A copper ion doped carbon nanotube composite material, a preparation method and application thereof
By using copper ion-doped carbon nanotube composite materials, a highly efficient three-dimensional conductive network is formed and synergistic sterilization is achieved. This solves the problem of insufficient conductivity and antibacterial properties of existing conductive fillers in conductive fibers, and realizes highly conductive and highly antibacterial conductive fibers.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SUZHOU STELLAN NEW MATERIALS TECHNOLOGY CO LTD
- Filing Date
- 2026-04-17
- Publication Date
- 2026-06-05
AI Technical Summary
Existing conductive fillers such as graphene and conductive carbon black offer limited improvement in conductivity when preparing conductive fibers and lack antibacterial properties, making it difficult to meet the multifunctional integration requirements of smart textiles. Furthermore, the combination of multiple materials presents compatibility and cost issues.
The method employs copper ion-doped carbon nanotube composite materials. By atomically dispersing copper ions or nanoclusters within the carbon nanotube framework, a highly efficient three-dimensional conductive network is formed. The slow release of copper ions and their binding with carbon nanotubes achieve a synergistic bactericidal effect.
It significantly improves conductivity with extremely low doping levels and possesses efficient and broad-spectrum antibacterial properties, with a conductivity of up to 2.9×10⁵ S/m and an antibacterial rate of 99.999%, while maintaining good mechanical properties.
Smart Images
Figure CN122147555A_ABST
Abstract
Description
Technical Field
[0001] This application relates to a copper ion-doped carbon nanotube composite material, its preparation method, and its application, belonging to the field of functional materials technology. Background Technology
[0002] Existing conductive fillers, such as graphene and conductive carbon black, have very limited effect on improving conductivity when used to prepare conductive fibers, and their properties are limited, especially lacking antibacterial properties. Single materials are difficult to meet the multifunctional integration requirements of smart textiles; while composite materials have defects in compatibility and cost. Summary of the Invention
[0003] In view of this, this application first provides a copper ion-doped carbon nanotube composite material, which has excellent electrical conductivity and good antibacterial properties.
[0004] Specifically, this application is implemented through the following scheme: A copper-doped carbon nanotube composite material is disclosed, wherein copper ions are doped into the carbon nanotube (CNT) framework or network in an atomically dispersed manner or in the form of nanoclusters. The copper ion content in the composite material is 0.1–5 wt%, and the electrical conductivity of the composite material is ≥1.0 × 10⁻⁶. 5 S / m.
[0005] In the above scheme, CNTs are used as carriers. Copper ions not only act as electron donors to increase the carrier concentration of CNTs, but also coordinate with the defect sites of CNTs to enhance the structural stability of CNTs. The combination of the two transforms the one-dimensional continuous conductive path of CNTs into a highly efficient three-dimensional conductive network under extremely low doping conditions, giving the composite material a significant improvement in conductivity.
[0006] Furthermore, as a preferred option: The composite material contains 0.5–3.0 wt% copper ions and has an electrical conductivity ≥ 4.2 × 10⁻⁶. 6 S / m. More preferably, the copper ion content is 1.0–1.5 wt%, and the electrical conductivity of the composite material is ≥5.5 × 10⁻⁶. 7 S / m.
[0007] The composite material exhibits an antibacterial rate of ≥98.5% against Escherichia coli and Staphylococcus aureus. In this application, the continuous and slow release of copper ions, combined with the adsorption of CNTs on bacteria, achieves a synergistic bactericidal effect, resulting in a broad antibacterial spectrum, high efficiency, and long-lasting effect.
[0008] The above-mentioned composite material can be prepared using the following steps: Step 1: Disperse carbon nanotubes in an aqueous solution containing copper ions until a uniform dispersion is obtained. Step 2: Transfer the dispersion to a hydrothermal reactor for hydrothermal reaction; Step 3: Wash and dry the product obtained from the hydrothermal reaction to obtain a copper ion-doped carbon nanotube composite material.
[0009] Preferred: The copper-containing aqueous solution is obtained by dissolving copper salts such as copper chloride, copper sulfate, and copper nitrate in deionized water. The concentration of copper ions in this aqueous solution is 0.1–5 mol / L.
[0010] The hydrothermal reaction temperature is 120–200°C. More preferably, the hydrothermal reaction temperature is 140–160°C.
[0011] The duration of the hydrothermal reaction is 2 to 8 hours. More preferably, the duration of the hydrothermal reaction is 4 to 6 hours.
[0012] The above-mentioned composite material can be applied to conductive fibers to obtain fibers with excellent conductivity, and in particular, the conductive fibers also have high antibacterial properties.
