CN114551871A - Spherical hard carbon composite material and preparation method and application thereof - Google Patents
Spherical hard carbon composite material and preparation method and application thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 24
- 239000007833 carbon precursor Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 13
- 238000005056 compaction Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 15
- 239000002028 Biomass Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000000197 pyrolysis Methods 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 3
- 240000007049 Juglans regia Species 0.000 claims description 2
- 235000009496 Juglans regia Nutrition 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 235000013555 soy sauce Nutrition 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 235000021419 vinegar Nutrition 0.000 claims description 2
- 239000000052 vinegar Substances 0.000 claims description 2
- 235000020234 walnut Nutrition 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 239000008187 granular material Substances 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910009819 Ti3C2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
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- 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
- 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
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
- C01B32/90—Carbides
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
The invention discloses a spherical hard carbon composite material and a preparation method thereof, wherein hard carbon precursor particles with the particle size of 1.5-3.5 mu m are used as raw materials and are compounded with a conductive two-dimensional material to obtain a spherical hard carbon composite material precursor, and the spherical hard carbon composite material precursor is carbonized at high temperature in an inert environmentThe obtained spherical granular hard carbon composite material comprises 5-25% of the conductive two-dimensional material by mass of the hard carbon composite material, and the granularity of spherical granules is 2-50 μm. The spherical hard carbon composite material has high compaction density which can reach 1.20-1.57 g/cm3The sodium ion battery cathode material has high rate performance and cycle stability, and the capacity retention rate is more than 95% after the sodium ion battery cathode material is cycled for 300 times at 0.5C.
Description
Technical Field
The invention belongs to the technical field of energy storage materials and electrochemistry, relates to a battery electrode material, and particularly relates to a spherical composite carbon material for a sodium-ion battery cathode material and a preparation method thereof.
Background
The content of lithium element in the earth crust is limited, and the large-scale application requirement of the lithium ion battery cannot be met. The sodium element resource reserves are abundant and uniformly distributed, and the sodium ion battery becomes the focus of common attention in the scientific and industrial fields.
The carbon material has wide source, abundant resource, various structures, higher specific capacity and long cycle life, and is an ideal sodium ion battery cathode material. The hard carbon material is used as amorphous carbon, the interlayer spacing is larger than that of graphite, and the disordered structure of the hard carbon enables the hard carbon material to have more defects, vacancies and more sodium storage sites, so that the hard carbon material is the most promising cathode material for the industrialization of the sodium ion battery.
CN 108439363A, CN 106299365A, CN 108059144A and the like disclose methods for preparing hard carbon materials by using various biomass raw materials, but the hard carbon materials prepared by using the biomass raw materials not only have irregular block shapes, but also have low compaction density of only 1.0g/cm3Resulting in a lower energy density of the battery. Meanwhile, the prepared hard carbon material has limited conductivity, so that the rapid charge and discharge performance of the hard carbon material is influenced.
Therefore, the method is particularly urgent to obtain the hard carbon material with high yield and excellent electrochemical performance by selecting a proper biomass raw material and adopting a simple and environment-friendly preparation process.
Disclosure of Invention
The invention aims to provide a spherical hard carbon composite material with higher compaction density and a preparation method thereof, and the spherical hard carbon composite material has high rate performance and cycling stability when used as a negative electrode material of a sodium ion battery.
The spherical hard carbon composite material is prepared by taking hard carbon precursor particles with the particle size of 1.5-3.5 mu m as a raw material, compounding the raw material with a conductive two-dimensional material to obtain a spherical hard carbon composite material precursor, and performing high-temperature carbonization treatment in an inert environment, wherein the conductive two-dimensional material accounts for 5-25% of the total mass of the hard carbon composite material, and the particle size of the spherical particles is 2-50 mu m.
The specific surface area of the spherical hard carbon composite material obtained by the invention is 2-45 m2(iv) g, tap density 0.85-1.45 g/cm3The compaction density is 1.20-1.57 g/cm3002 interplanar spacing d002The value is between 0.365 and 0.460 nm.
The hard carbon precursor is obtained by removing impurities from various biomasses serving as raw materials and then pyrolyzing the biomasses at low temperature in an inert environment at 300-500 ℃.
