CN117361496A - Sodium ion battery hard carbon negative electrode material with high compaction density and low specific surface area and preparation method thereof - Google Patents
Sodium ion battery hard carbon negative electrode material with high compaction density and low specific surface area and preparation method thereof Download PDFInfo
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- CN117361496A CN117361496A CN202311393498.8A CN202311393498A CN117361496A CN 117361496 A CN117361496 A CN 117361496A CN 202311393498 A CN202311393498 A CN 202311393498A CN 117361496 A CN117361496 A CN 117361496A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 71
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 39
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 25
- 238000005056 compaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007833 carbon precursor Substances 0.000 claims abstract description 60
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- 238000003763 carbonization Methods 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 230000003213 activating effect Effects 0.000 claims abstract description 21
- 238000007493 shaping process Methods 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 239000010426 asphalt Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 15
- 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
- 238000003801 milling Methods 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011294 coal tar pitch Substances 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 239000011295 pitch Substances 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- 239000003570 air Substances 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 235000009496 Juglans regia Nutrition 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920005546 furfural resin Polymers 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 238000003701 mechanical milling Methods 0.000 claims description 3
- 239000011306 natural pitch Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 235000014571 nuts Nutrition 0.000 claims description 3
- 239000011301 petroleum pitch Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000011318 synthetic pitch Substances 0.000 claims description 3
- 239000011271 tar pitch Substances 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- 240000007049 Juglans regia Species 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 230000004913 activation Effects 0.000 abstract description 12
- 239000012528 membrane Substances 0.000 description 12
- 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 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000004080 punching Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 241000758789 Juglans Species 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000011549 displacement method Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Abstract
The invention discloses a sodium ion battery hard carbon negative electrode material with high compaction density and low specific surface area and a preparation method thereof, wherein the preparation method comprises the following steps: s1, pre-carbonizing a carbon source: placing a carbon source in a low-temperature carbonization furnace, and performing low-temperature sintering pretreatment in a protective gas atmosphere to obtain a carbon precursor; s2, crushing and shaping: ball-crushing and shaping the carbon precursor to obtain a spherical carbon precursor; s3, activating and preparing a porous spherical carbon precursor: introducing an activating gas into the spherical carbon precursor for activation, so as to obtain a Kong Qiuxing carbon precursor; s4, melting and coating a carbon intermediate: performing heat treatment on the mixture of the porous spherical carbon precursor and the asphalt under the stirring condition to obtain a carbon intermediate; s5, high-temperature carbonization: and (3) placing the carbon intermediate in a high-temperature carbonization furnace, and performing high-temperature sintering in a protective gas atmosphere to obtain the sodium ion battery negative electrode hard carbon material. The invention has the characteristics of high compaction density, small specific surface area, high first coulomb efficiency and excellent processability.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a hard carbon negative electrode material of a sodium ion battery with high compaction density and low specific surface area and a preparation method thereof.
Background
In recent years, the price fluctuation of the raw materials of the lithium ion battery is large, the advantages of wide resource distribution, low price and the like of the sodium ion battery are gradually highlighted, and the lithium ion battery is taken as a technical route for replacing the lithium ion battery, and industrialization enters a rapid development stage.
The hard carbon negative electrode material has the advantages of wide sources, abundant resources, high sodium storage capacity, low sodium storage potential and the like, and is proved to be the sodium storage negative electrode material with the most commercial application prospect.
Hard carbon materials are typically obtained by high temperature heat treatment of an organic precursor in a protective gas atmosphere. In the pyrolysis process, the carbon precursor material is decomposed to release volatile gas, and the released gas forms pores in the hard carbon material, so that the hard carbon material has higher specific surface area, higher porosity and lower volume density, and the problems of low compaction density, low initial cycle coulomb efficiency, poor cycle performance and the like of the hard carbon material are caused; and the irregular morphology causes the rupture of the current collector under the high compaction condition, so that the safety problems of internal short circuit, thermal runaway, fire explosion and the like of the battery are caused.
Disclosure of Invention
The invention aims to provide a sodium ion battery hard carbon negative electrode material with high compaction density and low specific surface area and a preparation method thereof, and the sodium ion battery hard carbon negative electrode material has the characteristics of high compaction density, small specific surface area, high initial coulombic efficiency and excellent processability.