[0013] Specifically, the aforementioned conductive fibers can be obtained in two ways: Method 1 involves melt spinning the composite material with polyamide 6 (PA6) chips to obtain conductive fibers.
[0014] Method 2 involves uniformly mixing the composite material with a PA6 solution and then performing solution spinning to obtain conductive fibers.
[0015] In the conductive fiber, the mass percentage of the composite material is 0.5-5 wt%, and preferably 2-4 wt%.
[0016] The composite material of this application exhibits good dispersibility in a polymer matrix (such as PA6), is not prone to agglomeration, allows for smooth execution of the bonding process, has a low breakage rate, and the conductivity of the conductive fibers is ≥8.3×10⁻⁶. 3 S / m, up to 2.9×10 5 With an S / m and an antibacterial rate of over 99.999%, it combines high conductivity and strong antibacterial properties, while also exhibiting good mechanical properties. This solves the problem of the limitations of single-material functionality and can be applied to smart textiles, medical protective equipment, flexible electronic components, and more. Attached Figure Description
[0017] Figure 1 This is a SEM image of the composite material of this application.
[0018] Figure 2 SEM image of conductive fiber with 4.0 wt% composite material addition. Detailed Implementation
[0019] In the following embodiments, the intrinsic conductivity of the composite material was evaluated using the four-probe method, and the conductivity of the fibers was calculated from the fiber bundle resistance test (GB / T 45370-2025). Antibacterial properties were assessed using the oscillation method according to GB / T 20944.3-2008, targeting *Escherichia coli* ATCC 25922 and *Staphylococcus aureus* ATCC 6538. The mechanical property evaluation standard was GJB6919-2009.
[0020] Unless otherwise specified, all materials are commercially available. Example
[0021] This embodiment provides a copper ion-doped carbon nanotube composite material, the preparation process of which is as follows: Step 1: Using copper sulfate as the copper salt, dissolve 0.16g of the copper salt in 100mL of deionized water to obtain an aqueous solution containing the copper salt.
[0022] Step 2: Disperse 4g of carbon nanotubes in an aqueous solution containing copper ions and sonicate to form a uniform dispersion. The amount of copper ions doped in the dispersion is shown in Table 1.
[0023] Step 3: Transfer the dispersion to a hydrothermal reactor and carry out a hydrothermal reaction at 160°C for 6 hours.
[0024] Step four: Wash and dry the product obtained from the hydrothermal reaction to obtain a copper ion-doped carbon nanotube composite material.
[0025] Table 1: Effect of different copper ion doping concentrations .
[0026] As shown in Table 1, when the copper ion doping concentration increases from 0.5 wt% to 1.0 wt%, the conductivity shows a significant increase, from 4.2 × 10⁻⁶. 6 S / m increased to 5.5×10 7 S / m; the antibacterial rate against Staphylococcus aureus also increased from 98.5% to 99.99%, and the antibacterial rate against Escherichia coli increased from 98.7% to 99.99%. However, when the copper ion doping content exceeds 3.0 wt%, excessive copper will cause partial aggregation, resulting in a decrease in both conductivity and antibacterial rate. Therefore, it is appropriate to control the copper ion doping content between 1.0 and 1.5 wt%. The SEM image of the composite material with a copper ion doping content of 1.5 wt% is shown in the figure. Figure 1 As shown.
[0027] The setup for this comparative example is the same as that for Example 1, except that an aqueous solution containing copper ions was not added. The specific process is as follows: Step 1: Disperse 4g of carbon nanotubes in 100mL of deionized water and sonicate to form a uniform dispersion.
[0028] Step 2: Transfer the carbon nanotubes to a hydrothermal reactor and carry out a hydrothermal reaction at 160°C for 6 hours.
[0029] Step 3: Wash and dry the product obtained from the hydrothermal reaction to obtain Sample 1.
[0030] Sample 1 is a pure carbon nanotube, and its one-dimensional continuous conductive pathway has a conductivity of 3.3 × 10⁻⁶. 6 S / m; while the inhibition rate of Staphylococcus aureus was 62%.
[0031] Taking the scheme corresponding to the copper ion doping amount of 1.5wt% in serial number 3 as an example, the conductivity of its product is not much different from that of sample 1, but the antibacterial performance is quite different. This is mainly because carbon nanotubes themselves have certain antibacterial properties, but they are weaker than copper ions, so they show a large difference in antibacterial performance. Example
[0032] This embodiment has the same settings as Embodiment 1, except that in step three, the hydrothermal reaction temperature is replaced by 120℃, 140℃, and 200℃ respectively, and the results are shown in Table 2.
