CN116715239A - Coal-based porous sodium ion battery hard carbon negative electrode material and preparation method thereof - Google Patents
Coal-based porous sodium ion battery hard carbon negative electrode material and preparation method thereof Download PDFInfo
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- CN116715239A CN116715239A CN202310515172.1A CN202310515172A CN116715239A CN 116715239 A CN116715239 A CN 116715239A CN 202310515172 A CN202310515172 A CN 202310515172A CN 116715239 A CN116715239 A CN 116715239A
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- 239000003245 coal Substances 0.000 title claims abstract description 81
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 50
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 37
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 40
- 239000002817 coal dust Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 26
- 239000010405 anode material Substances 0.000 claims abstract description 22
- 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 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000004021 humic acid Substances 0.000 claims abstract description 20
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 20
- 239000011592 zinc chloride Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000003213 activating effect Effects 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 9
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003830 anthracite Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000009656 pre-carbonization Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002802 bituminous coal Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003077 lignite Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003415 peat Substances 0.000 claims description 2
- 239000003476 subbituminous coal Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 16
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 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
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- 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
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- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a hard carbon negative electrode material of a coal-based porous sodium ion battery and a preparation method thereof, wherein the preparation method comprises the following steps: (1) grinding coal raw materials to obtain coal powder; (2) Pre-carbonizing coal powder to obtain carbonized coal powder; (3) Mixing carbonized coal dust with humic acid, then adding zinc chloride, and stirring and mixing to obtain a mixed material; (4) Heating and activating the mixed material to obtain activated coal dust; (5) Carrying out acid washing treatment on activated coal dust, and then washing and drying the activated coal dust; (6) And (3) carrying out heat treatment on the dried material in the step (5) to obtain the hard carbon anode material. The hard carbon anode material prepared by the preparation method has uniform pores and increased coal seam spacing, is used as an anode material of a sodium ion battery, ensures that the battery has high first coulomb efficiency and good cycle stability, and has simple preparation process, lower cost and environmental friendliness.
Description
Technical Field
The invention relates to the technical field of sodium ion battery anode materials, in particular to a coal-based porous sodium ion battery hard carbon anode material and a preparation method thereof.
Background
With the development of society, the shortage of energy resources and the environmental problems brought by fossil energy are highly valued, and the development of new energy storage materials is urgent. The lithium ion battery is a preferred renewable energy storage material for people due to higher energy density, and is rapidly developed, but the long-term requirement of people for energy is difficult to meet due to the limited content of lithium element in the crust. The sodium element and the lithium element are in the same main group, the chemical properties are similar, the energy storage mechanism is similar, and the production and the manufacture of the sodium ion battery can directly utilize the production equipment and the design experience of the existing lithium ion battery, thereby being beneficial to the rapid production and the application of the sodium ion battery. The sodium element is the element with the sixth content on the earth, is distributed in the global scope, and has the characteristics of rich raw material resources, low price, higher specific capacitance and the like. Because the ionic radius and relative atomic mass of sodium ions are greater than those of lithium ions, rapid migration of sodium ions in the electrode material and electrolyte is detrimental, resulting in a lower energy density of the sodium ion battery than that of the lithium ion battery. Therefore, sodium ion batteries are more suitable for application in large-scale energy storage fields where energy density requirements are not particularly high.
Hard carbon is one of the main application materials of the negative electrode of the sodium ion battery. The microstructure of the hard carbon is amorphous carbon with long-range disorder and short-range order, and the structural characteristics are favorable for ion or electron transmission, and have good application prospect in lithium ion or sodium ion batteries. For hard carbon materials, modification treatment is generally performed by changing the morphology and adjusting the pore structure. The pore structure comprises porosity and pore size distribution, the pore structure greatly influences the performance of the hard carbon material, and activation is one of effective methods for improving the sodium storage performance of the hard carbon.