Specifically, the biomass raw material includes, but is not limited to, one or more of vinasse, vinegar residue, walnut shell, wood chips, rice hull and soy sauce residue.
The conductive two-dimensional material is one or more of graphene oxide, graphene, fluorinated graphene and MXene.
The preparation method comprises the steps of removing impurities from a biomass raw material in an alkaline aqueous solution, washing and drying, pyrolyzing at a low temperature in an inert environment at 300-500 ℃, crushing a low-temperature pyrolysis product into hard carbon precursor particles with the particle size of 1.5-3.5 micrometers, compounding the hard carbon precursor particles with a conductive two-dimensional material in a dispersing solvent to obtain a dispersing solution, spray drying to obtain a spherical hard carbon composite precursor with the particle size of 2-65 micrometers and the sphericity of 85-95%, heating to 800-1300 ℃ in the inert environment, and carrying out high-temperature carbonization treatment to prepare the spherical hard carbon composite with the particle size of 2-50 micrometers and the sphericity of 90-95%.
Further, the alkaline aqueous solution is 10-30 wt.% sodium hydroxide or potassium hydroxide aqueous solution.
Further, it is preferable that the biomass raw material is added to the alkaline aqueous solution so that the concentration thereof is 50 to 200 mg/mL.
Furthermore, the impurity removal treatment process is preferably carried out for 5-20 hours under stirring.
Further, the low-temperature pyrolysis is carried out at a temperature rise rate of 5-10 ℃/min until the temperature rises to 300-500 ℃, and the temperature is kept for 3-15 hours.
Further, the dispersion solvent is any one of water, ethanol, methanol, acetone, N-methylpyrrolidone and N, N-dimethylformamide.
Preferably, the mass ratio of the hard carbon precursor particles, the conductive two-dimensional material and the dispersion solvent is 100: 5-30: 2000-20000.
Further, the liquid inlet speed of the spray drying is 1-100 mL/min, the inlet temperature is 120-200 ℃, and the outlet temperature is 90-110 ℃.
Further, the spherical hard carbon composite material precursor is heated to 800-1300 ℃ at a heating rate of 1-5 ℃/min in an inert environment for high-temperature carbonization treatment.
Furthermore, the high-temperature carbonization treatment time is 1-10 h.
Further, the inert environment is nitrogen or argon.
Wherein, the biomass raw material subjected to the impurity removal treatment by the alkaline aqueous solution can be put into the acidic aqueous solution again for secondary treatment.
Further, the acidic aqueous solution is any one of nitric acid, hydrochloric acid, sulfuric acid or hydrofluoric acid aqueous solution.
Furthermore, the invention also provides application of the spherical hard carbon composite material as a negative electrode material of a sodium-ion battery.
Furthermore, the invention also provides a negative electrode material of the sodium-ion battery, which contains the spherical hard carbon composite material as an active material.
Compared with the prior art, the spherical hard carbon composite material prepared by the invention has the compacted density of more than 1.2g/cm3And the material has excellent rate performance and cycling stability, the capacity retention rate is more than 95% after the battery is cycled for 300 times at 0.5 ℃, and the material is an ideal sodium ion battery cathode material and is expected to be applied to the sodium ion battery to realize large-scale industrial production.
The preparation method of the spherical hard carbon composite material has the characteristics of simple and easy operation, low cost, environmental protection and the like.
Drawings
Fig. 1 is a transmission electron micrograph of a spherical hard carbon composite prepared in example 1.
Fig. 2 is a charge and discharge graph of the spherical hard carbon composite prepared in example 1.
Fig. 3 is a graph of cycle performance for the preparation of spherical hard carbon composite of example 1.
Fig. 4 is a graph of rate capability of the spherical hard carbon composite prepared in example 1.
Fig. 5 is an X-ray diffraction pattern of the spherical hard carbon composite prepared in example 2.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are only for more clearly illustrating the technical solutions of the present invention so as to enable those skilled in the art to better understand and utilize the present invention, and do not limit the scope of the present invention.
The names and abbreviations of the experimental methods, production processes, instruments and equipment involved in the examples and comparative examples of the present invention are those commonly known in the art and are clearly and clearly understood in the relevant fields of use, and those skilled in the art can understand the conventional process steps and apply the corresponding equipment according to the names and perform the operations according to the conventional conditions or conditions suggested by the manufacturers.
