CN116395667A - Preparation method and application of hard carbon material - Google Patents
Preparation method and application of hard carbon material Download PDFInfo
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- CN116395667A CN116395667A CN202310386088.4A CN202310386088A CN116395667A CN 116395667 A CN116395667 A CN 116395667A CN 202310386088 A CN202310386088 A CN 202310386088A CN 116395667 A CN116395667 A CN 116395667A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 127
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010426 asphalt Substances 0.000 claims abstract description 107
- 238000000498 ball milling Methods 0.000 claims abstract description 90
- 239000000843 powder Substances 0.000 claims abstract description 50
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 42
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000003763 carbonization Methods 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 8
- 238000002203 pretreatment Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005922 Phosphane Substances 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000064 phosphane Inorganic materials 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011294 coal tar pitch Substances 0.000 claims 1
- 239000011306 natural pitch Substances 0.000 claims 1
- 239000011301 petroleum pitch Substances 0.000 claims 1
- 239000011295 pitch Substances 0.000 claims 1
- 238000010000 carbonizing Methods 0.000 abstract description 16
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 210000002381 plasma Anatomy 0.000 description 32
- 230000008569 process Effects 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 16
- 239000003208 petroleum Substances 0.000 description 12
- 239000011734 sodium 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 11
- 238000002156 mixing Methods 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000005087 graphitization Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
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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
- C01B32/05—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)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method and application of a hard carbon material, and the preparation method of the hard carbon material provided by the invention comprises the following steps: ball milling asphalt in a mechanical ball mill to obtain asphalt powder with the particle size of 100-500 meshes; the obtained asphalt powder is put into a plasma ball mill for pretreatment to obtain doped asphalt powder; the pretreatment method comprises the following steps: ball milling rotation speed is 900-1500rpm, and ball milling time is 1-6h; and (3) carbonizing the obtained doped asphalt powder at high temperature in argon atmosphere to obtain a hard carbon material, wherein the carbonization temperature is 1000-1500 ℃ and the carbonization time is 2-6h. The doping pretreatment of asphalt preparation hard carbon is carried out by adopting plasma ball milling, and doping elements and doping amount can be regulated and controlled by regulating and controlling plasma ball milling parameters, so that hard carbon is better produced, and higher initial capacity, higher first-turn charge-discharge efficiency and stronger capacity stability are provided for sodium ion batteries.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a preparation method and application of a hard carbon material.
Background
At present, asphalt is used as graphitized carbon precursor and has related research and application in the field of lithium ion battery negative electrode materials, however, when asphalt is used as graphitized carbon precursor and is directly pyrolyzed without pretreatment process, graphite is easily and directly generated, and the electrochemical performance of the hard carbon material applied to sodium ion batteries is affected.
To solve this problem, the prior art adopts pretreatment to modify asphalt, including modifier mixed asphalt (phenolic resin, etc.), oxidant mixed asphalt (sodium nitrate, etc.), biomass mixed asphalt (walnut shell, etc.), etc.; the asphalt is mixed by a series of doping means so as to change the structural evolution process of the asphalt during high-temperature carbonization. These conventional pretreatment means require a series of additional process operations, impurities are easily introduced by blending other substances with asphalt, and cannot be fully mixed with asphalt, and the graphitization of asphalt itself is not significantly inhibited, which ultimately results in uneven quality of hard carbon produced by asphalt.
The existing method for preparing hard carbon by modifying asphalt is still remained in solid-solid mixing and liquid-solid mixing, and the phenomenon of low product quality caused by non-uniformity and impurity doping cannot be solved. For example, the conventional solid mixing pretreatment technology (CN 114709408A) of biomass mixed asphalt has battery performance of only 265mAh/g and the first-turn charge-discharge efficiency of 83%, and the conventional liquid mixing pretreatment technology (CN 115676804A) of phenolic resin mixed asphalt has battery performance of only 315.3mAh/g and the first-turn charge-discharge efficiency of 82.4%. It can be seen that the existing asphalt modification pretreatment means is insufficient for preparing asphalt as a main material to be suitable for Na + 、K + 、Mg + The carbon material used by the battery, in particular the hard carbon material required by the sodium ion battery, has higher requirement, and the carbon material prepared by the conventional treatment means can not meet the requirement of the hard carbon material required by the sodium ion battery.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a hard carbon material.
