CN113346074B - Electrode material with multilayer structure and preparation method thereof - Google Patents
Electrode material with multilayer structure and preparation method thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 52
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 52
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- ALRFTTOJSPMYSY-UHFFFAOYSA-N tin disulfide Chemical group S=[Sn]=S ALRFTTOJSPMYSY-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002048 multi walled nanotube Substances 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 15
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 38
- 239000010410 layer Substances 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 description 2
- 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 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- TUTLDIXHQPSHHQ-UHFFFAOYSA-N tin(iv) sulfide Chemical group [S-2].[S-2].[Sn+4] TUTLDIXHQPSHHQ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B32/158—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- 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
- H01M4/62—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an electrode material with a multilayer structure, which comprises carbon nanotubes, a carbon layer attached to the surface of the carbon nanotubes, and a tin compound layer between the carbon nanotubes and the carbon layer, wherein the tin compound layer is continuous and has a thickness of nanometer grade. The invention also provides a preparation method of the electrode material with the multilayer structure, which comprises the following steps: polymerizing the monomer and the carbon nano tube in situ to obtain a carbon nano tube/polymer; dropwise adding a stannous ion solution, uniformly mixing, and removing a solvent to obtain a precursor; and annealing the precursor to obtain the product. The preparation method disclosed by the invention is simple in steps, low in raw material price and free of pollution, and is suitable for large-scale production, and the obtained electrode material with the multilayer structure effectively reduces the diffusion path of sodium ions, so that the rate performance is improved, and excellent conductivity and cycle stability are shown.
Description
Technical Field
The present invention relates to the field of batteries, and more particularly, to an electrode material of a multi-layered structure and a method for preparing the same.
Background
At present, the development of human society still depends heavily on traditional fossil energy sources such as coal, petroleum, natural gas and the like. The unreasonable energy consumption structure can accelerate the exhaustion of fossil energy to cause energy crisis, and can bring about a large amount of greenhouse gas emission and corresponding environmental problems, thereby being unfavorable for the sustainable development of human society. The renewable clean new energy industries such as solar energy, wind energy and the like are greatly developed to become the trend of unblockable. However, the new energy is unstable in power supply and is easily interfered by natural factors, so that a large-scale energy storage system needs to be introduced to supplement the smart grid so as to ensure stable input of electric energy and meet the power supply requirements of different periods and different areas. Sodium ion batteries are regarded as key equipment of large-scale energy storage systems by virtue of the characteristics of abundant sodium resource reserves, wide operable temperature range and the like. The sodium ion battery has a similar working principle as the lithium ion battery, and realizes the charge and discharge process by means of shuttling of sodium ions between the anode and the cathode. However, compared with lithium ions, the greater mass and radius of sodium ions increase the difficulty of intercalation and deintercalation in the electrode material, and when the common lithium ion battery anode material is applied to a sodium ion battery, the electrochemical performance is not ideal, so that the search for a proper electrode material is a key for developing the sodium ion battery technology.
Some tin compounds, such as tin dioxide, tin disulfide, etc., are ideal negative electrode materials for sodium ion batteries due to their relatively high theoretical capacity. However, the material is a semiconductor, has poor conductivity, is difficult to maintain high capacity under high current density, and easily generates large shape change and volume change in the charge and discharge process, thereby causing pulverization and dissolution of the material and affecting the cycle stability and practical application of the material. At present, carbon nanotubes are introduced to enhance conductivity, stability and the like, but the tin compound particles obtained in a three-dimensional form in this way are combined with the carbon nanotubes, so that the volume inhibition capability of the tin compound is still weak, and the control of sodium ion diffusion is limited. Accordingly, there is an urgent need for a novel electrode material that overcomes the above-described drawbacks.
Disclosure of Invention
In view of the above-mentioned technical problems, an object of the present invention is to provide an electrode material of a multi-layered structure, which effectively reduces the diffusion path of sodium ions, thereby improving the rate performance thereof.
In order to achieve the above object, the present invention adopts the following technical scheme:
an electrode material of a multilayer structure includes a carbon nanotube, a carbon layer attached to a surface of the carbon nanotube, and a tin compound layer between the carbon nanotube and the carbon layer, the tin compound layer being continuous and having a thickness of a nano-scale.