As a known technology, the nano-sized and porous treatment on the hard carbon negative electrode material can improve gram capacity performance, however, the nano-sized and porous structure can inevitably introduce certain defects at the same time. For example, in chinese patent CN 114906836A, anthracite and diethanolamine are mixed at a suitable temperature and pressure, and the melted diethanolamine can effectively penetrate into the micropores of the anthracite, and then the pore-forming agent in the micropores of the anthracite is directly heated and cracked from solid state, so as to generate a large amount of gas, and increase the size of the micropores. However, the above method has a disadvantage in that the pore-forming agent in a molten state is difficult to uniformly disperse in coal in mass production, and the pore size is difficult to control. Also, for example, in chinese patent CN 112645305A, pores are produced by physical/chemical activation in advance, and then a preset pore structure is used to inhibit the long-range development of crystallites in anthracite during high-temperature carbonization, so as to obtain a hard carbon material with a short-range ordered graphite-like crystal structure. The method has the advantages of adding the preactivation step, prolonging the preparation time, increasing the energy consumption in the preparation process, along with complex process, high cost and being unfavorable for mass production.
Disclosure of Invention
In view of the above problems, the invention aims to provide a coal-based porous sodium ion battery hard carbon negative electrode material and a preparation method thereof, wherein the prepared hard carbon negative electrode material has uniform pores and increased coal seam spacing, and is used as a negative electrode material of a sodium ion battery, so that the battery has high first coulombic efficiency and good cycle stability.
In order to achieve the above purpose, the invention provides a preparation method of a hard carbon anode material of a coal-based porous sodium ion battery, which comprises the following steps:
(1) Grinding the coal raw material to obtain coal powder;
(2) Pre-carbonizing coal powder to obtain carbonized coal powder;
(3) Mixing carbonized coal dust with humic acid, then adding zinc chloride, and stirring and mixing to obtain a mixed material;
(4) Heating and activating the mixed material to obtain activated coal dust;
(5) Carrying out acid washing treatment on activated coal dust, and then washing and drying the activated coal dust;
(6) And (3) carrying out heat treatment on the dried material in the step (5) to obtain the hard carbon anode material.
Compared with the prior art, the preparation method of the coal-based porous sodium ion battery hard carbon negative electrode material comprises the steps of adding humic acid for crosslinking and zinc chloride for activation, hydrolyzing phosphate groups in the humic acid and reacting with carbon at high temperature, so that pores mainly comprising micropores are formed by coal activation, and the pores are uniform in size, so that uniform pores are prepared; after humic acid heat treatment, the humic acid is crosslinked to generate steric hindrance, so that the microcrystalline interlayer spacing is improved, and the coal seam spacing is increased; the inhibition effect of humic acid crosslinking on graphitization is favorable for forming a short-range ordered and long-range disordered structure, is more favorable for storing sodium ions, ensures that hydrogen and oxygen atoms in coal are separated out in a water vapor form to form a large number of pores by catalytic dehydration, and then removes the zinc chloride by acid washing, so that the hard carbon material with a short-range ordered graphite crystal structure with larger interlayer spacing, uniform holes and developed pores is obtained.
In some embodiments, in step (1), the coal feedstock is selected from at least one of anthracite, bituminous coal, subbituminous coal, lignite, peat.
In some embodiments, in step (1), the particle size of the pulverized coal is controlled to be 200 mesh to 400 mesh, and as an example, the particle size of the pulverized coal may be, but is not limited to, 200 mesh, 240 mesh, 280 mesh, 300 mesh, 350 mesh, 380 mesh, 400 mesh. It will be appreciated that grinding the coal material into a fine powder facilitates the subsequent uniformity of dispersion, and the specific grinding mode may be, but is not limited to, crushing the coal material and then treating it with an air flow mill.
In some embodiments, in step (2), the pre-carbonization treatment is carried out in an inert atmosphere and the treatment temperature is 500-800 ℃, preferably 600 ℃, with subsequent activation being facilitated by pre-carbonization.
In some embodiments, in step (3), the mass ratio of coal dust to humic acid is 1-10:1, further, the amount of coal dust is larger than the amount of humic acid, the mass ratio of coal dust to humic acid is 2-10:1, still further, the mass ratio of coal dust to humic acid is 2-8:1, as an example, the mass ratio of coal dust to humic acid can be but not limited to 2:1,4:1,5:1,6:1,8:1.
