CN117049506A - Preparation method of lignite-derived carbon and sodium ion battery - Google Patents
Preparation method of lignite-derived carbon and sodium ion battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 142
- 239000003077 lignite Substances 0.000 title claims abstract description 141
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 53
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 238000000197 pyrolysis Methods 0.000 claims abstract description 73
- 239000003245 coal Substances 0.000 claims abstract description 66
- 238000001035 drying Methods 0.000 claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000002817 coal dust Substances 0.000 claims abstract description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000010000 carbonizing Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 11
- 239000011847 coal-based material Substances 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 238000013021 overheating Methods 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 18
- 239000012535 impurity Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 14
- 239000002174 Styrene-butadiene Substances 0.000 description 13
- 239000001768 carboxy methyl cellulose Substances 0.000 description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 description 13
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 10
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 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 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000009768 microwave sintering Methods 0.000 description 5
- 238000002203 pretreatment Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 239000004021 humic acid Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 239000011115 styrene butadiene Substances 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application is suitable for the technical field of materials, and provides a preparation method of lignite-derived carbon, lignite-derived carbon and sodium ion battery, comprising the following steps: carrying out microwave drying treatment on lignite powder to obtain dehydrated coal powder; and carrying out microwave pyrolysis treatment on the dehydrated coal dust, and calcining to obtain lignite-derived carbon. According to the application, the lignite is subjected to microwave drying and microwave pyrolysis treatment, and the whole coal particle material can be heated rapidly and uniformly by utilizing microwave irradiation, so that the heat transfer resistance is eliminated, the local overheating is prevented, and the lignite is effectively upgraded; meanwhile, due to the fact that the dielectric loss factors of coal-based materials are different, the characteristic that selective heating of substances can be achieved through microwave heating is achieved, and removal and retention of specific substances are achieved through control of microwave temperature and time parameters, so that high-purity lignite-derived carbon is stably produced. In addition, when the lignite-derived carbon obtained by the method is applied to a sodium ion battery, high initial capacity, high initial coulombic efficiency and strong capacity stability can be provided.
Description
Technical Field
The application belongs to the technical field of materials, and particularly relates to a preparation method of lignite-derived carbon and a lignite-derived carbon and sodium ion battery.
Background
Lignite has a large amount of humic acid and a small amount of mineral substances, the fixed carbon content of the lignite is low, the lignite in each area is greatly different from each other due to geological influence, and the lignite is required to be purified in the pretreatment process. The humic acid is a complex mixture colloid composed of macromolecule hydroxyl and carboxylic acid, the basic structural units are condensed aromatic rings and aliphatic groups, tar, coal gas and the like can be generated by pyrolysis in heat treatment, a large number of defects can be generated by carbon deposit, the carbon deposit is converted into glass carbon, and high-quality hard carbon cannot be prepared. The mineral substances are silicate components, contain sulfur, phosphorus and other impurity elements, have an obstacle to the growth of carbon microcrystals during later sintering, and are harmful to battery circulation. Thus, the pretreatment and purification process and equipment options have complexity.
The existing preparation method of the lignite-based derived carbon is mainly to prepare a coal-based hard carbon material by blending waste plastics with lignite for co-thermal conversion, and the carbon microcrystal and pore structure are regulated and controlled by blending waste plastics with coal for co-carbonization, so that the interlayer spacing of graphite microcrystals is improved, the specific capacity is about 250mAh/g-360mAh/g, and the initial coulombic efficiency is kept at 75-85%.
However, the first coulombic efficiency of commercial sodium ion derived carbon materials has reached about 85-92% and the specific capacity is up to 350mAh/g. Therefore, the existing lignite-based derived carbon preparation technology cannot meet the requirements of derived carbon materials required by sodium ion batteries, and has the problems of low specific capacity and low initial coulombic efficiency. On the basis of the advantages of abundant lignite resources and low cost, the development of the preparation technology research and development of the sodium ion battery coal-based derived carbon material is significant.
Disclosure of Invention
The embodiment of the application aims to provide a preparation method of lignite-derived carbon, which aims to solve the problems that the existing lignite-based derived carbon preparation technology cannot meet the requirements of derived carbon materials required by sodium ion batteries, and has low specific capacity and low initial coulomb efficiency.
