WO2021237862A1 - 纳米片有序堆叠的宏观高导电性MXene带状纤维及柔性电容器 - Google Patents

纳米片有序堆叠的宏观高导电性MXene带状纤维及柔性电容器 Download PDF

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WO2021237862A1
WO2021237862A1 PCT/CN2020/098348 CN2020098348W WO2021237862A1 WO 2021237862 A1 WO2021237862 A1 WO 2021237862A1 CN 2020098348 W CN2020098348 W CN 2020098348W WO 2021237862 A1 WO2021237862 A1 WO 2021237862A1
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fibers
fiber
mxene
ribbon
nanosheets
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French (fr)
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耿凤霞
祝超
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Suzhou University
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Suzhou University
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Priority claimed from CN202010457150.0A external-priority patent/CN111809272B/zh
Priority claimed from CN202010457149.8A external-priority patent/CN111739739B/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor

Definitions

  • the invention belongs to flexible fibrous electrode technology, and specifically relates to macroscopically highly conductive MXene ribbon fibers with orderly stacked nanosheets and a flexible capacitor based on the macroscopically highly conductive MXene ribbon fibers.
  • fibers with a nearly perfectly ordered nanosheet structure can maximize the performance utilization of a single nanosheet.
  • graphene oxide nanosheets with a hydrophilic surface can be well dispersed in an aqueous medium, thereby helping to prepare continuous fibers using a scalable wet spinning method.
  • the mechanical strength and electrical properties of the fiber can be greatly improved.
  • hybrid fiber electrodes In order to enhance the electrochemical performance of fibers, hybrid fiber electrodes have been prepared by depositing pseudocapacitive materials (such as manganese oxide, cobalt oxide, and ruthenium oxide) on graphene or other conductive fiber substrates. Or, similar to the spinning process of graphene oxide, two-dimensional transition metal oxide nanosheets dispersed in an aqueous medium are directly assembled into fiber electrodes. Sometimes nanosheets are combined with graphene as a current collector. It should be noted that fibers containing large amounts of electrochemically active materials can generally provide enhanced energy storage capabilities, but the overall rate performance is largely limited by the inherent low conductivity. Therefore, although there is an urgent need for a conductive fibrous electrode with excellent energy storage capabilities, its development is an arduous task.
  • pseudocapacitive materials such as manganese oxide, cobalt oxide, and ruthenium oxide
  • MXene fibers Some recent experimental attempts have been reported for the production of macroscopic MXene fibers, but most studies have to incorporate components with fiber spinnability, such as reduced graphene oxide (rGO), conductive polymer PEDOT, etc.
  • rGO reduced graphene oxide
  • PEDOT conductive polymer
  • the strong MA bond This means that only by using harsh chemical methods to selectively etch the A layer can MXene be produced.
  • the breaking of the M-A bond during etching can damage the M-X bond based on their similar bond energies.
  • the length of the parent MAX crystals is tens of micrometers
  • most of the obtained MXenes only show limited lateral dimensions, only a few hundred nanometers, resulting in additional grain boundaries, which are important for the construction of macroscopic MXene fibers. obstacle.
  • the small size of MXene is a disadvantage of aligning the flakes in a macrostructure, which may require fine control of the flake interface and synthesis parameters.
  • the present invention discloses an orderly stacked macroscopic high-conductivity MXene ribbon fiber with nanosheets and a preparation method and application thereof.
  • the prepared pure MXene macro fiber has excellent mechanical properties, Electrical conductivity is a pioneering research work.
  • the invention called MXene macro-fiber has potential applications in the field of energy storage due to its unique physical and chemical properties.
  • MXene has the potential to deliver excellent electrochemical properties without the help of any auxiliary components.
  • the present invention adopts the following technical solutions.
  • the preparation method of the macroscopically high-conductivity MXene ribbon-shaped fiber in which the nanosheets are stacked in an orderly manner includes the following steps.
  • step (2) Inject the titanium carbide aqueous solution of step (1) into the coagulation bath to obtain initial fibers.
  • step (3) The initial fibers of step (2) are acid-treated and washed to obtain macroscopic highly conductive MXene ribbon fibers with orderly stacked nanosheets.
  • the macroscopic high-conductivity MXene ribbon fibers which are stacked in an orderly manner, are used as the negative electrode, and are assembled with the electrolyte, the positive electrode, and the separator to obtain a high-performance flexible supercapacitor.
