Preparation method of RuO2-MXene / CNTs fiber electrode material for wet spinning
By anchoring RuO2 and CNTs on the MXene surface, the construction of multi-dimensional nanomaterial-doped RuO2-MXene/CNTs composite fibers is solved, and the combination of high-performance electrochemical properties and mechanical properties is achieved. It is suitable for flexible supercapacitors and multifunctional electronic devices.
Patent Information
- Application Number
- CN202510514120.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-23
- Publication Date
- 2025-08-01
AI Technical Summary
The existing MXene-based composite fibers cannot take into account excellent mechanical and electrochemical properties, and the easy stacking of nanosheets leads to reduced electrolyte ion transport and electrochemical properties.
Ultrafine nanomaterials RuO2 and CNTs were anchored on the MXene surface by solvothermal method, and the RuO2-MXene/CNTs composite fibers were constructed using wet spinning technology to form a three-dimensional conductive network doped with multi-dimensional nanomaterials.
The prepared RuO2-MXene/CNTs composite fibers exhibit excellent electrical and electrochemical properties, and are suitable for flexible supercapacitors and multifunctional electronic devices, with good mechanical properties and electrochemical stability.
Smart Images
Figure CN120401062A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of MXene-based fibers and their preparation, and particularly relates to a preparation method of a RuO2-MXene / CNTs fiber electrode material by wet spinning. Background Art
[0002] As a new type of two-dimensional inorganic compound composed of 2D layered transition metal carbides or nitrides, MXene exhibits ultra-high theoretical electrochemical properties and excellent processability due to its high electrical conductivity, unique layered structure, and rich hydrophilic surface functional groups, making it one of the best candidates for constructing functional fibers. However, like other 2D layered nanomaterials, MXene nanosheets also tend to re-stack due to the van der Waals force between adjacent sheets, making it difficult to effectively assemble them into fibers. Moreover, this re-stacking between sheets also leads to the loss of a large specific surface area during electrolyte ion transport, thereby greatly reducing the electrochemical performance, resulting in the mechanical, electrical, and electrochemical properties of pure MXene fibers being far lower than the theoretical values, which severely limits the application of MXene-based fibers.
[0003] Currently, in order to ensure the formation and provide sufficient mechanical properties of MXene-based fibers, elastomeric materials such as SBS and TPU are usually introduced. However, the presence of these materials usually affects the electrochemical performance of MXene-based fibers. In addition, the introduction of elastomeric materials such as SBS and TPU also leads to the re-stacking of MXene nanosheets, further reducing the electrochemical performance. Therefore, it is of great significance to develop a high-performance MXene-based composite fiber with both excellent mechanical properties and electrochemical performance. Summary of the Invention
[0004] The purpose of the present invention is to solve the technical problem that existing MXene-based composite fibers cannot balance mechanical properties and electrochemical performance, and to provide a preparation method of a RuO2-MXene / CNTs fiber electrode material by wet spinning.
[0005] The technical solution of the present invention is as follows:
[0006] One of the purposes of the present invention is to provide a preparation method of a RuO2-MXene / CNTs fiber electrode material by wet spinning, and the method is carried out according to the following steps:
[0007] S1: Ultrasonically treat and magnetically stir RuCl3 powder, MXene solution, and deionized water in sequence to make them uniformly dispersed, then transfer them to a reaction kettle for hydrothermal reaction. After the reaction is completed, centrifuge, wash, vacuum dry, and grind the obtained suspension to obtain RuO2-MXene powder;
[0008] S2: Add RuO2-MXene powder and CNTs into deionized water, ultrasonically treat the mixture, and then add sodium alginate and stir magnetically to obtain a spinning solution.
[0009] S3: Extrude the spinning solution through a rotary nozzle, immerse it in a coagulation bath of CaCl2-ethanol solution for wet spinning, and then wash and dry it with ethanol to obtain RuO2-MXene / CNTs fibers.
[0010] Further specify that in S1, the preparation of the MXene solution: First, add HCl solution into a polytetrafluoroethylene reactor, then add LiF and stir, and then add Ti3AlC2 powder. Continue to stir under heating conditions to obtain a suspension of multi-layer MXene. Centrifuge and wash the suspension until a multi-layer Ti3C2Tx suspension with pH>6 is obtained. Finally, ultrasonically treat it in a nitrogen atmosphere, centrifuge and take the supernatant to obtain an MXene solution with a concentration of 5-10 mg / mL.
