CN112978713A - Nano-micron carbon tube, preparation method thereof, electrode and lithium ion battery - Google Patents
Nano-micron carbon tube, preparation method thereof, electrode and lithium ion battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002121 nanofiber Substances 0.000 claims abstract description 42
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000002861 polymer material Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000006258 conductive agent Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229960003638 dopamine Drugs 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229940072049 amyl acetate Drugs 0.000 claims description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims 2
- 150000002500 ions Chemical class 0.000 abstract description 11
- 230000010287 polarization Effects 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005056 compaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 229920001690 polydopamine Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000446 fuel Substances 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
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
-
- 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
- C01B32/16—Preparation
-
- 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
- C01B32/16—Preparation
- C01B32/164—Preparation involving continuous processes
-
- 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
- H01M4/62—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 nano-micron carbon tube, a preparation method thereof, an electrode and a lithium ion battery. The nano-micron carbon tube has a hollow tube structure, and the inner diameter is 100-4000 nm. The preparation method comprises the following steps: 1) carrying out electrostatic spinning on electrostatic spinning precursor solution containing a high polymer material to obtain nano-fiber yarns; 2) dispersing the nano-fiber filaments into hydrochloric acid solution containing organic monomers, and adding an initiator to perform polymerization reaction to obtain the nano-fiber filaments with the surfaces coated with polymers; 3) adding an organic solvent into the nanofiber filaments coated with the polymer on the surface, and stirring to fully dissolve the high polymer material to obtain a hollow polymer tube; 4) presintering and carbonizing in inert atmosphere, and cooling to obtain nanometer carbon tube. The nano-micron carbon tube has both conductive capability and good ion conductive capability, can be added into an electrode as a conductive agent, can effectively eliminate the polarization phenomenon caused by inconsistent electron and ion transmission capabilities under the condition of large-current charge and discharge, and improves the rate capability.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a nano-micron carbon tube, a preparation method thereof, an electrode and a lithium ion battery.
Background
The lithium ion battery is a high-capacity long-life environment-friendly battery, has the advantages of high voltage, large specific energy, long cycle life, good safety performance, small self-discharge, no memory effect, rapid charge and discharge, wide working temperature range and the like, and is widely applied to the fields of energy storage, electric automobiles, portable electronic products and the like. With the development of society and the popularization of charging piles, especially compared with fuel vehicles, the charging speed of the charging pile is far less than the demand of consumers. Therefore, the rate capability of lithium ion batteries is also increasingly required.
Currently, the commercial lithium ion battery generally uses SP, CNT and graphene as conductive carbon additives, and particularly, with the requirement of higher and higher rate performance, the application of the CNT and the graphene is more and more extensive. However, with the design of thick electrodes for increasing energy density, the transmission path of lithium ions is increasing continuously; along with the high compaction design of the electrode, the porosity of the pole piece is continuously reduced; leading to increasingly difficult electrolyte penetration. As the polarization of the electrode increases during high-rate charging of the battery, lithium deposition may occur in a local area, eventually leading to deterioration of the safety and cycle performance of the battery.
CN106941167A discloses a porous composite negative electrode material for a lithium ion battery, which is prepared by adding a pore-forming agent into an electrospinning solution, preparing composite fibers through electrospinning, and removing the pore-forming agent in the composite fibers through thermal decomposition, solvent in an organic solvent or chemical corrosion, so that pores are formed in the composite fibers, and the porosity of the negative electrode material is increased. However, the porous graphite used by the electrode plate is 3-15um micron-sized, and most of pores generated by cold pressing of the electrode plate after pore forming are still flattened by the pressing roller.
With the higher and higher energy density requirement of the market on the battery products, how to solve the problems of porosity and poor lithium ion conductivity caused by the continuous increase of the thickness and the continuous increase of the compaction density becomes a limitation for improving the rate capability. Therefore, it is urgently needed to solve the above problems by some new materials or processes.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a nano-micron carbon tube, a preparation method thereof, an electrode and a lithium ion battery. The tubular conductive structure is prepared by adopting an in-situ polymerization method of organic monomers on the nano cellulose fibers and a template sacrifice method, and the polarization of the battery is reduced by increasing a transmission channel of lithium ions and electron conductivity, so that the multiplying power performance of the battery is improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a nano-micron carbon tube is provided, which is a hollow tube structure with an inner diameter of 100 and 4000 nm.
