CN117550585A - Preparation method and application of coal tar pitch-based hard carbon material - Google Patents
Preparation method and application of coal tar pitch-based hard carbon material Download PDFInfo
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- CN117550585A CN117550585A CN202311669982.9A CN202311669982A CN117550585A CN 117550585 A CN117550585 A CN 117550585A CN 202311669982 A CN202311669982 A CN 202311669982A CN 117550585 A CN117550585 A CN 117550585A
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- hard carbon
- carbon material
- coal tar
- tar pitch
- ion battery
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 72
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 33
- 239000011294 coal tar pitch Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 61
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000004132 cross linking Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 9
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 102000020897 Formins Human genes 0.000 claims description 7
- 108091022623 Formins Proteins 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000010431 corundum Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- BJDDKZDZTHIIJB-UHFFFAOYSA-N 4,5,6,7-tetrafluoro-2-benzofuran-1,3-dione Chemical compound FC1=C(F)C(F)=C2C(=O)OC(=O)C2=C1F BJDDKZDZTHIIJB-UHFFFAOYSA-N 0.000 claims description 2
- UHIMKEGZFOQVHV-UHFFFAOYSA-N 4,5,6,7-tetraiodo-2-benzofuran-1,3-dione Chemical compound IC1=C(I)C(I)=C2C(=O)OC(=O)C2=C1I UHIMKEGZFOQVHV-UHFFFAOYSA-N 0.000 claims description 2
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 11
- 239000011734 sodium Substances 0.000 abstract description 9
- 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 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000011300 coal pitch Substances 0.000 abstract description 3
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- 229910052740 iodine Inorganic materials 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 239000007773 negative electrode material Substances 0.000 description 43
- 238000003763 carbonization Methods 0.000 description 20
- 239000010426 asphalt Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000630 rising effect Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical group C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- BTZNPZMHENLISZ-UHFFFAOYSA-M fluoromethanesulfonate Chemical compound [O-]S(=O)(=O)CF BTZNPZMHENLISZ-UHFFFAOYSA-M 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001291 vacuum drying 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A preparation method and application of coal tar pitch-based hard carbon material belong to the field of metal ion battery anode materials. Based on solid-phase heat treatment, anhydride substances rich in halogen atoms such as Br, F, cl, I are uniformly mixed with coal pitch, and the hard carbon anode material is obtained through high-temperature thermal field driven dehydrogenation and crosslinking. Thanks to the regulation and control effect of anhydride matter on the microcrystalline structure and pore structure of carbon material, the hard carbon material is prepared in the range of 30 mA g ‑1 Exhibits a higher initial charge specific capacity of 330.33 mAh g when storing sodium at a current density of (3) ‑1 The first coulomb efficiency is 77.29%, and meanwhile, the method has good cycle stability and rate capability. The preparation method of the hard carbon material is simple, low in cost and easy to scale, and lays a foundation for the large-scale preparation of the sodium ion battery anode material.
Description
Technical Field
The invention belongs to the field of metal ion battery cathode materials, and particularly relates to a coal tar pitch-based hard carbon material microcrystalline structure regulation and control method and a sodium ion battery application thereof.