The preparation method of the hard carbon material provided by the invention comprises the following steps:
step 1): ball milling asphalt in a mechanical ball mill to obtain asphalt powder with the particle size of 100-500 meshes;
step 2): placing the asphalt powder obtained in the step 1) into a plasma ball mill for pretreatment to obtain doped asphalt powder; the pretreatment method comprises the following steps: ball milling rotation speed is 900-1500rpm, and ball milling time is 1-6h; the atmosphere in the ball milling tank is one or more of argon, oxygen, nitrogen, ammonia, methane, phosphane, boron trichloride and hydrogen sulfide;
step 3): and (3) carrying out high-temperature carbonization on the doped asphalt powder obtained in the step (2) under the argon atmosphere to obtain the hard carbon material, wherein the carbonization temperature is 1000-1500 ℃ and the carbonization time is 2-6h.
Further, when the atmosphere in the ball milling tank is oxygen, the ball milling speed is 1000rpm, and the ball milling time is 6 hours.
Further, when the atmosphere in the ball milling tank is nitrogen, the ball milling speed is 1200rpm, and the ball milling time is 3 hours.
Further, the asphalt is one or more of petroleum asphalt, coal tar asphalt and natural asphalt.
The hard carbon material prepared by the preparation method provided by the invention is applied to sodium ion batteries.
Further, in the application in sodium ion batteries, the hard carbon material is prepared according to the following hard carbon: carbon black: CMC: sbr=94: 1.5:1.5:3, preparing slurry according to the proportion, and coating the slurry on a copper foil to obtain the hard carbon pole piece.
The beneficial effects of the invention are as follows:
1. the invention discovers that the key process for preparing the hard carbon material by asphalt adopts plasma ball milling for doping pretreatment, and the rotating speed and time of the plasma ball milling are related to the atmosphere adopted for doping.
The reduction of the crystallite size and the increase of the dislocation density of the asphalt during the plasma ball milling process can prevent graphitization of the asphalt during high-temperature pyrolysis. When the conventional method is adopted for production, due to the phenomenon of uneven mixing caused by a liquid mixing method and a solid mixing method, part of asphalt materials cannot be effectively doped, for example, the doping amount of hetero atoms is insufficient, asphalt is graphitized at high temperature to generate soft carbon, the doping amount is excessive, and asphalt can generate glass carbon. The gas mixing method can regulate and control doping elements and doping amount by regulating and controlling plasma ball milling parameters (such as ball milling speed, ball milling time and ball milling atmosphere), thereby better producing hard carbon and providing higher initial capacity, higher first-circle charge-discharge efficiency and stronger capacity stability for sodium ion batteries. For example, the sodium ion battery assembled by the hard carbon material prepared in the embodiment 1 has a first-cycle discharge specific capacity of 320mAh/g and a first-cycle charge-discharge efficiency of 92.9%.
2. By adjusting the doping process, the hard carbon material with better quality is obtained. For example, nitrogen atom doping can increase electron conductivity and provide more sodium active storage sites for hard carbon materials, sodium ion batteries will exhibit higher initial specific capacities; sulfur atom doping helps to increase the reversible capacity of the hard carbon material; phosphorus atom doping can expand the interlayer spacing of hard carbon, thereby increasing reversible capacity.
3. The pretreatment process provided by the invention, namely a plasma ball milling process, provides a method for stably preparing the hard carbon material by adjusting process parameters. The plasma ball milling technology can carry out the doped gas-solid reaction at normal temperature (the conventional liquid mixing method and the conventional solid mixing method can lead the materials to be successfully compounded only at 300-400 ℃ and the doping of elements to be successful). Therefore, the process has the advantages of reducing energy consumption and realizing industrial production, and does not need severe treatment conditions, thereby being an important mild modification mode.
4. The invention successfully realizes gas-solid doping by utilizing a plasma ball milling technology, realizes the doping content and the type of gas impurity in asphalt by parameter regulation, realizes the doping of impurity gas, further improves the battery performance of the asphalt when the sodium ion battery cathode is applied on the basis of inhibiting asphalt graphitization, and is the process technology most suitable for large-scale and industrialized production of hard carbon.
