CN117199282A - Preparation method of nitrogen-doped high-conductivity nano composite material for aluminum ion battery - Google Patents
Preparation method of nitrogen-doped high-conductivity nano composite material for aluminum ion battery Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 58
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
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- -1 aluminum ion Chemical class 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 15
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- 230000007547 defect Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 26
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- 239000000243 solution Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
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- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002238 carbon nanotube film Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000003837 high-temperature calcination Methods 0.000 description 1
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Classifications
-
- 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 relates to a preparation method of a nitrogen-doped high-conductivity nano composite material for an aluminum ion battery, and belongs to the technical field of aluminum ion batteries. The method comprises the steps of adding the carbon nano tube and a nitrogen source into water, uniformly mixing, then performing freeze drying treatment, and then placing the mixture in a protective gas atmosphere for calcination treatment to obtain the nitrogen doped high-conductivity nano composite material for the aluminum ion battery. The nitrogen-doped high-conductivity nano composite material prepared by the method effectively increases the defects and active sites of the carbon nano tube, reduces agglomeration of the composite material, forms a stable three-dimensional network structure, and can effectively improve the electrochemical performance of the aluminum ion battery.
Description
Technical Field
The invention relates to a preparation method of a nitrogen-doped high-conductivity nano composite material for an aluminum ion battery, and belongs to the technical field of aluminum ion batteries.
Background
Along with the world energy crisis and the aggravation of global environmental pollution, the development of green clean energy has become a trend, and secondary batteries have become one of the representatives of green clean energy. Among them, the lithium ion battery is most widely used and mature, but the problem of lithium resource shortage caused by rapid consumption of lithium ore resources is increasingly highlighted. Aluminum ion batteries have received much attention in recent years due to their inherent characteristics. The aluminum ion battery has a capacity of up to 8046mAh/cm 3 Is 4 times of the volume specific capacity of the lithium ion battery; meanwhile, the aluminum element has the characteristics of large storage capacity, low price, high safety, environmental friendliness and the like, and is considered to be one of the best choices for replacing lithium ion batteries.
The carbon nano tube has the characteristics of high conductivity and high mechanical strength, and is widely applied to industries such as new energy, semiconductors and the like. However, the carbon nanotubes have fewer defects on the surface, which reduces the aluminum storage performance of the carbon nanotubes and also results in a decrease in the capacity of the aluminum ion battery. The preparation of nitrogen doped carbon nanotube precursor is generally carried out by adding nitrogen source and carbon nanotube into water to form mixture solution, thermal drying, mechanical grinding, mixing, and calcining at high temperature. The method is easy to cause uneven material mixing and agglomeration, thereby reducing the capacity of the aluminum ion battery.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a nitrogen-doped high-conductivity composite material for an aluminum ion battery, and the nitrogen-doped high-conductivity composite material prepared by the method can effectively increase defects and active sites of carbon nanotubes, form a stable three-dimensional network structure while reducing agglomeration of the composite material, and provide a fast transfer channel for electron transmission; the nitrogen atoms can be uniformly distributed on the surface of the carbon nano tube, and the nitrogen atoms do not share isolated electron pairs, so that the electronic conductivity of the composite material is further enhanced. The composite material is applied to the anode of the aluminum ion battery, so that the problems of low capacity, poor cycle stability and the like of the aluminum ion battery are effectively solved.
The aim of the invention is achieved by the following technical scheme.
The preparation method of the nitrogen-doped high-conductivity nano composite material for the aluminum ion battery comprises the following steps:
(1) Adding carbon nanotubes and a nitrogen source into water and uniformly mixing to obtain a uniformly dispersed mixture solution;
(2) Performing freeze drying treatment on the mixture solution obtained in the step (1) to obtain a precursor;
(3) And (3) placing the precursor obtained in the step (2) in an inert gas protective atmosphere for calcination treatment to obtain the nitrogen-doped high-admittance nano composite material for the aluminum ion battery.
Further, the nitrogen source is urea, dicyandiamide or melamine; correspondingly, the mass ratio of the carbon nano tube to the nitrogen source is preferably 1:3-5.
Further, the concentration of the carbon nano tube in the mixture solution is 0.01-0.1 g/mL.
Further, the carbon nano tube and the nitrogen source are added into water, stirred for 2 to 4 hours at a stirring rate of 500 to 800r/min, and then placed under the ultrasonic power of 800 to 1200W for ultrasonic treatment for 20 to 60 minutes.