[0033] Table 2: Effect of different reaction temperatures .
[0034] Compared to Example 1 (taking 1.5 wt% copper ion doping as an example), when the hydrothermal reaction temperature is only 120°C, the 6-hour reaction time is insufficient to ensure a complete reaction, although the conductivity remains at 10. 7 It is at the S / m level, but relatively low. When the temperature is too high (above 200℃), it will cause damage to the CNT structure and reduce its antibacterial properties.
[0035] Therefore, the reaction temperature should be controlled between 140 and 160°C. Example
[0036] This embodiment has the same setup as Embodiment 1, except that in step three, the duration of the hydrothermal reaction is changed from 6h to 2h, 4h, and 8h respectively, and the results are shown in Table 3.
[0037] Table 3: Effect of different reaction times .
[0038] Compared to Example 1 (with a copper ion doping content of 1.5 wt%), the conductivity is approximately 2.3 × 10⁻⁶ when the hydrothermal reaction time is 2 h. 7The conductivity was initially measured at S / m, but the inhibition rate against Staphylococcus aureus was only 98.8%, and against Escherichia coli was 93.5%. However, when the reaction time was increased to 4 hours, the conductivity doubled, and the inhibition rate against Staphylococcus aureus exceeded 99.2%, while the inhibition rate against Escherichia coli reached 99.4%. After the reaction time exceeded 8 hours, the improvement effect on conductivity and the inhibition rate against Staphylococcus aureus became no longer significant.
[0039] Therefore, considering both cost and preparation cycle, the reaction time should be controlled within 4 to 6 hours.
[0040] As can be seen from the above embodiments, the core parameters of the composite material in this application are the copper ion doping amount and the temperature and duration of the hydrothermal reaction. The preferred composite material preparation conditions are: a copper ion doping amount of 1.5 wt%, a hydrothermal reaction temperature of 160°C, and a hydrothermal reaction duration of 6 hours. Under these conditions, the corresponding composite material conductivity is 6.7 × 10⁻⁶. 7 S / m, with an inhibition rate of 99.9999% for Staphylococcus aureus and 99.9999% for Escherichia coli.
[0041] In this comparative example, graphene sheets and carbon black were used as conductive materials, and were designated as Sample 2 and Sample 3, respectively.
[0042] Sample 2 is pure graphene with a conductivity of 2.2 × 10⁻⁶. 5 S / m; the inhibition rate against Staphylococcus aureus was 71%, and the inhibition rate against Escherichia coli was 74%.
[0043] Sample 3 is pure conductive carbon black, with a conductivity of 3.5 × 10⁻⁶. 3 S / m; the inhibition rate against Staphylococcus aureus was 72%, and the inhibition rate against Escherichia coli was 75%. This is because: Graphene sheets are prone to stacking, and the conductive network is easily destroyed during spinning and stretching; conductive carbon black requires a high addition amount (usually >10%) to form a percolation network. However, the composite material of this application further reduces the interfacial resistance by doping copper ions on the continuous one-dimensional CNT pathways, forming a highly efficient three-dimensional conductive network in the fiber with an extremely low addition amount (below 3.0 wt%), and the conductivity is significantly higher than that of the graphene / carbon black system of the same proportion.
[0044] Meanwhile, graphene and carbon black themselves have weak antibacterial properties, and their antibacterial activity mainly relies on physical cleavage or limited reactive oxygen species. In the composite material of this application, copper ions are continuously and slowly released, which, combined with the adsorption of bacteria by CNTs, produces a synergistic bactericidal effect, with a broad antibacterial spectrum, high efficiency, and long-lasting effect.
[0045] The setup for this comparative example is the same as that for Example 1, except that carbon nanotubes are replaced with graphene sheets and carbon black, respectively, to obtain Sample 4 and Sample 5.
[0046] Sample four is composed of graphene doped with copper ions, and its conductivity is 2.3 × 10⁻⁶. 5 S / m; the inhibition rate against Staphylococcus aureus was 75%, and the inhibition rate against Escherichia coli was 78%.
[0047] Sample 5 is composed of conductive carbon black doped with copper ions, and its conductivity is 3.7 × 10⁻⁶. 3 S / m; the inhibition rate against Staphylococcus aureus was 74%, and the inhibition rate against Escherichia coli was 79%.