Background
Lithium ion batteries are excellent due to their high energy densityThe cyclic stability occupies a large share in the global energy market, and promotes the upgrading of electronic products and the rapid development of information society. In recent years, the increasing scale of the global energy market makes lithium resources supply and demand and the price continuously rise, and the double restriction of the price element and the resource element seriously affects the development of the future large-scale energy storage market. The sodium ion battery which takes abundant and cheap sodium resources as main raw materials and is similar to the rocking chair mechanism of the lithium ion battery has wide application prospect. The structure and performance of the cathode material as a key component of the sodium ion battery can directly influence the energy density and other performance indexes of the sodium ion battery. Graphite is a relatively mature commercial negative electrode material in lithium ion batteries, but the performance of graphite is poor in sodium storage, mainly due to Na + With larger radius, the resistance of intercalation between graphite layers is larger, and the formation of Na-C compound is extremely unstable in thermodynamics, so that other negative electrode materials besides graphite must be developed to meet the requirements of sodium ion batteries. The hard carbon material is an amorphous carbon material, and the theoretical capacity of the hard carbon material can reach 300.33 mAh g during sodium storage -1 . However, most of the precursors for producing hard carbon are biomass, and the yield is low. The coal chemical industry by-product represented by asphalt is used as a main raw material, and the characteristics of high carbon content, condensed polycyclic aromatic hydrocarbon molecules and the like are utilized to obtain the carbon material with higher yield, so that the method is an effective way for high-efficiency and high-value utilization of coal chemical industry resources in China. However, the polycyclic aromatic hydrocarbon substance is easy to graphitize in the heat treatment process, the prepared carbon material has a orderly microcrystalline structure and smaller interlayer spacing, and the specific capacity of sodium storage is lower, which is a bottleneck problem of the asphalt-based carbon material of the negative electrode of the sodium ion battery.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of coal tar pitch-based hard carbon material with low cost, large-scale preparation, low graphitization degree and abundant closed cell structure and application of a sodium ion battery. In order to achieve the above object, the present invention solves the problems existing in the prior art, and the technical scheme of the present invention is as follows: the invention provides a preparation method of a coal tar pitch-based hard carbon material, which comprises the following steps:
(1) Uniformly mixing and grinding coal tar pitch and halogen-containing anhydride substances in a mortar according to a certain proportion to obtain a powder sample A; the mass ratio of the coal tar pitch to the halogen-containing anhydride substance is 2: (1-5);
the halogen-containing anhydride substance is tetrabromophthalic anhydride, tetrafluorophthalic anhydride, tetrachlorophthalic anhydride or tetraiodophthalic anhydride.
(2) The powder sample A is placed in a corundum boat and is placed in the central position of a tube furnace, and argon is pre-introduced for 30 min to remove air in the clean tube. Under the protection of argon atmosphere, the cross-linking and high-temperature carbonization of a tubular furnace are utilized, the temperature is raised to 350-400 ℃ from room temperature at a certain temperature raising rate, the pre-cross-linking time is 0.5-2 h, and then the carbonization is carried out at a certain temperature, the holding time is 1-3h, so that the coal tar pitch-based hard carbon material with a closed pore structure and wide interlayer spacing is prepared.
As a preferable technical scheme of the invention, the preparation method of the sodium ion battery anode hard carbon material comprises the following steps:
coal pitch in step (1): the mass ratio of tetrabromophthalic anhydride is 2:1,1:1,1:1.5,1:2 and 1:2.5 respectively.
The carbonization temperature in the step (2) is 1100-1300 ℃.
The temperature rising rate in the step (2) is 2,5 and 10 ℃ for min -1 。
The invention also provides a half cell prepared from the carbon material, which comprises the following steps:
preparing a negative electrode: grinding 80 mg anode carbon material, 10 mg conductive carbon black and 10 mg polyvinylidene fluoride (PVDF) in a mortar for 15 min, adding 200 microliters of N-methyl pyrrolidone (NMP), grinding for 6 min to obtain uniform slurry, uniformly coating the slurry on the surface of copper foil by using a scraper, and vacuum drying at 120 ℃ for 12 h to obtain the anode material with the load of 1-1.5 mg cm -2 Is a negative electrode sheet.
And (3) assembling: in a glove box filled with inert Ar atmosphere, the positive electrode shell, the positive electrode plate (sodium plate), the glass fiber diaphragm, the electrolyte, the negative electrode plate, the gasket, the elastic sheet and the negative electrode shell are sequentially stacked and sealed by a sealing machine, and the electrolyte adopts three materialsSodium fluoromethanesulfonate (NaCF) 3 SO 3 ) As a solute, diethylene glycol dimethyl ether (Degdme) was used as a solvent to prepare a solution having a concentration of 1 mol L -1 As an electrolyte, completing the battery assembly.
And (3) testing: the battery test system is a blue battery test system, and the voltage window of the test is 0.001-3V.