Further, in the step (2), freeze drying is carried out for 24 hours or more under the condition that the temperature is less than or equal to minus 30 ℃.
Further, in the step (3), the calcination treatment is carried out at 800-900 ℃ for 1-2 hours. More preferably, the heating is carried out at a heating rate of not more than 2.5 ℃/min to 800-900 ℃.
Further, the flow rate of the protective gas in the step (3) is 20-80 mL/min.
The beneficial effects are that:
(1) The invention combines the freeze drying and high temperature calcination methods, can effectively avoid agglomeration generated by the composite material, can uniformly distribute nitrogen atoms on the surface of the carbon nano tube, can form a stable three-dimensional network structure by the composite material, effectively increases defects and active sites of the carbon nano tube, simultaneously improves the electron conductivity and provides an electron rapid transfer channel, and further can effectively improve the electrochemical performance of the aluminum ion battery.
(2) The ratio of carbon nanotubes to nitrogen source, i.e., the amount of nitrogen doping, also has a significant impact on the composite properties. Too much doping amount may instead decrease the conductivity of the composite material, so that the capacity of the aluminum ion battery is reduced. Therefore, the nitrogen doping amount is regulated, the conductivity of the composite material can be effectively improved, and the capacity of the aluminum ion battery is increased.
(3) The freeze drying treatment step introduced by the invention mainly utilizes rapid freezing at a low enough temperature to avoid aggregation of materials, and is favorable for forming a stable three-dimensional network structure, thereby providing a channel for rapid transfer of electrons.
(4) The method disclosed by the invention is simple in steps and easy to operate, and the composite material prepared by the method is applied to an aluminum ion battery, so that the problems of low battery capacity, poor cycle stability and the like can be effectively solved, and the method has a good application prospect.
Drawings
Fig. 1 is a schematic diagram of a process for preparing a nitrogen-doped high-conductivity nanocomposite of example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the nitrogen-doped high-conductivity nanocomposite prepared in example 1.
Fig. 3 is a Transmission Electron Microscope (TEM) image of the nitrogen doped high admittance nanocomposite material prepared in example 1.
Fig. 4 is an X-ray diffraction (XRD) pattern of the nitrogen-doped high-conductivity nanocomposite prepared in example 1.
Fig. 5 is a high-resolution X-ray photoelectron spectroscopy (XPS) chart of N1s of the nitrogen-doped high-conductivity nanocomposite prepared in example 1.
Fig. 6 is a graph of charge-discharge cycle plateau of an aluminum ion soft-pack battery assembled using the nitrogen-doped high-conductivity nanocomposite prepared in example 1.
Fig. 7 is a cycle efficiency graph of an aluminum ion pouch cell assembled using the nitrogen-doped high-conductivity nanocomposite prepared in example 1.
Fig. 8 is a graph of charge-discharge cycle plateau of an aluminum ion soft-pack battery assembled using the nitrogen-doped high-conductivity nanocomposite prepared in example 2.
Fig. 9 is a cycle efficiency graph of an aluminum ion pouch cell assembled using the nitrogen-doped high-conductivity nanocomposite prepared in example 2.
Fig. 10 is a graph of charge-discharge cycle plateau of an aluminum ion soft pack battery assembled using the nitrogen-doped high-conductivity nanocomposite prepared in example 3.
Fig. 11 is a cycle efficiency graph of an aluminum ion pouch cell assembled using the nitrogen-doped high-conductivity nanocomposite prepared in example 3.
Fig. 12 is a graph showing a charge-discharge cycle plateau of an aluminum ion soft pack battery assembled using the undoped carbon nanotubes prepared in comparative example 1.
Fig. 13 is a cycle efficiency graph of an aluminum ion pouch cell assembled using the undoped carbon nanotubes prepared in comparative example 1.
Fig. 14 is a graph of charge-discharge cycle plateau of an aluminum ion soft pack battery assembled using the nitrogen-doped carbon nanotube composite material prepared in comparative example 2.
Fig. 15 is a cycle efficiency graph of an aluminum ion pouch cell assembled using the nitrogen-doped carbon nanotube composite material prepared in comparative example 2.