In some embodiments, in step (3), the mass ratio of the pulverized coal to the zinc chloride is 1-10:1, further, the amount of the pulverized coal is larger than the amount of the zinc chloride, the mass ratio of the pulverized coal to the zinc chloride is 2-10:1, still further, the mass ratio of the pulverized coal to the zinc chloride is 2-8:1, and as an example, the mass ratio of the pulverized coal to the zinc chloride can be, but is not limited to, 2:1,4:1,5:1,6:1,8:1.
In some embodiments, after the coal fines are mixed with humic acid, a suitable dispersant may be added to enhance the dispersion.
In some embodiments, in step (4), the temperature of the activation treatment is 400-900 ℃, preferably 600 ℃.
In some embodiments, in step (5), the acid-washing treatment is performed with at least one acid selected from sulfuric acid, hydrochloric acid, hydrofluoric acid, and nitric acid, and by way of example, the acid-washing treatment is performed with a mixture of hydrochloric acid and hydrofluoric acid.
In some embodiments, in step (5), the temperature of the acid wash treatment is 60-90 ℃, preferably 80 ℃.
In some embodiments, in step (6), the heat treatment is performed at a temperature of 1200-1500 ℃, preferably 1400 ℃, and in an inert atmosphere.
Correspondingly, the invention also provides a coal-based porous sodium ion battery hard carbon negative electrode material, which is prepared by adopting the preparation method of the coal-based porous sodium ion battery hard carbon negative electrode material.
The coal-based porous sodium ion battery hard carbon anode material has the following technical effects:
(1) According to the preparation method, humic acid crosslinking and zinc chloride are adopted for activation, part of oxygen-containing groups are pyrolyzed to form gas pore-forming, the pore size is concentrated in micropores, and the holes are uniform, so that industrial mass production is facilitated;
(2) The preparation method adopts humic acid crosslinking and zinc chloride for activation, the required temperature is low, the process is simple, and the energy consumption is saved;
(3) The method disclosed by the invention is simple, low in cost and environment-friendly, and the obtained coal-based hard carbon material has the characteristics of high compaction density, high first reversible capacity and first coulomb efficiency, and excellent processability and cycle stability.
Drawings
Fig. 1 is an SEM image of a hard carbon anode material prepared in example 1 of the present invention.
Fig. 2 is a charge-discharge graph of the hard carbon negative electrode materials prepared in examples 1 to 3 and comparative example 1 according to the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
A preparation method of a coal-based porous sodium ion battery hard carbon anode material comprises the following steps:
(1) Grinding: sequentially crushing and air-stream grinding anthracite raw materials to obtain refined coal powder, and controlling the particle size of the coal powder to be 300 meshes;
(2) Pre-carbonization: placing pulverized coal in a box furnace, carbonizing in an inert atmosphere, performing constant temperature treatment at 600 ℃ for 3 hours, naturally cooling to room temperature, and removing volatile matters to obtain carbonized pulverized coal;
(3) Mixing: carbonizing coal dust and humic acid according to a proportion of 5:1 into deionized water solution, adding a small amount of dispersant sodium dodecyl benzene sulfonate, heating to 70 ℃, stirring for 30min, drying, and then adding zinc chloride (the mass ratio of coal powder to zinc chloride is 5:1) into the mixture, and mechanically stirring to obtain a mixed material;
(4) Activating: activating the mixed material at 600 ℃ for 2 hours to obtain activated coal dust;
(5) Removing impurities and drying: carrying out acid washing treatment on activated coal powder by adopting a hydrochloric acid and hydrofluoric acid mixed solution, stirring for 10 hours at the constant temperature of 80 ℃, then carrying out water washing treatment to be neutral to obtain a washed product, and then carrying out drying treatment;
(6) And (3) heat treatment: and (3) carrying out high-temperature heat treatment on the dried material in the step (5) for 3 hours at 1400 ℃ in an inert atmosphere, naturally cooling to room temperature, and sieving with a 325-mesh screen to obtain a finished product, namely the hard carbon anode material.