The beneficial effects of the invention are as follows: the tetrabromophthalic anhydride is used as a crosslinking and pore-forming agent to introduce a closed pore structure into the carbon material, so that the surface property and the microcrystalline structure of asphalt derived carbon are regulated and controlled, and the sodium storage performance of the carbon material is improved. The tetrabromophthalic anhydride can absorb redundant hydrogen on the polycyclic aromatic hydrocarbon molecules in the high-temperature carbonization process, and the oxygen-containing phthalic anhydride group of the tetrabromophthalic anhydride can inhibit condensed ring molecules from condensing, so that the interlayer spacing is enlarged, and sodium ions can be embedded into or extracted from the condensed ring molecules. Compared with other processes, the process flow is short, the synthesis method is simple, the production cost is greatly reduced, and the industrialization is facilitated.
Based on solid-phase heat treatment, anhydride substances rich in halogen atoms such as Br, F, cl, I are uniformly mixed with coal pitch, and the hard carbon anode material is obtained through high-temperature thermal field driven dehydrogenation and crosslinking. Thanks to the regulation and control effect of anhydride matter on the microcrystalline structure and pore structure of carbon material, the hard carbon material is prepared in the range of 30 mA g -1 Exhibits a higher initial charge specific capacity of 330.33 mAh g when storing sodium at a current density of (3) -1 The first coulomb efficiency is 77.29%, and meanwhile, the method has good cycle stability and rate capability. The preparation method of the hard carbon material is simple, low in cost and easy to scale, and is beneficial to researching the regulation and control action and evolution mechanism of the microcrystalline structure and the pore structure of the hard carbon material, thereby laying a foundation for the large-scale preparation of the negative electrode material of the sodium ion battery.
Drawings
FIG. 1 shows that the hard carbon negative electrode material of the sodium ion battery prepared in examples 1-5 is prepared in a concentration of 30 mA g -1 The second charge-discharge curve graph at current density illustrates the best mass ratio of asphalt to tetrabromophthalic anhydride, and in the graph, 2:1,1:1,1:1.5,1:2 and 1:2.5 represent the mass ratio of asphalt to tetrabromophthalic anhydride.
FIG. 2 is a sodium ion battery hard carbon prepared in examples 3,6-9The negative electrode material was 30 mA g -1 And a second charge-discharge curve graph under the current density shows the optimal carbonization temperature.
FIG. 3 is a graph showing that the hard carbon negative electrode material of the sodium ion battery prepared in example 3, 10-11 is 30 mA g -1 And a second circle of charge-discharge curve graph under the current density shows the optimal temperature rising rate.
Fig. 4 is a High Resolution Transmission Electron Microscope (HRTEM) image of the hard carbon negative electrode material of the sodium ion battery prepared in example 3.
FIG. 5 is an assembled half cell of the hard carbon negative electrode material of the sodium ion battery prepared in example 3 at 0.1 mV s -1 CV curve at sweep speed.
FIG. 6 is an assembled half cell of the hard carbon negative electrode material of the sodium ion battery prepared in example 3 at 30 mA g -1 And (5) testing the cycle performance under the current density.
FIG. 7 is an assembled half cell of the hard carbon negative electrode material of the sodium ion battery prepared in comparative example 1 at 30 mA g -1 And a second charge-discharge curve graph at current density.
FIG. 8 is an assembled half cell of the hard carbon negative electrode material of the sodium ion battery prepared in comparative example 2 at 30 mA g -1 And a second charge-discharge curve graph at current density.
Description of the embodiments
The invention is further illustrated below with reference to examples.
Example 1
(1) Taking 400 mg asphalt and 200 mg tetrabromophthalic anhydride, uniformly mixing and grinding the asphalt and the tetrabromophthalic anhydride in a mortar to obtain a powder sample A;
(2) The powder sample A is placed in a corundum boat and is placed in the central position of a tube furnace, and argon is pre-introduced for 30 min to remove air in the clean tube. Under the protection of argon atmosphere, using a tubular furnace for crosslinking and high-temperature carbonization, and heating from room temperature to 5 ℃ for min -1 The temperature rising rate is increased to 400 ℃, the pre-crosslinking time is 1 h, the pre-crosslinking time is increased to 1200 ℃ for carbonization, and the temperature holding time is 2 h, so that the hard carbon anode material of the sodium ion battery is prepared. The electrochemical properties of the hard carbon negative electrode material of the sodium ion battery prepared in example 1 were 30 mA g -1 At a current density of (1) its first charge specific volumeThe amount can reach 210.24 mAh g -1 The first coulombic efficiency was 68.82%.
