CN114620713B - Preparation method of Na ion and nonmetal co-doped carbon nanotube and lithium ion battery - Google Patents
Preparation method of Na ion and nonmetal co-doped carbon nanotube and lithium ion battery Download PDFInfo
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- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
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- 239000001488 sodium phosphate Substances 0.000 claims description 3
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- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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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
- C01B32/168—After-treatment
-
- 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
- H01M4/62—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 provides a preparation method of a Na ion and nonmetal co-doped carbon nanotube and a lithium ion battery, wherein by doping Na ions, the radius is small, the doping steric hindrance is small, and the doping amount is large; non-metal atoms can enter the graphite sheet layer to activate and disperse the carbon nano tube; na ions and nonmetal are co-doped, so that the active reaction sites on the surface of the carbon nano tube are increased, a stable conductive network can be constructed in a battery active material, and the performance of the battery material is favorably exerted; according to the Na ion and nonmetal co-doped carbon nanotube prepared by the method, due to the introduction of other atoms in the structure, the surface contact with a battery active material is enhanced, and the stability of slurry after homogenate is improved; meanwhile, because Na ions and nonmetal atoms are introduced into the doped Na ions and nonmetal co-doped carbon nanotubes at the same time, the agglomeration condition among the carbon nanotubes is relieved, and the dispersibility of the carbon nanotubes in a solvent is improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a preparation method of a Na ion and nonmetal co-doped carbon nanotube and a lithium ion battery.
Background
The carbon nano tube material has a larger length-diameter ratio, has a better electrochemical performance due to a unique molecular structure, has a stable chemical structure and is not easy to damage under extreme conditions. The carbon nano tube has a wide application range, shows excellent performance as a traditional lithium ion battery conductive agent, can provide a channel for electron conduction due to a typical tube diameter structure of the carbon nano tube, improves the conductivity of a battery material, and is beneficial to exerting the gram specific capacity of an active substance and improving the rate capability of a lithium ion battery.
Although the micro chemical structure and the morphology of the carbon nano tube enable the carbon nano tube to have great application advantages in the aspect of lithium ion battery conductive agents, the carbon nano tube is not absolutely perfect. Firstly, the carbon nano tube has few surface defects and lacks some necessary active groups, so that the carbon nano tube shows surface inertia and is not tightly contacted with an active material of a lithium ion battery, and a conductive agent is gradually weakened in contact with the active material along with the use of the battery, thereby causing the performance deterioration of the lithium ion battery; in addition, the carbon nanotube material is easy to agglomerate due to the high length-diameter ratio and the van der waals force between the carbon nanotubes, so that the carbon nanotube material is difficult to disperse in a solvent, and the homogenization difficulty is increased.
At present, some metal and nonmetal element codoped carbon nanotube modification technologies exist, but the problems of complex preparation process and poor doping effect generally exist. Generally, the doping amount of the doped carbon nanotube is limited, the doping amount of the single-walled carbon nanotube is at most 1%, the doping amount of the multi-walled carbon nanotube is slightly high, and the preparation of the doped carbon nanotube with high doping amount still has a great challenge at present; in addition, after part of dopant atoms enter the carbon nanotube structure, the inherent morphology of the carbon nanotube is changed, which is not beneficial to the performance of the carbon nanotube.
Disclosure of Invention
In view of this, the invention provides a preparation method of a Na ion and nonmetal co-doped carbon nanotube and a lithium ion battery, which are beneficial to increasing the doping amount of Na ions in the carbon nanotube and improving the surface activity of the carbon nanotube.