The various starting materials or reagents used in the examples of the present invention and comparative examples are not particularly limited in their sources, and are all conventional products commercially available. They may also be prepared according to conventional methods well known to those skilled in the art.
Example 1.
Adding dried Fenjiu lees from Fenjiu group into 20wt.% potassium hydroxide aqueous solution at an amount of 10mg/mL, stirring at 800rpm for 12h to remove impurities, washing with deionized water to neutrality, and drying.
And (3) placing the dried distilled grains after impurity removal in a nitrogen atmosphere, heating to 500 ℃ at the heating rate of 5 ℃/min, and preserving heat for 5 hours to carry out low-temperature pyrolysis treatment.
And ball-milling and crushing the low-temperature pyrolysis product to obtain a hard carbon precursor with the particle size of 1.5-3.5 microns.
Uniformly mixing the hard carbon precursor, graphene and water according to the mass ratio of 100: 10: 10000 to obtain a dispersion solution.
And controlling the liquid inlet speed to be 20mL/min, the inlet temperature to be 130 ℃, and the outlet temperature to be 110 ℃, and carrying out spray drying on the dispersion solution to obtain the spherical hard carbon composite precursor.
Under the protection of nitrogen atmosphere, heating the spherical hard carbon composite precursor to 1200 ℃ at the heating rate of 1 ℃/min, preserving the heat for 3h, carrying out high-temperature carbonization treatment, and cooling to room temperature to obtain the spherical hard carbon composite material.
The specific surface area of the spherical hard carbon composite material prepared by the embodiment is 15m by adopting a full-automatic specific surface area and porosity analyzer2/g。
The tap density of the spherical hard carbon composite material of the embodiment measured by a pycnometer method is 0.95g/cm3. The compacted density is 1.29g/cm measured by a compacted density measuring instrument3。
As can be seen from the transmission electron microscope photograph shown in FIG. 1, the interlayer spacing of the spherical hard carbon composite material is larger, 0.385nm, and the spherical hard carbon composite material is suitable for serving as a negative electrode material of a sodium ion battery.
The prepared spherical hard carbon composite material is uniformly mixed with polyvinylidene fluoride (PVDF) serving as a binder and a Super-P serving as a conductive agent in a mass ratio of 8: 1, N-methyl pyrrolidone (NMP) serving as a dispersing agent is added and stirred to prepare slurry, the slurry is uniformly coated on a copper foil, the copper foil is dried at 100 ℃ for 12 hours and is pressed into a sheet, and the sheet is cut into a circular electrode slice with the diameter of 12 mm.
Using a metal sodium sheet as a counter electrode, and using 1mol/L NaClO4Or NaPF6The EC/DMC (1: 1) solution of (A) was used as an electrolyte, a polypropylene film was used as a separator, and a CR2032 type coin cell was assembled in a glove box filled with argon gas.
The charge and discharge test of the battery is carried out on a LAND CT2001A battery test system (blue electronic Co., Ltd., Wuhan city), and the specific capacity, the cycle performance and the rate capability of the battery are tested.
FIG. 2 shows the charge-discharge curve of 0.1C for the spherical hard carbon composite material prepared in this example, and it can be seen that the reversible specific capacity of the material is up to 281 mAh/g.
Fig. 3 is a rate performance graph of the spherical hard carbon composite material prepared in the embodiment, and the specific capacities of 0.2C, 0.5C and 1C are 210 mAh/g, 171 mAh/g and 125mAh/g respectively, which shows good rate performance.
Fig. 4 shows a graph of cycle performance for the preparation of spherical hard carbon composites of this example. As can be seen from the figure, after the spherical hard carbon composite material is cycled for 300 times at the current density of 0.5C, the specific capacity of the spherical hard carbon composite material is still as high as 165mAh/g, the capacity retention rate is 96%, and excellent cycling stability is shown.
Comparative example 1.
Adding dried Fenjiu vinasse from Fenjiu group into 20wt.% potassium hydroxide aqueous solution at a dosage of 10mg/mL, stirring at 800rpm for 12h to remove impurities, washing with deionized water to neutrality, and drying.