[0011] Further specify that in S1, the ratio of RuCl3 powder to the MXene solution and deionized water is 100 mg:(10-15) mL:(20-40) mL.
[0012] Further specify that in S1, the ultrasonic treatment time is 0.5-1.5 h, and the magnetic stirring time is 5-10 h.
[0013] Further specify that in S1, the hydrothermal reaction temperature is 110-130 °C, and the time is 8-12 h.
[0014] Further specify that in S1, the vacuum drying temperature is 50-70 °C, and the time is 10-14 h.
[0015] Further specify that in S2, the mass ratio of RuO2-MXene powder to CNTs is 1:(0.5-2).
[0016] Further specify that in S2, the volume ratio of the total mass of RuO2-MXene powder and CNTs to deionized water is (50-80) mg:(4-6) mL.
[0017] Further specify that in S2, the ultrasonic treatment time is 20-40 min.
[0018] Further specify that in S2, the mass ratio of the total mass of RuO2-MXene powder and CNTs to sodium alginate is (5-7):1.
[0019] Further specify that in S2, the magnetic stirring speed is 500-700 rpm, and the time is 5-7 h.
[0020] Further specify that in S3, the mass fraction of CaCl2 in the coagulation bath of CaCl2-ethanol solution is 5-10%.
[0021] The second object of the present invention is to provide a RuO2-MXene / CNTs fiber prepared by the above method.
[0022] The third object of the present invention is to provide an application of the RuO2-MXene / CNTs fiber prepared by the above method in micro-batteries, flexible supercapacitors and multifunctional electronic devices.
[0023] Compared with the prior art, the advantages of the present invention are as follows:
[0024] In the present invention, ultrafine nanomaterials are anchored on the surface of MXene by a solvothermal method, and then mixed with CNTs. The RuO2-MXene / CNTs composite fiber doped with multidimensional nanomaterials between the layers is prepared by using a wet spinning device, endowing it with excellent electrical and electrochemical properties, and showing great application potential in flexible supercapacitors and multifunctional electronic devices. The specific advantages are as follows:
[0025] (1) In the present invention, RuO2·nH2O and CNTs are used as molecular intercalating agents to construct 0D nanoparticles between the MXene nanosheets, preventing the re-stacking of the MXene nanosheets and generating more sufficient electrochemically active substances and more activatable electrochemically active sites on the surface of the conductive MXene sheets. Further, one-dimensional CNTs are introduced to finally construct a composite fiber doped with multidimensional nanomaterials between the layers. In addition, by adjusting the addition amount of CNTs, a high-performance RuO2-MXene / CNTs composite fiber with a three-dimensional conductive network structure is constructed by using a simple wet spinning process, which is expected to have great application prospects in micro-batteries, flexible supercapacitors and multifunctional electronic devices.
[0026] (2) The preparation method provided by the present invention is simple, environmentally friendly, and low in energy consumption, and the prepared RuO2-MXene / CNTs composite fiber electrode material exhibits excellent electrical and electrochemical properties. Description of the Drawings
[0027] Figure 1 XRD pattern of MXene obtained in step (1) of Example 1;
[0028] Figure 2 SEM image of RuO2-MXene obtained in step (2) of Example 1;
[0029] Figure 3 SEM and EDS images of the surface of the RuO2-MXene / CNTs fiber obtained in Example 1;
[0030] Figure 4The stress-strain comparison diagram of the RuO2-MXene / CNTs fiber obtained in Example 1, the pure MXene fiber obtained in Comparative Example 1, and the MXene / CNTs fiber obtained in Comparative Example 2;
[0031] Figure 5 The SEM image of the fracture surface of the RuO2-MXene / CNTs fiber obtained in Example 1;
[0032] Figure 6 For Figure 5 Local enlarged view;
[0033] Figure 7 The CV curves of the RuO2-MXene / CNTs fiber obtained in Example 1 at different scanning rates;
[0034] Figure 8 The CV curve of the RuO2-MXene / CNTs fiber obtained in Example 1 under 1000 cycles. Detailed implementation manners
[0035] In order to make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
[0036] The experimental methods used in the following embodiments are all conventional methods unless otherwise specified. The materials, reagents, methods and instruments used, unless otherwise specified, are all conventional materials, reagents, methods and instruments in the art, and those skilled in the art can obtain them through commercial channels.
