CN113809304A - Preparation method and application of tin dioxide/carbon nanotube composite material based on plasma - Google Patents
Preparation method and application of tin dioxide/carbon nanotube composite material based on plasma Download PDFInfo
- Publication number
- CN113809304A CN113809304A CN202111093893.5A CN202111093893A CN113809304A CN 113809304 A CN113809304 A CN 113809304A CN 202111093893 A CN202111093893 A CN 202111093893A CN 113809304 A CN113809304 A CN 113809304A
- Authority
- CN
- China
- Prior art keywords
- tin dioxide
- composite material
- carbon nano
- nano tube
- tin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 98
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000004020 conductor Substances 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000012530 fluid Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 239000010406 cathode material Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011343 solid material Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 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(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- H01M4/362—Composites
-
- 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
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method and application of a tin dioxide/carbon nano tube composite material based on plasma, wherein micron-sized high-purity tin metal powder, a carbon nano tube and deionized water are uniformly mixed according to a certain proportion to be in a semi-fluid state and are pressed into a cylinder shape to be used as a cathode; the method comprises the following steps of adopting a refractory conductive material as a positive electrode, keeping a certain distance from the positive electrode, switching on a power supply to generate direct current arc plasma, realizing uniform loading of tin dioxide nanoparticles on the surface of a carbon nanotube while dispersing the carbon nanotube to obtain a tin dioxide/carbon nanotube composite material, and drying the tin dioxide/carbon nanotube composite material to be used as a negative electrode of a lithium ion battery; compared with a chemical method, the preparation method has the advantages of simplicity, rapidness, green and the like, and the carbon nano tube conductive network structure not only provides enough space for the volume expansion of tin dioxide, but also is beneficial to electron transfer; the method is expected to realize industrialization, and provides a new idea for preparation of other nano composite materials.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a preparation method and application of a plasma-based stannic oxide/carbon nano tube composite material.
Background
The information in this background section is disclosed only to enhance an understanding of the general background of the disclosure and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The lithium ion battery is used as an ideal energy storage device, and is widely applied to energy storage of electric vehicles, power grids and electronic devices due to the advantages of high energy density, long cycle life, low cost and the like. At present, as a commercial lithium ion battery cathode material, graphite cannot meet increasing energy storage requirements due to the defects of low theoretical specific capacitance, limited cycle rate and the like, so that the search for a new high-performance alternative cathode material becomes urgent.
Tin dioxide is widely applied to lithium battery electrode materials due to the fact that tin dioxide has high theoretical specific capacity (781 mAh/g). However, in the application process, the problems that the irreversible capacity is large for the first time, a large volume effect (volume expansion of 250-300%) exists during lithium intercalation, agglomeration is easy to occur in the circulation process and the like exist, so that the tin dioxide is often compounded with other materials to improve the dispersibility of tin dioxide particles, inhibit the agglomeration of particles and improve the circulation stability of electrode materials. The carbon nano tube has the advantages of large specific surface area, good conductivity, strong chemical stability and the like, and becomes a carrier material widely applied at present.
However, in the prior art, a complicated chemical method is mostly adopted for preparing the carbon nanotube/tin dioxide composite material, and in some techniques, purified and modified carbon nanotubes and a tin tetrachloride solution are mixed and subjected to ultrasonic treatment, concentrated ammonia water is added dropwise into the obtained solution, the pH value is adjusted to 9, the solution is stirred for 3 hours, then the solution is subjected to suction filtration, washing and drying, and the obtained filter residue is calcined for 1 hour at 600 ℃ to obtain the carbon nanotube/tin dioxide composite electrode. For a chemical preparation method, on one hand, the use of chemical reagents causes that impurities are easily introduced in the preparation process, adverse effects are generated on the performance, and environmental pollution is caused; on the other hand, the complexity of the preparation process is not beneficial to large-scale production, so that the development of a simple and clean tin dioxide/carbon nanotube preparation method is of great significance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a tin dioxide/carbon nano tube composite material based on plasma, which solve the problems of complex process for preparing the tin dioxide/carbon nano tube composite material by a chemical method, difficulty in removing impurities caused by the use of various chemical reagents and the like in the background technology.