According to the scheme, the wall thickness of the nano-micron carbon tube is 100-500 nm.
The preparation method of the nano-micron carbon tube comprises the following steps:
1) carrying out electrostatic spinning on electrostatic spinning precursor solution containing a high polymer material to obtain nano-fiber yarns;
2) uniformly dispersing the nano-fiber filaments obtained in the step 1) into a hydrochloric acid solution containing an organic monomer, adding a certain initiator, and carrying out polymerization reaction to obtain nano-fiber filaments with the surfaces coated with polymers;
3) adding an organic solvent into the nanofiber filaments with the polymer-coated surfaces obtained in the step 2), and stirring to fully dissolve the high polymer material to obtain a hollow polymer tube;
4) under the protection of inert gas, pre-sintering and carbonizing the hollow polymer tube obtained in the step 3), and cooling to obtain the nano-micron carbon tube.
According to the scheme, in the step 1), the high polymer material is any one or a combination of at least two of polymethyl methacrylate, polystyrene, polyethylene and polyvinyl acetate.
According to the scheme, in the step 1), the electrostatic spinning precursor solution containing the high polymer material is prepared by the following steps: adding the high molecular material into a solvent, and stirring for 5-60min at 40-100 ℃ to obtain the electrostatic spinning precursor solution containing the high molecular material, wherein the solvent is any one or a combination of at least two of N, N-dimethylformamide, dimethyl furan, dimethyl sulfoxide and N-methylpyrrolidone. The purpose of heating and stirring is to sufficiently dissolve the polymer material in the solvent.
According to the scheme, in the step 1), the concentration of the high molecular material in the electrostatic spinning precursor solution is 5-20%.
According to the scheme, in the step 1), the technological parameters of electrostatic spinning are as follows: the voltage is 10-30kV, the spinning speed is 20-100mL/min, and the electrode distance is 15-30 cm.
The nanofiber material with a specific size is obtained by regulating and controlling the voltage, the spinning speed and the electrode distance, and the diameter of the obtained nanofiber is about small when the voltage is higher, the spinning speed is slower or the electrode distance is about long. In addition, the solvent is fully volatilized by adjusting the parameters: the slower the spinning speed or the larger the electrode distance, the more the solvent evaporation is favored. The solvent is only required to be fully volatilized.
According to the scheme, in the step 2), the mass ratio of the organic monomer to the nano-fiber yarn is 0.8-1: 1. The higher the proportion of the organic monomer is, the thicker the hollow pipe wall is, and the stronger the pressure resistance is.
According to the scheme, in the step 2), the organic monomer is any one of aniline, pyrrole and dopamine.
According to the scheme, in the step 2), the concentration of the hydrochloric acid solution is 0.5-1.5 mol/L.
According to the scheme, in the step 2), the nano-fiber filaments are uniformly dispersed into hydrochloric acid solution containing organic monomers by stirring for 2-6 hours.
According to the scheme, in the step 2), the mass ratio of the initiator to the organic monomer is 1: 1-1.5.
According to the scheme, in the step 2), the initiator is any one of ferric trichloride, ammonium persulfate, potassium persulfate and hydrogen peroxide.
According to the scheme, in the step 2), the polymerization reaction temperature is-20-30 ℃, and the polymerization reaction time is 6-18 h.
According to the scheme, in the step 3), the organic solvent is any one or a combination of at least two of toluene, tetrahydrofuran, xylene and amyl acetate.
According to the scheme, in the step 3), the mass ratio of the nanofiber filaments with the polymer coated on the surface to the organic solvent is 1: 10-20.
According to the scheme, in the step 3), the stirring time is 2-6 h.
According to the scheme, in the step 4), the inert gas is nitrogen or argon. The protective atmosphere effectively prevents oxidation of the amorphous carbon during heat treatment.
According to the scheme, in the step 4), the pre-sintering temperature is 300-.
According to the scheme, in the step 4), the carbonization temperature is 1000-1500 ℃, and the carbonization time is 1-6 h.
The pre-sintering is mainly used for preventing the microstructure of the conductive material from being influenced by a pore passage caused by too fast volatilization of gas in the sintering process of the high polymer material. By slowing down this process in a pre-sintering manner, a more perfect pipe structure can be obtained. The high-temperature sintering is mainly used for completely carbonizing the high polymer material, and incomplete carbonization can be caused by low temperature or short time, so that the conductivity of the material is influenced.