Drawings
FIG. 1 is an XRD pattern of the hard carbon material prepared in example 1;
FIG. 2 is a plot of the first specific capacity voltage of the sodium ion battery of example 1;
FIG. 3 is an SEM image of hard carbon materials prepared at various ion ball milling times in example 2;
FIG. 4 is an SEM image of a hard carbon material prepared in example 3;
fig. 5 is an SEM image of the hard carbon material prepared in comparative example 1.
Detailed Description
The invention is further illustrated by the following examples.
Example 1: the preparation method comprises the steps of performing hard carbon pretreatment and preparation by taking oxygen as a specific atmosphere, and applying the sodium ion battery.
1. Ball milling 50g petroleum asphalt in a mechanical ball mill to obtain asphalt powder, wherein the particle size of the asphalt powder is 200 meshes;
2. the asphalt powder obtained in the step 1) is put into a plasma ball mill to be pretreated under the oxygen atmosphere to obtain oxidized asphalt powder, the ball milling speed is 1000r, the ball milling time is 6h, and the doping amount of oxygen atoms is about 3.3%;
3. carbonizing the oxidized asphalt powder obtained in the step 2) at high temperature under argon atmosphere to obtain hard carbon material (refer to figure 1), wherein the carbonization temperature is 1400 ℃, the carbonization time is 2h, 34g of hard carbon is obtained, the yield is about 68%, and the pore volume is about 0.003cm 3 /g；
4. And (3) carbonizing the carbonized hard carbon material according to hard carbon: carbon black: CMC: sbr=94: 1.5:1.5:3, preparing slurry according to the proportion, and coating the slurry on a copper foil to obtain a hard carbon pole piece;
and (3) taking the hard 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 hard 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 assembly is static for 8 hours at 25 ℃, when the charge-discharge circulation is carried out between 0.01V and 2.5V at the rate of 0.1C, the specific capacity of the first-circle discharge can reach 320mAh/g; the first charge and discharge efficiency reaches 92.9% (refer to figure 2), and the reversible capacity is 297.3mAh/g.
The result shows that the hard carbon material manufactured by the method can provide high initial capacity, high first-turn charge and discharge efficiency and strong capacity stability for the sodium ion battery.
Example 2: sodium ion battery performance comparison under oxygen doping and different ion ball milling parameters
1. Ball milling 50g petroleum asphalt in a mechanical ball mill to obtain asphalt powder, wherein the particle size of the asphalt powder is 200 meshes;
2. the asphalt powder obtained in the step 1) is put into a plasma ball mill to be pretreated under the oxygen atmosphere to obtain oxidized asphalt powder, the ball milling rotating speed is 900-1500r, and the ball milling time is 1-6h (the plasma ball milling parameters are shown in the table 1);
3. carbonizing the oxidized asphalt powder obtained in the step 2) at a high temperature in an argon atmosphere to obtain a hard carbon material, wherein the carbonization temperature is 1400 ℃, and the carbonization time is 2 hours; FIG. 3 is an SEM image of hard carbon materials at 1000r ball mill times;
4. and (3) carbonizing the carbonized hard carbon material according to hard carbon: carbon black: CMC: sbr=94: 1.5:1.5:3, preparing slurry according to the proportion, and coating the slurry on a copper foil to obtain a hard carbon pole piece;
and (3) taking the hard 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 hard 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 completion of the assembly, the battery was allowed to stand at 25℃for 8 hours, and then charge and discharge cycles were carried out at a rate of 0.1℃between 0.01V and 2.5V.
Table 1 comparison of sodium ion battery performance under oxygen doping with different plasma ball milling parameters
By material characteristics and electrochemical properties under oxygen atmosphere and different plasma ball milling parameters, the following conclusion is drawn:
(1) The higher the ball milling speed is, the longer the ball milling time is, the smaller the particle size of the obtained pretreated asphalt is, and meanwhile, the higher the doping amount of oxygen atoms is contained. The reason is that the longer the ball milling time is, the smaller the particle size of asphalt is, the larger the relative specific surface area is, the larger the cross-linking doping area of oxygen atoms and asphalt is when plasma is impacted, and the larger the doping amount is; the higher the ball milling speed is, the higher the frequency and impact force of the bombarded asphalt are, the local heat energy is changed, and the easier the asphalt is crosslinked and compounded with oxygen atoms under the bombardment of plasmas, so that the higher the ball milling speed is, the larger the oxygen atom doping amount is.