The tin compound layer of the present application is not intermittent particulate in the prior art, is continuous and has a very small thickness, on the order of nanometers, and in one embodiment is about 5nm. The continuous layer of nano-sized tin compound effectively reduces the diffusion path of ions such as sodium ions in the battery, thereby improving the rate performance thereof, compared to three-dimensional micro-sized tin compound particles. In addition, the carbon layer formed on the surface of the tin compound realizes a sandwich-like multi-layer structure of the carbon nano tube/tin compound/carbon layer, which is more beneficial to inhibiting morphology and volume change of the tin compound, is further beneficial to the cycling stability as an electrode material, and can effectively prevent the active material from falling off from the carbon nano tube. Preferably, the carbon layer is an amorphous carbon layer.
Further, the tin compound layer is tin disulfide (SnS 2 ) Tin trisulfide (Sn) 2 S 3 ) Or tin sulfide (SnS). Preferably, the tin compound layer is tin disulfide. Tin disulfide has a relatively high theoretical capacity (-1000 mA h-1). In addition, tin disulfide has a unique layered structure with larger layer spacing, and stacks between layers with weaker van der waals forces, which is more conducive to diffusion processes of ions such as sodium ions in the cell.
The second object of the present invention is to provide a method for preparing an electrode material of a multi-layered structure, which has simple steps, low raw material cost and no pollution, and is suitable for mass production.
In order to achieve the above object, the present invention adopts the following technical scheme:
a method for preparing an electrode material of a multilayer structure, comprising the steps of:
polymerizing the monomer and the carbon nano tube in situ to obtain a carbon nano tube/polymer;
dropwise adding a stannous ion solution, uniformly mixing, and removing a solvent to obtain a precursor;
and annealing the precursor to obtain the product.
After in-situ polymerization, tin ions are uniformly adsorbed on the surface of the carbon substrate, thereby spatially restricting the growth of tin compounds.
Further, the monomer and the carbon nano tube in-situ polymerization is carried out under the action of ultraviolet light by uniformly mixing the monomer, the solution of the carbon nano tube and the photoinitiator.
The solution of carbon nanotubes refers to a solution obtained by uniformly dispersing carbon nanotubes in a solvent, and solvents commonly used in the art for dispersing carbon nanotubes are applicable to the present application, for example, ethanol, isopropanol, or a mixture of water and isopropanol. Preferably, the photoinitiator is 2-hydroxy-2-methyl-1-phenylpropionic acid.
Further, the monomer is a nitrogen-containing monomer. The nitrogen-containing monomer can introduce nitrogen element into the product, thereby improving the conductivity of the carbon nanotubes, and in addition, can enhance the binding energy between the tin compound and the carbon nanotubes.
Further, the nitrogen-containing monomer is one or more of methacrylic acid gelatin, acrylamide or methylene bisacrylamide.
Further, the mass ratio of the carbon nano tube to the monomer is 1-10; the mass ratio of the carbon nano tube to the stannous ion is 0.2-12.
Further, the solvent was removed by lyophilization. And freeze-drying under the conditions of low pressure and low temperature to enable the solvent in the sample to be sublimated directly, so that the three-dimensional porous structure of the sample is maintained, and the sample has larger specific surface area.
Further, the precursor is mixed with sulfur powder prior to annealing. Preferably, the mass ratio of the precursor to the sulfur powder is 0.5-5.
Further, the annealing process comprises the following steps: heating the tube furnace to 300-800 ℃ at a heating rate of 5-50 ℃/min under inert gas atmosphere, and naturally cooling after maintaining for 5-200 min
The term "carbon nanotubes" herein includes single-walled carbon nanotubes and multi-walled carbon nanotubes.
The beneficial effects of the invention are that
The preparation method has simple steps, low raw material cost and no pollution, and is suitable for large-scale production;
the electrode material with the multilayer structure effectively reduces the diffusion path of sodium ions, thereby improving the rate performance;
the electrode material of the multilayer structure obtained by the present invention exhibits excellent conductivity and cycle stability.
