CN114361412A - Multi-walled carbon nanotube negative electrode material and preparation method and application thereof - Google Patents
Multi-walled carbon nanotube negative electrode material and preparation method and application thereof Download PDFInfo
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- CN114361412A CN114361412A CN202111543481.7A CN202111543481A CN114361412A CN 114361412 A CN114361412 A CN 114361412A CN 202111543481 A CN202111543481 A CN 202111543481A CN 114361412 A CN114361412 A CN 114361412A
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Abstract
The invention provides a multi-walled carbon nanotube negative electrode material and a preparation method and application thereof, belonging to the technical field of negative electrode materials of potassium ion batteries; in the present invention, Al is performed on multi-walled carbon nanotubes by varying the number of ALD cycles2O3Depositing to obtain the multi-walled carbon nanotube negative electrode material; the charge-discharge cycle efficiency of the multiwalled carbon nanotube negative electrode material is greatly improved, and the multiwalled carbon nanotube negative electrode material can be used in a potassium ion battery very high.
Description
Technical Field
The invention belongs to the technical field of potassium ion battery cathode materials, and particularly relates to a multiwalled carbon nanotube cathode material as well as a preparation method and application thereof.
Background
The potassium has rich reserves and wide sources, and has the functions of lithium and sodiumSimilar physicochemical properties have received attention from some researchers in recent years. K/K+The standard electrode potential of (2) is closer to Li/Li+This makes potassium ion batteries more advantageous in terms of output voltage and energy than sodium ion batteries. And, K+Specific to Li+And Na+Has weaker Lewis acidity, so that K+Faster migration rates in the electrolyte and at the electrolyte-electrode interface may contribute to superior performance of potassium ion batteries in rate capability. However, potassium ions have a large ionic radius, which restricts the development of potassium storage materials.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a multi-walled carbon nanotube negative electrode material and a preparation method and application thereof. In the present invention, Al is performed on multi-walled carbon nanotubes by varying the number of ALD cycles2O3Depositing to obtain the multi-walled carbon nanotube negative electrode material; the charge-discharge cycle efficiency of the multiwalled carbon nanotube negative electrode material is greatly improved, and the multiwalled carbon nanotube negative electrode material can be used in a potassium ion battery very high.
The invention firstly provides a multiwalled carbon nanotube negative electrode material, which is made of Al2O3The film-coated multi-wall carbon nanotube material has the length of 20-40 mu m and the diameter of 30-100 nm.
The invention also provides a preparation method of the multi-walled carbon nanotube negative electrode material, which comprises the following steps:
surface coating Al of multi-walled carbon nano-tube by utilizing atomic layer deposition technology2O3And then mixing the treated multi-walled carbon nanotube with acetylene black, grinding, adding a sodium carboxymethylcellulose solution, stirring and mixing uniformly, coating the mixed material on a copper foil, and drying to obtain the multi-walled carbon nanotube negative electrode material.
Further, the surface coating treatment comprises the following specific steps: by mixing trimethylaluminum and H2O as a precursor introduced into the ALD reactor (GEMStar) in successionTMXT atomLayer deposition system) for Al2O3And (6) depositing.
Specifically, the Al2O3The deposition was carried out at 150 deg.C using nitrogen as a carrier gas at a flow rate of 20sccm and an ALD reactor maintained at a base pressure of 200 mTorr at a deposition rate of
And/period, performing ALD cycle on the alumina coating on the MWCNTs for 10-100 times.
Furthermore, the mass ratio of the treated multi-wall carbon nano-tube is 70-90%, and the total mass ratio of the acetylene black and the sodium carboxymethyl cellulose is 10-30%.
Further, the coating thickness is 150-200 mm.
Further, the drying conditions are as follows: the temperature is 60-80 ℃, and the time is 10-12 h.
Further, the concentration of the sodium carboxymethyl cellulose solution is 20 mg/mL.
Furthermore, after being dried, the multi-walled carbon nanotube negative electrode material is punched to form a pole piece with the diameter of 8 mm.
The invention also provides application of the multi-walled carbon nanotube negative electrode material in a potassium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
compared with untreated multi-wall carbon nano tube anode material, AI is carried out by ALD technology in the invention2O3The electrochemical performance of the multi-wall carbon nano tube after deposition treatment is improved. Under the current density of 0.5C, the electrode after surface coating treatment has higher specific discharge capacity than the original multi-wall carbon nanotube electrode.
Compared with the multi-wall carbon nano-tube with different coating thicknesses, the MWCNTs-20 has higher discharge specific capacity under the current density (0.5C). For the electric automobile, the higher the discharge specific capacity is, the better the cruising mileage is, and the short plate with short mileage of the electric automobile is made up. The potassium ion battery prepared by the multi-wall carbon nanotube material coated on the surface has obvious advantages.
The multi-walled carbon nanotube negative electrode material prepared by the invention has excellent cycling stability, and has obviously improved discharge specific capacity and better rate capability compared with the original material.
Drawings
FIG. 1 is an SEM image of multi-walled carbon nanotubes.
FIG. 2 is a graph comparing the cycling performance at 0.5C rate of multi-walled carbon nanotubes with different coating thicknesses to the original multi-walled carbon nanotubes.