The invention can be realized by the following technical scheme:
the invention discloses a preparation method of a hard carbon negative electrode material of a sodium ion battery with high compaction density and low specific surface area, which comprises the following steps:
s1, pre-carbonizing a carbon source: placing a carbon source in a low-temperature carbonization furnace, and performing low-temperature sintering pretreatment in a protective gas atmosphere to obtain a carbon precursor;
s2, crushing and shaping: ball crushing and shaping are carried out on the carbon precursor obtained in the step S1, so as to obtain a spherical carbon precursor;
s3, activating and preparing a porous spherical carbon precursor: introducing an activating gas into the spherical carbon precursor obtained in the step S2 to activate the spherical carbon precursor to obtain a Kong Qiuxing carbon precursor;
s4, melting and coating a carbon intermediate: performing heat treatment on the mixture of the porous spherical carbon precursor and asphalt obtained in the step S3 under the stirring condition to obtain a carbon intermediate;
s5, high-temperature carbonization: and (3) placing the carbon intermediate obtained in the step (S4) into a high-temperature carbonization furnace, and performing high-temperature sintering in a protective gas atmosphere to obtain the sodium ion battery negative electrode hard carbon material.
Further, in step S1, the carbon source is one or more of wood dust powder, walnut shell powder, coffee shell powder, nut shell powder, wheat straw powder, phenolic resin, epoxy resin, furfural resin, glucose, sucrose, and starch.
Further, in step S1, the conditions for the pretreatment are: the temperature rising rate is 5-20 ℃/min, the pretreatment temperature is 250-900 ℃, and the pretreatment time is 2-5 h; the shielding gas is nitrogen and/or argon. In the present invention, the pre-carbonization temperature affects the effect of the present invention. Specifically, if the pretreatment temperature is too low and the carbon source is not completely cracked, the cracking can be continued to generate volatile gas in the high-temperature carbonization process, and the effect of the invention can not be achieved; if the treatment temperature is too high, the graphitization degree of the carbon precursor is too high, which is unfavorable for the subsequent activation reaction.
Further, in the step S2, the crushing adopts one or more of ball milling, air flow milling, vibration milling and/or mechanical milling, D50 of the crushed carbon material is 4.5-12 μm, and Dmax is less than or equal to 30 μm.
Further, in the step S2, the shaping time of the shaping machine is 5-60 min; the frequency is 10-40H.
Further, in step S3, the activating gas includes at least one of air, oxygen, carbon dioxide and steam, the activating temperature is 450-800 ℃, and the activating time is 1-3 h. In step S3, the closed microporous structure formed in the carbonization process is opened to form a pore structure communicated with the outside, so that the pitch can penetrate into the pores inside the carbon material in the subsequent melting and cladding process. In the present invention, the activation temperature and activation time affect the effect of the present invention. Specifically, if the activation temperature and activation time are too low, the carbon layer blocking the micropores inside the carbon material cannot be sufficiently etched, so that the pitch cannot penetrate into the pores inside the carbon material in the subsequent melt-coating process. If the activation temperature and activation time are too high, the carbon layer in the carbon material is excessively etched, resulting in too low a material yield.
Further, in step S4, the pitch comprises at least one of natural pitch, petroleum pitch, coal tar pitch, ethylene tar pitch, synthetic pitch, or heavy aromatics; the addition amount of the asphalt is 1-10% of the addition mass of the porous carbon precursor.
Further, in step S4, the coating temperature is 100 to 600 ℃; the coating treatment time is 10-180 min; the stirring speed is 5-100 HZ.
Further, in step S5, the conditions for high temperature sintering are: the temperature rising rate is 0.5-10 ℃/min, the carbonization temperature is 1000-1600 ℃, and the carbonization time is 2-10 h. In the present invention, the high temperature sintering temperature also affects the structure and performance of the hard carbon material. Specifically, if the high-temperature sintering temperature is insufficient, the graphitization degree of the hard carbon material is low, and sodium ions cannot be effectively stored; too high a carbonization temperature will result in too narrow an interlayer spacing of the carbon layers in the hard carbon material, which is detrimental to sodium ion migration in the hard carbon material, affecting the electrochemical properties of the hard carbon material.
The invention also provides a hard carbon negative electrode material of a sodium ion battery, which is prepared by the preparation method.