The embodiment of the application is realized in such a way that the preparation method of the lignite-derived carbon comprises the following steps:
carrying out microwave drying treatment on lignite powder to obtain dehydrated coal powder; the drying temperature is 60-150deg.C, and the drying time is 30-120min;
carrying out microwave pyrolysis treatment on the dehydrated coal dust, and calcining to obtain lignite-derived carbon; the pyrolysis temperature is 300-700 ℃, and the pyrolysis time is 30-240min.
Another object of the embodiment of the present application is a lignite derived carbon, which is prepared by the above method for preparing lignite derived carbon.
Another object of an embodiment of the application is a sodium ion battery comprising the lignite-derived carbon described above.
According to the preparation method of the lignite derived carbon, disclosed by the embodiment of the application, the lignite is subjected to microwave drying and microwave pyrolysis treatment, and the whole coal particle material can be quickly and uniformly heated by utilizing microwave irradiation, so that the heat transfer resistance is eliminated, the local overheating is prevented, and the lignite is effectively upgraded; meanwhile, due to the fact that the dielectric loss factors of coal-based materials are different, the characteristic that selective heating of substances can be achieved through microwave heating is achieved, and removal and retention of specific substances are achieved through control of microwave temperature and time parameters, so that high-purity lignite-derived carbon is stably produced. In addition, when the lignite-derived carbon obtained by the method is applied to a sodium ion battery, high initial capacity, high initial coulombic efficiency and strong capacity stability can be provided.
Drawings
FIG. 1 is an SEM image of lignite-derived carbon provided according to example 1 of the present application;
FIG. 2 is an XRD pattern for lignite derived carbon as provided in example 1 of the present application;
fig. 3 is a graph of the first charge and discharge of the sodium ion battery provided in example 1 of the present application;
FIG. 4 is an SEM image of lignite derived carbon provided by comparative example 1 of the present application;
fig. 5 is a graph of the first charge and discharge of the sodium ion battery provided in comparative example 1 of the present application;
FIG. 6 is an SEM image of lignite derived carbon provided by comparative example 2 of the present application;
fig. 7 is a graph showing the first charge and discharge of the sodium ion battery provided in comparative example 2 of the present application;
FIG. 8 is an SEM image of lignite derived carbon provided by comparative example 3 of the present application;
fig. 9 is a graph of the first charge and discharge of the sodium ion battery provided in comparative example 3 of the present application;
FIG. 10 is an SEM image of lignite derived carbon provided by comparative example 4 of the present application;
fig. 11 is a graph of the first charge and discharge of the sodium ion battery provided in comparative example 4 of the present application.
Detailed Description
The present application will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The embodiment of the application provides a preparation method of lignite-derived carbon, which aims to solve the problems that the existing lignite-based derived carbon preparation technology cannot meet the requirements of derived carbon materials required by sodium ion batteries, has low specific capacity and low initial coulomb efficiency, and can be used for quickly and uniformly heating the whole coal particle materials by utilizing microwave irradiation through microwave drying and microwave pyrolysis treatment of lignite, eliminating heat transfer resistance, preventing local overheating and realizing the effective quality improvement of lignite; meanwhile, due to the fact that the dielectric loss factors of coal-based materials are different, the characteristic that selective heating of substances can be achieved through microwave heating is achieved, and removal and retention of specific substances are achieved through control of microwave temperature and time parameters, so that high-purity lignite-derived carbon is stably produced. In addition, when the lignite-derived carbon obtained by the method is applied to a sodium ion battery, high initial capacity, high initial coulombic efficiency and strong capacity stability can be provided.
Specifically, the preparation method of the lignite-derived carbon comprises the following steps:
carrying out microwave drying treatment on lignite powder to obtain dehydrated coal powder; the drying temperature is 60-150deg.C, and the drying time is 30-120min;
carrying out microwave pyrolysis treatment on the dehydrated coal dust, and calcining to obtain lignite-derived carbon; the pyrolysis temperature is 300-700 ℃, and the pyrolysis time is 30-240min.