[0048] The above results demonstrate that although graphene sheets and carbon black are both used as conductive materials, they cannot form a synergistic effect with copper ions in the composite system of this application. Therefore, their conductivity and Staphylococcus aureus inhibition rate are lower than the corresponding performance of the composite material in Example 1 (taking 1.5wt% copper ion doping as an example). Example
[0049] This embodiment describes the preparation of conductive fibers, and the specific process is as follows: A composite material obtained under the conditions of 1.5 wt% copper ion doping, hydrothermal reaction temperature of 160℃, and reaction time of 6 h was used as the research object. This composite material was melt-spun with PA6 chips at a spinning temperature of 275℃ and a spinning speed of 2000 m / min to obtain conductive fibers. The mass percentages of the composite material in the conductive fibers were set to 0% (i.e., pure PA6 fibers without the composite material), 0.5 wt%, 1.0 wt%, 2.0 wt%, 3.0 wt%, 4.0 wt%, and 5.0 wt%, respectively. The results are shown in Table 4.
[0050] Table 4: Effect of different proportions of composite materials on the properties of conductive fibers .
[0051] Table 4 shows that compared with pure PA6 fibers, conductive fibers with added composite materials exhibit significant improvements in conductivity and Staphylococcus aureus inhibition rate. Specifically, when the mass percentage of the composite material in the conductive fibers is less than 2.0 wt%, a complete conductive network is not formed within the fibers, and conductivity increases with increasing filler content. When the mass percentage of the composite material increases to above 2.0 wt%, the conductivity stabilizes at 10. 5 At the S / m level, the antibacterial rate against Staphylococcus aureus remained above 99.5%, and the antibacterial rate against Escherichia coli was 99.8%. The elongation at break was stable at 30-40%, and when the mass percentage of the composite material was 4.0 wt%, excellent balance was achieved in conductivity, bactericidal properties, and elongation at break, with a clear and complete conductive network (see...). Figure 2 (part (b) in the text), and exhibits a conductivity as high as 2.8 × 10⁻⁶. 5The conductivity (S / m) of the composite material reached 99.999% against Staphylococcus aureus and 99.999% against Escherichia coli, while the elongation at break was 28%. However, when the mass percentage of the composite material increased to above 5.0 wt%, the improvement in conductivity was not significant, and the elongation at break decreased to 20% (the standard requires an elongation at break >25%). Therefore, it is appropriate to control the mass percentage of the composite material in the conductive fiber between 2.0 and 4.0 wt% to better balance conductivity, bactericidal properties, and fiber mechanical properties.
[0052] The composite material in Example 4 was replaced with Sample 1, Sample 2, Sample 3, Sample 4, and Sample 5, respectively, and the corresponding fibers were labeled as Fiber 1, Fiber 2, Fiber 3, Fiber 4, and Fiber 5, respectively. The results are shown in Figure 5.
[0053] Table 5: Spinning performance of different schemes .
Claims
1. A copper ion-doped carbon nanotube composite material, characterized in that: In the composite material, copper ions are doped into the carbon nanotube framework in an atomically dispersed manner or in the form of nanoclusters. The copper ion content in the composite material is 0.1–5 wt%, and the electrical conductivity of the composite material is ≥1.0 × 10⁻⁶. 5 S / m.
2. The copper ion-doped carbon nanotube composite material according to claim 1, characterized in that: The copper ion content in the composite material is 0.5–3.0 wt%, and the electrical conductivity of the composite material is ≥4.2 × 10⁻⁶. 6 S / m.
3. The copper ion-doped carbon nanotube composite material according to claim 1, characterized in that: The copper ion content in the composite material is 1.0–1.5 wt%, and the electrical conductivity of the composite material is ≥5.5 × 10⁻⁶. 7 S / m.
4. The copper ion-doped carbon nanotube composite material according to claim 1, characterized in that: The composite material has an inhibition rate of ≥98.5% against Escherichia coli and Staphylococcus aureus.
5. A method for preparing the composite material according to claim 1, characterized in that, The steps are as follows: Step 1: Disperse carbon nanotubes in an aqueous solution containing copper ions until a uniform dispersion is obtained. Step 2: Transfer the dispersion to a hydrothermal reactor for hydrothermal reaction; Step 3: Wash and dry the product obtained from the hydrothermal reaction to obtain a copper ion-doped carbon nanotube composite material.
6. The method for preparing composite materials according to claim 5, characterized in that: The temperature for the hydrothermal reaction is 120–200℃.
7. The method for preparing composite materials according to claim 5, characterized in that: The hydrothermal reaction temperature is 140–160℃.
8. The application of the composite material of claim 1 in conductive fibers.
9. The application according to claim 8, characterized in that: Conductive fibers are obtained by melt spinning the composite material with PA6 chips, or by solution spinning the composite material with PA6 solution after uniform mixing.
10. The application according to claim 8, characterized in that: The mass percentage of the composite material in the conductive fiber is 0.5 to 5 wt%.