Example 2
(1) Taking 400 mg asphalt and 400 mg tetrabromophthalic anhydride, uniformly mixing and grinding the asphalt and the tetrabromophthalic anhydride in a mortar to obtain a powder sample A;
(2) The powder sample A is placed in a corundum boat and is placed in the central position of a tube furnace, and argon is pre-introduced for 30 min to remove air in the clean tube. Under the protection of argon atmosphere, using a tubular furnace for crosslinking and high-temperature carbonization, and heating from room temperature to 5 ℃ for min -1 The temperature rising rate is increased to 400 ℃, the pre-crosslinking time is 1 h, the pre-crosslinking time is increased to 1200 ℃ for carbonization, and the temperature holding time is 2 h, so that the hard carbon anode material of the sodium ion battery is prepared. The electrochemical properties of the hard carbon negative electrode material of the sodium ion battery prepared in example 2 were 30 mA g -1 The specific capacity of the battery can reach 273.45 mAh g at the first charge under the current density -1 The first coulombic efficiency was 67.55%.
Example 3
(1) Taking 400 mg asphalt and 600 mg tetrabromophthalic anhydride, uniformly mixing and grinding the asphalt and the tetrabromophthalic anhydride in a mortar to obtain a powder sample A;
(2) The powder sample A is placed in a corundum boat and is placed in the central position of a tube furnace, and argon is pre-introduced for 30 min to remove air in the clean tube. Under the protection of argon atmosphere, using a tubular furnace for crosslinking and high-temperature carbonization, and heating from room temperature to 5 ℃ for min -1 The temperature rising rate is increased to 400 ℃, the pre-crosslinking time is 1 h, the pre-crosslinking time is increased to 1200 ℃ for carbonization, and the temperature holding time is 2 h, so that the hard carbon anode material of the sodium ion battery is prepared. The electrochemical properties of the hard carbon negative electrode material of the sodium ion battery prepared in example 3 were 30 mA g -1 The specific capacity of the battery can reach 330.3 mAh g when the battery is charged for the first time -1 The first coulombic efficiency was 77.29%.
Example 4
(1) Taking 400 mg asphalt and 800 mg tetrabromophthalic anhydride, uniformly mixing and grinding the asphalt and the tetrabromophthalic anhydride in a mortar to obtain a powder sample A;
(2) The powder sample A is placed in a corundum boat and is placed in the central position of a tube furnace, and argon is pre-introduced for 30 min to remove air in the clean tube. Under the protection of argon atmosphere, a tube furnace is utilizedCrosslinking and high temperature carbonization, and heating to 5deg.C for min from room temperature -1 The temperature rising rate is increased to 400 ℃, the pre-crosslinking time is 1 h, the pre-crosslinking time is increased to 1200 ℃ for carbonization, and the temperature holding time is 2 h, so that the hard carbon anode material of the sodium ion battery is prepared. The electrochemical properties of the hard carbon negative electrode material of the sodium ion battery prepared in example 4 were 30 mA g -1 The specific capacity of the battery can reach 288.07 mAh g at the first charge under the current density -1 The first coulombic efficiency was 76.97%.
Example 5
(1) Taking 400 mg asphalt and 1000 mg tetrabromophthalic anhydride, uniformly mixing and grinding the asphalt and the tetrabromophthalic anhydride in a mortar to obtain a powder sample A;
(2) The powder sample A is placed in a corundum boat and is placed in the central position of a tube furnace, and argon is pre-introduced for 30 min to remove air in the clean tube. Under the protection of argon atmosphere, using a tubular furnace for crosslinking and high-temperature carbonization, and heating from room temperature to 5 ℃ for min -1 The temperature rising rate is increased to 400 ℃, the pre-crosslinking time is 1 h, the pre-crosslinking time is increased to 1200 ℃ for carbonization, and the temperature holding time is 2 h, so that the hard carbon anode material of the sodium ion battery is prepared. The electrochemical properties of the hard carbon negative electrode material of the sodium ion battery prepared in example 5 were 30 mA g -1 The specific capacity of the battery can reach 277.57 mAh g at the first charge under the current density -1 The first coulombic efficiency was 74.68%.