The electrode comprises an active substance, a binder, a conductive agent and a current collector, wherein the conductive agent is the nano-micron carbon tube.
According to the scheme, the electrode is a battery anode or a battery cathode.
According to the scheme, the nano-micron carbon tubes account for 0.5-5% of the total mass of the electrode active substance, the binder and the conductive agent in percentage by mass.
Preferably, the electrode includes 90 parts of a positive or negative active material, 5 parts of a binder, 5 parts of nano-micron carbon tubes, and a current collector. More preferably, the positive electrode active material is lithium iron phosphate, and the binder is PVDF.
A lithium ion battery is provided that includes the above-described electrode as at least one of a battery positive electrode or a battery negative electrode.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, firstly, the nanofiber silk containing a high polymer material is obtained through electrostatic spinning, and through mutual attraction between a large number of groups with negative charges and organic monomers with positive charges in the nanofibers, the organic monomers can be preferentially polymerized on the surface of the nanofiber silk, so that the surface of the nanofiber silk is uniformly polymerized and coated; dissolving the nano-fiber material by a solvent, and sintering at high temperature to obtain a hollow nano-micron carbon tube; compared with the commercial carbon nano tube CNT, the production process is simpler and is beneficial to large-scale production.
2. The nano-micron carbon tube provided by the invention has a hollow tube structure, the inner diameter can be controlled between 100 and 4000nm, and the circulation of electrolyte in a pipeline is facilitated, so that the nano-micron carbon tube not only has the conductive capability, but also has good ion conductive capability, and is not possessed by all the existing carbon tubes.
3. The nano-micron carbon tube prepared by the invention is used as a conductive agent to be added into an electrode of a lithium ion battery, and due to good conductive and ion conductive properties of the nano-micron carbon tube, the polarization phenomenon caused by inconsistent electron and ion transmission capacities under the condition of large-current charge and discharge can be effectively eliminated, so that the battery rate discharge platform is higher, and the rate performance is better.
Drawings
Fig. 1 is an SEM topography of a nano-micro carbon tube prepared in example 2 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the nano-micron carbon tube comprises the following steps:
step 1, adding polymethyl methacrylate into an organic solvent N, N-dimethylformamide, heating and stirring at 40 ℃ for 60min, and preparing a solution A with the concentration of 5%. And (3) carrying out electrostatic spinning on the solution A by electrostatic spinning equipment with the voltage of 10kV, the spinning speed of 100mL/min and the electrode distance of 30cm to obtain the nanofiber yarn with the diameter of 430 nm.
Step 2, adding the nanofiber filaments obtained in the step 1 into a 1mol/L hydrochloric acid solution of aniline, wherein the mass ratio of aniline to nanofiber filaments is 0.8:1, and stirring at 500 revolutions per minute for 6 hours to obtain a mixed liquid B;
and 3, adding ammonium persulfate into the mixed liquid B obtained in the step 2, wherein the mass ratio of aniline to ammonium persulfate is 1.5:1, and polymerizing for 18 hours at the temperature of-20 ℃ at the rotating speed of 600 revolutions per minute. Filtering the reaction product by using suction filtration equipment to obtain the nano-fiber filaments coated with polyaniline on the surface;
and 4, adding tetrahydrofuran into the nano-fiber filaments coated with polyaniline in the surface obtained in the step 3, wherein the mass ratio of the nano-fiber filaments coated with polyaniline to the tetrahydrofuran is 1:10, stirring at 200 rpm for 6 hours, and then performing suction filtration to obtain the hollow polymer tube.
And 5, under the protection of nitrogen inert gas, pre-sintering the polymer tube obtained in the step 4 at 300 ℃ for 2h, then carrying out high-temperature calcination and carbonization at 1200 ℃ for 6h, and cooling to obtain the nano-micron carbon tube.
Example 2
The preparation method of the nano-micron carbon tube comprises the following steps:
step 1, adding polystyrene into an organic solvent dimethylfuran, heating and stirring at 60 ℃ for 30min, and preparing a solution A with the concentration of 10%. And (3) carrying out electrostatic spinning on the solution A by using electrostatic spinning equipment with the voltage of 20kV, the spinning speed of 60mL/min and the electrode distance of 20cm to obtain the nano-fiber yarn with the diameter of 766 nm.