In the embodiment of the application, the microwave drying process parameters (including the drying temperature and the drying time) have a significant influence on the yield and the electrochemical performance of the obtained lignite-derived carbon, the higher the drying temperature is, the longer the time is, the higher the carbon yield is and the better the electrochemical performance is, but when the drying temperature is higher than 120 ℃, the water in the lignite is further removed, but when the subsequent microwave pyrolysis treatment and calcination treatment are carried out, the mutual reaction impurity removal process of water molecules and impurities is restrained to a certain extent, so that the electrochemical performance of the lignite-derived carbon is reduced, therefore, the drying temperature is preferably 120 ℃, and the drying time is preferably 120min.
In the embodiment of the application, the microwave pyrolysis process parameters (including pyrolysis temperature and pyrolysis time) have obvious influence on the yield and electrochemical performance of the obtained lignite-derived carbon, and the quality of the lignite-derived carbon is gradually reduced along with the rise of the pyrolysis time and the pyrolysis temperature, and the reduced quality is mainly caused by the decomposition of free acid and low-molecular fatty chain substances; when the free acid and the fatty chain substance are lost, the carbon yield tends to be stable, and the electrochemical performance of the sodium ion battery is improved, wherein the improvement is caused by the loss of a huge amount of defects caused by the free acid, and the coulombic efficiency is improved; when the pyrolysis temperature is too low, impurities such as free acid in dehydrated coal dust cannot be removed well, a large number of defects are generated finally, sodium ions can be well embedded (specific capacity is high), but coulomb efficiency is low (generated SEI film) and commercial application cannot be met; when the pyrolysis temperature is too high, impurities such as free acid in dehydrated coal dust can be further removed and even completely removed, and in the case, the blockage of impurity elements to graphitization is absent, so that the coal dust is sintered into graphitized soft carbon, sodium ions cannot be effectively embedded, the capacity of a sodium ion battery is reduced, and the coulomb efficiency is also reduced. Accordingly, the pyrolysis temperature is preferably 300℃and the pyrolysis time is preferably 120 to 180 minutes. More preferably, the pyrolysis time is preferably 120min.
In the embodiment of the application, in the microwave drying treatment and the microwave pyrolysis treatment, the microwave output frequency is 0.433 GHz-2.45 GHz. The microwave output frequency is mainly three kinds of frequencies of 0.433GHz/0.915GHz/2.45GHz in industry, and the main influence of the microwave output frequency is as follows: the high microwave output frequency (2.45 GHz) can enable the microwave heating speed to be higher and the response speed to be higher; the small microwave output frequency (0.433 GHz/0.915 GHz) is slow in heating speed, but the penetration depth is large, so that the low microwave output frequency is selected for large materials. The application uses lignite powder (particle size is 100-500 meshes), so that the microwave output frequency is preferably 2.45GHz, and the microwave frequency can rapidly remove impurity components and improve the production efficiency.
In the embodiment of the application, in the calcination treatment, the calcination temperature is 1200-1600 ℃ and the calcination time is 60-240min. The definition of the calcination temperature and calcination time parameters can be determined by referring to the conventional technology in the art, and the following specific examples are only given by taking 1500 ℃ and 2 hours as examples, and should not limit the scope of the present application.
In the embodiment of the application, before the lignite powder is subjected to microwave drying treatment to obtain dehydrated coal dust, the method comprises the following steps:
ball milling the brown coal until the grain size is 100-500 meshes to obtain brown coal powder.
In the embodiment of the present application, the microwave pyrolysis treatment is performed on the dehydrated coal dust, and after the calcination treatment, lignite derived carbon is obtained, including:
placing the dehydrated coal powder in a pyrolysis atmosphere for microwave pyrolysis treatment to obtain purified coal powder; the pyrolysis atmosphere comprises one or more of argon, nitrogen, oxygen and ammonia.
And (3) placing the purified coal dust in an argon atmosphere for calcining and carbonizing treatment to obtain lignite-derived carbon.
The embodiment of the application also provides a sodium ion battery, namely, the lignite derived carbon prepared by the preparation method is applied to the sodium ion battery.