Example 2
A preparation method of a coal-based porous sodium ion battery hard carbon anode material comprises the following steps:
(1) Grinding: sequentially crushing and jet milling the bituminous coal raw material to obtain refined coal powder, and controlling the particle size of the coal powder to be 350 meshes;
(2) Pre-carbonization: placing pulverized coal in a box furnace, carbonizing in an inert atmosphere, performing constant temperature treatment at 600 ℃ for 3 hours, naturally cooling to room temperature, and removing volatile matters to obtain carbonized pulverized coal;
(3) Mixing: carbonizing coal dust and humic acid according to a ratio of 2:1 into deionized water solution, adding a small amount of dispersant sodium dodecyl benzene sulfonate, heating to 70 ℃, stirring for 30min, drying, and then adding zinc chloride (the mass ratio of coal powder to zinc chloride is 5:1) into the mixture, and mechanically stirring to obtain a mixed material;
(4) Activating: activating the mixed material at 600 ℃ for 2 hours to obtain activated coal dust;
(5) Removing impurities and drying: carrying out acid washing treatment on activated coal powder by adopting a hydrochloric acid and hydrofluoric acid mixed solution, stirring for 10 hours at the constant temperature of 80 ℃, then carrying out water washing treatment to be neutral to obtain a washed product, and then carrying out drying treatment;
(6) And (3) heat treatment: and (3) carrying out high-temperature heat treatment on the dried material in the step (5) for 3 hours at 1400 ℃ in an inert atmosphere, naturally cooling to room temperature, and sieving with a 325-mesh screen to obtain a finished product, namely the hard carbon anode material.
Example 3
A preparation method of a coal-based porous sodium ion battery hard carbon anode material comprises the following steps:
(1) Grinding: sequentially crushing and air-stream grinding anthracite raw materials to obtain refined coal powder, and controlling the particle size of the coal powder to be 300 meshes;
(2) Pre-carbonization: placing pulverized coal in a box furnace, carbonizing in an inert atmosphere, performing constant temperature treatment at 600 ℃ for 3 hours, naturally cooling to room temperature, and removing volatile matters to obtain carbonized pulverized coal;
(3) Mixing: carbonizing coal dust and humic acid according to the proportion of 8:1 into deionized water solution, adding a small amount of dispersant sodium dodecyl benzene sulfonate, heating to 70 ℃, stirring for 30min, drying, and then adding zinc chloride (the mass ratio of coal powder to zinc chloride is 5:1) into the mixture, and mechanically stirring to obtain a mixed material;
(4) Activating: activating the mixed material at 600 ℃ for 2 hours to obtain activated coal dust;
(5) Removing impurities and drying: carrying out acid washing treatment on activated coal powder by adopting a hydrochloric acid and hydrofluoric acid mixed solution, stirring for 10 hours at the constant temperature of 80 ℃, then carrying out water washing treatment to be neutral to obtain a washed product, and then carrying out drying treatment;
(6) And (3) heat treatment: and (3) carrying out high-temperature heat treatment on the dried material in the step (5) for 3 hours at 1400 ℃ in an inert atmosphere, naturally cooling to room temperature, and sieving with a 325-mesh screen to obtain a finished product, namely the hard carbon anode material.
Comparative example 1
A preparation method of a coal-based porous sodium ion battery hard carbon anode material comprises the following steps:
(1) Grinding: sequentially crushing and air-stream grinding anthracite raw materials to obtain refined coal powder, and controlling the particle size of the coal powder to be 300 meshes;
(2) Pre-carbonization: placing pulverized coal in a box furnace, carbonizing in an inert atmosphere, performing constant temperature treatment at 600 ℃ for 3 hours, naturally cooling to room temperature, and removing volatile matters to obtain carbonized pulverized coal;
(3) Mixing: mixing carbonized coal powder with zinc chloride according to a ratio of 5:1, mixing the materials in a mass ratio, and mechanically stirring the materials to obtain a mixed material;
(4) Activating: activating the mixed material at 600 ℃ for 2 hours to obtain activated coal dust;
(5) Removing impurities and drying: carrying out acid washing treatment on activated coal powder by adopting a hydrochloric acid and hydrofluoric acid mixed solution, stirring for 10 hours at the constant temperature of 80 ℃, then carrying out water washing treatment to be neutral to obtain a washed product, and then carrying out drying treatment;
(6) And (3) heat treatment: and (3) carrying out high-temperature heat treatment on the dried material in the step (5) for 3 hours at 1400 ℃ in an inert atmosphere, naturally cooling to room temperature, and sieving with a 325-mesh screen to obtain a finished product, namely the hard carbon anode material.