According to the preparation method of the tin dioxide/carbon nano tube composite material based on the plasma, on one hand, the contact area of the tin dioxide and the carbon nano tube can be increased on the basis of ensuring the dispersion uniformity of the carbon nano tube, and the combination of the tin dioxide and the carbon nano tube is promoted; on the other hand, the tin dioxide/carbon nano tube composite material coated with different tin dioxide contents can be obtained by adjusting the mass ratio of the carbon nano tube to the tin source, so that the requirements of the lithium battery electrode material on the performances such as electrochemistry and the like are met.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of a tin dioxide/carbon nano tube composite material based on plasma comprises the following steps:
s1: uniformly mixing tin metal powder, carbon nano tubes and deionized water to a semi-fluid state;
s2: pressing the semi-fluid mixture prepared in S1 into a cylindrical solid;
s3: taking the cylindrical solid material prepared in the step S2 as a negative electrode, taking a refractory conductive material as a positive electrode, and respectively and correspondingly connecting the negative electrode and the positive electrode with a power supply;
s4: switching on a power supply, generating direct current arc plasma between the cathode and the anode to form carbon nano tube dispersed mist, and simultaneously gasifying and oxidizing the tin metal powder to obtain tin dioxide nano particles which are uniformly loaded on the surface of the carbon nano tube to form a tin dioxide/carbon nano tube composite material;
s5: and (5) collecting the tin dioxide/carbon nano tube composite material prepared in the step S4, and carrying out ultrasonic treatment, filtration and drying.
Preferably, the tin metal powder is micron-sized high-purity tin metal powder; the mass ratio of the micron-sized high-purity tin metal powder to the carbon nano tubes to the deionized water is 8:1: 5.
Preferably, the refractory conductive material is one of iron, copper, aluminum, tungsten and graphite.
Preferably, the refractory conductive material is tungsten or graphite.
Preferably, in step S3, the distance between the negative electrode and the positive electrode is 2-5mm, and the power supply parameters are: voltage 8000 + 10000V, power 50W, frequency 0.1HZ-10 HZ.
Preferably, in the step S5, the ultrasonic time of the tin dioxide/carbon nanotube composite material is 0.5h, the drying temperature is 60-150 ℃, and the drying time is 1-2 h.
An application of a plasma-based stannic oxide/carbon nanotube composite material in a lithium battery cathode material.
The invention has the beneficial effects that:
1. compared with a chemical method, the preparation method of the tin dioxide/carbon nano tube composite material based on the plasma has the advantages of no use of any chemical reagent, simple preparation, rapidness, green and the like, and can realize uniform loading of tin dioxide nano particles on the surface of the carbon nano tube while the carbon nano tube is dispersed. The carbon nano tube conductive network structure not only can provide enough space for the volume expansion of the tin dioxide, but also is beneficial to realizing the electron transfer between the electrode and the tin dioxide in the lithium ion intercalation/deintercalation process. The method is expected to realize industrialization, and provides a new idea for preparation of other nano composite materials.
2. According to the invention, the cylindrical solid material is used as a negative electrode, a power supply is switched on, direct current arc plasma is generated between the negative electrode and a positive electrode, carbon nano tube dispersed mist is formed, and meanwhile, tin metal powder is gasified and oxidized; the carbon nano tube and the tin metal powder are mixed and pressed into a cylindrical solid material and simultaneously used as a negative electrode, the dispersion of the carbon nano tube and the gasification and oxidation of the tin metal powder have a synergistic effect, namely the formation of the dispersion mist of the carbon nano tube hinders the collision and aggregation among tin metal steam, and effectively inhibits the particle agglomeration caused by the collision among the tin steam, and the tin dioxide particles formed by adopting the preparation method disclosed by the invention are all in a nanometer level; simultaneously, the tin vapor and the carbon nano tube dispersion mist are better combined, and the dispersibility of the tin dioxide on the surface of the carbon nano tube is improved; the combination of the tin dioxide and the carbon nano tube is attributed to the condensation and oxidation of tin vapor on the surface of the carbon nano tube, and the tin dioxide still stably exists on the surface of the carbon nano tube after ultrasonic treatment, thereby showing good combination strength.