Detailed Description
The present invention will be further described with reference to the following detailed description, wherein the processes are conventional, and wherein the starting materials are commercially available from the open market, unless otherwise specified.
In the following examples:
medicine and raw materials used in experiments:
table 1 pharmaceutical products and raw materials used in experiments
Assembling the battery:
stamping the carbon nanotube films prepared in the examples and the comparative examples by using an automatic stamping machine to cut electrode slices, so as to obtain positive electrode slices of the examples and the comparative examples; similarly, the negative aluminum foil is also the same, and a negative plate is correspondingly obtained;
spot welding the punched positive plate and the nickel tab together, and similarly spot welding the negative plate and the nickel tab together;
laminating a positive plate containing nickel tabs, a glass fiber diaphragm and a negative plate containing nickel tabs in sequence, putting the positive plate, the glass fiber diaphragm and the negative plate into an aluminum plastic film bag to expose the nickel tabs, leaving out a liquid injection hole, and packaging the aluminum plastic film bag into a semi-sealed aluminum ion soft package battery by a heat sealing machine;
the electrolyte is ionic liquid electrolyte 1 ethyl 3 methylimidazole chloride/anhydrous aluminum chloride (the molar ratio is [ EMIm ]]Cl:AlCl 3 =1.3:1), injecting electrolyte from a liquid injection port, (the electrolyte is used in an amount of 200 μl), fully wetting a glass fiber diaphragm, and finally sealing by a vacuum heat sealing machine to prepare an aluminum ion soft package battery;
wherein, the aluminum ion soft package battery is assembled in a glove box with the atmosphere of argon gas and water and oxygen of less than 0.1 ppm.
Example 1
Referring to fig. 1, the preparation of the nitrogen-doped high-conductivity nanocomposite for an aluminum ion battery specifically comprises the following steps:
(1) Mixing carbon nano tubes and urea according to a mass ratio of 1:4, adding the mixture into deionized water, stirring for 3 hours at a stirring rate of 600r/min, and then moving the mixture into an ultrasonic cleaner with ultrasonic power of 1000W for ultrasonic treatment for 40min to obtain a uniformly dispersed mixture solution with the concentration of the carbon nano tubes of 0.04 g/mL;
(2) The mixture solution obtained in the step (1) is placed in liquid nitrogen for low-temperature quick freezing, and then is placed in a freeze dryer for freeze drying for 24 hours at the temperature of minus 30 ℃ to obtain a precursor;
(3) Placing the precursor obtained in the step (2) in a tube furnace, introducing argon with the flow rate of 80mL/min into the tube furnace as a protective atmosphere, heating to 800 ℃ at the heating rate of 2.5 ℃/min, calcining at 800 ℃ for 1h, and cooling along with the furnace to obtain the nitrogen-doped high-conductivity nano composite material for the aluminum ion battery, which is abbreviated as CNT-N 1 。
For CNT-N 1 As can be seen from the SEM image of fig. 2, the carbon nanotubes are stacked together in a staggered manner to form a three-dimensional carbon nanotube network, and the staggered carbon nanotube network can promote rapid transfer of electrons; as can be seen from the TEM image of fig. 3, the carbon nanotubes are multi-walled carbon nanotubes with a number of layers between 2 and 5 and a diameter between 2 and 7 nm.
For CNT-N 1 As can be seen from the XRD spectrum of fig. 4, there is one diffraction peak at 2θ=21.5°, 2θ=25.9° and 2θ=43.5°, respectively, the first diffraction peak corresponds to amorphous carbon, and the last two diffraction peaks correspond to (002) and (100) crystal planes of graphitic carbon, respectively.
For CNT-N 1 XPS tests were performed and it can be seen from FIG. 5 that the binding energy peaks were located at 397.76eV, 399.31eV, 400.35eV and 401.18eV, corresponding to pyridine nitrogen, pyrrole nitrogen, graphite nitrogen and nitric oxide, respectively, indicating that the nitrogen atoms were successfully incorporated into the carbon nanotubes.
CNT-N 1 The aluminum ion soft package battery is assembled, and an electrochemical performance test is carried out by using a CT3001A battery test system manufactured by Wuhan blue electric and electronic company, inc.; wherein the test temperature is 25 ℃, the test voltage window range is 0.4-2.3V, and the test current density is 1.2mA. From the test results of FIGS. 6 and 7, it can be seen that CNT-N 1 The initial specific discharge capacity of the lithium ion battery is 32.4mAh/g, and after 300 cycles of charge and discharge, the specific discharge capacity is still 33.4mAh/g, so that the lithium ion battery has good cycle stability and higher specific discharge capacity.
