fixed carbon content represents the content of carbon elements in the negative electrode material, and the higher the fixed carbon content is, the lower the contents of ash and volatile components in the material are, and the better the product performance is. The fixed carbon content of high performance petroleum coke is generally between 99.7% and 99.97%.
Example 1 the performance test data of the lithium battery graphite cathode material prepared by using lignin is shown in table 1, and the table 1 also lists the performance standard of petroleum common coke in artificial graphite under the national standard GB/T2433and 2019.
TABLE 1
As can be seen from Table 1, the lithium battery graphite cathode material prepared in example 1 of the present invention has quality performance equivalent to the quality performance parameter of petroleum coke in artificial graphite. The method for preparing the graphite cathode material of the lithium battery by using the lignin disclosed by the invention meets the use standard of the cathode material of the lithium battery. The method can develop and produce downstream graphite material products with high added value by using biomass as a raw material.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (6)
1. The application of the lignin in preparing the lithium battery graphite cathode material is characterized in that the preparation process of the lignin is as follows: adding 2-10 volume times of water into the hydrolyzed feed liquid, stirring, separating out solids, filtering, washing filter residues with clear water, and drying to obtain lignin;
the method for preparing the lithium battery graphite cathode material by taking lignin as a raw material comprises the following steps:
1) mixing lignin and a stabilizer solution according to a mass ratio of 1: 2-12, standing and stabilizing at 40-70 ℃ for 3-6 hours, filtering, and drying filter residues to obtain stable lignin;
2) placing the stabilized lignin obtained in the step 1) in a rotary kiln, and calcining for 2-4 hours at 1200-1500 ℃ in a nitrogen protective atmosphere to obtain calcined lignin;
3) placing the calcined lignin obtained in the step 2) in a graphitization furnace, calcining for 3-15 hours at 2500-2800 ℃ in an argon protective atmosphere, and naturally cooling to room temperature to obtain the lithium battery graphite cathode material.
2. The application of the lignin in preparing the graphite cathode material of the lithium battery according to claim 1, wherein the stabilizer solution is a diammonium hydrogen phosphate aqueous solution with the mass concentration of 10-20%.
3. The application of the lignin according to claim 1 in preparing a graphite negative electrode material of a lithium battery, wherein a reaction solution obtained after hydrolysis reaction of biomass in an acid solution is prepared according to the following processes:
s1: adding biomass particles into a reaction kettle, adding a water cosolvent in an anaerobic state, heating to 150-220 ℃ under stirring, adding Lewis acid, and performing hydrolysis reaction for 20-40 minutes to obtain a hydrolyzed biomass mixed solution;
s2: and (4) adding alkali into the biomass mixed liquid obtained in the step (S1) to neutralize and adjust the pH value to 4.5-8, cooling, and filtering to remove precipitates obtained by neutralization and ash in the biomass to obtain the reaction liquid.
4. The use of lignin according to claim 3 in the preparation of graphite negative electrode material for lithium battery, wherein the water content of biomass particles in step S1 is less than 8%, the particle size is less than 25mm, and the biomass is any one or more of straw, paper products, pine, grasses, rice hulls, bagasse, cotton, jute, flax, bamboo, sisal, abaca, straw, and corn cob.
5. The application of the lignin according to claim 3 in the preparation of a lithium battery graphite negative electrode material, wherein in the step S1, the mass ratio of the water cosolvent is 1: 1-1: 5 water and tetrahydrofuran.
6. The application of the lignin in preparing the graphite cathode material of the lithium battery according to claim 3, wherein in the step S1, the mass ratio of the biomass to the water cosolvent is 1: 2-7; the Lewis acid is at least one of sulfuric acid, hydrochloric acid and nitric acid, and the mass of the Lewis acid is 0.3-3% of that of the water cosolvent.
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