(2) The doping amount of the oxygen content needs to be controlled, when the doping amount is low, the growth of graphite-like microcrystals cannot be inhibited, and when the doping amount is too high, amorphous glass carbon is easy to generate, so that defects are too many, and the first-ring coulomb efficiency of the sodium ion battery is low.
(3) From the design of changing the plasma ball milling parameters, when the ball milling is carried out until the particle size is about 8 mu m and the oxygen doping amount is 3.3%, the sodium ion battery with the first-circle specific capacity of 320mAh/g and the first-circle coulomb efficiency of 92.9% can be obtained. It can also be seen that a low oxygen doping level will result in a low first-turn specific capacity, since no graphitization is inhibited and sodium ions cannot be effectively intercalated; too high oxygen doping amount results in high first-ring specific capacity and low first-ring coulombic efficiency because high oxygen doping amount causes large defects in the extraction during high-temperature carbonization, which are capable of embedding sodium but require additional generation of more SEI film, resulting in low coulombic efficiency.
Example 3 hard carbon pretreatment and preparation, and sodium ion battery application were performed with nitrogen as a specific atmosphere.
1. Ball milling 50g petroleum asphalt in a mechanical ball mill to obtain asphalt powder, wherein the particle size of the asphalt powder is 200 meshes;
2. pre-nitriding the asphalt powder obtained in the step 1) in a plasma ball mill under nitrogen atmosphere to obtain nitrided asphalt powder, wherein the ball milling speed is 1200r, the ball milling time is 3h, and the doping amount of nitrogen atoms is about 0.3%;
3. carbonizing the nitrided asphalt powder obtained in the step 2) at a high temperature under argon atmosphere to obtain a hard carbon material (shown in figure 4), wherein the carbonization temperature is 1400 ℃, the carbonization time is 2 hours, 33g of hard carbon is obtained, and the yield is about 66%; the pore volume is about 0.002cm 3 /g。
4. And (3) carbonizing the carbonized hard carbon material according to hard carbon: carbon black: CMC: sbr=94: 1.5:1.5:3, preparing slurry according to the proportion, and coating the slurry on a copper foil to obtain a hard carbon pole piece;
and (3) taking the hard 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 hard 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 assembly is static for 8 hours at 25 ℃, when the charge-discharge circulation is carried out between 0.01V and 2.5V at the rate of 0.1C, the specific capacity of the initial discharge can reach 331mAh/g; the first charge and discharge efficiency reaches 91.1 percent, and the reversible capacity is 301.5mAh/g. .
The result shows that the hard carbon material manufactured by the method can provide high initial capacity, high first-turn charge and discharge efficiency and strong capacity stability for the sodium ion battery.
Example 4: sodium ion battery performance comparison under nitrogen doping and different ion ball milling parameters
1. Ball milling 50g petroleum asphalt in a mechanical ball mill to obtain asphalt powder, wherein the particle size of the asphalt powder is 200 meshes;
2. pre-nitriding the asphalt powder obtained in the step 1) in a plasma ball mill under nitrogen atmosphere to obtain nitrided asphalt powder, wherein the ball milling speed is 900-1500r, and the ball milling time is 1-6h (the plasma ball milling parameters are shown in table 2);
3. and (3) carbonizing the nitrided asphalt powder obtained in the step (2) at a high temperature in an argon atmosphere to obtain a hard carbon material, wherein the carbonization temperature is 1400 ℃, and the carbonization time is 2h.
4. And (3) carbonizing the carbonized hard carbon material according to hard carbon: carbon black: CMC: sbr=94: 1.5:1.5:3, preparing slurry according to the proportion, and coating the slurry on a copper foil to obtain a hard carbon pole piece;
and (3) taking the hard 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 hard 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 completion of the assembly, the battery was allowed to stand at 25℃for 8 hours, and then charge and discharge cycles were carried out at a rate of 0.1℃between 0.01V and 2.5V.