Specifically, when the modified carbon sheet is applied to sodium ion batteries, brown coal derived carbon, carbon black, sodium carboxymethylcellulose (CMC) and styrene butadiene latex (SBR) are prepared into slurry according to mass ratios (50:20:20:10) - (97:1:1:1) and coated on copper foil to obtain the modified carbon sheet. The mass ratio of the lignite derived carbon, the carbon black, the sodium carboxymethyl cellulose (CMC) and the styrene-butadiene latex (SBR) can be determined according to actual requirements and conventional technologies in the art, and the following examples are that the mass ratio of the lignite derived carbon, the carbon black, the sodium carboxymethyl cellulose (CMC) and the styrene-butadiene latex (SBR) is 94:1.5:1.5:3 are given as examples, and should not be construed as limiting the scope of the application.
Specific examples of certain embodiments of the application are given below and are not intended to limit the scope of the application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1: lignite derived carbon prepared by microwave impurity removal process and application of lignite derived carbon to sodium ion battery
1) Ball milling 50g of lignite in a mechanical ball mill to obtain pulverized coal, wherein the particle size of the pulverized coal is 100-500 meshes;
2) Placing the coal powder obtained in the step 1) into a microwave drying oven for pretreatment to obtain dehydrated coal powder, wherein the weight of the dehydrated coal powder is 35g; the pretreatment method comprises the following steps: microwave output frequency: 2.45GHz, drying temperature: drying at 120deg.C for 120min;
3) Placing the dehydrated coal powder obtained in the step 2) into a microwave sintering furnace for pyrolysis under a certain atmosphere to obtain purified coal powder, wherein the weight of the purified coal powder is 23g, and the pyrolysis parameters are as follows: microwave output frequency: 2.45GHz, pyrolysis temperature: pyrolysis time is 120min at 300 ℃; the pyrolysis atmosphere is argon;
4) And (3) heating the purified coal powder obtained in the step (3) to 1500 ℃ under argon atmosphere, carbonizing for 2 hours to obtain lignite derived carbon, wherein the weight of the lignite derived carbon is 14.5g.
SEM morphology observation and XRD test were carried out on the lignite derived carbon prepared in example 1, and the test results are shown in FIGS. 1-2.
According to mass ratio 94:1.5:1.5:3, preparing slurry by using lignite derived carbon, carbon black, CMC and SBR, and coating the slurry on a copper foil to obtain a derived carbon pole piece; and taking the derivative carbon pole piece as a negative electrode of the sodium ion battery, and assembling the battery in a glove box filled with argon, wherein the derivative carbon pole piece, glass fiber and sodium piece are respectively used as a working electrode, a diaphragm and a counter electrode. A conventional electrolyte (100 μl) was added to each cell. The conventional electrolyte is a mixed solvent of EC and DMC (1:1, v/v). After the assembly is completed and the material is static for 8 hours at 25 ℃, when the material is subjected to charge-discharge circulation between 0.01V and 2.5V at the rate of 0.1C, the initial discharge specific capacity can reach 312.78mAh/g, and the initial cycle coulomb efficiency can reach 90.67 percent (as shown in figure 3). The results demonstrate that the lignite derived carbon prepared in the examples of the present application can provide sodium ion batteries with high initial capacity and high first-turn coulombic efficiency.
Example 2: preparation of lignite-derived carbon under different microwave drying process parameters and application of lignite-derived carbon to sodium ion battery
1) Ball milling 50g of lignite in a mechanical ball mill to obtain pulverized coal, wherein the particle size of the pulverized coal is 100-500 meshes;
2) Placing the coal powder obtained in the step 1) into a microwave drying oven for pretreatment to obtain dehydrated coal powder; the pretreatment method comprises the following steps: microwave output frequency: 2.45GHz, the drying temperature is 60 ℃/80 ℃/100 ℃/110 ℃/120 ℃ and the drying time is 60min/120min respectively;
3) Placing the dehydrated coal powder obtained in the step 2) into a microwave sintering furnace for pyrolysis under a certain atmosphere to obtain purified coal powder, wherein the pyrolysis parameters are as follows: microwave output frequency: 2.45GHz, pyrolysis temperature: pyrolysis time is 120min at 300 ℃; the pyrolysis atmosphere is argon;
4) And (3) heating the purified coal powder obtained in the step (3) to 1500 ℃ under the argon atmosphere, and carbonizing for 2 hours to obtain lignite derived carbon.