The technical scheme of the invention is realized as follows:
in one aspect, the invention provides a preparation method of a Na ion and nonmetal co-doped carbon nanotube, which comprises the following steps,
s1, providing a carbon nano tube raw material;
s2, mixing the carbon nano tube and the salt rich in Na elements and non-metal elements, and dispersing the mixture in a solvent A;
s3, performing high-temperature water bath evaporation on the mixed solution obtained in the step S2, wherein the water bath temperature is between 80 and 100 ℃, the reducing gas environment is guaranteed in the water bath process, and a sodium salt/carbon nano tube mixture is obtained after evaporation is completed;
s4, performing ball milling dispersion on the sodium salt/carbon nanotube mixture obtained in the step S3;
s5, thenPutting the sodium salt/carbon nano tube mixture obtained in the step S4 into a tube furnace, and reacting in H 2 Under the atmosphere, the temperature rise rate is kept at 3-20 ℃ min -1 Heating to 500-1200 ℃, preserving heat for 1-3h, and cooling after the reaction is finished to obtain the Na ion and nonmetal co-doped carbon nanotube.
On the basis of the above technical solution, preferably, in the step S1, a carbon nanotube raw material with a tube diameter of 15-28nm is used. In addition to the above technical solutions, preferably, in the step S2, the nonmetal element is P or S.
Further preferably, in step S2, the salt rich in Na element and nonmetal element is one or a combination of sodium sulfate, sodium sulfite, sodium sulfide, sodium phosphate, sodium phosphite, sodium dihydrogen phosphate and disodium hydrogen phosphate.
On the basis of the above technical scheme, preferably, in the step S2, water or ethanol is adopted as the solvent a, the dispersion time is 2-5h, and the dispersion temperature is 10-40 ℃.
On the basis of the above technical solution, preferably, in the step S2, the carbon nanotubes: salts rich in Na element and nonmetal element: the mass ratio of the solvent A is 10-20:10-15:40-60.
On the basis of the above technical solution, preferably, in the step S3, the reducing gas adopts H 2 。
On the basis of the above technical scheme, preferably, in the step S4, zirconia ball milling beads are selected for the ball milling process, the diameters of the ball milling beads are respectively 1 mm, 3 mm and 5mm, the mass ratio of the three correspondingly added ball milling beads is 2.
In a second aspect, the present invention provides a lithium ion battery, wherein the doped carbon nanotube prepared in the first aspect of the present invention is used as a conductive agent.
Compared with the prior art, the preparation method of the Na ion and nonmetal co-doped carbon nanotube and the lithium ion battery have the following beneficial effects:
(1) Compared with other metal atoms, the Na ion doping has the advantages of small radius, small doping steric hindrance, large doping amount, mild doping conditions, rich sodium salt source and convenience in doping; by doping the non-metal atoms, the non-metal atoms can enter the graphite sheet layer to activate and disperse the carbon nano tubes;
(2) Na ions and nonmetal are co-doped, so that the active reaction sites on the surface of the carbon nanotube are increased, a stable conductive network can be constructed in the active material of the battery, and the performance of the material of the battery can be favorably exerted; according to the Na ion and nonmetal co-doped carbon nanotube prepared by the method, due to the introduction of other atoms in the structure, the surface contact with a battery active material is enhanced, and the stability of slurry after homogenization is improved; meanwhile, because Na ions and nonmetal atoms are introduced into the doped Na ion and nonmetal co-doped carbon nano tubes at the same time, the agglomeration condition among the carbon nano tubes is relieved, and the dispersibility of the carbon nano tubes in a solvent is improved;
(3) The compound rich in metallic element Na and non-metallic element and the carbon nano tube are subjected to water bath, ball milling and pyrolysis to carry out doping modification, and one doping agent is adopted to realize double doping of Na ions and non-metallic atoms of the carbon nano tube, so that the synthesis technical process route is simple, the original structure of the carbon nano tube cannot be damaged in the doping process, and the performance of the carbon nano tube can be improved in all aspects;
(4) The carbon nano tube is easy to be doped unevenly or fails, so that the performance of the carbon nano tube is influenced negatively; in order to ensure that Na ions and non-metal atoms are uniformly doped into the carbon nano tube, the implementation process needs to be optimized, for example, a normal-temperature dissolving process of the carbon nano tube and a sodium salt solution is changed into a high-temperature hydrothermal composite process, and solid powder is subjected to planetary ball milling, so that the dispersion uniformity and the connection tightness of the sodium salt on the carbon nano tube are enhanced, and further pyrolysis doping is facilitated;
(5) The lithium ion battery prepared by the invention has better slurry stability and better rate capability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an SEM picture of the sodium sulfate-doped carbon nanotube prepared in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments of the present invention, belong to the protection scope of the present invention.