And (3) placing the dried distilled grains after impurity removal in a nitrogen atmosphere, heating to 500 ℃ at the heating rate of 5 ℃/min, and preserving heat for 5 hours to carry out low-temperature pyrolysis treatment.
And ball-milling and crushing the low-temperature pyrolysis product to obtain a hard carbon precursor with the particle size of 1.5-3.5 microns.
Uniformly mixing the hard carbon precursor, graphene and water according to the mass ratio of 100: 10: 10000, and drying in a forced air oven to obtain the hard carbon composite material precursor.
Under the protection of nitrogen atmosphere, heating the composite material precursor to 1200 ℃ at the heating rate of 1 ℃/min, preserving the heat for 3h, carrying out high-temperature carbonization treatment, and cooling to room temperature to obtain the non-spherical hard carbon composite material.
The specific surface area of the hard carbon composite material prepared in the embodiment is 14m by adopting a full-automatic specific surface area and porosity analyzer2/g。
The tap density of the hard carbon composite material of the embodiment measured by a pycnometer method is 0.96g/cm3. The compacted density is 1.02g/cm measured by a compacted density measuring instrument3。
The compacted density of the non-spherical hard carbon composite prepared in comparative example 1 was significantly lower than that of the spherical hard carbon composite prepared in example 1.
Example 2.
Adding dried Fenjiu lees from Fenjiu group into 15wt.% potassium hydroxide aqueous solution at an amount of 50mg/mL, stirring at 600rpm for 20h to remove impurities, washing with deionized water to neutrality, and drying.
And (3) placing the dried distilled grains after impurity removal in a nitrogen atmosphere, heating to 400 ℃ at the heating rate of 10 ℃/min, and preserving heat for 8 hours to carry out low-temperature pyrolysis treatment.
And ball-milling and crushing the low-temperature pyrolysis product to obtain a hard carbon precursor with the particle size of 1.5-3.5 microns.
Mixing hard carbon precursor and Ti3C2Uniformly mixing MXene nanosheet graphene and N, N-dimethylformamide according to the mass ratio of 100: 30: 15000 to obtain a dispersion solution.
And controlling the liquid inlet speed to be 45mL/min, the inlet temperature to be 110 ℃ and the outlet temperature to be 90 ℃, and carrying out spray drying on the dispersion solution to obtain the spherical hard carbon composite precursor.
Under the protection of nitrogen atmosphere, heating the spherical hard carbon composite precursor to 800 ℃ at the heating rate of 2 ℃/min, preserving the heat for 2h, carrying out high-temperature carbonization treatment, and cooling to room temperature to obtain the spherical hard carbon composite material.
The specific surface area of the spherical hard carbon composite material prepared by the embodiment is 39m by adopting a full-automatic specific surface area and porosity analyzer2/g。
The tap density of the spherical hard carbon composite material of the embodiment measured by a pycnometer method is 0.89g/cm3. The compacted density is 1.22g/cm measured by a compacted density measuring instrument3。
In the XRD pattern of the spherical hard carbon composite prepared according to this example provided in fig. 4, it can be seen that MXene diffraction peak appears around 7 °.
Example 3.
Adding the dried wood chips into 30wt.% of potassium hydroxide aqueous solution according to the dosage of 25mg/mL, stirring at 800rpm for 15h to remove impurities, washing with deionized water to be neutral, and drying.
And (3) placing the dried sawdust subjected to impurity removal in a nitrogen atmosphere, heating to 350 ℃ at a heating rate of 5 ℃/min, and preserving heat for 8 hours to carry out low-temperature pyrolysis treatment.
And ball-milling and crushing the low-temperature pyrolysis product to obtain a hard carbon precursor with the particle size of 1.5-3.5 microns.
Uniformly mixing the hard carbon precursor, the graphene oxide and solvent water according to the mass ratio of 100: 25: 8000 to obtain a dispersion solution.
And controlling the liquid inlet speed to be 55mL/min, the inlet temperature to be 120 ℃, and the outlet temperature to be 100 ℃, and carrying out spray drying on the dispersion solution to obtain the spherical hard carbon composite precursor.
Under the protection of nitrogen atmosphere, heating the spherical hard carbon composite precursor to 1300 ℃ at the heating rate of 1 ℃/min, preserving the heat for 2h, carrying out high-temperature carbonization treatment, and cooling to room temperature to obtain the spherical hard carbon composite material.