According to mass ratio 94:1.5:1.5:3, preparing slurry by using lignite derived carbon, carbon black, CMC and SBR, and coating the slurry on a copper foil to obtain a derived carbon pole piece; and taking the derivative carbon pole piece as a negative electrode of the sodium ion battery, and assembling the battery in a glove box filled with argon, wherein the derivative carbon pole piece, glass fiber and sodium piece are respectively used as a working electrode, a diaphragm and a counter electrode. A conventional electrolyte (100 μl) was added to each cell. The conventional electrolyte is a mixed solvent of EC and DMC (1:1, v/v). After completion of the assembly, the test was carried out at a rate of 0.1C for 8 hours at a rest time of 25℃and a charge-discharge cycle was carried out between 0.01V and 2.5V, and the corresponding test results are shown in Table 1.
TABLE 1 influence of Brown coal derived carbon preparation and application on sodium ion batteries under different microwave drying process parameters (temperature and time)
From table 1, it is clear that the higher the temperature and the longer the time, the lower the quality of the brown coal after drying, and the higher the carbon yield, because the moisture gradually volatilizes and the lower the water content, and the lower the loss of the substance by the reaction between carbon and water during the subsequent high-temperature calcination, and the higher the carbon yield. In addition, when the moisture in the lignite is regulated and controlled, the performance of the sodium ion battery is fluctuated and bent, which shows that the existence of the moisture in the lignite has a certain influence on the production of lignite-derived carbon, and the higher the moisture content is, the lower the coulomb efficiency is. This example shows that when dried at 120 ℃ for 120min, the lignite is able to obtain better performance and the cell exhibits higher initial specific capacity. When the drying temperature is further increased (> 120 ℃), water in the lignite is further removed, but when the subsequent steps are pyrolyzed and sintered, the mutual reaction of water molecules and impurities and impurity removal steps are suppressed to a certain extent; meanwhile, the temperature is higher, and the production cost is also higher.
Example 3: preparation of lignite-derived carbon under different microwave pyrolysis processes and application of lignite-derived carbon to sodium ion battery
1) Ball milling 50g of lignite in a mechanical ball mill to obtain pulverized coal, wherein the particle size of the pulverized coal is 100-500 meshes;
2) Placing the coal powder obtained in the step 1) into a microwave drying oven for pretreatment to obtain dehydrated coal powder, wherein the weight of the dehydrated coal powder is 35g; the pretreatment method comprises the following steps: microwave output frequency: 2.45GHz, drying temperature: drying at 120deg.C for 120min;
3) Placing the dehydrated coal powder obtained in the step 2) into a microwave sintering furnace for pyrolysis under a certain atmosphere to obtain purified coal powder, wherein the pyrolysis parameters are as follows: microwave output frequency: 2.45GHz, wherein the pyrolysis temperature is respectively 200 ℃/300 ℃/400 ℃/500 ℃/600 ℃ and the pyrolysis time is respectively 60min/120min/180min; the pyrolysis atmosphere is argon;
4) And (3) heating the purified coal powder obtained in the step (3) to 1500 ℃ under the argon atmosphere, and carbonizing for 2 hours to obtain lignite derived carbon.
According to mass ratio 94:1.5:1.5:3, preparing slurry by using lignite derived carbon, carbon black, CMC and SBR, and coating the slurry on a copper foil to obtain a derived carbon pole piece; and taking the derivative carbon pole piece as a negative electrode of the sodium ion battery, and assembling the battery in a glove box filled with argon, wherein the derivative carbon pole piece, glass fiber and sodium piece are respectively used as a working electrode, a diaphragm and a counter electrode. A conventional electrolyte (100 μl) was added to each cell. The conventional electrolyte is a mixed solvent of EC and DMC (1:1, v/v). After completion of the assembly, the test was carried out at a rate of 0.1C for 8 hours at a rest time of 25℃and a charge-discharge cycle was carried out between 0.01V and 2.5V, and the corresponding test results are shown in Table 2.