Example 1
First, doped carbon nanotubes are prepared.
S1, providing a carbon nano tube raw material with the tube diameter of 15-28 nm. In particular, fe-Mo/Al may be used 2 O 3 As a reaction catalyst, the vapor deposition reaction is carried out in a vertical furnace to generate the carbon nano tube raw material.
S2, mixing the carbon nano tube with sodium sulfate, and dispersing in water for 2h at the dispersion temperature of 40 ℃, wherein the carbon nano tube: sodium sulfate: the mass ratio of the water is 10:10:40.
s3, evaporating the mixed solution obtained in the step S2 in a high-temperature water bath at 80 ℃, wherein H is adopted in the water bath process 2 As reducing gas, sodium salt/carbon nano tube mixture is obtained after evaporation.
And S4, performing ball milling dispersion on the sodium salt/carbon nanotube mixture obtained in the step S3, wherein zirconia ball milling beads are adopted in the ball milling process, the diameters of the ball milling beads are respectively 1 mm, 3 mm and 5mm, the mass ratio of the three correspondingly added ball milling beads is 2.
S5, putting the sodium salt/carbon nano tube mixture obtained in the step S4 into a tubeIn a kiln of the formula H 2 Under the atmosphere, the temperature rise rate is kept at 3 ℃ min -1 And heating to 500 ℃, preserving the heat for 1h, and cooling after the reaction is finished to obtain the doped carbon nano tube.
Then, a lithium ion battery was prepared.
LiFePO is added 4 The positive electrode material, the prepared doped carbon nanotube and polyvinylidene fluoride are dispersed in N-methylpyrrolidone (NMP) according to the mass ratio of 96.5.
Artificial graphite, binder styrene butadiene rubber, thickener carboxymethylcellulose sodium and prepared doped carbon nanotubes are mixed according to a mass ratio of 96.6:1.2:1.6:0.6 is dispersed in N-methyl pyrrolidone, then is evenly coated on a current collector copper foil, is dried and then is rolled to the required compaction density, and is subjected to strip cutting and tab welding to obtain the negative pole piece used by the lithium ion battery.
And winding the positive pole piece, the high-molecular porous diaphragm and the negative pole piece into a winding core, adding the lithium ion battery electrolyte, and then forming to obtain the lithium ion battery capable of being charged and discharged.
Example 2
First, doped carbon nanotubes are prepared.
S1, providing a carbon nano tube raw material with the tube diameter of 15-28 nm. In particular, fe-Mo/Al may be used 2 O 3 As a reaction catalyst, a vapor deposition reaction is carried out in a vertical furnace to produce a carbon nanotube raw material.
S2, mixing the carbon nano tube with sodium sulfate, dispersing in water for 3.5h, wherein the dispersion temperature is 25 ℃, and the carbon nano tube: sodium sulfate: the mass ratio of the water is 15:12:50.
s3, evaporating the mixed solution obtained in the step S2 in a high-temperature water bath at 90 ℃, wherein H is adopted in the water bath process 2 As reducing gas, sodium salt/carbon nano tube mixture is obtained after evaporation.
And S4, performing ball milling dispersion on the sodium salt/carbon nanotube mixture obtained in the step S3, wherein zirconia ball milling beads are adopted in the ball milling process, the diameters of the ball milling beads are respectively 1 mm, 3 mm and 5mm, the mass ratio of the three correspondingly added ball milling beads is 2.
S5, putting the sodium salt/carbon nano tube mixture obtained in the step S4 into a tube furnace, and putting the mixture into a tube furnace in the presence of H 2 Under the atmosphere, the temperature rise rate is kept at 10 ℃ for min -1 And heating to 900 ℃, preserving the temperature for 2 hours, and cooling after the reaction is finished to obtain the doped carbon nano tube.