Table 2 comparison of sodium ion battery performance under different plasma ball milling parameters under nitrogen doping
By material characteristics and electrochemical properties under nitrogen atmosphere at different plasma ball milling parameters, the following conclusion is drawn:
(1) The plasma ball milling speed and the ball milling time are main factors influencing the nitrogen doping amount, because nitrogen is stable, and high thermal stress is locally generated under high-temperature particles of an electric field of asphalt molecules only under high-speed and long-time ball milling, so that nitrogen doping is caused to enter. At the same time, a plurality of fresh surfaces are produced for nitrogen doping under the continuous ball mill. Therefore, the longer the ball milling time is, the smaller the particle size of the obtained pretreated asphalt is, and the higher the doping amount of nitrogen atoms is; (2) Nitrogen doping can improve electron conductivity and provide more sodium active storage sites for hard carbon materials, so that the performance of the sodium ion battery is shown as a phenomenon that the first circle of specific capacity is higher; as shown in Table 2, the ball milling rotation speed was 1200r and the ball milling time was 3h, the doping amount of nitrogen atoms was about 0.3%, the first-turn specific capacity of the sodium ion battery was 331mAh/g and the first-turn coulomb efficiency was 91.1%.
Example 5 hard carbon pretreatment and preparation, and sodium ion battery application with phosphane as a specific atmosphere.
1. Ball milling 50g petroleum asphalt in a mechanical ball mill to obtain asphalt powder, wherein the particle size of the asphalt powder is 200 meshes;
2. the asphalt powder obtained in the step 1) is put into a plasma ball mill to be pretreated under the phosphane atmosphere to obtain phosphated asphalt powder, the ball milling speed is 1000r, the ball milling time is 6h, and the doping amount of phosphorus atoms is about 11%;
3. carbonizing the oxidized asphalt powder obtained in the step 2) at a high temperature under an argon atmosphere to obtain a hard carbon material, wherein the carbonization temperature is 1400 ℃, the carbonization time is 2 hours, 36g of hard carbon is obtained, and the yield is about 72%;
the pore volume was about 0.008cm 3 /g。
4. And (3) carbonizing the carbonized hard carbon material according to hard carbon: carbon black: CMC: sbr=94: 1.5:1.5:3, preparing slurry according to the proportion, and coating the slurry on a copper foil to obtain a hard carbon pole piece;
and (3) taking the hard 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 hard 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 assembly is static for 8 hours at 25 ℃, when the charge-discharge circulation is carried out between 0.01V and 2.5V at the rate of 0.1C, the specific capacity of the first-circle discharge can reach 359mAh/g; the first charge and discharge efficiency reaches 87.8 percent, and the reversible capacity is 315.2mAh/g. The reversible capacity represents a stable capacity after the subsequent second turn, representing a cyclic stability, because the phosphorus element helps to expand the interlayer spacing of the hard carbon, so that the phosphorus element doped hard carbon can have a greater reversible capacity.
From the above examples, the plasma ball milling process is adopted to perform the doping pretreatment, so that other elements can be well doped, and hard carbon materials with different characteristics can be produced. For example, the oxygen doping in the embodiment 1 can crosslink and inhibit graphitization to generate high-quality hard carbon; example 3 nitrogen incorporation can improve the conductivity of hard carbon; example 5 phosphorus incorporation can improve specific capacity and reversible capacity of the battery.
Comparative example 1 comparative test of preparation of hard carbon by direct pyrolysis of Petroleum asphalt as raw Material and application to sodium ion Battery
1. Ball milling 50g petroleum asphalt in a ball mill to obtain asphalt powder, wherein the particle size of the asphalt powder is 200 meshes;
2. and (3) carbonizing the asphalt powder subjected to ball milling in the step (1) at a high temperature in an inert atmosphere at 1400 ℃ for 2 hours to obtain a hard carbon material (see figure 5), wherein the mass of the obtained hard carbon is 25.5g, the yield of the hard carbon is 51%, and the pore volume is about 0.