FIG. 3 is a graph comparing the rate capability of multi-walled carbon nanotubes with different coating thicknesses at different rates with the original multi-walled carbon nanotubes.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1:
(1) surface coating treatment
And mixing the prepared multi-wall carbon nano-wire, acetylene black (a conductive agent) and a sodium carboxymethyl cellulose (CMC binder) solution according to a weight ratio of 75:15:10 to prepare the multi-wall carbon nano-tube. The prepared multi-walled carbon nanotube electrode is used for depositing Al2O3A substrate of thin film prepared by mixing Trimethylaluminum (TMA) and H2O as a precursor introduced into the ALD reactor (GEMStar) in successionTMXT atomic layer deposition system), Al at 150 ℃2O3And (4) depositing. Using nitrogen as a carrier gas at a flow rate of 20sccm, the ALD reactor was maintained at a base pressure of 200 mTorr with a deposition rate of approximately
The number of ALD cycles was 10, and 10-coated multi-walled carbon nanotubes were obtained.
The ALD procedure was set up as follows:
a: providing 21 milliseconds of TMA;
b: the prolonged irradiation time of TMA to the CNTs electrode was 5 s;
c: purge for 20 seconds of supply excess TMA and any by-products;
d: 21 milliseconds of water vapor supply;
E：H2performing prolonged irradiation on CNTs for 5s by O;
f: the excess water and any by-products were rinsed for 20 seconds.
(2) Mixing grinding materials:
weighing 80mg of the coated multi-walled carbon nanotube (MWCNTs) powder, and putting the powder into a mortar for grinding for 30-50 min. After uniform grinding, 16mg of acetylene black (conductive agent) is weighed and added into the mortar, and grinding is continued for 30-50 min. The milled mixture was placed in a small stirred pot and 500. mu.L of sodium carboxymethylcellulose (CMC binder) solution was added thereto. And then placing the small stirring pot on a magnetic stirrer to stir for 2-4 h at normal temperature.
(3) Tabletting:
after the stirring was completed, the material was coated on a copper foil with a thickness of 150mm by a wet film coater, and after 10 minutes, the coated copper foil was placed in a vacuum drying oven and vacuum-dried at 80 ℃ for 12 hours. And (3) punching a pole piece with the diameter of 8mm after drying, namely obtaining the MWCNTs-10 as the multi-walled carbon nanotube negative electrode material.
Example 2:
the number of ALD cycles in example 1 was set to 20, 50, and 100, and the other reaction conditions and procedure settings were exactly the same as in example 1, thereby obtaining coated multi-walled carbon nanotubes having coatings of 20, 50, and 100. The steps (2) and (3) are the same as the step 1, and the multi-walled carbon nanotube negative electrode materials are respectively prepared and are marked as MWCNTs-20, MWCNTs-50 and MWCNTs-100
FIG. 1 is an SEM image showing the length of carbon nanotube of 20-40 μm and the diameter of carbon nanotube of about 30-100 nm.
Fig. 2 is a plot of cycling performance for each sample at a current density of 0.5C. As can be seen from the figure, the surface coating treatment of the multi-wall carbon nano-tube can obviously improve the discharge capacity of the multi-wall carbon nano-tube. And when the number of the coating layers is 20, the multiwalled carbon nanotube negative electrode material has the highest stable discharge capacity. After 100 cycles, the cycle stability of the multiwall carbon nanotube negative electrode material is obviously better than that of the original multiwall carbon nanotube.
Fig. 3 is a graph comparing the rate capability of each sample. It can be obviously seen that the multiwalled carbon nanotube negative electrode material has excellent rate capability compared with the multiwalled carbon nanotube.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A preparation method of a multi-wall carbon nanotube negative electrode material is characterized by comprising the following steps:
surface coating Al of multi-walled carbon nano-tube by utilizing atomic layer deposition technology2O3And then mixing the coated multi-walled carbon nanotube with acetylene black, grinding, adding a sodium carboxymethylcellulose solution, stirring and mixing uniformly, coating the mixed material on a copper foil, and drying to obtain the multi-walled carbon nanotube negative electrode material.
2. The method for preparing a multi-walled carbon nanotube negative electrode material as claimed in claim 1, wherein the surface coating treatment comprises the following specific steps: by mixing trimethylaluminum and H2Introducing O as a precursor into an ALD reactor in sequence for Al2O3And (6) depositing.
3. The method of claim 2, wherein the Al is present in the multi-walled carbon nanotube anode material2O3The deposition was carried out at 150 deg.C using nitrogen as a carrier gas at a flow rate of 20sccm and an ALD reactor maintained at a base pressure of 200 mTorr at a deposition rate of
And performing ALD cycle on the alumina coating on the MWCNTs for 10-100 times.
4. The preparation method of the multi-wall carbon nanotube negative electrode material as claimed in claim 1, wherein the mass ratio of the treated multi-wall carbon nanotube is 70-90%, and the total mass ratio of acetylene black and sodium carboxymethyl cellulose is 10-30%.
5. The preparation method of the multi-walled carbon nanotube negative electrode material as claimed in claim 1, wherein the coating thickness is 150-200 mm.
6. The method for preparing a multi-walled carbon nanotube negative electrode material as claimed in claim 1, wherein the drying conditions are as follows: the temperature is 60-80 ℃, and the time is 10-12 h.
7. The method of claim 1, wherein the sodium carboxymethyl cellulose solution is present at a concentration of 20 mg/mL.
8. The method for preparing the multi-walled carbon nanotube negative electrode material of claim 1, wherein the multi-walled carbon nanotube negative electrode material is baked and then punched to form a pole piece with a diameter of 8 mm.
9. The multi-walled carbon nanotube negative electrode material prepared by the preparation method of any one of claims 1 to 9, wherein the multi-walled carbon nanotube negative electrode material is made of Al2O3The film-coated multi-wall carbon nanotube material has the length of 20-40 mu m and the diameter of 30-100 nm.
10. Use of the multi-walled carbon nanotube anode material of claim 9 in a potassium ion battery.
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