The sodium ion battery hard carbon negative electrode material with high compaction density and low specific surface area and the preparation method thereof have the following beneficial effects:
firstly, the compaction density is high, the true density of the hard carbon material is improved by filling asphalt into micropores in the hard carbon material, the bulk density of hard carbon particles can be effectively improved by sphericizing the hard carbon, the purpose of improving the compaction density of the hard carbon is achieved, and the volume energy density of the sodium ion battery is further improved;
the second and first week coulomb efficiency is high, and the invention can reduce the specific surface area of the carbon material by penetrating the molten asphalt into the pores inside the hard carbon material, thereby improving the first week coulomb efficiency of the hard carbon material;
thirdly, the processing performance is excellent, the processing performance of the hard carbon material in the preparation process of the sodium ion battery cathode can be improved by the spherical shape, the production efficiency is further improved, and the production cost is reduced; and the current collector breakage caused by irregular morphology due to excessive compaction is avoided, and the safety performance of the battery is improved.
Drawings
FIG. 1 is an SEM image of practical example 1;
fig. 2 is an SEM image of comparative example 1.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following further details of the present invention will be described with reference to examples and drawings.
The invention discloses a preparation method of a hard carbon negative electrode material of a sodium ion battery with high compaction density and low specific surface area, which comprises the following steps:
s1, pre-carbonizing a carbon source: placing a carbon source in a low-temperature carbonization furnace, and performing low-temperature sintering pretreatment in a protective gas atmosphere to obtain a carbon precursor;
s2, crushing and shaping: ball crushing and shaping are carried out on the carbon precursor obtained in the step S1, so as to obtain a spherical carbon precursor;
s3, activating and preparing a porous spherical carbon precursor: introducing an activating gas into the spherical carbon precursor obtained in the step S2 to activate the spherical carbon precursor to obtain a Kong Qiuxing carbon precursor;
s4, melting and coating a carbon intermediate: performing heat treatment on the mixture of the porous spherical carbon precursor and asphalt obtained in the step S3 under the stirring condition to obtain a carbon intermediate;
s5, high-temperature carbonization: and (3) placing the carbon intermediate obtained in the step (S4) into a high-temperature carbonization furnace, and performing high-temperature sintering in a protective gas atmosphere to obtain the sodium ion battery negative electrode hard carbon material.
Further, in step S1, the carbon source is one or more of wood dust powder, walnut shell powder, coffee shell powder, nut shell powder, wheat straw powder, phenolic resin, epoxy resin, furfural resin, glucose, sucrose, and starch.
Further, in step S1, the conditions for the pretreatment are: the temperature rising rate is 5-20 ℃/min, the pretreatment temperature is 250-900 ℃, and the pretreatment time is 2-5 h; the shielding gas is nitrogen and/or argon.
Further, in the step S2, the crushing adopts one or more of ball milling, air flow milling, vibration milling and/or mechanical milling, D50 of the crushed carbon material is 4.5-12 μm, and Dmax is less than or equal to 30 μm.
Further, in the step S2, the shaping time of the shaping machine is 5-60 min; the frequency is 10-40 HZ.
Further, in step S3, the activating gas includes at least one of air, oxygen, carbon dioxide and steam, the activating temperature is 450-800 ℃, and the activating time is 1-3 h.
Further, in step S4, the pitch comprises at least one of natural pitch, petroleum pitch, coal tar pitch, ethylene tar pitch, synthetic pitch, or heavy aromatics; the addition amount of the asphalt is 1-10% of the addition mass of the porous carbon precursor.
Further, in step S4, the coating temperature is 100 to 600 ℃; the coating treatment time is 10-180 min; the stirring speed is 5-100 HZ.
Further, in step S5, the conditions for high temperature sintering are: the temperature rising rate is 0.5-10 ℃/min, the carbonization temperature is 1000-1600 ℃, and the carbonization time is 2-10 h.
Application example 1
The embodiment discloses a preparation method of a hard carbon negative electrode material of a sodium ion battery with high compaction density and low specific surface area, which comprises the following steps:
s1, pre-carbonizing a carbon source: and (3) placing the phenolic resin in a low-temperature carbonization furnace, heating to 600 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a carbon precursor.
S2, crushing and shaping: grinding the carbon precursor in the step S1 by a jet mill until the D50 is 5.5 mu m and Dmax is less than or equal to 25 mu m; shaping for 30min at 15 HZ frequency by using a shaper to obtain spherical carbon precursor.
S3, activating porous spherical carbon: and (3) activating the spherical carbon precursor in the step (S2) in a carbon dioxide atmosphere, wherein the activation temperature is 500 ℃, and the activation time is 2h, so that the spherical carbon precursor is Kong Qiuxing carbon precursor.