  • the concentration of the HF solution is 8-12 wt%; the concentration of the tetramethylammonium hydroxide aqueous solution is 22-28 wt%; the concentration of the titanium carbide aqueous solution is 10-30 mg/mL,
  • the lateral dimension of titanium carbide is 1 to 2.5 microns, preferably 1.6 to 2 microns.
  • the nanosheets have the characteristics of large size, uniform size distribution, and high orderliness of the nanosheets, which are beneficial to solution spinnability and the preparation of continuous long fibers.
  • the coagulation bath is a chitosan-acetic acid coagulation bath.
  • the solvent is water
  • the chitosan concentration is 0.6 wt%
  • the acetic acid concentration is 4 wt%
  • conventional syringes are used for injection
  • rotating disks are used for receiving.
  • the specific preparation process is based on the prior art to obtain Ti 3 C 2 initial fibers containing chitosan.
  • the acid treatment is immersion in a sulfuric acid solution, such as immersion in a 1M sulfuric acid aqueous solution for 3 days, and the washing is alcohol washing, such as ethanol washing.
  • the electrolyte is polyvinyl alcohol-sulfuric acid as the electrolyte
  • the positive electrode is rGO fiber
  • the electrolyte and the positive electrode are existing products; the specific method for assembling the supercapacitor is the prior art.
  • the currently disclosed Ti 3 C 2 nanosheet solution is difficult to have spinnability, and it needs to be assisted by graphene or other spinnable binders to prepare Ti 3 C 2 composite fibers, and the present invention achieves spinnability.
  • the Ti 3 C 2 solution and the pure MXene fiber were prepared by wet spinning process and acid treatment method; due to the preparation of Ti 3 C 2 solution and the design of spinning parameters, the prepared pure Ti 3 C 2 fiber macroscopically It presents a ribbon-like structure with a highly ordered stack of Ti 3 C 2 nanosheets in the microscopic interior.
  • the acid-treated fiber of the present invention makes the fiber have an open two-dimensional ion transport channel inside, and the fiber has high electrochemical performance (the current density is 1 A g -1 when the capacity When the current density reaches 309 F g -1 and the current density is 10 A g -1 , the capacity is 231 F g -1 , and the capacity retention rate after 10,000 cycles is 97.24%); the pure Ti 3 C 2 fiber of the present invention and reduced graphene oxide Fiber (rGO) matched and assembled asymmetric supercapacitors, and the assembled asymmetric capacitors have a high volumetric energy density (58.4 mW h cm -3 ).
  • Figure 1 is a schematic diagram of fiber preparation and a structural diagram of the initial fiber and pure titanium carbide fiber.
  • Figure 2 is an atomic force microscope image of the titanium carbide nanosheets and the statistics of the size distribution of the nanosheets, indicating that the size of the nanosheets in the optimized solution is generally between 1.6-2.0 ⁇ m and the size distribution range is narrow.
  • Figure 3 is a polarized light microscope image of a titanium carbide solution at different concentrations, indicating that as the concentration increases, the order of the nanosheets in the solution increases.
  • FIG. 4 is a simulation diagram and calculation of the distance between the nanosheets in the solution, which shows that the free volume of the nanosheets in the solution of the present invention is reduced, and the restrained force becomes larger and more orderly.
  • Figure 5 is (a) the schematic diagram of the wet spinning equipment and the structure of the obtained fiber, (b) the typical atomic force microscope (AFM) image of the Ti 3 C 2 thin plate, (c) the cross-section and top view of the original fiber at different stages Optical microscope image, distance from the needle exit: I (1 cm), II (11 cm), III (21 cm), IV (31 cm), (d) photos of continuous long macroscopic fibers.
  • AFM atomic force microscope
  • Figure 6 shows the thermogravimetric data of the initial fiber and pure titanium carbide film. It can be seen from the data graph that the initial fiber contains a small amount of flocculant chitosan.
  • Figure 7 is (a) XPS data of the initial fiber and pure titanium carbide fiber.
  • the initial fiber contains chitosan.
  • the pure titanium carbide fiber obtained after acid treatment has no chitosan, indicating that the chitosan has been removed;
  • Figure 9 shows the element analysis under the transmission electron microscope after fiber ultrathin sectioning.
  • Figure 10 shows the mechanical strength of the initial fiber and pure titanium carbide fiber; after acid treatment, the chitosan is removed, resulting in a slight decrease in the mechanical strength of the fiber, but it still has good mechanical strength.
  • Figure 11 is a photograph of pure Ti 3 C 2 fibers wound on a glass rod and an SEM image of tightly knotted fibers.