The SEM picture of the sodium sulfate-doped carbon nanotube prepared in the step S5 is shown in figure 1; the conductive adhesive was dispersed in a certain amount of NMP to prepare a conductive adhesive solution with a mass fraction of 4%, and the viscosity was measured to obtain the results shown in table 1.
Then, a lithium ion battery was prepared, as in example 1. The prepared positive electrode slurry was subjected to a viscosity test to obtain the results shown in table 1. And coating a little of the positive electrode slurry on the PET film, and testing the resistivity of the pole piece by using four probes to obtain the results of the resistivity of the pole piece shown in the table 2.
The rate discharge performance of the prepared lithium ion battery was tested, and the experimental results are shown in table 2.
Example 3
First, doped carbon nanotubes are prepared.
S1, providing a carbon nano tube raw material with the tube diameter of 15-28 nm. In particular, fe-Mo/Al may be used 2 O 3 As a reaction catalyst, the vapor deposition reaction is carried out in a vertical furnace to generate the carbon nano tube raw material.
S2, mixing the carbon nano tube and sodium sulfate, dispersing in water for 5 hours at a dispersion temperature of 10 ℃, and mixing the carbon nano tube: sodium sulfate: the mass ratio of the water is 20:15:60.
s3, evaporating the mixed solution obtained in the step S2 in a high-temperature water bath at 100 ℃, wherein H is adopted in the water bath process 2 As reducing gas, sodium salt/carbon nano tube mixture is obtained after evaporation.
And S4, performing ball milling dispersion on the sodium salt/carbon nanotube mixture obtained in the step S3, wherein zirconia ball milling beads are adopted in the ball milling process, the diameters of the ball milling beads are respectively 1 mm, 3 mm and 5mm, the mass ratio of the three correspondingly added ball milling beads is 2.
S5, putting the sodium salt/carbon nano tube mixture obtained in the step S4 into a tube furnace, and reacting in a reaction chamber H 2 Under the atmosphere, the temperature rise rate is kept at 20 ℃ for min -1 And heating to 1200 ℃, preserving the heat for 3 hours, and cooling after the reaction is finished to obtain the doped carbon nano tube.
Then, a lithium ion battery was prepared, as in example 1.
Example 4
First, doped carbon nanotubes were prepared in substantially the same manner as in example 2, except that: in the step S2, the salt rich in Na elements and nonmetal elements is sodium sulfite.
Example 5
First, doped carbon nanotubes were prepared in substantially the same manner as in example 2, except that: in the step S2, the salt rich in Na elements and nonmetal elements is sodium sulfide.
Example 6
First, doped carbon nanotubes were prepared in substantially the same manner as in example 2, except that: in the step S2, the salt rich in Na elements and nonmetal elements is sodium phosphate.
Example 7
First, doped carbon nanotubes were prepared in substantially the same manner as in example 2, except that: in the step S2, the salt rich in Na elements and nonmetal elements is sodium phosphite.
Example 8
First, doped carbon nanotubes were prepared in substantially the same manner as in example 2, except that: in the step S2, the salt rich in Na element and nonmetal element is sodium dihydrogen phosphate.
Example 9
First, doped carbon nanotubes were prepared in substantially the same manner as in example 2, except that: in the step S2, the salt rich in Na elements and nonmetal elements is disodium hydrogen phosphate.
Comparative example
Firstly, providing a carbon nano tube raw material with the tube diameter of 15-28 nm. In particular, fe-Mo/Al may be used 2 O 3 As a reaction catalyst, a vapor deposition reaction is carried out in a vertical furnace to produce a carbon nanotube raw material.
The carbon nanotubes were dispersed in a certain amount of NMP to prepare a conductive adhesive solution with a mass fraction of 4%, and the viscosity was measured to obtain the results shown in table 1.