Referring to fig. 1, a second charge-discharge curve of the sodium-ion hard carbon negative electrode material prepared in examples 1-5 is shown. The electrochemical properties of the hard carbon negative electrode materials for sodium ion batteries prepared by comparative examples 1 to 5, wherein the electrochemical properties of example 3 were the highest at 30 mA g -1 The specific capacity of the battery can reach 330.33 mAh g at the first charge under the current density -1 The first coulombic efficiency was 77.29%.
Example 6
On the basis of the embodiment 3, other conditions are kept unchanged, and the carbonization temperature in the step (2) in the embodiment 3 is changed to 1100 ℃, so that the hard carbon anode material of the sodium ion battery is prepared. The electrochemical properties of the hard carbon negative electrode material of the sodium ion battery prepared in example 6 were 30 mA g -1 The specific capacity of the battery can reach 252.97 mAh g at the first charge under the current density -1 First coulombic efficiency of 67.05%。
Example 7
On the basis of example 3, other conditions were kept unchanged, and the carbonization temperature in step (2) in example 3 was changed to 1150 ℃ to prepare a hard carbon negative electrode material for sodium ion batteries. The electrochemical properties of the hard carbon negative electrode material of the sodium ion battery prepared in example 7 were 30 mA g -1 The specific capacity of the battery can reach 264.86 mAh g at the first charge under the current density -1 The first coulombic efficiency was 67.58%.
Example 8
On the basis of example 3, other conditions were kept unchanged, and the carbonization temperature in step (2) in example 3 was changed to 1250 ℃, so as to prepare a hard carbon negative electrode material of a sodium ion battery. The electrochemical properties of the hard carbon negative electrode material of the sodium ion battery prepared in example 8 were 30 mA g -1 The specific capacity of the battery can reach 296.98 mAh g at the first charge under the current density -1 The first coulombic efficiency was 74.72%.
Example 9
On the basis of the embodiment 3, other conditions are kept unchanged, and the carbonization temperature in the step (2) in the embodiment 3 is changed to 1300 ℃, so that the hard carbon cathode material of the sodium ion battery is prepared. The electrochemical properties of the hard carbon negative electrode material of the sodium ion battery prepared in example 9 were 30 mA g -1 The specific capacity of the battery can reach 301.39 mAh g at the first charge under the current density -1 The first coulombic efficiency was 74.18%.
Referring to fig. 2, a second charge-discharge curve of the hard carbon negative electrode material of the sodium ion battery prepared in examples 3 and 6-9 is shown. As can be seen from the comparison of the hard carbon negative electrode materials for sodium-ion batteries prepared in examples 3 and 6-9, the electrochemical performance of the hard carbon negative electrode material for sodium-ion battery prepared under the condition of example 3 is best at 30 mA g -1 The specific capacity of the battery can reach 330.33 mAh g at the first charge under the current density -1 The first coulombic efficiency was 77.29%.
Example 10
On the basis of example 3, other conditions were kept unchanged, and the temperature rising rate in step (2) in example 3 was changed to 2℃for min -1 Preparation of hard carbon negative electrode material of sodium ion batteryAnd (5) material. The electrochemical properties of the hard carbon negative electrode material of the sodium ion battery prepared in example 10 were 30 mA g -1 The specific capacity of the battery can reach 202.58 mAh g at the first charge under the current density -1 The first coulombic efficiency was 60.43%.
Example 11
On the basis of example 3, other conditions were kept unchanged, and the temperature rising rate in step (2) in example 3 was changed to 10℃for min -1 And preparing the hard carbon negative electrode material of the sodium ion battery. The electrochemical properties of the hard carbon negative electrode material of the sodium ion battery prepared in example 11 were 30 mA g -1 The specific capacity of the battery can reach 260.62 mAh g at the first charge under the current density -1 The first coulombic efficiency was 73.18%.
Referring to fig. 3, a second charge-discharge curve of the hard carbon negative electrode material of the sodium ion battery prepared in examples 3, 10 and 11 is shown. The sodium-ion battery hard carbon negative electrode material prepared by comparative examples 3, 10, 11 was found to have the best electrochemical performance at 30 mA g under the conditions of example 3 -1 The specific capacity of the battery can reach 330.33 mAh g at the first charge under the current density -1 The first coulombic efficiency was 77.29%.