TABLE 2 influence of Brown coal derived carbon preparation and application on sodium ion batteries at different microwave pyrolysis process parameters (temperature and time)
From Table 2, it can be seen that as pyrolysis time and pyrolysis temperature rise, the quality gradually declines, and the decline quality is mainly caused by decomposition of free acid and low-molecular fatty chain substances; when free acid and fatty chain materials are lost, the carbon yield tends to be stable, and the electrochemical performance of the sodium ion battery is improved. The reason for the improvement is that the mass defect caused by the free acid is lost, and the coulomb efficiency is improved; when the pyrolysis temperature is too low, impurities such as free acid in dehydrated coal dust cannot be removed well, a large number of defects are generated finally, sodium ions can be well embedded (specific capacity is high), but coulomb efficiency is low (generated SEI film) and commercial application cannot be met; when the pyrolysis temperature is too high, impurities such as free acid in dehydrated coal dust can be further removed and even completely removed, and in the case, the obstruction of impurity elements to graphitization is absent, so that the coal dust is sintered into graphitized soft carbon, sodium ions cannot be effectively embedded, therefore, the capacity of a sodium ion battery is reduced, and the coulomb efficiency is also reduced.
Comparative example 1: preparation of lignite-derived carbon without microwave drying and application of lignite-derived carbon to sodium ion battery
1) Ball milling 50g of lignite in a mechanical ball mill to obtain pulverized coal, wherein the particle size of the pulverized coal is 100-500 meshes;
2) Placing the pulverized coal obtained in the step 1) in a microwave sintering furnace for pyrolysis under an argon atmosphere to obtain purified pulverized coal, wherein the weight of the purified pulverized coal is 14g, and the pyrolysis parameters are as follows: microwave output frequency: 2.45GHz, pyrolysis temperature: pyrolysis time is 120min at 300 ℃; the pyrolysis atmosphere is argon;
3) And (3) heating the purified coal powder obtained in the step (2) to 1500 ℃ under the argon atmosphere, carbonizing for 2 hours to obtain lignite derived carbon, wherein the weight of the lignite derived carbon is 10g.
SEM morphology observation is carried out on the lignite derived carbon prepared in comparative example 1, and the test results are shown in FIG. 4.
According to mass ratio 94:1.5:1.5:3, preparing slurry by using lignite derived carbon, carbon black, CMC and SBR, and coating the slurry on a copper foil to obtain a derived carbon pole piece; and taking the derivative carbon pole piece as a negative electrode of the sodium ion battery, and assembling the battery in a glove box filled with argon, wherein the derivative carbon pole piece, glass fiber and sodium piece are respectively used as a working electrode, a diaphragm and a counter electrode. A conventional electrolyte (100 μl) was added to each cell. The conventional electrolyte is a mixed solvent of EC and DMC (1:1, v/v). After the assembly is completed and the material is static for 8 hours at 25 ℃, when the material is subjected to charge-discharge circulation between 0.01V and 2.5V at the rate of 0.1C, the initial discharge specific capacity can reach 298.71mAh/g, and the initial cycle coulomb efficiency is 54.2 percent (as shown in figure 5).
From the above results, it can be seen that comparative example 1 was not subjected to the microwave drying for water removal, and the brown coal-derived carbon yield was lowered due to volatilization of gas-forming substances generated by the reaction of water with the carbon component of the pulverized coal at high temperature. At the same time, battery performance is also affected.
Comparative example 2: brown coal derived carbon prepared by thermal drying and application thereof in sodium ion battery
1) Ball milling 50g of lignite in a mechanical ball mill to obtain pulverized coal, wherein the particle size of the pulverized coal is 100-500 meshes;
2) Placing the coal powder obtained in the step 1) into a blast drying box for pretreatment to obtain dehydrated coal powder, wherein the weight of the dehydrated coal powder is 41g; the pretreatment method comprises the following steps: drying temperature: drying at 120deg.C for 120min;
3) Placing the dehydrated coal powder obtained in the step 2) into a microwave sintering furnace for pyrolysis under a certain atmosphere to obtain purified coal powder, wherein the weight of the purified coal powder is 21g, and the pyrolysis parameters are as follows: microwave output frequency: 2GHz, pyrolysis temperature: pyrolysis time is 120min at 300 ℃; the pyrolysis atmosphere is argon;
4) And (3) heating the purified coal powder obtained in the step (3) to 1500 ℃ under argon atmosphere, carbonizing for 2 hours to obtain lignite derived carbon, wherein the weight of the lignite derived carbon is 12g.