Then, a lithium ion battery was prepared, and as in example 1, the prepared positive electrode slurry was subjected to a viscosity test, and the experimental results are shown in table 1, and then a small amount of the positive electrode slurry was coated on a PET film, and the sheet resistivity was tested using four probes, to obtain the sheet resistivity results shown in table 2.
The performance of the prepared lithium ion battery is detected, and the experimental results are shown in table 2.
TABLE 1, examples and comparative examples carbon nanotubes and Positive electrode paste Properties
TABLE 2 Performance of lithium ion batteries of examples and comparative examples
As can be seen from fig. 1: na ions and nonmetal are codoped, so that the intrinsic morphology structure of the carbon nano tube cannot be damaged, and the conductivity of the carbon nano tube cannot be influenced;
as can be seen from tables 1 and 2: the viscosity of the conductive glue solution and the positive electrode paste of the Na ion and nonmetal co-doped carbon nanotube system is generally lower than that of the comparative example, which shows that the Na ion and nonmetal co-doped carbon nanotube can improve the dispersibility of the carbon nanotube; and secondly, the pole piece using the Na ion and nonmetal co-doped carbon nanotube as the conductive agent shows lower pole piece resistivity, and the prepared lithium ion battery has better rate discharge characteristic, so that the doped carbon nanotube establishes a more excellent conductive network in the slurry and can obviously improve the electrochemical performance of the lithium ion battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (7)
1. A preparation method of a Na ion and nonmetal co-doped carbon nanotube is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
s1, providing a carbon nano tube raw material;
s2, mixing the carbon nano tube and the salt rich in Na elements and nonmetal elements, and dispersing the mixture in a solvent A; in the step S2, the non-metal element is P or S, and the salt rich in Na elements and non-metal elements is one or a combination of more of sodium sulfate, sodium sulfite, sodium sulfide, sodium phosphate, sodium phosphite, sodium dihydrogen phosphate and disodium hydrogen phosphate;
s3, evaporating the mixed solution obtained in the step S2 in a high-temperature water bath, wherein the water bath temperature is 80-100 ℃, the reducing gas environment is guaranteed in the water bath process, and a sodium salt/carbon nano tube mixture is obtained after evaporation is finished;
s4, performing ball milling dispersion on the sodium salt/carbon nanotube mixture obtained in the step S3;
s5, putting the sodium salt/carbon nano tube mixture obtained in the step S4 into a tube furnace, and putting the mixture into a tube furnace in the presence of H 2 Under the atmosphere, the temperature rising rate is kept to be 3-20 ℃ per minute -1 Heating to 500-1200 ℃, preserving heat for 1-3h, and cooling after the reaction is finished to obtain the Na ions and nonmetal co-doped carbon nano tube.
2. The method for preparing the Na ion and nonmetal co-doped carbon nanotube according to claim 1, wherein: in the step S1, a carbon nano tube raw material with the tube diameter of 15-28nm is adopted.
3. The method for preparing the Na ion and nonmetal co-doped carbon nanotube according to claim 1, wherein: in the step S2, the solvent A adopts water or ethanol, the dispersion time is 2-5h, and the dispersion temperature is 10-40 ℃.
4. The method for preparing Na ion and nonmetal co-doped carbon nanotube according to claim 1, wherein: in the step S2, the carbon nanotube: salts rich in Na element and nonmetal element: the mass ratio of the solvent A is 10-20:10-15:40-60.
5. The method for preparing the Na ion and nonmetal co-doped carbon nanotube according to claim 1, wherein: in the step S3, the reducing gas adopts H 2 。
6. The method for preparing the Na ion and nonmetal co-doped carbon nanotube according to claim 1, wherein: in the step S4, zirconia ball milling beads are selected for the ball milling process, the diameters of the ball milling beads are respectively 1 mm, 3 mm and 5mm, the mass ratio of the three correspondingly added ball milling beads is 2.
7. A lithium ion battery, which adopts the doped carbon nanotube prepared according to any one of claims 1 to 6 as a conductive agent.
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