Fig. 1 shows an SEM image of the hard carbon anode material prepared in example 1. As can be seen from fig. 1, the hard carbon anode material has a large number of pores.
Fig. 2 shows charge and discharge graphs of the hard carbon anode materials prepared in examples 1 to 3 and comparative example 1. As can be seen from FIG. 2, the specific capacity of the first discharge in comparative example 1 was 260mAh/g, and the specific capacity of the first discharge in examples 1-3 was 290mAh/g or more, even reached 310mAh/g, and the charging was fast and the capacitance was large.
The hard carbon negative electrode materials prepared in examples 1 to 3 and comparative example 1 were subjected to the relevant performance test, and the results thereof are shown in table 1.
Table 1 test results
As can be seen from the results in table 1, the hard carbon negative electrode materials of examples 1 to 3 according to the present invention have a better reversible capacity and a higher first coulombic efficiency than those of comparative example 1, and can reduce the occurrence of side reactions during the first charge and discharge process, thereby providing a battery with a high first coulombic efficiency and good cycle stability.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the coal-based porous sodium ion battery hard carbon anode material is characterized by comprising the following steps:
(1) Grinding the coal raw material to obtain coal powder;
(2) Pre-carbonizing coal powder to obtain carbonized coal powder;
(3) Mixing carbonized coal dust with humic acid, then adding zinc chloride, and stirring and mixing to obtain a mixed material;
(4) Heating and activating the mixed material to obtain activated coal dust;
(5) Carrying out acid washing treatment on activated coal dust, and then washing and drying the activated coal dust;
(6) And (3) carrying out heat treatment on the dried material in the step (5) to obtain the hard carbon anode material.
2. The method for preparing a hard carbon negative electrode material of a coal-based porous sodium ion battery according to claim 1, wherein in the step (1), the coal raw material is at least one selected from anthracite, bituminous coal, subbituminous coal, lignite and peat.
3. The method for preparing a hard carbon negative electrode material of a coal-based porous sodium ion battery according to claim 1, wherein in the step (1), the particle size of pulverized coal is controlled to be 200-400 meshes.
4. The method for preparing a hard carbon negative electrode material for a coal-based porous sodium ion battery according to claim 1, wherein in the step (2), the pre-carbonization treatment is performed in an inert atmosphere and the treatment temperature is 500-800 ℃.
5. The method for preparing the hard carbon negative electrode material of the coal-based porous sodium ion battery, according to claim 1, wherein in the step (3), the mass ratio of coal dust to humic acid is 1-10:1, and the mass ratio of coal dust to zinc chloride is 1-10:1.
6. The method for preparing a hard carbon negative electrode material of a coal-based porous sodium ion battery according to claim 1, wherein in the step (4), the activation treatment temperature is 400-900 ℃.
7. The method for producing a hard carbon negative electrode material for a coal-based porous sodium ion battery according to claim 1, wherein in the step (5), the acid treated by the acid washing is at least one selected from sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid.
8. The method for preparing a hard carbon negative electrode material for a coal-based porous sodium ion battery according to claim 1, wherein in the step (5), the temperature of the acid washing treatment is 60-90 ℃.
9. The method for preparing a hard carbon negative electrode material for a coal-based porous sodium ion battery according to claim 1, wherein in the step (6), the heat treatment is performed at a temperature of 1200 to 1500 ℃ in an inert atmosphere.
10. The hard carbon negative electrode material of the coal-based porous sodium ion battery, which is characterized by being prepared by adopting the preparation method of the hard carbon negative electrode material of the coal-based porous sodium ion battery as claimed in any one of claims 1 to 9.
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| CN104817082A (en) * | 2015-05-22 | 2015-08-05 | 安徽工业大学 | Method for preparing nitrogen-enriched porous carbon material for supercapacitor by taking lignite as raw material |
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