  • the obtained pure titanium carbide fiber has good flexibility.
  • Figure 12 shows the electrical conductivity of the pure Ti 3 C 2 fiber compared with other reported MXene-based fibers under the same test method.
  • the pure titanium carbide fiber obtained in the present invention has a high electrical conductivity.
  • Figure 13 shows the resistance comparison between the initial fiber and the pure titanium carbide fiber, (a) the resistance of the 11 cm long initial fiber, the calculated conductivity is 767 S cm -1 , (b) the resistance of the 11 cm long pure titanium carbide fiber, The calculated electrical conductivity is 2458 S cm -1 , (c) the resistance of the initial fiber and pure titanium carbide fiber varies with length, showing a linear relationship, indicating that the fiber is uniform, (d) pure titanium carbide fiber is bent at different angles The resistance below shows that the resistance of pure titanium carbide fiber is stable under bending.
  • Figure 14 shows the electrochemical performance of pure pure titanium carbide fibers in a three-electrode system.
  • A Schematic diagram of three-electrode setup.
  • B CV curves recorded at different scan rates.
  • C GCD curves recorded at different current densities.
  • D Specific capacitance and corresponding length capacitance at different scan rates. Illustration: Comparison of the capacitance retention capacity of MXene-based optical fiber supercapacitors at different current densities.
  • E Cycle stability of 10 4 cycles. Illustration: GCD curve of the first and last cycle.
  • Figure 15 is a cross-sectional SEM image of pure titanium carbide fiber after 10,000 cycles at 10 A g -1; pure titanium carbide fiber has good electrode working stability.
  • Figure 16 shows the performance difference between the initial fiber and the pure titanium carbide fiber after acid treatment.
  • A is the electrochemical performance data of the initial titanium carbide fiber and the pure titanium carbide fiber, and B is the electrochemical impedance data.
  • the pure titanium carbide fiber has a smaller value Ion diffusion resistance.
  • Figure 17 shows the H + diffusion coefficient calculated from impedance data.
  • Figure 18 shows that GCD bends acid-treated pure Ti 3 C 2 fibers of different lengths.
  • Figure 19 shows the electrochemical performance of asymmetric fiber supercapacitors.
  • A Schematic diagram of flexible asymmetric equipment.
  • B CV curves of pure Ti 3 C 2 fiber and rGO fiber at the same scanning rate.
  • C CV curves of asymmetric devices at different scanning speeds and
  • D GCD curves at different current densities.
  • E The volumetric energy density and power density of the assembled asymmetric device are compared with other fiber supercapacitors and fiber batteries.
  • F A photo of the blue LED logo fiber driven by three flexible devices connected in series, and (g) a photo of two tandem fibers woven into gloves to illuminate an electronic watch.
  • Figure 20 is (a) the SEM surface image of the redox graphene fiber; (b) the cross-sectional view of the redox graphene fiber.
  • Figure 21 shows the cyclic voltammetry (CV) curves of redox graphene fibers at different scanning speeds.
  • Figure 22 shows the working range of the assembled device, the working voltage is 0-1.5 V.
  • Figure 23 shows the data of 10,000 cycles of the assembled device at a current density of 10 A g -1 .
  • the inset figure shows the data of the first and last constant current charge and discharge before the device is cycled.
  • Figure 24 shows (a) the titanium carbide nanosheets of the present invention, the coagulation bath is chitosan-acetic acid aqueous solution; the effect: can form continuous fibers with high mechanical strength; (b) the titanium carbide nanosheets of the present invention, the coagulation bath is 5% chlorine Calcium water-isopropanol (volume ratio 3:1); effect: only short fibers can be obtained and are very brittle, almost without strength; (c) small nano-sheets, coagulation bath is chitosan-acetic acid aqueous solution; effect: Short fibers have a certain strength.
  • Figure 25 shows the spinning effect of a 10 mg mL -1 titanium carbide solution in a chitosan-acetic acid solution. Only short fibers can be obtained, not continuous fibers.
  • Electrode test method the electrode clamps the fiber directly as the working electrode, Ag/AgCl as the reference electrode, and Pt as the counter electrode.
  • the electrochemical test is carried out in 1M sulfuric acid electrolyte. (Test equipment CHI660E electrochemical workstation).
  • Two-electrode test CHI660E electrochemical workstation is used to test its electrochemical performance.
  • the positive and negative electrodes of the fiber device are respectively connected to the electrochemical workstation for direct testing.