Step 2, adding the nanofiber filaments obtained in the step 1 into a 1mol/L hydrochloric acid solution of pyrrole, wherein the mass ratio of the pyrrole to the nanofiber filaments is 0.9:1, and stirring at 1000 rpm for 4 hours to obtain a mixed liquid B;
and 3, adding hydrogen peroxide into the mixed liquid B obtained in the step 2, wherein the mass ratio of pyrrole to hydrogen peroxide is 1.2:1, and polymerizing for 12 hours at the temperature of 0 ℃ and at the rotating speed of 1000 revolutions per minute. Filtering the reaction product by using suction filtration equipment to obtain the nano-fiber filaments coated with polypyrrole on the surface;
and 4, adding toluene into the polypyrrole-coated nano-fiber obtained in the step 3, wherein the mass ratio of the polypyrrole-coated nano-fiber to the toluene is 1:15, stirring at 400 rpm for 4 hours, and performing suction filtration to obtain the polymer tube.
And 5, under the protection of argon inert gas, pre-sintering the polymer tube obtained in the step 4 at 320 ℃ for 1.5h, then carrying out high-temperature calcination and carbonization at 1300 ℃ for 3h, and cooling to obtain the nano-micron carbon tube.
Example 3
The preparation method of the nano-micron carbon tube comprises the following steps:
step 1, adding polyvinyl acetate into an organic solvent N-methyl pyrrolidone, heating and stirring at 100 ℃ for 50min, and preparing a solution A with the concentration of 20%. And (3) carrying out electrostatic spinning on the solution A by using electrostatic spinning equipment, wherein the voltage is 30kV, the spinning speed is 20mL/min, and the electrode distance is 15cm, so as to obtain the 1673 nm-diameter nano-fiber yarn.
Step 2, adding the nanofiber filaments obtained in the step 1 into a 1mol/L hydrochloric acid solution of dopamine, wherein the mass ratio of the dopamine to the nanofiber filaments is 1:1, and stirring at 2000 rpm for 2 hours to obtain a mixed liquid B;
and 3, adding ferric trichloride into the mixed liquid B obtained in the step 2, wherein the mass ratio of dopamine to ferric trichloride is 1:1, and polymerizing for 6 hours at the temperature of 30 ℃ at the rotating speed of 1500 rpm. Filtering the reaction product by using suction filtration equipment to obtain the nano-fiber yarns coated with polydopamine on the surface;
and 4, adding xylene into the nano-fiber filaments coated with the polydopamine on the surface obtained in the step 3, wherein the mass ratio of the nano-fiber filaments coated with the polydopamine to the xylene is 1:20, stirring at 600 rpm for 2 hours, and then performing suction filtration to obtain the polymer tube.
And 5, under the protection of nitrogen inert gas, pre-sintering the polymer tube obtained in the step 4 at 350 ℃ for 1h, then carrying out high-temperature calcination carbonization at 1500 ℃ for 1h, and cooling to obtain the nano-micron carbon tube.
Comparative example 1
This comparative example used a commercially available carbon nanotube with a diameter of 8 nm.
Comparative example 2
This comparative example used commercially available conductive carbon black.
The nano-micron carbon tubes prepared in examples 1-3 and the commercially available conductive agent provided in comparative examples 1-2 were used in a conventional 2016 coin cell battery, in which the positive and negative electrode formulations of all samples were kept consistent. In the positive electrode, the proportion of the active material of the lithium iron phosphate positive electrode is 90.0 percent, the nano-micron carbon tube or the commercial conductive agent is 5.0 percent, and the adhesive PVDF is 5.0 percent. The negative electrode uses a metallic lithium plate.
The thickness of the positive electrode sheet obtained in examples 1 to 3 and comparative example 2 was about 200 um. The thickness of the positive pole piece prepared in the comparative example 1 is about 200um and about 50um of the conventional positive pole piece, wherein the compaction density is 2.5g/cm3。
And respectively carrying out rate performance test on the prepared batteries. The results are shown in table 1 below:
TABLE 1
From the data results of examples 1-3, it can be seen that the smaller the inner diameter is, the more dense the ion and electron flow channels are, and the better the corresponding rate performance is, under the same thickness of the positive electrode and the same formulation ratio.
From the results of the two sets of data of different thicknesses of comparative example 1, it can be seen that the larger the thickness is, the longer the migration distance of ions is, under the same formulation ratio and the same compacted density. The battery rate performance is reduced due to the increase of battery polarization.