Drawings
FIGS. 1 a) and b) are transmission electron microscopy images of the product of example 1 according to the invention;
FIG. 2 is an X-ray diffraction pattern of the product of example 1 according to the present invention;
fig. 3 a), b), c), d) are X-ray photoelectron spectra of the product of example 1 according to the invention;
FIG. 4 shows the product of example 1 according to the invention at a current density of 200mA g 1 The cyclic performance at that time;
FIG. 5 shows the product of example 1 according to the invention at a current density of 50mA g 1 The cyclic performance at that time;
fig. 6 shows the rate performance of the product of example 1 according to the invention (1c=500 mA g 1 )；
FIG. 7 is an X-ray diffraction pattern of the product of example 2 according to the present invention;
FIG. 8 is a transmission electron micrograph of the product of example 3 according to the invention;
FIG. 9 is an X-ray diffraction pattern of the product of example 3 according to the present invention;
FIG. 10 is a transmission electron microscopy image of the product of example 4 according to the invention;
FIG. 11 is an X-ray diffraction pattern of the product of example 4 according to the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
Example 1
Deionized water and isopropanol are prepared into a mixture according to the volume ratio of 1:1, then 20mg of multi-wall carbon nano tubes are added, and the mixture is subjected to ultrasonic treatment for 1h to form a uniform and stable solution. To this solution, 10mg of gelatin methacrylate and 10. Mu.L of 2-hydroxy-2-methyl-1-phenylpropion as a photoinitiator were sequentially added, and shaking was performed for 20 minutes to obtain a carbon nanotube/methacrylic acid solution. The carbon nanotube/methacrylic acid solution was exposed to a 365nm ultraviolet lamp (light intensity 1.35W/cm 2 ) Irradiating for 15min to polymerize the methacrylic acid monomer on the surface of the carbon nanotube. 1.34mL of 0.15M stannous chloride solution was then added dropwise and stirred for 4 hours to ensure adsorption of stannous ions by the polymer. After stirring, the resulting solution was frozen in a refrigerator for 1 hour, then put in a freeze dryer, and taken out after 2 days. Stirring and mixing the freeze-dried precursor and sulfur powder, and putting the mixture into a quartz boat, wherein the mass ratio of the precursor to the sulfur powder is 0.67. Then, putting the quartz boat into a heating center of a tube furnace, introducing 200sccm of argon for 20min to take out residual air in the tube furnace, heating the tube furnace to 550 ℃ at a heating rate of 35 ℃/min, annealing for 20min, opening a furnace cover, naturally cooling to obtain a product, and introducing 50sccm of argon in the heating and annealing processes.
The resulting product was observed by transmission electron microscopy, FIGS. 1 a) and b) being transmission electron microscopy images at dimensions of 100nm and 5nm, respectively. As shown in fig. 1 a), the carbon nanotubes are uniformly dispersed, and the surface thereof is covered with a layered modifier. Enlarged as shown in fig. 1 b), the sandwich-like multi-layer structure of the product can be clearly seen. The upper left of fig. 1 b) is a carbon nanotube, the surface of which (shown as the right side of the carbon nanotube) is covered with a tin disulfide layer having a thickness of about 5nm, the interlayer spacing of the tin disulfide layer is 0.59nm, and the entire tin disulfide layer has a nano-scale lamellar structure. The tin disulfide is also covered with an amorphous carbon layer about 2nm thick (shown on the right side of the tin disulfide). The crystal structure of the product was further confirmed by X-ray diffraction pattern, and the result is shown in fig. 2. The upper curve in fig. 2 is the product of example 1, the lower curve is tin disulfide, and the characteristic peaks of the product are found from tin disulfide when comparing the diffraction peak positions with the standard alignment card. FIG. 3 a) is an X-ray photoelectron spectrum of a product, confirming the presence of tin, sulfur, carbon, nitrogen and oxygen elements in the product. Fig. 3 b), 3 c) and 3 d) are the results of high resolution scanning of nitrogen, tin and sulfur, respectively, the peak positions of which confirm that tin is +4 valent and sulfur is-2 valent in the product, and further that the results confirm nitrogen doping and sulfur doping of the carbon nanotubes.