  • the fiber cross-sectional area is calculated by using the inner image of the SEM cross-section, and the mechanical strength of the fiber is measured by the Instron 3365 universal material extensometer.
  • the preparation method of the macroscopically highly conductive MXene ribbon fiber with orderly stacked nanosheets of the present invention is as follows.
  • step (2) Inject the titanium carbide aqueous solution of step (1) into the coagulation bath to obtain initial fibers.
  • step (3) The initial fibers of step (2) are acid-treated and washed to obtain macroscopic highly conductive MXene ribbon fibers with orderly stacked nanosheets.
  • the raw materials of the present invention are all commercially available, and the test methods involved are all conventional test methods in the field.
  • Example 1 Preparation of titanium carbide colloidal aqueous solution: Ti 3 AlC 2 powder (1g) was put into HF solution (10 wt%, 30 mL), stirred for 10 minutes, centrifuged with distilled water and washed 3 times, and then placed in a vacuum oven at 80°C Dry for 24 hours.
  • the titanium carbide colloidal aqueous solution into a plastic syringe with a rotating nozzle (a conventional stainless steel spinning needle with a diameter of 500 ⁇ m), and inject it (40 mL h -1 ) into the coagulation bath, which is received by the rotating disk;
  • the coagulation bath contains 4 wt% acetic acid aqueous solution of chitosan (chitosan 0.6 wt%), the speed of the spinning disk is set to 560 rph, the distance from the nozzle to the center of the spinning disk: 6 cm;
  • the titanium carbide colloidal aqueous solution is in contact with the coagulation bath, immediately A continuous initial fiber is formed; the initial fiber is allowed to stand in the coagulation bath for 15 minutes, and then washed with water and ethanol; then the initial fiber is immersed in a 1 M sulfuric acid aqueous solution for 3 d; the acid-treated fiber is separated with deionized water and ethanol Washed for 5 times and dried under ambient
  • the initial fiber was washed with deionized water and ethanol for 5 times, and dried under ambient conditions to obtain Ti 3 C 2 -chitosan fiber, which was used as a comparative fiber and was called the initial Ti 3 C 2 fiber.
  • a solution containing Ti 3 C 2 tablets (20 mg mL -1 ) is extruded from a needle (with a diameter of 500 ⁇ m) through a syringe pump into a coagulation bath placed on a turntable, through the coagulation of protonated chitosan Wet-spin Ti 3 C 2 solution in a bath and then remove chitosan in acid to prepare macroscopic pure Ti 3 C 2 fibers, as shown in Figure 1.
  • the lateral size of the prepared nanosheets is 1.6-2 ⁇ m, and the average thickness is about 1.6 nm ( Figure 2).
  • the solution shows high stability even when the concentration is increased to 20 mg mL -1
  • the theoretical critical concentration of liquid crystal phase is calculated to be 10.88 mg mL -1 , but it is twice as close to the critical concentration (20 mg mL -1)
  • the polarized optical microscopy characterization of the solution did not reveal the typical birefringence characteristics of the liquid crystal phase (Figure 3).
  • the average spacing between the nanoplatelets in the 20 mg mL -1 solution is estimated to be about 170 nm ( Figure 4). Continuous fiber manufacturing.
  • Spinning larger transverse size nanosheets in a protonated chitosan coagulation bath can obtain continuous fibers with good strength.
  • the Ti 3 C 2 solution is passed through a narrow spinning nozzle (diameter 500 ⁇ m) at a certain speed
  • flocculation occurred immediately, and its cross section was the same as that of the injection needle.
  • the cylindrical fiber gradually transformed into a ribbon fiber, as shown in Figure 5c.
  • the morphological evolution of the cross-sectional view and the top view showed that the abnormal formation of ribbon-like fibers was caused by the formation of densely oriented sheet stacks.
  • the cross-sectional area of the four stages was calculated and showed a gradually decreasing trend.
  • the actual fiber is shown in Figure 5d.
  • the fiber length only depends on the feed. There are enough raw materials to spin a long enough continuous fiber.
  • TGA thermogravimetric data
  • the initial Ti 3 C 2 fiber and the pure Ti 3 C 2 fiber can be obtained.
  • the difference is shown in Figure 6; the chitosan between the nanosheets can be completely removed by treatment in sulfuric acid.
  • the density of the pure MXene fiber obtained is 3.26 g cm -3 , which is equivalent to commercial carbon fiber.