Example 2
The preparation method of the nitrogen-doped high-conductivity nano composite material for the aluminum ion battery specifically comprises the following steps:
(1) Mixing carbon nano tubes and dicyandiamide according to the mass ratio of 1:4, adding the mixture into deionized water, stirring for 2 hours at the stirring rate of 800r/min, and then moving the mixture into an ultrasonic cleaning machine with the ultrasonic power of 1000W for ultrasonic treatment for 20min to obtain a uniformly dispersed mixture solution with the concentration of the carbon nano tubes of 0.01 g/mL;
(2) Placing the mixture solution obtained in the step (1) into a freeze dryer, and freeze-drying for 24 hours at the temperature of minus 30 ℃ to obtain a precursor;
(3) Placing the precursor obtained in the step (2) in a tube furnace, introducing argon with the flow rate of 60mL/min into the tube furnace as a protective atmosphere, heating to 800 ℃ at the heating rate of 1.5 ℃/min, calcining for 1h at 900 ℃, and then cooling along with the furnace to obtain the nitrogen-doped high-conductivity nano composite material for the aluminum ion battery, which is abbreviated as CNT-N 2 。
CNT-N 2 The aluminum ion soft package battery is assembled, and an electrochemical performance test is carried out by using a CT3001A battery test system manufactured by Wuhan blue electric and electronic company, inc.; wherein the test temperature is 25 ℃, the test voltage window range is 0.4-2.3V, and the test current density is 1.2mA. From the test results of FIGS. 8 and 9, it can be seen that CNT-N 2 The initial specific discharge capacity of the battery is 28.4mAh/g, and after 300 cycles of charge and discharge, the specific discharge capacity is still 27.4mAh/g, so that the battery has good cycle stability and higher specific discharge capacity.
Example 3
The preparation method of the nitrogen-doped high-conductivity nano composite material for the aluminum ion battery specifically comprises the following steps:
(1) Mixing carbon nano tubes and melamine according to a mass ratio of 1:4, adding the mixture into deionized water, stirring for 3 hours at a stirring rate of 600r/min, and then moving the mixture into an ultrasonic cleaning machine with ultrasonic power of 1000W for ultrasonic treatment for 60 minutes to obtain a uniformly dispersed mixture solution with the concentration of the carbon nano tubes of 0.06 g/mL;
(2) Placing the mixture solution obtained in the step (1) into a freeze dryer, and freezing at the temperature of minus 40 ℃ for 24 hours to obtain a precursor;
(3) The steps are%2) Placing the obtained precursor in a tubular furnace, introducing argon with the flow rate of 80mL/min into the tubular furnace as a protective atmosphere, heating to 900 ℃ at the heating rate of 2.5 ℃/min, calcining at 900 ℃ for 2 hours, and cooling along with the furnace to obtain the nitrogen-doped high-admittance nano composite material for the aluminum ion battery, which is abbreviated as CNT-N 3 。
CNT-N 3 The aluminum ion soft package battery is assembled, and an electrochemical performance test is carried out by using a CT3001A battery test system manufactured by Wuhan blue electric and electronic company, inc.; wherein the test temperature is 25 ℃, the test voltage window range is 0.4-2.3V, and the test current density is 1.2mA. As can be seen from the test results of FIGS. 10 and 11, CNT-N 3 The initial specific discharge capacity of the battery is 29.4mAh/g, and after 300 cycles of charge and discharge, the specific discharge capacity is still 29.1mAh/g, so that the battery has good cycle stability and higher specific discharge capacity.
Comparative example 1
(1) Adding carbon nanotubes into deionized water, stirring for 3 hours at a stirring rate of 600r/min, and then moving to an ultrasonic cleaning machine with ultrasonic power of 1000W for ultrasonic treatment for 40min to obtain a uniformly dispersed mixture solution with the concentration of the carbon nanotubes of 0.04 g/mL;
(2) Placing the mixture solution obtained in the step (1) into a freeze dryer, and freezing at the temperature of minus 30 ℃ for 24 hours to obtain a precursor;
(3) Placing the precursor obtained in the step (2) in a tube furnace, introducing argon with the flow rate of 80mL/min into the tube furnace as a protective atmosphere, heating to 800 ℃ at the heating rate of 2.5 ℃/min, calcining at 800 ℃ for 1h, and cooling along with the furnace to obtain undoped carbon nanotubes, which are abbreviated as CNTs.
Assembling the CNT into an aluminum ion soft package battery, and performing electrochemical performance test by using a CT3001A battery test system manufactured by Wuhan blue electric electronics Co., ltd; wherein the test temperature is 25 ℃, the test voltage window range is 0.4-2.3V, and the test current density is 1.2mA. From the test results of FIGS. 12 and 13, the initial specific discharge capacity of CNT was only 16.1mAh/g, and after 300 cycles, the specific discharge capacity was also only 18.2mAh/g.
Comparative example 2
Mixing carbon nano tube and urea according to the mass ratio of 1:4, placing the mixture in a tube furnace after uniform mixing, introducing argon with the flow rate of 80mL/min into the tube furnace as a protective atmosphere, heating to 800 ℃ at the heating rate of 2.5 ℃/min, calcining at 800 ℃ for 1h, and cooling along with the furnace to obtain the nitrogen-doped carbon nano tube composite material, which is abbreviated as CNT-N 4 。
CNT-N 4 The aluminum ion soft package battery is assembled, and an electrochemical performance test is carried out by using a CT3001A battery test system manufactured by Wuhan blue electric and electronic company, inc.; wherein the test temperature is 25 ℃, the test voltage window range is 0.4-2.3V, and the test current density is 1.2mA. As can be seen from the test results of FIGS. 14 and 15, CNT-N 4 The initial discharge specific capacity of the battery is 20.2mAh/g, and the discharge specific capacity is 22.5mAh/g after 300 charge-discharge cycles.
In summary, the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the nitrogen-doped high-conductivity nano composite material for the aluminum ion battery is characterized by comprising the following steps of: the method comprises the following steps:
(1) Adding carbon nanotubes and a nitrogen source into water and uniformly mixing to obtain a uniformly dispersed mixture solution;
(2) Performing freeze drying treatment on the mixture solution obtained in the step (1) to obtain a precursor;
(3) And (3) placing the precursor obtained in the step (2) in an inert gas protective atmosphere for calcination treatment, and keeping the temperature for 1-2 h to obtain the nitrogen-doped high-conductivity nano composite material for the aluminum ion battery.
2. The method for preparing the nitrogen-doped high-conductivity nanocomposite for an aluminum ion battery according to claim 1, wherein: in the step (1), the nitrogen source is urea, dicyandiamide or melamine; the mass ratio of the carbon nano tube to the nitrogen source is 1:3-5.
3. The method for preparing the nitrogen-doped high-conductivity nanocomposite for an aluminum ion battery according to claim 1 or 2, characterized in that: in the step (1), the concentration of the carbon nano tube in the mixture solution is 0.01-0.1 g/mL.
4. The method for preparing a nitrogen-doped high-conductivity nanocomposite for an aluminum ion battery according to claim 3, wherein: adding carbon nanotube and nitrogen source into water, stirring at 500-800 r/min for 2-4 hr, and ultrasonic treating at 800-1200W for 20-60 min.
5. The method for preparing the nitrogen-doped high-conductivity nanocomposite for an aluminum ion battery according to claim 1, wherein: and (3) freeze-drying for 24 hours or more at the temperature of less than or equal to minus 30 ℃ in the step (2).
6. The method for preparing the nitrogen-doped high-conductivity nanocomposite for an aluminum ion battery according to claim 1, wherein: in the step (3), the calcination treatment is carried out for 1 to 2 hours at the temperature of 800 to 900 ℃.
7. The method for preparing the nitrogen-doped high-conductivity nanocomposite for aluminum ion batteries according to claim 6, wherein: in the step (3), heating to 800-900 ℃ at a heating rate of not higher than 2.5 ℃/min.
8. The method for preparing the nitrogen-doped high-conductivity nanocomposite for an aluminum ion battery according to claim 1, wherein: the flow rate of the protective gas in the step (3) is 20-80 mL/min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311130056.4A CN117199282A (en) | 2023-09-04 | 2023-09-04 | Preparation method of nitrogen-doped high-conductivity nano composite material for aluminum ion battery |
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