SEM morphology observation is carried out on the lignite derived carbon prepared in comparative example 2, and the test results are shown in FIG. 6.
According to mass ratio 94:1.5:1.5:3, preparing slurry by using lignite derived carbon, carbon black, CMC and SBR, and coating the slurry on a copper foil to obtain a derived carbon pole piece; and taking the derivative carbon pole piece as a negative electrode of the sodium ion battery, and assembling the battery in a glove box filled with argon, wherein the derivative carbon pole piece, glass fiber and sodium piece are respectively used as a working electrode, a diaphragm and a counter electrode. A conventional electrolyte (100 μl) was added to each cell. The conventional electrolyte is a mixed solvent of EC and DMC (1:1, v/v). After the assembly is completed and the material is static for 8 hours at 25 ℃, when the material is subjected to charge-discharge circulation between 0.01V and 2.5V at the rate of 0.1C, the initial discharge specific capacity can reach 278.23mAh/g, and the initial cycle coulomb efficiency is 79 percent (as shown in figure 7).
From the above results, it can be seen that comparative example 2 has a problem of insufficient drying degree, insufficient uniformity of heating, incomplete water removal, and gas loss by reaction with the pulverized coal carbon component in the subsequent reaction, compared with the microwave drying treatment by the thermal drying treatment. Therefore, the carbon yield decreases, and the battery performance deteriorates.
Comparative example 3: preparation of lignite-derived carbon without microwave pyrolysis and application of lignite-derived carbon to sodium ion battery
1) Ball milling 50g of lignite in a mechanical ball mill to obtain pulverized coal, wherein the particle size of the pulverized coal is 100-500 meshes;
2) Placing the coal powder obtained in the step 1) into a microwave drying oven for pretreatment to obtain dehydrated coal powder, wherein the weight of the dehydrated coal powder is 35g; the pretreatment method comprises the following steps: microwave output frequency: 2.5GHz, drying temperature: drying at 120deg.C for 120min;
3) And (3) heating the dehydrated coal powder obtained in the step (2) to 1500 ℃ under the argon atmosphere, carbonizing for 2 hours to obtain lignite derived carbon, wherein the weight of the lignite derived carbon is 13g.
SEM morphology observation is carried out on the lignite derived carbon prepared in comparative example 3, and the test results are shown in FIG. 8.
According to mass ratio 94:1.5:1.5:3, preparing slurry by using lignite derived carbon, carbon black, CMC and SBR, and coating the slurry on a copper foil to obtain a derived carbon pole piece; and taking the derivative carbon pole piece as a negative electrode of the sodium ion battery, and assembling the battery in a glove box filled with argon, wherein the derivative carbon pole piece, glass fiber and sodium piece are respectively used as a working electrode, a diaphragm and a counter electrode. A conventional electrolyte (100 μl) was added to each cell. The conventional electrolyte is a mixed solvent of EC and DMC (1:1, v/v). After the assembly is completed and the material is static for 8 hours at 25 ℃, when the material is subjected to charge-discharge circulation between 0.01V and 2.5V at the rate of 0.1C, the initial discharge specific capacity can reach 182.11mAh/g, and the initial cycle coulomb efficiency is 75.41 percent (as shown in figure 9).
From the above results, it can be obtained that the addition of the microwave pyrolysis process can effectively purify the pulverized coal, remove impurities, and prepare high-quality derived carbon, so that the prepared sodium ion battery has high initial capacity and first-coil coulomb efficiency.
Comparative example 4: direct carbonization for preparing lignite derived carbon and application of direct carbonization to sodium ion battery
1) Ball milling 50g of lignite in a mechanical ball mill to obtain pulverized coal, wherein the particle size of the pulverized coal is 100-500 meshes;
2) And (3) heating the pulverized coal obtained in the step (1) to 1500 ℃ under the argon atmosphere for carbonization, wherein the carbonization time is 2 hours, and the lignite-derived carbon is obtained, and the weight of the lignite-derived carbon is 9.5g.
SEM morphology observation is carried out on the lignite derived carbon prepared in comparative example 4, and the test results are shown in FIG. 10.