S4, melting and coating a carbon intermediate: and (3) performing heat treatment on the mixture of the porous spherical carbon precursor and the coal tar pitch in the step (S3) under the stirring condition of 20 and HZ to obtain a carbon intermediate. Wherein the addition amount of the asphalt is 5% of the mass of the carbon precursor, the heat treatment temperature is 500 ℃, and the heat treatment time is 30min.
S5, high-temperature carbonization: and (3) placing the carbon intermediate obtained in the step (S4) into a high-temperature carbonization furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, and preserving heat for 2h to obtain the sodium ion battery negative electrode hard carbon material.
The resulting material was subjected to electrochemical performance testing according to the following method: after the S-doped hard carbon material, super P, CMC and SBR are mixed into homogenate according to the mass ratio of 94:1.5:2:2.5, a 120 um four-side preparation machine is used for coating black paste on copper foil, and then the film is dried in a vacuum drying oven at 100 ℃ for 2 hours. And (3) punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, taking metal sodium as a counter electrode, taking 1mol/L NaClO4EC+DEC (1:1vol%) as electrolyte, and assembling the membrane into the CR2016 type button cell in a glove box, wherein the membrane is a PP/PE/PP three-layer membrane. The button cell was subjected to constant current charge and discharge test at a current density of 0.1C (1c=300 mAh/g) and a voltage range of 2 to 0.005V.
Comparative example 1
The embodiment discloses a preparation method of a hard carbon negative electrode material of a high-sodium ion battery, which comprises the following steps:
s1, pre-carbonizing a carbon source: and (3) placing the phenolic resin in a low-temperature carbonization furnace, heating to 600 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a carbon precursor.
S2, crushing: and (3) grinding the carbon precursor obtained in the step S1 by using a jet mill until the D50 is 5.5 mu m and the Dmax is less than or equal to 20 mu m, so as to obtain the ground carbon precursor.
S3, high-temperature carbonization: and (2) placing the crushed carbon precursor obtained in the step (S2) into a high-temperature carbonization furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, and preserving heat for 2h to obtain the sodium ion battery negative electrode hard carbon material.
The resulting material was subjected to electrochemical performance testing according to the following method: after the S-doped hard carbon material, super P, CMC and SBR are mixed into homogenate according to the mass ratio of 94:1.5:2:2.5, a 120 um four-side preparation machine is used for coating black paste on copper foil, and then the film is dried in a vacuum drying oven at 100 ℃ for 2 hours. And (3) punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, taking metal sodium as a counter electrode, taking 1mol/L NaClO4EC+DEC (1:1vol%) as electrolyte, and assembling the membrane into the CR2016 type button cell in a glove box, wherein the membrane is a PP/PE/PP three-layer membrane. The button cell was subjected to constant current charge and discharge test at a current density of 0.1C (1c=300 mAh/g) and a voltage range of 2 to 0.005V.
Application example 2
The embodiment discloses a preparation method of a hard carbon negative electrode material of a sodium ion battery with high compaction density and low specific surface area, which comprises the following steps:
s1, pre-carbonizing a carbon source: and (3) placing the wood chips in a low-temperature carbonization furnace, heating to 650 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a carbon precursor.
S2, crushing and shaping: grinding the carbon precursor in the step S1 by a jet mill until the D50 is 5.5 mu m and Dmax is less than or equal to 25 mu m; shaping for 40min at 15 HZ frequency by using a shaper to obtain spherical carbon precursor.
S3, activating porous spherical carbon: and (3) activating the spherical carbon precursor in the step (S2) in a carbon dioxide atmosphere, wherein the activation temperature is 550 ℃, and the activation time is 2h, so that the spherical carbon precursor is Kong Qiuxing carbon precursor.
S4, melting and coating a carbon intermediate: and (3) performing heat treatment on the mixture of the porous spherical carbon precursor and the coal tar pitch in the step (S3) under the stirring condition of 20 and HZ to obtain a carbon intermediate. Wherein the addition amount of the asphalt is 7% of the mass of the carbon precursor, the heat treatment temperature is 500 ℃, and the heat treatment time is 30min.
S5, high-temperature carbonization: and (3) placing the carbon intermediate obtained in the step (S4) into a high-temperature carbonization furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, and preserving heat for 2h to obtain the sodium ion battery negative electrode hard carbon material.