From the data results of examples 1-3 and comparative examples 1-2, it can be seen that the rate performance improvement of all examples is very significant under extreme conditions of ultra-high thickness of 200um and high compaction. The reason is mainly that under the conditions of ultrahigh thickness and high compaction, the migration capability of ions is poor, and the battery polarization is increased, so that the rate performance of the battery is reduced. Comparative example 1 is a carbon nanotube, which has almost no ion conduction capability, so the rate performance is the worst; comparative example 2 is conductive carbon black, which has a weak ion conductivity, so the performance is better than that of comparative example 1.
For commercial batteries, the greater the thickness of the positive electrode, the higher the energy density of the battery that can be designed. Compared with commercial conductive carbon black and carbon nanotubes, the conductive material provided by the invention can greatly improve the rate capability of the button cell under the condition that the thickness of the positive electrode is several times of the conventional thickness. Provides a very excellent composite material which can conduct electricity and ions for the design of commercial batteries. Meanwhile, the design of active materials with different particle sizes in different commercial batteries can be matched by regulating and controlling the size of the inner diameter.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. A nano-micron carbon tube is characterized in that the nano-micron carbon tube is a hollow tube structure, and the inner diameter is 100-4000 nm.
2. The carbon nanotube of claim 1, wherein the wall thickness of the carbon nanotube is 100 nm and 500 nm.
3. A method for preparing a carbon nanotube of one of claims 1 to 2, comprising the steps of:
1) carrying out electrostatic spinning on electrostatic spinning precursor solution containing a high polymer material to obtain nano-fiber yarns;
2) uniformly dispersing the nano-fiber filaments obtained in the step 1) into a hydrochloric acid solution containing an organic monomer, adding a certain initiator, and carrying out polymerization reaction to obtain nano-fiber filaments with the surfaces coated with polymers;
3) adding an organic solvent into the nanofiber filaments with the polymer-coated surfaces obtained in the step 2), and stirring to fully dissolve the high polymer material to obtain a hollow polymer tube;
4) under the protection of inert gas, pre-sintering and carbonizing the hollow polymer tube obtained in the step 3), and cooling to obtain the nano-micron carbon tube.
4. The production method according to claim 3,
in the step 1), the high polymer material is any one or a combination of at least two of polymethyl methacrylate, polystyrene, polyethylene and polyvinyl acetate;
in the step 2), the organic monomer is any one of aniline, pyrrole and dopamine; the initiator is any one of ferric trichloride, ammonium persulfate, potassium persulfate and hydrogen peroxide.
The organic solvent in the step 3) is any one or a combination of at least two of toluene, tetrahydrofuran, xylene and amyl acetate.
5. The preparation method according to claim 3, wherein in the step 2), the mass ratio of the organic monomer to the nanofiber filaments is 0.8-1: 1; the mass ratio of the initiator to the organic monomer is 1: 1-1.5; in the step 3), the mass ratio of the nanofiber filaments with the polymer coated on the surface to the organic solvent is 1: 10-20.
6. The preparation method according to claim 3, wherein in the step 2), the polymerization reaction temperature is-20 to 30 ℃, and the polymerization reaction time is 6 to 18 hours; in the step 3), stirring for 2-6 h; in the step 4), the pre-sintering temperature is 300-; the carbonization temperature is 1000-1500 ℃, and the carbonization time is 1-6 h.
7. The method according to claim 3, wherein the electrostatic spinning precursor solution containing the polymer material in the step 1) is configured to: adding a high molecular material into a solvent, and stirring for 5-60min at the temperature of 40-100 ℃ to obtain an electrostatic spinning precursor solution containing the high molecular material, wherein the concentration of the high molecular material in the electrostatic spinning precursor solution is 5-20%; the solvent is any one or the combination of at least two of N, N-dimethylformamide, dimethyl furan, dimethyl sulfoxide and N-methylpyrrolidone; the technological parameters of electrostatic spinning are as follows: the voltage is 10-30kV, the spinning speed is 20-100mL/min, and the electrode distance is 15-30 cm.
8. A lithium ion battery electrode comprising an electrode active material, a binder, a conductive agent and a current collector, wherein the conductive agent is the nano-micro carbon tube according to any one of claims 1 to 2.
9. The electrode according to claim 8, wherein the nano-micro carbon tubes account for 0.5 to 5% by mass of the total mass of the electrode active material, the binder and the conductive agent.
10. A lithium ion battery comprising the electrode of claim 8 as at least one of a positive electrode or a negative electrode of the lithium ion battery.
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