Drawings
FIG. 1 is a graphical representation of a tin dioxide/carbon nanotube composite material prepared in accordance with the present invention;
wherein: (a) is SnO2Scanning Electron Micrographs (SEM) of/CNTs; (b) and (c) SnO under different magnifications2Transmission Electron Microscopy (TEM) of/CNTs; (d) is SnO2High Resolution Transmission Electron Microscopy (HRTEM) of/CNTs;
FIG. 2 shows SnO prepared by the present invention2X-ray diffraction (XRD) patterns of/CNTs and commercially available tin dioxide;
FIG. 3 shows SnO prepared by the present invention2The specific surface area and the pore size distribution of the/CNTs composite material;
wherein: (e) is SnO2Nitrogen adsorption/desorption isotherms of the/CNTs composite; (f) SnO obtained for Barrett-Joyner-Halenda process2The pore size distribution of the/CNTs composite material;
FIG. 4 shows SnO prepared by the invention2CNTs and commercially available SnO2100mAg as negative electrode material of lithium ion battery-1Cycling stability at current density.
FIG. 5 shows SnO prepared by the invention2CNTs and commercially available SnO2As negative electrode of lithium ion batteryElectrochemical impedance spectrum of the electrode material in the frequency range of 0.01Hz-100 KHz;
Detailed Description
In order to clearly illustrate the technical features of the present solution, the following explains the present solution by way of specific embodiments and with reference to the accompanying drawings.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, and/or combinations thereof, unless the context clearly indicates otherwise.
Examples
Preparation of stannic oxide/carbon nano tube composite material
A preparation method of a tin dioxide/carbon nano tube composite material based on plasma comprises the following steps:
s1: uniformly mixing micron-sized high-purity tin metal powder, carbon nano tubes and deionized water according to the mass ratio of 8:1:5 to a semifluid state;
s2: pressing the semi-fluid mixture prepared in S1 into a cylindrical solid;
s3: taking the cylindrical solid material prepared in the step S2 as a negative electrode, taking a metal tungsten wire conductive material as a positive electrode, and respectively and correspondingly connecting the negative electrode and the positive electrode with a power supply; the distance between the two electrodes of the negative electrode and the positive electrode is 2-5 mm; the power supply parameters are as follows: voltage 8000V, power 50W, frequency 5 HZ;
s4: switching on a power supply, generating direct current arc plasma between the cathode and the anode to form carbon nano tube dispersed mist, and simultaneously gasifying and oxidizing the tin metal powder to obtain tin dioxide nano particles which are uniformly loaded on the surface of the carbon nano tube to form a tin dioxide/carbon nano tube composite material;
s5: and (4) collecting the tin dioxide/carbon nano tube composite material prepared in the step S4, carrying out ultrasonic treatment for 0.5h, and drying for 2h at 100 ℃.
Second, application of tin dioxide/carbon nano tube composite material based on plasma
The invention discloses an application of a plasma-based tin dioxide/carbon nanotube composite material, which is applied to a lithium battery cathode material.
Electrochemical performance test
The electrochemical performance was performed under the following conditions: and mixing the prepared stannic oxide/carbon nanotube composite material as a negative electrode active substance with conductive carbon black and polyvinylidene fluoride, wherein the weight ratio of the stannic oxide/carbon nanotube composite material to the conductive carbon black and the polyvinylidene fluoride is 8:1:1, fully mixing the stannic oxide/carbon nanotube composite material with the conductive carbon black and the polyvinylidene fluoride, uniformly coating the mixture on a copper foil, and drying the punched sheet at 80 ℃ to obtain the working electrode. Assembling 2032 button cell in glove box by using pure lithium sheet as counter electrode, wherein the diaphragm is polypropylene/polyethylene microporous film, and the electrolyte is LiPF of 1.15M6The battery is assembled and then subjected to charge and discharge tests on a blue test system, and the voltage window is 0.01V-3V. Electrochemical impedance spectroscopy testing was performed using an electrochemical workstation (CHI660D) at a frequency range of 0.01Hz-100 KHz.