[0037] The terms "comprising", "including", "having", "containing" or any other variation thereof used in the following embodiments are intended to cover non-exclusive inclusion. For example, a composition, step, method, article or device containing the listed elements does not necessarily refer only to those elements, but may include other elements not explicitly listed or elements inherent to such composition, step, method, article or device.
[0038] When an equivalent, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values and lower preferred values, this should be understood to specifically disclose all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed individually. For example, when the range "1 to 5" is disclosed, the described range should be interpreted to include ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described herein, unless otherwise specified, the range is intended to include its endpoint values and all integers and fractions within the range. In the specification and claims of this application, range limitations can be combined and / or interchanged, and if not otherwise stated, these ranges include all sub-ranges contained therein.
[0039] The indefinite articles "a" and "an" before an element or component of the present invention do not limit the quantity requirement (i.e., the number of occurrences) of the element or component. Therefore, "a" or "an" should be interpreted to include one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity clearly refers only to the singular form.
[0040] The endpoints and any values of the ranges disclosed in the invention are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.
[0041] Example 1. The preparation method of the RuO2-MXene / CNTs fiber electrode material by wet spinning in this example is carried out according to the following steps:
[0042] (1) First, measure 20 mL of 9M HCl and pour it into a polytetrafluoroethylene reactor. Subsequently, add 1 g of LiF, stir for 10 min, then add 1 g of Ti3AlC2 powder, and further stir at 45 °C for 48 h to obtain a suspension of multi-layer MXene. The obtained stable suspension is washed three times in 1M HCl and then three times in deionized water, centrifuged at 3500 rpm for 5 min each time, to obtain a multi-layer Ti3C2Tx suspension with a pH value greater than 6. Finally, the obtained multi-layer Ti3C2Tx is ultrasonically treated in a nitrogen atmosphere for 2 h, centrifuged at 3500 rpm for 1 h, and the supernatant is taken and its concentration is measured for standby to obtain an 8 mg / mL MXene solution. Figure 1XRD pattern of the obtained MXene. As shown in the figure, after etching the MAX phase in a lithium fluoride and hydrochloric acid solution, the distinct diffraction peak (104) at 39° disappeared in the XRD spectrum, indicating the successful removal of Al atoms from Ti3AlC2.
[0043] (2) Weigh 100 mg of RuCl3 powder and 12.5 mL of MXene (8 mg / mL) solution, dissolve them in 30 mL of deionized water, ultrasonically treat for 1 h first, then magnetically stir for 8 h to make them evenly dispersed. Transfer the solution to a reaction kettle with a capacity of 80 mL and react in a forced-air drying oven at 120 °C for 10 h. Centrifuge the obtained suspension, wash it three times with deionized water and ethanol respectively, dry it at 60 °C for 12 h, and grind it into powder to obtain RuO2-MXene powder. Figure 2 SEM image of the obtained RuO2-MXene. As can be seen from the figure, the prepared RuO2-MXene is a single-layer or few-layer flaky structure, and relatively completely retains the original single-layer or few-layer flaky structure of MXene itself.
[0044] (3) Weigh 30 mg of RuO2-MXene and 30 mg of CNTs respectively and add them to 5 mL of deionized water and ultrasonically treat for 30 min. Then, add 10 mg of sodium alginate (SA), place it on a magnetic stirrer, and stir at a speed of 580 rpm at room temperature for 6 h to obtain a spinning solution.
[0045] (4) Extrude the spinning solution through a rotating nozzle with a diameter of 0.9 mm and immerse it in a coagulation bath of a CaCl2-ethanol solution (ethanol volume fraction is 75%) with a mass fraction of CaCl2 of 10% for wet spinning, where the injection speed is 1.2 mL / min. After washing with ethanol for 30 min, dry it for 24 h. Obtain RuO2-MXene / CNTs fibers. Figure 3 SEM and EDS images of the surface of the obtained RuO2-MXene / CNTs composite fibers. From the SEM and energy-dispersive spectroscopy (EDS) elemental mapping images of the fiber surface, it can be observed that the elemental distributions of C, Ti, O, Ru, and Ca are relatively uniform, indicating that the internal structure and component distribution of the hybrid fibers are uniform.