3. And (3) carbonizing the carbonized hard carbon material according to hard carbon: carbon black: CMC: sbr=94: 1.5:1.5:3, preparing slurry according to the proportion, and coating the slurry on a copper foil to obtain a hard carbon pole piece;
and (3) taking the hard 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 hard 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 specific capacity of the initial discharge can reach 267.8mAh/g.
The results show that the hard carbon material prepared by the process has low yield, and the sodium ion battery prepared by the hard carbon material has low initial capacity, low first-turn charge-discharge efficiency and poor capacity stability.
Comparative example 2 comparative test for preparing hard carbon Using Petroleum asphalt under mechanical ball milling Process as raw Material and applying it on sodium ion Battery
1. Ball milling 50g petroleum asphalt in a ball mill to obtain asphalt powder, wherein the particle size of the asphalt powder is 200 meshes;
2. placing the asphalt powder obtained in the step 1) into a mechanical ball mill, and continuously ball-milling under an oxygen atmosphere to obtain re-ball-milled asphalt powder, wherein the ball-milling speed is 1000r, the ball-milling time is 6h, and the oxygen atom doping amount is about 0% in the mechanical ball milling;
3. and 2) performing high-temperature carbonization on the ball-milled asphalt powder obtained in the step 2) in an inert atmosphere, wherein the carbonization temperature is 1400 ℃, the carbonization time is 2 hours, the mass of the obtained hard carbon is 28g, the yield of the hard carbon is 56%, and the pore channel volume is about 0.
4. And (3) carbonizing the carbonized hard carbon material according to hard carbon: carbon black: CMC: sbr=94: 1.5:1.5:3, preparing slurry according to the proportion, and coating the slurry on a copper foil to obtain the hard carbon pole piece.
And (3) taking the hard 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 hard 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 assembly is static for 8 hours at 25 ℃, when the charge-discharge cycle is carried out between 0.01V and 2.5V at the rate of 0.1C, the specific capacity of the initial discharge can reach 271.2mAh/g; the first charge and discharge efficiency reaches 67%, and the specific capacity is kept at 48.6% after 80 cycles.
The results show that the hard carbon material prepared by the process has low yield, and the hard carbon material prepared by using the mechanical ball milling has significantly lower electrochemical performance than the hard carbon material prepared by using the plasma ball milling when being applied to a sodium ion battery.
Comparative example 3 comparative test for preparing hard carbon Using high temperature Pre-oxidized Petroleum asphalt as raw Material and application on sodium ion Battery
1. Ball milling 50g petroleum asphalt in a ball mill to obtain asphalt powder, wherein the particle size of the asphalt powder is 200 meshes;
2. placing the asphalt powder obtained in the step 1) into a tubular furnace, and pre-oxidizing in an oxygen atmosphere at 400 ℃ for 3 hours to obtain oxidized asphalt powder;
3. carbonizing the oxidized asphalt powder obtained in the step 2) at a high temperature in an inert atmosphere at 1400 ℃ for 2 hours to obtain 30.5g of hard carbon with a hard carbon yield of 61%;
4. and (3) carbonizing the carbonized hard carbon material according to hard carbon: carbon black: CMC: sbr=94: 1.5:1.5:3, preparing slurry according to the proportion, and coating the slurry on a copper foil to obtain a hard carbon pole piece;
and (3) taking the hard 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 hard 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 assembly is static for 8 hours at 25 ℃, when the charge-discharge cycle is carried out between 0.01V and 2.5V at the rate of 0.1C, the specific capacity of the initial discharge can reach 303.8mAh/g; the first-circle charge-discharge efficiency reaches 87.6 percent.
The results of this example show that the hard carbon material prepared by this process has lower yield than the oxygen-doped or nitrogen-doped hard carbon in the plasma ball milling process of the present invention, and the electrochemical performance of the hard carbon material pretreated by high temperature pretreatment is not as good as that of the method of pretreatment at normal temperature of the present invention.