FIG. 1 shows a tin dioxide/carbon nanotube composite material (SnO) prepared by the present invention2/CNTs), the apparent tubular structure of the carbon nanotubes can be seen from fig. 1, and SnO2The tin dioxide/carbon nano tube composite material is uniformly loaded on the carbon nano tube, and has no obvious agglomeration phenomenon, so that the tin dioxide/carbon nano tube composite material based on the plasma has good dispersibility.
FIG. 2 shows SnO prepared by the present invention2/CNTs and commercially available tin dioxide (SnO)2) By comparing with a standard value card (JCPDS 41-1445), it can be seen that the main diffraction peak is associated with SnO2The tetragonal rutile phase is well matched, which shows that the tin metal powder forms SnO under the action of direct current arc plasma2And (3) nanoparticles.
FIG. 3 shows SnO prepared by the present invention2The specific surface area and the pore size distribution of the/CNTs composite material show that SnO is shown2The specific surface area of the/CNTs composite material is 181.92m2 g-1Pore size distribution was analyzed by the Barrett-Joyner-Halenda (BJH) method and had a pore volume of 0.89mL g-1The average pore diameter is 16.76nm, and the large specific surface area and pore volume are favorable for relieving strain generated in the electrochemical cycle process, relieving the volume expansion of tin dioxide and improving the cycle stability.
FIG. 4 shows SnO prepared by the present invention2CNTs and commercially available SnO2100mAg as negative electrode material of lithium ion battery-1The cycling stability at current density, although commercially available SnO, can be seen from the figure2Shows a higher initial discharge capacity, but the capacity drops rapidly to 200mAh g after 60 cycles-1Below, the cycling stability is poor, while the SnO prepared by the present application2the/CNTsshowed high cycling stability at 100mA g-1The lower circulation still has 472mAh g after 200 circles-1The capacity of (c).
FIG. 5 shows SnO prepared by the present invention2CNTs and commercially available SnO2As an Electrochemical Impedance Spectroscopy (EIS) of the lithium ion battery cathode material in the frequency range of 0.01Hz-100KHz, SnO can be seen in the figure2The charge transfer resistance of the/CNTs is 119.8 omega, which is lower than that of the commercially available SnO2198.7 Ω, indicating that the introduction of carbon nanotubes accelerates electron transport during the electrochemical reaction and has higher charge transfer efficiency. At the same time, at low frequencies, the slope of the line represents the ionic conductivity, SnO, of the material2The impedance slope of the/CNTs is larger than that of the commercially available SnO2The slope of the impedance of (A), indicating SnO2/CNTs have excellent Li+The diffusion rate thus has better lithium storage characteristics and exhibits better electrochemical performance.
In summary, compared with a chemical method, the preparation method of the tin dioxide/carbon nanotube composite material based on the plasma has the advantages of simple preparation, rapidness, green and the like without using any chemical reagent, and uniform loading of the tin dioxide nanoparticles on the surface of the carbon nanotube is realized while the carbon nanotube is dispersed. The carbon nano tube conductive network structure not only can provide enough space for the volume expansion of the tin dioxide, but also is beneficial to realizing the electron transfer between the electrode and the tin dioxide in the lithium ion intercalation/deintercalation process; the invention prepares a high-performance tin dioxide/carbon nano tube composite material, and can be used as a good lithium battery cathode material.
The above embodiments are preferred embodiments of the present disclosure, but the embodiments of the present disclosure are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present disclosure should be regarded as equivalent replacements within the scope of the present disclosure.
Claims (8)
1. A preparation method of a tin dioxide/carbon nano tube composite material based on plasma is characterized by comprising the following steps:
s1: uniformly mixing tin metal powder, carbon nano tubes and deionized water to a semi-fluid state;
s2: pressing the semi-fluid mixture prepared in S1 into a cylindrical solid;
s3: taking the cylindrical solid material prepared in the step S2 as a negative electrode, taking a refractory conductive material as a positive electrode, and respectively and correspondingly connecting the negative electrode and the positive electrode with a power supply;
s4: switching on a power supply, generating direct current arc plasma between the cathode and the anode to form carbon nano tube dispersed fog, gasifying and oxidizing tin metal powder to obtain tin dioxide nano particles, and uniformly loading the tin dioxide nano particles on the surface of the carbon nano tube to form a tin dioxide/carbon nano tube composite material;
s5: and (5) collecting the tin dioxide/carbon nano tube composite material prepared in the step S4, and carrying out ultrasonic treatment, filtration and drying.