According to mass ratio 94:1.5:1.5:3, preparing slurry by using lignite derived carbon, carbon black, CMC and SBR, and coating the slurry on a copper foil to obtain a derived carbon pole piece; and taking the derivative carbon pole piece of the derivative carbon pole piece as a negative electrode of the sodium ion battery, and assembling the battery in a glove box filled with argon, wherein the derivative carbon pole piece, the glass fiber and the sodium piece are respectively used as a working electrode, a diaphragm and a counter electrode. A conventional electrolyte (100 μl) was added to each cell. The conventional electrolyte is a mixed solvent of EC and DMC (1:1, v/v). After the assembly is completed and the material is static for 8 hours at 25 ℃, when the material is subjected to charge-discharge circulation between 0.01V and 2.5V at the rate of 0.1C, the initial discharge specific capacity can reach 180.38mAh/g, and the initial cycle coulomb efficiency can reach 71.07 percent (as shown in figure 11).
In summary, the embodiment of the application prepares high-quality lignite-derived carbon by screening proper microwave parameters for microwave purification of lignite and obtains good electrochemical performance when applied to sodium ion batteries, and the main advantages are as follows: (1) The deep dehydration of lignite can be realized by microwave drying, so that the thermal decomposition loss of carbon in pyrolysis and sintering is effectively reduced, and high carbon yield is realized; (2) The microwave pyrolysis enables humic acid and low aromatic compounds in the lignite to be cracked according to the selective heating characteristic and catalytic effect of microwaves, so that the purposes of carbon fixation and harmful substance cracking are achieved, and finally, a high-quality lignite-derived carbon material is prepared, and high-performance sodium ion battery application is realized; (3) According to the application, the microwave impurity removal technology is applied to lignite production of derived carbon for the first time and applied to sodium ion batteries, and high-quality production of the derived carbon is realized by exploring different technological parameters, so that the application of the lignite-based carbon material in the sodium ion batteries is filled.
It will be evident to those skilled in the art that the application is not limited to the details of the foregoing illustrative embodiments, and that the present application may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. A method for preparing lignite-derived carbon, comprising:
carrying out microwave drying treatment on lignite powder to obtain dehydrated coal powder; the drying temperature is 60-150deg.C, and the drying time is 30-120min;
carrying out microwave pyrolysis treatment on the dehydrated coal dust, and calcining to obtain lignite-derived carbon; the pyrolysis temperature is 300-700 ℃, and the pyrolysis time is 30-240min.
2. The method for preparing lignite-derived carbon according to claim 1, wherein the drying temperature is 120 ℃ and the drying time is 120min.
3. The method for preparing lignite derived carbon according to claim 1, wherein the pyrolysis temperature is 300 ℃ and the pyrolysis time is 120-180min.
4. The method for preparing lignite-derived carbon according to claim 1, wherein in the microwave drying treatment and the microwave pyrolysis treatment, the microwave output frequency is 0.433GHz to 2.45GHz.
5. The method for producing lignite-derived carbon according to claim 1, wherein the microwave output frequency in the microwave drying process and the microwave pyrolysis process is 2.45GHz.
6. The method for producing lignite-derived carbon according to claim 1, wherein in the calcination treatment, the calcination temperature is 1200 to 1600 ℃ and the calcination time is 60 to 240min.
7. The method for preparing lignite-derived carbon according to claim 1, wherein before said subjecting lignite powder to microwave drying treatment, it comprises:
ball milling the brown coal until the grain size is 100-500 meshes to obtain brown coal powder.
8. The method for preparing lignite-derived carbon according to claim 1, wherein the step of subjecting the dehydrated pulverized coal to microwave pyrolysis treatment and calcining treatment to obtain lignite-derived carbon comprises:
placing the dehydrated coal powder in a pyrolysis atmosphere for microwave pyrolysis treatment to obtain purified coal powder; the pyrolysis atmosphere comprises one or more of argon, nitrogen, oxygen and ammonia;
and (3) placing the purified coal dust in an argon atmosphere for calcining and carbonizing treatment to obtain lignite-derived carbon.
9. A lignite derived carbon, characterized in that it is produced by the method for producing lignite derived carbon according to any one of claims 1-8.
10. A sodium ion battery comprising the lignite-derived carbon of claim 9.
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