Electrode sheet preparation
The product, carbon black and polyvinylidene fluoride are mixed according to the mass ratio of 70:20:10, and are smeared on copper foil, and then the copper foil is put into a vacuum drying oven for drying for 24 hours at the temperature of 80 ℃. In a glove box with the nitrogen protection and the water and oxygen concentrations lower than 0.5ppm, assembling the dried electrode plate and the counter electrode sodium metal plate into a CR2032 button cell for testing
The electrode sheet manufactured as above was subjected to half cell test.
Fig. 4 and 5 show the cycle performance of the products. As shown in FIG. 4, the current density is in the charge/discharge interval of 0.02 to 2.5V - 200mA g 1 At 80 cycles, the capacity of the negative electrode of the sodium ion battery prepared by the product of the example 1 can be maintained at 417mAh g -1 As shown in FIG. 5, the current density was in the charge/discharge interval of 0.02 to 2.5V - 50mA g 1 At 60 cycles, the capacity of the negative electrode of the sodium ion battery prepared by the product of the example 1 can be maintained at 500mAh g -1 And the left and right sides show better circulation stability. As shown in FIG. 6, when the current densities were 50, 100, 200, 500, 1000, 1500, 2000 and 2500mA g, respectively -1 The corresponding capacities of the electrodes are 738, 613, 538, 463, 411, 382, 360 and 344mAh g -1 . When the current density is set to 50mA g again -1 Its capacity is 700mAh g -1 And the multiplying power performance is higher.
Example 2
The procedure of example 1 was repeated except that the lyophilized sample was directly annealed at about 500 ° without adding sulfur powder, and tin dioxide dispersed on carbon nanotubes was obtained. The annealing process may be performed without introducing inert gas or with introducing air or oxygen. Fig. 7 shows an X-ray diffraction pattern, the upper curve being the product of this example, the lower curve being tin dioxide, the comparison of characteristic peaks indicating that the characteristic peaks of the product are all from tin dioxide.
Example 3
The procedure of example 1 above was repeated except that the annealing temperature was 600℃and the annealing time was 60 minutes, to finally obtain a product of a multi-layered structure of carbon nanotube/SnS/carbon layer. Fig. 8 shows a transmission electron microscope image of the product, and it can be seen that the surface of the carbon nanotube is uniformly covered with the layered modification. Fig. 9 shows an X-ray diffraction pattern, the upper curve being the product of this example, the lower curve being the ditin trisulfide, the comparison of the characteristic peaks indicating that the characteristic peaks of the product are all from ditin trisulfide.
Example 4
The procedure of example 1 was repeated except that the annealing temperature was 600℃and the annealing time was 90min, to finally obtain carbon nanotubes/Sn 2 S 3 Product of the multilayer structure of the carbon layer. Fig. 10 shows a transmission electron microscope image of the product, and it can be seen that the surface of the carbon nanotube is uniformly covered with the layered modification. Fig. 11 shows an X-ray diffraction pattern, the upper curve being the product of this example, the lower curve being stannous sulfide, the comparison of the characteristic peaks indicating that the characteristic peaks of the product are all from stannous sulfide.
Example 5
Deionized water and isopropanol are prepared into a mixture in a volume ratio of 5:1, then 20mg of multi-wall carbon nano tubes are added, and the mixture is subjected to ultrasonic treatment for 2 hours to form a uniform and stable solution. To this solution, 20mg of acrylamide and 50L of 2-hydroxy-2-methyl-1-phenylpropion as a photoinitiator were sequentially added, and shaking was performed for 60 minutes to obtain a carbon nanotube/acrylamide solution. The carbon nanotube/acrylamide solution was exposed to a 365nm ultraviolet lamp (light intensity 1.35W/cm) 2 ) Irradiating for 60min to polymerize the acrylamide monomer on the surface of the carbon nanotube. Then 5mL of stannous chloride solution at a concentration of 0.15M was added dropwise and stirred for 12 hours to ensure adsorption of stannous ions by the polymer. After stirring, the resulting solution was frozen in a refrigerator for 3 hours, then put in a freeze dryer, and taken out after 3 days. The precursor after freeze-drying treatment and sulfur powderStirring and mixing, and putting into a quartz boat, wherein the mass ratio of the precursor to the sulfur powder is 5. Then, the quartz boat is placed in a heating center of a tube furnace, 200sccm of argon is firstly introduced for 30min to take out residual air in the tube furnace, then the tube furnace is heated to 800 ℃ at a heating rate of 50 ℃/min, and after annealing for 200min, rapid cooling is performed, and 500sccm of argon is introduced in the heating and annealing processes. And cooling the furnace to obtain the product.