[0046] Comparative Example 1:
[0047] The preparation method of the pure MXene fiber in this comparative example is carried out according to the following steps:
[0048] (1) First, measure 20 mL of 9 M HCl and pour it into a polytetrafluoroethylene reactor. Then add 1 g of LiF and stir for 10 min. Next, add 1 g of Ti3AlC2 powder and further stir at 45 °C for 48 h to obtain a suspension of multi-layer MXene. Wash the obtained stable suspension three times in 1 M HCl and then three times in deionized water, centrifuging at 3500 rpm for 5 min each time, to obtain a multi-layer Ti3C2Tx suspension with a pH value greater than 6. Finally, ultrasonically treat the obtained multi-layer Ti3C2Tx in a nitrogen atmosphere for 2 h, centrifuge at 3500 rpm for 1 h, and take the supernatant to obtain an MXene solution.
[0049] (2) Dry the MXene solution prepared above in a vacuum drying oven at 60 °C for 12 h and grind it into powder. Weigh 60 mg of MXene and add it to 5 mL of deionized water and stir for 30 min. Then, add 10 mg of sodium alginate (SA), place it on a magnetic stirrer, and continue to stir at a speed of 580 rpm at room temperature for 6 h to obtain a spinning solution.
[0050] (3) Extrude the spinning solution through a rotating nozzle with a diameter of 0.9 mm and immerse it in a coagulation bath of a CaCl2-ethanol solution (ethanol volume fraction is 75%) with a CaCl2 mass fraction of 10% for wet spinning, where the injection speed is 1.2 mL / min. Wash with ethanol for 30 min and then dry for 24 h. Obtain MXene fibers.
[0051] Comparative Example 2:
[0052] The preparation method of the MXene / CNTs fibers in this comparative example is carried out according to the following steps:
[0053] (1) First, measure 20 mL of 9 M HCl and pour it into a polytetrafluoroethylene reactor. Then add 1 g of LiF and stir for 10 min. Next, add 1 g of Ti3AlC2 powder and further stir at 45 °C for 48 h to obtain a suspension of multi-layer MXene. Wash the obtained stable suspension three times in 1 M HCl and then three times in deionized water, centrifuging at 3500 rpm for 5 min each time, to obtain a multi-layer Ti3C2Tx suspension with a pH value greater than 6. Finally, ultrasonically treat the obtained multi-layer Ti3C2Tx in a nitrogen atmosphere for 2 h, centrifuge at 3500 rpm for 1 h, and take the supernatant to obtain an MXene solution.
[0054] (2) The prepared MXene solution was dried in a vacuum drying oven at 60 °C for 12 h and then ground into powder. 30 mg of MXene and 30 mg of CNTs were weighed and added to 5 mL of deionized water, followed by ultrasonic treatment for 30 min. Then, 10 mg of sodium alginate (SA) was added, and the mixture was placed on a magnetic stirrer and stirred at a speed of 580 rpm at room temperature for 6 h to obtain a spinning solution.
[0055] (3) The spinning solution was extruded through a rotating nozzle with a diameter of 0.9 mm and immersed in a coagulation bath of CaCl2-ethanol solution (ethanol volume fraction of 75%) with a CaCl2 mass fraction of 10% for wet spinning, where the injection speed was 1.2 mL / min. After washing with ethanol for 30 min, it was dried for 24 h. MXene / CNTs fibers were obtained.
[0056] The RuO2-MXene / CNTs fibers obtained in Example 1, the pure MXene fibers obtained in Comparative Example 1, and the MXene / CNTs fibers obtained in Comparative Example 2 were subjected to a tensile test using a mechanical testing machine. The stress-strain comparison diagram obtained is as Figure 4 shown. The figure shows that the stress (44.45 MPa) and strain (1.76%) of the RuO2-MXene / CNTs three-dimensional composite fibers are significantly better than those of the MXene / CNTs fibers and the pure MXene fibers.