The resulting material was subjected to electrochemical performance testing according to the following method: after the S-doped hard carbon material, super P, CMC and SBR are mixed into homogenate according to the mass ratio of 94:1.5:2:2.5, a 120 um four-side preparation machine is used for coating black paste on copper foil, and then the film is dried in a vacuum drying oven at 100 ℃ for 2 hours. And (3) punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, taking metal sodium as a counter electrode, taking 1mol/L NaClO4EC+DEC (1:1vol%) as electrolyte, and assembling the membrane into the CR2016 type button cell in a glove box, wherein the membrane is a PP/PE/PP three-layer membrane. The button cell was subjected to constant current charge and discharge test at a current density of 0.1C (1c=300 mAh/g) and a voltage range of 2 to 0.005V.
Comparative example 2
The embodiment discloses a preparation method of a hard carbon anode material of a sodium ion battery, which comprises the following steps:
s1, pre-carbonizing a carbon source: and (3) placing the wood chips in a low-temperature carbonization furnace, heating to 650 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a carbon precursor.
S2, crushing: and (3) grinding the carbon precursor obtained in the step S1 by using a jet mill until the D50 is 5.5 mu m and the Dmax is less than or equal to 15 mu m, so as to obtain the ground carbon precursor.
S3, high-temperature carbonization: and (2) placing the crushed carbon precursor obtained in the step (S2) into a high-temperature carbonization furnace, heating to 1300 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, and preserving heat for 2h to obtain the sodium ion battery negative electrode hard carbon material.
The resulting material was subjected to electrochemical performance testing according to the following method: after the S-doped hard carbon material, super P, CMC and SBR are mixed into homogenate according to the mass ratio of 94:1.5:2:2.5, a 120 um four-side preparation machine is used for coating black paste on copper foil, and then the film is dried in a vacuum drying oven at 100 ℃ for 2 hours. And (3) punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, taking metal sodium as a counter electrode, taking 1mol/L NaClO4EC+DEC (1:1vol%) as electrolyte, and assembling the membrane into the CR2016 type button cell in a glove box, wherein the membrane is a PP/PE/PP three-layer membrane. The button cell was subjected to constant current charge and discharge test at a current density of 0.1C (1c=300 mAh/g) and a voltage range of 2 to 0.005V. .
TABLE 1 Performance test results
Fig. 1 is an SEM image of the hard carbon material of application example 1, showing a spheroid-like morphology. Fig. 2 is an SEM image of the hard carbon material of comparative example 1, which shows an irregular morphology, hard carbon particles have significant corners, which affect the bulk density of the hard carbon material, and sharp corners cause the current collector to be split under high compaction conditions, thereby causing internal short circuit of the battery, which causes serious safety problems.
As shown in Table 1, the actual densities of the hard carbon materials in application example 1 and comparative example 1 were 1.95 and 1.88 g/cm3, respectively, as measured by the He gas displacement method; the hard carbon materials of application example 1 and comparative example 1 had compaction densities of 1.25 and 1.05 g/cm, respectively 3 The method comprises the steps of carrying out a first treatment on the surface of the The reversible specific capacity of the electrode of application example 1 is 325 mAh/g, and the first week coulomb efficiency is 93%; the reversible specific capacity of the electrode of comparative example 1 was only 302 mAh/g, and the first week coulombic efficiency was only 90%.
As shown in Table 1, the actual densities of the hard carbon materials in application example 2 and comparative example 2 were 1.92 and 1.83 g/cm3, respectively, as measured by the He gas displacement method; the hard carbon materials of application example 2 and comparative example 2 had compaction densities of 1.22 and 0.98 g/cm, respectively 3 The method comprises the steps of carrying out a first treatment on the surface of the The reversible specific capacity of the electrode of example 2 was 346 mAh/g and the first week coulombic efficiency was 92%; the reversible specific capacity of the electrode of comparative example 2 was only 317 mAh/g, and the first week coulombic efficiency was only 88%.
The root cause of the compaction density improvement of the application example 1 and the application example 2 is that the molten asphalt permeates into the gaps inside the hard carbon material in the process of molten cladding, so that the aim of improving the true density of the hard carbon material is fulfilled; on the other hand, the sphericizing treatment can further improve the stacking density of hard carbon particles, further improve the compaction density of hard carbon materials, and further effectively improve the volume energy density of the sodium ion battery. Meanwhile, the reversible specific capacity and the first effect of the embodiment 1 and the embodiment 2 are effectively improved, because the molten asphalt permeates into the gaps inside the hard carbon material in the process of melting and cladding, on one hand, the specific surface area of the hard carbon material is reduced, and therefore, the side reaction of the hard carbon material and electrolyte is reduced; on the other hand, some pores with larger pore diameters in the hard carbon material do not have the sodium storage capacity, and the carbon layer is used as an active site for sodium storage after the carbon layer is filled, so that the sodium storage capacity of the hard carbon material is improved.