2. The method of claim 1, wherein the tin metal powder is a micron-sized high purity tin metal powder; the mass ratio of the micron-sized high-purity tin metal powder to the carbon nano tubes to the deionized water is 8:1: 5.
3. The method of claim 1, wherein the refractory conductive material is one of iron, copper, aluminum, tungsten, and graphite.
4. The method of claim 3, wherein the refractory conductive material is tungsten or graphite.
5. The method for preparing tin dioxide/carbon nanotube composite material according to claim 1, wherein in step S3, the distance between the two electrodes of the negative electrode and the positive electrode is 2-5mm, and the power supply parameters are as follows: the voltage is 8000-10000V, the power is 50W, and the frequency is 0.1HZ-10 HZ.
6. The method of claim 1, wherein in step S5, the ultrasonic time of the tin dioxide/carbon nanotube composite material is 0.5 h.
7. The method of claim 1, wherein in step S5, the drying temperature of the tin dioxide/carbon nanotube composite material is 60-150 ℃ and the drying time is 1-2 h.
8. The application of the plasma-based tin dioxide/carbon nanotube composite material is characterized in that the plasma-based tin dioxide/carbon nanotube composite material is applied to a lithium battery cathode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111093893.5A CN113809304B (en) | 2021-09-17 | 2021-09-17 | Preparation method and application of plasma-based tin dioxide/carbon nanotube composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111093893.5A CN113809304B (en) | 2021-09-17 | 2021-09-17 | Preparation method and application of plasma-based tin dioxide/carbon nanotube composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113809304A true CN113809304A (en) | 2021-12-17 |
| CN113809304B CN113809304B (en) | 2023-03-03 |
Family
ID=78939672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111093893.5A Active CN113809304B (en) | 2021-09-17 | 2021-09-17 | Preparation method and application of plasma-based tin dioxide/carbon nanotube composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113809304B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115101762A (en) * | 2022-07-05 | 2022-09-23 | 青岛科技大学 | Preparation method of carbon nano tube/metal selenide material |
| CN115332518A (en) * | 2022-08-31 | 2022-11-11 | 华南理工大学 | Quantum dot tin oxide loaded multi-walled carbon nanotube composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623669A (en) * | 2012-03-31 | 2012-08-01 | 大连理工大学 | Preparation method and application of carbon tin nanometer composite powder |
| CN103482623A (en) * | 2013-09-05 | 2014-01-01 | 大连理工大学 | Method for preparing nano diamonds by using direct-current arc process |
| CN106953079A (en) * | 2017-03-27 | 2017-07-14 | 华中科技大学 | A kind of multilevel hierarchy carbon nano tube/tin dioxide composite and preparation method thereof |
| CN111203249A (en) * | 2019-09-18 | 2020-05-29 | 杭州电子科技大学 | Preparation method of graphene-coated transition metal carbide nanocapsules and application of nanocapsules in microwave catalysis field |
-
2021
- 2021-09-17 CN CN202111093893.5A patent/CN113809304B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623669A (en) * | 2012-03-31 | 2012-08-01 | 大连理工大学 | Preparation method and application of carbon tin nanometer composite powder |
| CN103482623A (en) * | 2013-09-05 | 2014-01-01 | 大连理工大学 | Method for preparing nano diamonds by using direct-current arc process |
| CN106953079A (en) * | 2017-03-27 | 2017-07-14 | 华中科技大学 | A kind of multilevel hierarchy carbon nano tube/tin dioxide composite and preparation method thereof |
| CN111203249A (en) * | 2019-09-18 | 2020-05-29 | 杭州电子科技大学 | Preparation method of graphene-coated transition metal carbide nanocapsules and application of nanocapsules in microwave catalysis field |
Non-Patent Citations (3)
| Title |
|---|
| CHANG-HAN XU: "Atmospheric-pressure plasma jet processed SnO2/CNT nanocomposite for supercapacitor application", 《CERAMICS INTERNATIONAL》 * |