  • the structure and morphological characteristics of Ti 3 C 2 fibers before and after acid treatment were analyzed.
  • the X-ray powder diffraction (XRD) curve shown in Figure 8a shows reflection peaks in the low-angle state of the two samples, which means that the two structures are regularly stacked.
  • the spacing between the nanosheets from the original Ti 3 C 2 - chitosan fiber spacing is reduced to 1.43 nm 1.33 nm, clearly detected characteristics associated with the inner surface of the Ti 3 C 2 diffraction layer (110 ), which shows that the main structure of Ti 3 C 2 nanosheets is well preserved after acid treatment.
  • the tensile strength of the macroscopically pure Ti 3 C 2 fiber obtained above reaches 30 MPa, as shown in Figure 10.
  • the small picture shows the pure titanium carbide fiber of the present invention that can lift the key And continuously, therefore, based on the inheritance of the oriented sheet stack structure, the acid treatment does not cause significant deterioration in mechanical properties.
  • these fibers have sufficient strength and flexibility to be bent and knotted on a ⁇ 5 mm glass rod without any signs of breakage, so they are satisfactory for flexible energy storage devices.
  • the two-dimensional open nanochannels between the flakes and the electron channels provided by the metal Ti 3 C 2 flakes facilitate the rapid transmission of ions and electrons.
  • the measured electrical conductivity of the pure Ti 3 C 2 fiber is 2458 S cm -1 , which is several orders of magnitude larger than that of the MXene-based composite fiber, as shown in Figure 12.
  • the number in the upper right corner of the existing fiber is the reference number. Due to its compact stacked structure and excellent mechanical flexibility, the electrical conductivity value of the fiber changes little with the bending angle, as shown in Figure 13. Therefore, the abnormally highly oriented stack structure of Ti 3 C 2 nanosheets can produce excellent ion conductivity, rapid ion diffusion in the crystal lattice and acceptable mechanical strength, which provides a solid foundation for the realization of flexible energy storage devices.
  • the electrochemical properties of the obtained fibers were first characterized in a standard three-electrode configuration in a 1 MH 2 SO 4 electrolyte, in which one end of the long fiber was directly Clamp it on the electrode as the working electrode, Ag/AgCl as the reference electrode, and the Pt sheet as the counter electrode ( Figure 14a).
  • This arrangement is a harsh condition for the optical fiber electrode, because the electrons at one end of the optical fiber electrode must pass a long distance before passing through the optical fiber before reaching the current collector.
  • Figure 14c shows the constant current charge and discharge (GCD) curve, which clearly deviates from the perfect triangle, indicating the surface oxidation-reduction reaction of Ti 3 C 2 nanosheets, which is consistent with the CV analysis results, even at a high of 10 A g -1 There is no obvious ohmic drop under the current density, indicating the high conductivity of the fiber electrode.
  • the fiber has a specific capacitance of 309 F g -1 (52.38 mF cm -1 ) at a current density of 1 A g -1. When the current density increases to 10 A g -1 , the capacitance remains at 231 F g -1 (39.16 mF cm -1 ), which means that the capacitance retention rate is 74.76%.
  • the initial Ti 3 C 2 fiber used as the electrode to replace the pure Ti 3 C 2 fiber did not exhibit excellent cycle stability at a current density of 10 A g -1 .
  • the capacitance After 10 4 cycles, the capacitance The retention rate is about 91.38%.
  • Figure 16A shows the electrochemical performance data (CV data) of the initial titanium carbide fiber and pure titanium carbide fiber. At a sweep speed of 10 mV s -1 , the capacity of the titanium carbide-chitosan fiber is significantly smaller than that of the pure titanium carbide fiber.
  • Electrochemical impedance spectroscopy (EIS) analysis was performed to gain insight into the charge transfer and ion transport characteristics of Ti 3 C 2 fibers.
  • the Ti 3 C 2 fiber electrode shows a shorter Warburg area at high frequency, indicating a fast electron transfer rate, while at low frequency, it shows an almost vertical curve, indicating ideal capacitance characteristics ( Figure 16).
  • the excellent ion transport performance of the fiber was also analyzed from the perspective of kinetics.
  • the diffusion coefficient is estimated to be 9.2 ⁇ 10 -7 cm 2 s -1 , which is 1.43 ⁇ 10 -7 cm 2 compared to the original Ti 3 C 2 chitosan fiber.
  • s -1 Figure 17
  • the designed Ti 3 C 2 fiber has the advantages of an orderly stacked structure and a prepreg channel.