The superior characteristics of the hard carbon pretreatment method of the present patent are shown by the comparison of the above comparative examples with examples:
(1) Under the action of plasma arc and shearing force, the plasma ball milling technology reduces the size of microcrystal of asphalt and increases dislocation density, can prevent graphitization of asphalt during high-temperature pyrolysis, and remarkably improves the yield of hard carbon;
(2) The plasma ball milling technology can dope asphalt through gas-solid reaction under normal temperature, and the obtained hard carbon material has high yield and good electrochemical performance after being applied to sodium ion batteries;
(3) The doping elements and the plasma ball milling process parameters are related, and the types and the doping amounts of the doping elements can be regulated and controlled by regulating and controlling the plasma ball milling parameters, so that the properties of the hard carbon material can be better improved;
(4) The pore volume of the hard carbon material prepared by plasma ball milling doping pretreatment asphalt is increased, which is caused by the fact that doped hetero atoms become gaseous and volatilize in high-temperature carbonization, and the generated vacancies prevent the graphitization process of the asphalt. And meanwhile, the pore canal formed after the heteroatom is removed can provide sodium ion embedding sites, so that the specific capacity of the battery is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention 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 invention 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 (6)
1. The preparation method of the hard carbon material is characterized by comprising the following steps:
step 1): ball milling asphalt in a mechanical ball mill to obtain asphalt powder with the particle size of 100-500 meshes;
step 2): placing the asphalt powder obtained in the step 1) into a plasma ball mill for pretreatment to obtain doped asphalt powder; the pretreatment method comprises the following steps: ball milling rotation speed is 900-1500rpm, and ball milling time is 1-6h; the atmosphere in the ball milling tank is one or more of argon, oxygen, nitrogen, ammonia, methane, phosphane, boron trichloride and hydrogen sulfide;
step 3): and (3) carrying out high-temperature carbonization on the doped asphalt powder obtained in the step (2) under the argon atmosphere to obtain the hard carbon material, wherein the carbonization temperature is 1000-1500 ℃ and the carbonization time is 2-6h.
2. The method for preparing a hard carbon material according to claim 1, wherein when the atmosphere in the ball milling tank is oxygen, the ball milling speed is 1000rpm, and the ball milling time is 6 hours.
3. The method for producing hard carbon according to claim 1, wherein when the atmosphere in the ball milling tank is nitrogen, the ball milling speed is 1200rpm and the ball milling time is 3 hours.
4. The method for producing a hard carbon material according to claim 1, wherein the pitch is one or more of petroleum pitch, coal tar pitch, and natural pitch.
5. Use of a hard carbon material prepared by the method for preparing a hard carbon material according to any one of claims 1 to 4 in a sodium ion battery.
6. The use of a hard carbon material according to claim 5 in a sodium ion battery, wherein the hard carbon material is prepared as a hard carbon: carbon black: CMC: sbr=94: 1.5:1.5:3, preparing slurry according to the proportion, and coating the slurry on a copper foil to obtain the hard carbon pole piece.
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| CN116621159A (en) * | 2023-07-24 | 2023-08-22 | 深圳海辰储能控制技术有限公司 | Nitrogen-doped hard carbon material, preparation method thereof, hard carbon negative electrode material and battery |
| CN116812913A (en) * | 2023-08-30 | 2023-09-29 | 乌海宝杰新能源材料有限公司 | High-reversible-capacity hard carbon negative electrode material and preparation method thereof |
| CN117466278A (en) * | 2023-11-01 | 2024-01-30 | 东北大学 | Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116621159A (en) * | 2023-07-24 | 2023-08-22 | 深圳海辰储能控制技术有限公司 | Nitrogen-doped hard carbon material, preparation method thereof, hard carbon negative electrode material and battery |
| CN116812913A (en) * | 2023-08-30 | 2023-09-29 | 乌海宝杰新能源材料有限公司 | High-reversible-capacity hard carbon negative electrode material and preparation method thereof |
| CN116812913B (en) * | 2023-08-30 | 2023-11-21 | 乌海宝杰新能源材料有限公司 | High-reversible-capacity hard carbon negative electrode material and preparation method thereof |
| CN117466278A (en) * | 2023-11-01 | 2024-01-30 | 东北大学 | Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery |
| CN117466278B (en) * | 2023-11-01 | 2024-05-17 | 东北大学 | Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery |
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