Example 6
Deionized water and isopropanol are prepared into a mixture according to the volume ratio of 3:1, then 20mg of multi-wall carbon nano tubes are added, and the mixture is subjected to ultrasonic treatment for 3 hours to form a uniform and stable solution. To this solution, 2mg of methylene bisacrylamide and 5L of 2-hydroxy-2-methyl-1-phenylpropion as a photoinitiator were sequentially added, and shaking was performed for 10min to obtain carbon nanotube/methylene bisacrylamide. The carbon nanotube/methylene bisacrylamide solution was exposed to 365nm ultraviolet lamp (light intensity 1.35W/cm) 2 ) Irradiating for 10min to polymerize the methylene bisacrylamide monomer on the surface of the carbon nano tube. Then, 0.1mL of stannous chloride solution having a concentration of 0.15M was added dropwise, and stirred for 1 hour to ensure adsorption of stannous ions by the polymer. After stirring, the resulting solution was frozen in a refrigerator for 1 hour, then put in a freeze dryer, and taken out after 1 day. Stirring and mixing the freeze-dried precursor and sulfur powder, and putting the mixture into a quartz boat, wherein the mass ratio of the precursor to the sulfur powder is 0.5. Then, the quartz boat is placed in a heating center of a tube furnace, 200sccm of argon is firstly introduced for 5min to take out residual air in the tube furnace, then the tube furnace is heated to 300 ℃ at a heating rate of 5 ℃/min, and after 5min of annealing, rapid cooling is performed, and 1sccm of argon is introduced in the heating and annealing processes. And cooling the furnace to obtain the product.
It should be understood that the above examples of the present invention are only illustrative of the present invention and are not limiting of the embodiments of the present invention. It is not intended to be exhaustive of all embodiments, and other variations or modifications of the various forms, such as a simple combination of the embodiments, may be made by those skilled in the art based on the above description. Obvious changes and modifications which are extended by the technical proposal of the invention are still within the protection scope of the invention.
Claims (2)
1. An electrode material of a multilayer structure, characterized by comprising carbon nanotubes, a carbon layer attached to the surface of the carbon nanotubes, and a tin compound layer between the carbon nanotubes and the carbon layer, the tin compound layer being continuous and having a thickness of nanometer scale;
the tin compound layer is tin disulfide;
the preparation method of the electrode material comprises the following steps:
polymerizing a monomer and a carbon nano tube in situ to obtain a carbon nano tube/polymer; the monomer is methacrylic acid gelatin, and the carbon nano tube is a multi-wall carbon nano tube; the mass ratio of the carbon nano tube to the monomer is 1-10; the in-situ polymerization is carried out under the condition of light initiator and illumination;
dropwise adding a stannous ion solution, uniformly mixing, and removing a solvent through freeze drying to obtain a precursor; the stannous ion solution is stannous chloride solution; the mass ratio of the carbon nano tube to the stannous ion is 0.2-12;
mixing the precursor with sulfur powder, and annealing the precursor to obtain a product; the annealing process comprises the following steps: and heating the tube furnace to 300-800 ℃ at a heating rate of 5-50 ℃/min under the inert gas atmosphere, and naturally cooling after keeping for 5-200 min.