[0057] The SEM images of the fracture surface of the RuO2-MXene / CNTs fibers obtained in Example 1 and the SEM images of its magnified fracture surface are as Figures 5 - 6 shown. From the high-magnification SEM images of the fracture surface of the hybrid fibers, it can be observed that the lamellar RuO2-MXene is tightly combined with the carbon nanotubes, and adding a certain amount of carbon nanotubes can construct a compact structure with narrow-distribution mesopores in the hybrid fibers, which is beneficial to improving the tensile strength of the fibers, improving the internal conductivity of the fiber electrodes, and increasing the carrier migration rate.
[0058] Using a typical three-electrode system, with a platinum auxiliary electrode, a saturated Ag / AgCl reference electrode, and the RuO2-MXene / CNTs fibers obtained in Example 1 as the working electrode, 1 M NaOH as the electrolyte, the electrochemical performance was tested using a CHI 660B (Chenhua Company) workstation. The CV curves at different scan rates are as Figure 7 shown. From Figure 7 it can be seen that the CV curves maintain a quasi-rectangular shape at different scan rates, proving that the prepared fiber electrodes have good rate performance, and the volume capacitance of the RuO2-MXene / CNTs hybrid fiber electrode can reach 72.49 ± 5.4 F / cm 3 3, showing good electrochemical energy storage characteristics.
[0059] The CV curves under 1000 cycles are as follows Figure 8 shown. It can be seen from Figure 8 that when the scanning rate is 50 mV / s and the charge-discharge cycle is 1000 times, the capacity retention rate is as high as 88.1%, showing good electrochemical capacitance and stability.
[0060] As mentioned above, the above are only the preferred specific embodiments of the present invention. These specific embodiments are all different implementation manners based on the overall concept of the present invention, and the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims
1. A preparation method of a RuO2-MXene / CNTs fiber electrode material by wet spinning, characterized in that, The method: S1: Ultrasonically treat and magnetically stir RuCl3 powder, MXene solution and deionized water in sequence to make them uniformly dispersed, then transfer them to a reaction kettle for hydrothermal reaction. After the reaction, centrifuge, wash, vacuum dry and grind the obtained suspension to obtain RuO2-MXene powder; S2: Add RuO2-MXene powder and CNTs to deionized water for ultrasonic treatment, then add sodium alginate and magnetically stir to obtain a spinning solution; S3: Extrude the spinning solution through a rotary nozzle and immerse it in a coagulation bath of CaCl2-ethanol solution for wet spinning, and then wash and dry with ethanol to obtain RuO2-MXene / CNTs fibers.
2. The method according to claim 1, characterized in that Preparation of MXene solution in S1: First, add HCl solution to a polytetrafluoroethylene reactor, then add LiF and stir, then add Ti3AlC2 powder, and continue to stir under heating conditions to obtain a suspension of multi-layer MXene. Centrifuge and wash the suspension until a multi-layer Ti3C2Tx suspension with pH>6 is obtained. Finally, ultrasonically treat it in a nitrogen atmosphere, centrifuge and take the supernatant to obtain an MXene solution with a concentration of 5-10 mg / mL.
3. The method according to claim 1, characterized in that, In S1, the ratio of RuCl3 powder to MXene solution and deionized water is 100 mg: (10-15) mL: (20-40) mL.
4. The method according to claim 1, characterized in that, In S1, the hydrothermal reaction temperature is 110-130 °C and the time is 8-12 h.
5. The method according to claim 1, wherein In S2, the mass ratio of RuO2-MXene powder to CNTs is 1: (0.5-2), and the volume ratio of the total mass of RuO2-MXene powder and CNTs to deionized water is (50-80) mg: (4-6) mL.
6. The method according to claim 1, wherein In S2, the mass ratio of the total mass of RuO2-MXene powder and CNTs to sodium alginate is (5-7):
1.
7. The method according to claim 1, wherein In S2, the ultrasonic treatment time is 20-40 min, the magnetic stirring speed is 500-700 rpm, and the time is 5-7 h.
8. The method according to claim 1, wherein In S3, the mass fraction of CaCl2 in the coagulation bath of CaCl2-ethanol solution is 5-10%.
9. RuO2-MXene / CNTs fibers prepared by the method according to any one of claims 1-8.
10. Application of the RuO2-MXene / CNTs fibers according to claim 9 in micro-batteries, flexible supercapacitors and multifunctional electronic devices.