The specific surface area of the spherical hard carbon composite material prepared by the embodiment is tested to be 5m by adopting a full-automatic specific surface area and porosity analyzer2/g。
The tap density of the spherical hard carbon composite material of the embodiment measured by a pycnometer method is 1.26g/cm3. The compacted density is 1.55g/cm measured by a compacted density measuring instrument3。
The above embodiments of the present invention are not intended to be exhaustive or to limit the invention to the precise form disclosed. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Claims (11)
1. A spherical hard carbon composite material is prepared by taking hard carbon precursor particles with the particle size of 1.5-3.5 microns as a raw material, compounding the raw material with a conductive two-dimensional material to obtain a spherical hard carbon composite material precursor, and carrying out high-temperature carbonization treatment in an inert environment to obtain the spherical granular hard carbon composite material, wherein the conductive two-dimensional material accounts for 5-25% of the total mass of the hard carbon composite material, and the particle size of the spherical particles is 2-50 microns.
2. According toThe spherical hard carbon composite material as set forth in claim 1, wherein the specific surface area of the spherical hard carbon composite material is 2 to 45m2(iv) g, tap density 0.85-1.45 g/cm3The compaction density is 1.20-1.57 g/cm3002 interplanar spacing d002The value is between 0.365 and 0.460 nm.
3. The spherical hard carbon composite material as claimed in claim 1, wherein the hard carbon precursor is obtained by removing impurities from biomass as a raw material and pyrolyzing the biomass at low temperature in an inert environment at 300-500 ℃, wherein the biomass raw material is one or more of vinasse, vinegar residue, walnut shell, wood chips, rice shell and soy sauce residue.
4. The spherical hard carbon composite material according to claim 1, wherein the conductive two-dimensional material is one or more of graphene oxide, graphene fluoride and MXene.
5. The preparation method of the spherical hard carbon composite material according to claim 1, comprising the steps of removing impurities from a biomass raw material in an alkaline aqueous solution, washing and drying, pyrolyzing at a low temperature in an inert environment at 300-500 ℃, crushing a low-temperature pyrolysis product into hard carbon precursor particles with the particle size of 1.5-3.5 microns, compounding the hard carbon precursor particles with a conductive two-dimensional material in a dispersion solvent to obtain a dispersion solution, performing spray drying to obtain a spherical hard carbon composite material precursor with the particle size of 2-65 microns and the sphericity of 85-95%, and heating to 800-1300 ℃ in the inert environment to perform high-temperature carbonization treatment to obtain the spherical hard carbon composite material with the particle size of 2-50 microns and the sphericity of 90-95%.
6. The method for preparing the spherical hard carbon composite material according to claim 5, wherein the alkaline aqueous solution is 10-30 wt.% sodium hydroxide or potassium hydroxide aqueous solution, the biomass raw material is added into the alkaline aqueous solution to make the concentration of the biomass raw material be 50-200 mg/mL, and the impurity removal treatment is performed for 5-20 hours under stirring.
7. The method for preparing the spherical hard carbon composite material according to claim 5, wherein the low-temperature pyrolysis is carried out at a temperature rise rate of 5-10 ℃/min to 300-500 ℃ and is carried out for 3-15 hours.
8. The method for preparing the spherical hard carbon composite material according to claim 5, wherein the mass ratio of the hard carbon precursor particles, the conductive two-dimensional material and the dispersion solvent is 100: 5-30: 2000-20000, and the dispersion solvent is any one of water, ethanol, methanol, acetone, N-methylpyrrolidone and N, N-dimethylformamide.
9. The method for preparing the spherical hard carbon composite material according to claim 5, wherein the liquid inlet speed of the spray drying is 1 to 100mL/min, the inlet temperature is 120 to 200 ℃, and the outlet temperature is 90 to 110 ℃.
10. The method for preparing the spherical hard carbon composite material according to claim 5, wherein the spherical hard carbon composite material precursor is carbonized at a high temperature of 800-1300 ℃ for 1-10 hours at a heating rate of 1-5 ℃/min in an inert environment.
11. Use of the spherical hard carbon composite material according to claim 1 as a negative electrode material for sodium ion batteries.
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