2. The method for preparing the electrode material with the multilayer structure according to claim 1, wherein the in-situ polymerization of the monomer and the carbon nanotube is performed under the action of ultraviolet light by uniformly mixing the monomer, the solution of the carbon nanotube and the photoinitiator.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121791A (en) * | 2006-08-09 | 2008-02-13 | 清华大学 | Method for preparing carbon nano-tube/polymer composite material |
| JP2010202455A (en) * | 2009-03-03 | 2010-09-16 | China Steel Chemical Corp | Modified carbon material, manufacturing method therefor and lithium ion secondary battery using the same as negative-electrode material |
| KR20110008518A (en) * | 2009-07-20 | 2011-01-27 | 주식회사 엑사이엔씨 | Method for manufacturing carbon nano tube solution having polymer and method for manufacturing transparency conductivity film using the same and transparency conductivity film manufacured by the method |
| CN105514356A (en) * | 2015-12-25 | 2016-04-20 | 东莞威胜储能技术有限公司 | Composite cathode material for sodium battery and preparation method of composite cathode material |
| CN106058198A (en) * | 2016-07-26 | 2016-10-26 | 陕西科技大学 | Method for preparing SnS2/CNTs (carbon nano-tubes) cathode materials for sodium-ion batteries in in-situ manner |
| CN106887578A (en) * | 2017-04-01 | 2017-06-23 | 中南大学 | A kind of artificial gold/CNT composite Nano negative material and preparation method thereof |
| CN107394129A (en) * | 2017-06-20 | 2017-11-24 | 陕西科技大学 | A kind of preparation method of stannic disulfide carbon nano-tube combination electrode material |
| CN107887586A (en) * | 2017-11-06 | 2018-04-06 | 陈少华 | A kind of preparation method of ion cathode material lithium |
| CN109873149A (en) * | 2019-03-13 | 2019-06-11 | 中国石油大学(华东) | Molybdenum disulfide and the co-modified stannous sulfide nanosphere and preparation method thereof of double carbon-coatings |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7745047B2 (en) * | 2007-11-05 | 2010-06-29 | Nanotek Instruments, Inc. | Nano graphene platelet-base composite anode compositions for lithium ion batteries |
-
2020
- 2020-03-03 CN CN202010137911.4A patent/CN113346074B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121791A (en) * | 2006-08-09 | 2008-02-13 | 清华大学 | Method for preparing carbon nano-tube/polymer composite material |
| JP2010202455A (en) * | 2009-03-03 | 2010-09-16 | China Steel Chemical Corp | Modified carbon material, manufacturing method therefor and lithium ion secondary battery using the same as negative-electrode material |
| KR20110008518A (en) * | 2009-07-20 | 2011-01-27 | 주식회사 엑사이엔씨 | Method for manufacturing carbon nano tube solution having polymer and method for manufacturing transparency conductivity film using the same and transparency conductivity film manufacured by the method |
| CN105514356A (en) * | 2015-12-25 | 2016-04-20 | 东莞威胜储能技术有限公司 | Composite cathode material for sodium battery and preparation method of composite cathode material |
| CN106058198A (en) * | 2016-07-26 | 2016-10-26 | 陕西科技大学 | Method for preparing SnS2/CNTs (carbon nano-tubes) cathode materials for sodium-ion batteries in in-situ manner |
| CN106887578A (en) * | 2017-04-01 | 2017-06-23 | 中南大学 | A kind of artificial gold/CNT composite Nano negative material and preparation method thereof |
| CN107394129A (en) * | 2017-06-20 | 2017-11-24 | 陕西科技大学 | A kind of preparation method of stannic disulfide carbon nano-tube combination electrode material |
| CN107887586A (en) * | 2017-11-06 | 2018-04-06 | 陈少华 | A kind of preparation method of ion cathode material lithium |
| CN109873149A (en) * | 2019-03-13 | 2019-06-11 | 中国石油大学(华东) | Molybdenum disulfide and the co-modified stannous sulfide nanosphere and preparation method thereof of double carbon-coatings |
Non-Patent Citations (2)
| Title |
|---|
| Confining SnS2 Ultrathin Nanosheets in Hollow Carbon Nanostructures for Efficient Capacitive Sodium Storage;Yuhan Liu et al.;JOULE;第2卷;725-735 * |
| N-doped CMK-3 anchored with SnS2 nanosheets as anode of lithium ion batteries with superior cyclicperformance and enhanced reversible capacity;Jingchao Liang et al.;Journal of Solid Chemistry;第265卷;424-430 * |
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