Referring to fig. 4, an HRTEM image of the hard carbon negative electrode material of the sodium ion battery prepared in example 3 shows that the hard carbon negative electrode material of the sodium ion battery shows a rich closed cell structure and long-range graphite region after high temperature carbonization and tetrabromophthalic anhydride crosslinking.
Referring to FIG. 5, a half cell of example 3 based on hard carbon negative electrode material of sodium ion battery was assembled at 0.1 mV s -1 CV curve at sweep speed. As shown, the redox peak is very sharp near 0V and the CV curves of the first five turns are highly coincident, indicating the reversible intercalation/deintercalation behavior of sodium ions in the material.
Referring to FIG. 6, a half cell of example 3 based on hard carbon negative electrode material of sodium ion battery was assembled at 30 mA g -1 Results of cycle performance test at current density. As shown, at 30 mA g -1 After 30 cycles, its charge ratioThe capacity can still reach 300.9 mAh g -1 。
Comparative example 1
On the basis of example 3, other conditions were kept unchanged, and tetrabromophthalic anhydride was changed to phthalic anhydride. Referring to fig. 7, a second charge-discharge curve of the hard carbon negative electrode material of the sodium ion battery prepared in comparative example 1 is shown. The electrochemical performance of the hard carbon negative electrode material of the sodium ion battery prepared in comparative example 1 is 30 mA g -1 The specific capacity of the battery can reach 149.42 mAh g at the first charge under the current density -1 The first coulombic efficiency was 67.90%.
Comparative example 2
On the basis of example 3, other conditions were kept unchanged without adding tetrabromophthalic anhydride. Referring to fig. 8, a second charge-discharge curve of the hard carbon negative electrode material of the sodium ion battery prepared in comparative example 2 is shown. The electrochemical performance of the hard carbon negative electrode material of the sodium ion battery prepared in comparative example 2 is 30 mA g -1 The specific capacity of the battery can reach 156.53 mAh g at the first charge under the current density -1 The first coulombic efficiency was 59.18%.
The battery performance test results show that: the hard carbon negative electrode material of the sodium ion battery provided by the invention has excellent electrochemical performance, wherein tetrabromophthalic anhydride has a regulating and controlling effect on the pore structure, the microcrystalline structure and the surface chemical property of the carbon material. Because the presence of Br atoms absorbs H atoms on the pitch to build up a rich closed cell structure in the carbon material, the oxy-phthalic anhydride groups can both inhibit graphitization and provide active oxygen groups to store sodium ions. Based on the characteristics, the hard carbon negative electrode material of the sodium ion battery has the advantages of high specific capacity, good cycle stability and good rate capability.
Claims (5)
1. The preparation method of the coal tar pitch-based hard carbon material is characterized by comprising the following steps:
(1) Uniformly mixing and grinding coal tar pitch and halogen-containing anhydride substance in a mortar to obtain a powder sample A; the mass ratio of the coal tar pitch to the tetrabromophthalic anhydride is 2: (1-5);
(2) Placing the powder sample A in a corundum boat, placing in a tube furnace, and pre-introducing argon; under the protection of argon atmosphere, heating to 350-400 ℃, pre-crosslinking for 0.5-2 h, heating to 1100-1300 ℃, carbonizing, and maintaining for 1-3h to obtain the coal tar pitch-based hard carbon material.
2. A preparation method of coal tar pitch-based hard carbon material is characterized in that: the halogen-containing anhydride substance is tetrabromophthalic anhydride, tetrafluorophthalic anhydride, tetrachlorophthalic anhydride or tetraiodophthalic anhydride.
3. The method for preparing the coal tar pitch-based hard carbon material according to claim 1, which is characterized in that: the mass ratio of the coal tar pitch to the tetrabromophthalic anhydride in the step (1) is 2:1,1:1,1:1.5,1:2 or 1:2.5 respectively.
4. The method for preparing coal tar pitch-based hard carbon material according to claim 1, wherein the heating rate in the step (2) is 5, 10 ℃ for min -1 。
5. Use of coal tar pitch-based hard carbon material prepared according to the method of claims 1-3, characterized in that: the coal tar pitch-based hard carbon material is applied to sodium ion batteries.
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