| LI SHAOLONG: "A novel preparation and formation mechanism of carbon nanotubes aerogel", 《ORIGINAL ARTICLES》 * |
| M. ALAF: "Tin/Tinoxide (Sn/SnO2) Nanocomposites Thin Films as Negative-Electrode Materials for Li-Ion Batteries", 《ACTA PHYSICA POLONICA A》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115101762A (en) * | 2022-07-05 | 2022-09-23 | 青岛科技大学 | Preparation method of carbon nano tube/metal selenide material |
| CN115332518A (en) * | 2022-08-31 | 2022-11-11 | 华南理工大学 | Quantum dot tin oxide loaded multi-walled carbon nanotube composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113809304B (en) | 2023-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Graphene-wrapped MnO2-graphene nanoribbons as anode materials for high-performance lithium ion batteries | |
| Liu et al. | In situ fabrication of three-dimensional, ultrathin graphite/carbon nanotube/NiO composite as binder-free electrode for high-performance energy storage | |
| Zhou et al. | Hydrothermal synthesis of flower-like MoS2 nanospheres for electrochemical supercapacitors | |
| Wang et al. | Reduced graphene oxide-wrapped FeS 2 composite as anode for high-performance sodium-ion batteries | |
| Wang et al. | Ni 12 P 5 nanoparticles decorated on carbon nanotubes with enhanced electrocatalytic and lithium storage properties | |
| WO2016150174A1 (en) | Carbon nanotube-graphene composite conductive paste, preparation method therefor, and uses thereof | |
| Ramesh et al. | A nanocrystalline structured NiO/MnO 2@ nitrogen-doped graphene oxide hybrid nanocomposite for high performance supercapacitors | |
| Xu et al. | Nano-structured red phosphorus/porous carbon as a superior anode for lithium and sodium-ion batteries | |
| CN106374087A (en) | Cathode material for long-circulation lithium-sulfur battery and preparation method thereof | |
| CN113809304B (en) | Preparation method and application of plasma-based tin dioxide/carbon nanotube composite material | |
| Lei et al. | High-Performance Li-CO 2 Batteries with α-MnO 2/CNT Cathodes | |
| Chen et al. | Hierarchical flower-like NiCo 2 O 4@ TiO 2 hetero-nanosheets as anodes for lithium ion batteries | |
| JP2018532224A (en) | Semi-solid flow Li / O2 battery | |
| Zhuang et al. | Synthesis and characterization of electrospun molybdenum dioxide–carbon nanofibers as sulfur matrix additives for rechargeable lithium–sulfur battery applications | |
| Ye et al. | Constructing Li 3 VO 4 nanoparticles anchored on crumpled reduced graphene oxide for high-power lithium-ion batteries | |
| Ji et al. | Electrospinning preparation of one-dimensional Co 2+-doped Li 4 Ti 5 O 12 nanofibers for high-performance lithium ion battery | |
| Liu et al. | Fe 3 O 4 nanoparticle anchored layered graphene films for high performance lithium storage | |
| Zhang et al. | Morphology and electrochemical properties of NiCo2O4 powders prepared by a facile hydrothermal method | |
| WO2012141308A1 (en) | Carbon black composite and lithium-ion secondary battery using same | |
| Liu et al. | Facile fabrication of graphene-encapsulated Mn 3 O 4 octahedra cross-linked with a silver network as a high-capacity anode material for lithium ion batteries | |
| Farahpour et al. | In situ synthesis of advantageously united copper stannate nanoparticles for a new high powered supercapacitor electrode | |
| Ning et al. | Elasticity-related periodical Li storage behavior delivered by porous graphene | |
| Zhao et al. | A CoSe 2-based 3D conductive network for high-performance potassium storage: enhancing charge transportation by encapsulation and restriction strategy | |
| Liu et al. | N-doped reduced graphene oxide loading nano lead oxide as negative additive for enhanced properties of lead-carbon batteries | |
| Hong et al. | A comparative study of the effects of different methods for preparing RGO/Metal-Oxide nanocomposite electrodes on supercapacitor performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |