Preparation method of tannic acid modified hydrogen bond reinforced carbon nanotube
By modifying amino-walled carbon nanotubes with tannic acid, the mechanical stability and stress dissipation capacity of carbon nanotubes are enhanced by utilizing hydrogen bonding networks, which solves the problems of limited performance improvement and easy desorption in existing technologies and achieves higher performance of energy storage devices.
Patent Information
- Application Number
- CN202510887969.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-30
- Publication Date
- 2026-01-20
AI Technical Summary
Existing carbon nanotube functionalization methods are insufficient to significantly improve performance, and the modification process is prone to agglomeration and desorption, which limits their mechanical stability and stress dissipation capabilities in energy storage devices.
Tannic acid was used to modify amino-enhanced single-walled carbon nanotubes. By using hydrogen bonding to anchor catechol groups and convert some amino groups into protonated amino groups, three hydrogen bond networks were formed, which enhanced the mechanical stability and stress dissipation capacity of carbon nanotubes.
By forming three hydrogen bond networks, the mechanical stability and stress dissipation capacity of carbon nanotubes in energy storage devices are significantly improved.
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Figure CN121361787A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of functional materials, and particularly relates to a preparation method of tannic acid modified hydrogen bond reinforced carbon nanotubes. BACKGROUND
[0002] Energy is the material cornerstone of modern society. With the increasingly urgent problem of non-renewable energy depletion, new energy development has become a top priority in global research. The current new energy mainly refers to renewable energy such as solar energy, wind energy, biomass energy and nuclear energy (atomic energy). The common feature of these energies is abundant reserves and low environmental burden. Solar energy and wind energy are currently the most mature forms of new energy, and in recent years, the installed capacity and power generation have shown explosive growth. However, due to the instability of power generation, many places have been forced to "abandon wind and light", resulting in great waste of energy. In order to reduce this waste, the new power system is gradually developing into a "source-grid-load-storage" mode, and energy storage has become an important part of new energy application. As an important part of new energy application, electrochemical energy storage can convert electrical energy into chemical energy for storage, and has the advantages of stable and continuous power output, quiet operation, and small size. The special physical structure of the covalent sp2 bond between the individual carbon atoms of carbon nanotubes makes them have high electrical conductivity, effectively reducing the resistance of the system. In addition, carbon nanotubes also have a large specific surface area, which helps to build a large electrode / electrolyte interface and achieve energy storage through the principle of double-layer capacitance. Therefore, carbon nanotubes can be used as important additives in energy storage devices (such as lithium-sulfur batteries, high-nickel cathodes for lithium-ion batteries, silicon-carbon anodes, sodium-ion batteries, zinc-ion batteries, lithium-ion capacitors, and supercapacitors), and the functionalization research is of great significance to fully exert the electrochemical performance of energy storage devices and improve the cycle stability.
[0003] Currently, the main commercial methods for functionalizing carbon nanotubes include carboxylation, amination, hydroxylation, and fluorination, which can achieve certain performance improvement in different energy storage devices. However, the functional groups provided by the above methods have a very limited mass fraction in carbon nanotubes and are difficult to significantly improve. Interface molecular modification is an important means to achieve further performance breakthrough, but macromolecular modification and small molecule modification respectively face the problems of easy aggregation of carbon nanotubes, easy detachment leading to rapid failure, and other problems, which seriously limit the performance of functionalized carbon nanotubes. The present application uses tannic acid to modify aminated single-walled carbon nanotubes. The amino groups on the carbon nanotubes can anchor the hydroxyl groups on the catechol groups in tannic acid under the action of hydrogen bonds, and at the same time, the weak acidity of tannic acid can convert part of the amino groups on the surface of the carbon nanotubes into protonated amino groups during the modification process. Therefore, the modified carbon nanotubes have a hydrogen bond network composed of three different hydrogen bonds, which can effectively improve the mechanical stability and stress dissipation capacity in the device. SUMMARY
[0004] In view of the deficiencies of the prior art, the present application provides a tannic acid modified hydrogen bond reinforced carbon nanotube preparation method, which can provide a hydrogen bond network composed of three different hydrogen bonds for energy storage devices, thereby effectively improving the mechanical stability and stress dissipation capacity in the device.
[0005] The present application adopts the following technical solutions:
[0006] A tannic acid modified hydrogen bond reinforced carbon nanotube preparation method, characterized by comprising the following steps:
[0007] S1: Tannic acid (TA) powder and deionized water (H2O) are added into a 50ml beaker at room temperature, and after stirring for 30-120min, a tannic acid aqueous solution (a-TA) with a certain concentration is prepared;
[0008] S2: 40mg of commercial amino-functionalized single-walled carbon nanotubes (NCNT) are placed in 10-40mL of H2O containing a certain amount of polyvinylpyrrolidone (PVP) in a 50mL beaker, and after 8-24h of sufficient ultrasonic dispersion, a carbon nanotube dispersion (d-NCNT) is obtained;
[0009] S3: A certain amount of a-TA is added to d-NCNT, and after sufficient stirring for 12-72h, a TA modified carbon nanotube dispersion (d-TNCNT) is obtained;
[0010] S4: After centrifugal treatment, the solid precipitate is collected, washed with H2O, and centrifuged again, and the process is repeated 3-6 times until the supernatant is completely clear, and the tannic acid modified hydrogen bond reinforced carbon nanotube TNCNT is obtained.
[0011] The present application also has the following technical features:
[0012] The a-TA concentration in step S1 is 5-150mmol / L.
[0013] The PVP content in the H2O used in step S2 is 0.1-1.5wt%.
[0014] The amount of a-TA used in step S3 is 0.25ml-15mL.
[0015] The centrifugation speed in step S4 is 6000-12000rpm.
[0016] Compared with the prior art, the present application has the following beneficial effects:
[0017] The tannic acid is used for modifying the amino single-wall carbon nanotube. The amino on the carbon nanotube can anchor the hydroxyl on the catechol group in the tannic acid under the hydrogen bond effect. Meanwhile, the weak acidity of the tannic acid can convert part of the amino on the surface of the carbon nanotube into the protonated amino during the modification process. Therefore, the modified carbon nanotube has a hydrogen bond network formed by three different hydrogen bonds, so that the mechanical stability and stress dissipation capacity in the device can be effectively improved. BRIEF DESCRIPTION OF DRAWINGS
[0018] Figure 1 is the X-ray photoelectron spectroscopy of the prepared example 1, the basic control group NCNT and the commercial single-wall carbon nanotube (CNT) of the present application.
[0019] Figure 2 is the Fourier infrared spectroscopy of the example 1, the example 2 and the basic control group NCNT, CNT and TA powder of the present application.
[0020] Figure 3 is the scanning electron microscope graph of the example 1 of the present application.
[0021] Figure 4 is the scanning electron microscope graph of the example 3 of the present application.
[0022] Figure 5 is the scanning electron microscope graph of the control group NCNT of the present application.
[0023] Figure 6 is the scanning electron microscope graph of the control group CNT of the present application. DETAILED DESCRIPTION
[0024] The embodiments of the present application will be described in detail by specific concrete examples. Those skilled in the art can easily understand other advantages and effects of the present application from the contents disclosed in the specification. The present application can also be implemented or applied by other different specific embodiments, and each detail in the specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present application.
[0025] Figure 1 is the X-ray photoelectron spectroscopy of the prepared example 1, the basic control group NCNT and the commercial single-wall carbon nanotube (CNT) of the present application. From the results, it can be found that the TNCNT modified by the TA generates the protonated amino-NH3 + while retaining part of the -NH2, and the -NH2 peak in the TNCNT appears a slight blue shift of 0.3 eV-0.5 eV, indicating that the TA modification strengthens the hydrogen bond network on the surface of the carbon tube. With the appearance of the catechol-OH and the -NH3 + , the hydrogen bond type and the hydrogen bond density on the surface of the carbon tube are improved.
[0026] Figure 2 is the Fourier transform infrared spectroscopy (FTIR) of Example 1 of the present application, Comparative Example 1 and base control group NCNT, CNT and TA powder. From the results, it can be determined that NCNT can anchor TA by strong hydrogen bonding between the surface amino group and the catechol group of TA, so that the characteristic peak of TA can appear in the FTIR results; while the base control group CNT has no special group on the surface, and cannot form a relatively stable interaction with TA, so that there is almost no TA characteristic peak observed on the surface after the same process, indicating that NCNT can more effectively adsorb TA and thus realize surface modification compared with CNT.
[0027] Figure 3 is the scanning electron microscope (SEM) image of Example 1 of the present application. From it, it can be observed that there is effective adsorption of spherical TA on the surface of the carbon nanotubes of Example 1.
[0028] Figure 4 is the scanning electron microscope (SEM) image of Example 3 of the present application. From it, it can be observed that there is effective adsorption of spherical TA on the surface of the carbon nanotubes of Example 3.
[0029] Figure 5 、 Figure 6 are the scanning electron microscope (SEM) images of the base control group NCNT and CNT, respectively. From them, the original morphology of the samples used in Example 1 and Example 2 can be observed.
[0030] Example 1:
[0031] The preparation method of this example is as follows:
[0032] S1: At room temperature, add tannic acid (TA) powder and deionized water (H2O) into a 50ml beaker, and after stirring for 60min, prepare a tannic acid aqueous solution (a-TA) with a concentration of 24mmol / L;
[0033] S2: Put 40mg of commercial amino-functionalized single-walled carbon nanotubes (NCNT) into 20ml of H2O containing 0.1wt% polyvinylpyrrolidone (PVP) in a 50ml beaker, and after 12h of sufficient ultrasonic dispersion, obtain a carbon nanotube dispersion (d-NCNT);
[0034] S3: Take 3ml of a-TA and add it to d-NCNT, and after sufficient stirring for 24h, obtain a TA-modified carbon nanotube dispersion (d-TNCNT);
[0035] S4: After centrifugal treatment of d-TNCNT, collect the solid precipitate, wash it with H2O, and centrifuge again, repeat 3 times until the supernatant is completely clear, and obtain tannic acid-modified hydrogen-bonding enhanced carbon nanotubes TNCNT.
[0036] Example 2:
[0037] The preparation method of this example is exactly the same as Example 1 except for the following point:
[0038] The single-walled carbon nanotubes (CNT) used in Step S2 are commercially available.
[0039] Example 3:
[0040] The amount of a-TA added in Step S3 is 1 mL.
[0041] Basic control group:
[0042] The NCNT, CNT and TA are all commercially available from pharmaceutical units, and are not subjected to any further treatment before use.
[0043] The above examples are only illustrative of the principles and effects of the present application, and are not intended to limit the present application. Any person skilled in the art can modify or change the above examples without departing from the spirit and scope of the present application. Therefore, all equivalent modifications or changes completed by those skilled in the art without departing from the spirit and technical thought disclosed by the present application should be covered by the claims of the present application.
Claims
1. A method for preparing a tannin-modified hydrogen-bonding reinforced carbon nanotube, characterized by, The method comprises the following steps: S1: adding tannic acid (TA) powder and deionized water (H2O) into a 50ml beaker at room temperature, stirring for 30-120min to prepare a tannic acid aqueous solution (a-TA) with a certain concentration; S2: putting 40mg of commercial amino-functionalized single-walled carbon nanotubes (NCNT) into 10-40ml of H2O containing a certain amount of polyvinylpyrrolidone (PVP) in a 50ml beaker, and then performing ultrasonic dispersion for 8-24h to obtain a carbon nanotube dispersion (d-NCNT); S3: adding a certain amount of a-TA into the d-NCNT, and fully stirring for 12-72h to obtain a TA-modified carbon nanotube dispersion (d-TNCNT); S4: centrifuging the d-TNCNT to collect the solid precipitate, washing with H2O, and then centrifuging again, repeating 3-6 times until the supernatant is completely clear, thereby obtaining a hydrogen-bond-strengthened tannic acid-modified carbon nanotube TNCNT.
2. The method for preparing tannic acid-modified hydrogen bond-strengthened carbon nanotubes according to claim 1, characterized in that: The concentration of the a-TA in step S1 is 5-150mmol / L.
3. The method for preparing tannic acid-modified hydrogen bond-reinforced carbon nanotubes according to claim 1, characterized in that: The PVP content in the H2O used in step S2 is 0.1-1.5wt%.
4. The method for preparing tannic acid-modified hydrogen bond-strengthened carbon nanotubes according to claim 1, characterized in that: The amount of a-TA used in step S3 is 0.25ml-15ml.
5. The method for preparing tannic acid-modified hydrogen bond-reinforced carbon nanotubes according to claim 1, characterized in that: The centrifugation speed in step S4 is 6000-12000rpm.