The foregoing examples are merely exemplary embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and that these obvious alternatives fall within the scope of the invention.
Claims (10)
1. The preparation method of the hard carbon negative electrode material of the sodium ion battery with high compaction density and low specific surface area is characterized by comprising the following steps:
s1, pre-carbonizing a carbon source: placing a carbon source in a low-temperature carbonization furnace, and performing low-temperature sintering pretreatment in a protective gas atmosphere to obtain a carbon precursor;
s2, crushing and shaping: ball crushing and shaping are carried out on the carbon precursor obtained in the step S1, so as to obtain a spherical carbon precursor;
s3, activating and preparing a porous spherical carbon precursor: introducing an activating gas into the spherical carbon precursor obtained in the step S2 to activate the spherical carbon precursor to obtain a Kong Qiuxing carbon precursor;
s4, melting and coating a carbon intermediate: performing heat treatment on the mixture of the porous spherical carbon precursor and asphalt obtained in the step S3 under the stirring condition to obtain a carbon intermediate;
s5, high-temperature carbonization: and (3) placing the carbon intermediate obtained in the step (S4) into a high-temperature carbonization furnace, and performing high-temperature sintering in a protective gas atmosphere to obtain the sodium ion battery negative electrode hard carbon material.
2. The method for preparing the hard carbon negative electrode material of the sodium ion battery with high compacted density and low specific surface area according to claim 1, which is characterized by comprising the following steps: in the step S1, the carbon source is one or more of wood dust powder, walnut shell powder, coffee shell powder, nut shell powder, wheat straw powder, phenolic resin, epoxy resin, furfural resin, glucose, sucrose and starch.
3. The method for preparing the hard carbon negative electrode material of the sodium ion battery with high compacted density and low specific surface area according to claim 1, which is characterized by comprising the following steps: in step S1, the conditions for the pretreatment are: the temperature rising rate is 5-20 ℃/min, the pretreatment temperature is 250-900 ℃, and the pretreatment time is 2-5 h; the shielding gas is nitrogen and/or argon.
4. The method for preparing the hard carbon negative electrode material of the sodium ion battery with high compacted density and low specific surface area according to claim 1, which is characterized by comprising the following steps: in the step S2, the crushing adopts one or more of ball milling, air flow milling, vibration milling and/or mechanical milling, the D50 of the crushed carbon material is 4.5-12 μm, and Dmax is less than or equal to 30 μm.
5. The method for preparing the hard carbon negative electrode material of the sodium ion battery with high compacted density and low specific surface area according to claim 1, which is characterized by comprising the following steps: in the step S2, the shaping time of the shaping machine is 5-60 min; the frequency is 10-40 HZ.
6. The method for preparing the hard carbon negative electrode material of the sodium ion battery with high compacted density and low specific surface area according to claim 1, which is characterized by comprising the following steps: in step S3, the activating gas includes at least one of air, oxygen, carbon dioxide and water vapor, the activating temperature is 450-800 ℃, and the activating time is 1-3 h.
7. The method for preparing the hard carbon negative electrode material of the sodium ion battery with high compacted density and low specific surface area according to claim 1, which is characterized by comprising the following steps: in step S4, the pitch comprises at least one of natural pitch, petroleum pitch, coal tar pitch, ethylene tar pitch, synthetic pitch, or heavy aromatics; the addition amount of the asphalt is 1-10% of the addition mass of the porous carbon precursor.
8. The method for preparing the hard carbon negative electrode material of the sodium ion battery with high compacted density and low specific surface area according to claim 1, which is characterized by comprising the following steps: in the step S4, the coating temperature is 100-600 ℃; the coating treatment time is 10-180 min; the stirring speed is 5-100 HZ.
9. The method for preparing the hard carbon negative electrode material of the sodium ion battery with high compacted density and low specific surface area according to claim 1, which is characterized by comprising the following steps: in step S5, the conditions for high temperature sintering are: the temperature rising rate is 0.5-10 ℃/min, the carbonization temperature is 1000-1600 ℃, and the carbonization time is 2-10 h.
10. A hard carbon negative electrode material of a sodium ion battery, which is characterized by being prepared by the preparation method of any one of claims 1-9.
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