  • the GCD curve of the fiber with a length extension of 5 times to 15 cm was also tested at a current density of 2 A g -1, as shown in FIG. 18. Even at such a length, no significant ohmic drop is observed, and the curves almost completely overlap. All these results provide clear evidence that the prepared fiber electrode with the oriented stack of Ti 3 C 2 flakes provides excellent ion and electron transport performance between the layers, resulting in excellent overall electrochemical performance.
  • Embodiment 2 Take the macroscopically highly conductive MXene ribbon fibers with orderly stacked nanosheets of Embodiment 1 as the negative electrode, and assemble it with the polyvinyl alcohol-sulfuric acid electrolyte and the positive rGO fiber to obtain a high-performance flexible supercapacitor.
  • the titanium carbide colloidal aqueous solution was replaced with a commercially available GO aqueous solution with a concentration of 10 mg/mL (the thickness of the GO sheet was about 1 nm, and the lateral size was 3 to 5 ⁇ m) to obtain the initial GO fibers, which were then immersed in In hydroiodic acid (57wt%) aqueous solution at 90°C for 5 hours, then washed with water to obtain rGO fiber as a positive electrode.
  • In hydroiodic acid (57wt%) aqueous solution at 90°C for 5 hours
  • the positive and negative electrodes are respectively connected with silver paste and copper wire current collectors and then placed in a heat shrinkable tube in parallel, added with the existing polymer separator and polyvinyl alcohol-sulfuric acid electrolyte, heated and sealed to form a high-performance flexible supercapacitor; the specific assembly method is as follows: current technology.
  • the electrode pair can provide an effective voltage of up to 1.5 V without polarization (Figure 22).
  • the CV and GCD curves of asymmetric fiber supercapacitors exhibit curvatures at similar voltages, and have ideal electrochemical behaviors at different scan rates and current densities.
  • the asymmetric fiber supercapacitor can provide a capacitance of 88.67 F g -1 (256 F cm -3 ) at a scan rate of 5 mV s -1 , which is comparable to the value of a typical fiber supercapacitor.
  • the asymmetric fiber supercapacitor has a capacitance retention rate of 92.4% and has long-term cycle stability (Figure 23).
  • Figure 19e shows a Ragone chart comparing the volumetric energy and power density between different fiber supercapacitors and fiber batteries.
  • the invention can provide a high volume density of 58.38 mW h cm -3 at 1679 mW cm -3 , and can provide a high volume power density of about 7466 mW cm -3 at 17.63 mW h cm -3.
  • These energy densities are comparable to existing typical asymmetric optical fiber supercapacitors, but the energy density is close to existing optical fiber batteries.
  • the LEDs and electronic watches lit by the asymmetric fiber supercapacitor of the present invention did not show obvious dimming during the bending of the device, which proved the mechanical strength and flexibility of the device of the present invention ( Figures 19f and 19g).
  • Example 1 On the basis of Example 1, the existing small-size titanium carbide nanosheet aqueous solution is used, as shown in Fig. 24c. The same spinning method cannot obtain continuous macroscopic fibers.
  • Example 1 On the basis of Example 1, the existing inorganic ion coagulation bath (5wt% calcium chloride water-isopropanol solution, in which the volume ratio of water to isopropanol is 3:1), see Figure 24b, the same spinning Method, it is impossible to obtain continuous macroscopic fibers.
  • Example 1 On the basis of Example 1, using a 10 mg/mL titanium carbide nanosheet aqueous solution and the same spinning method, continuous macroscopic fibers could not be obtained, as shown in Figure 25.
  • the disk rotation speed of 400 rph is adopted, and the rest is the same, and continuous macroscopic fibers cannot be obtained.
  • Example 1 On the basis of Example 1, using the existing large-size titanium carbide nanosheet aqueous solution (lateral size 3-4 microns), the same spinning and acid soaking methods, the macro-continuous Ti 3 C 2 fiber obtained through the same test It is calculated that the fiber has a specific capacitance of 283 F g -1 at a current density of 1 A g -1.
  • the nanosheets in the fiber have a highly ordered stacked structure, which means that the mechanical properties of each nanosheet are effectively integrated.
  • This pure Ti 3 C 2 fiber can provide a tensile strength of 30.0 MPa, which is sufficient for practical equipment applications.
  • each nanosheet is an excellent conductor, and the nanosheets are tightly connected to help build a continuous conductive network and provide a conductivity of 2458 S cm -1 , which is higher than the conductivity of the previously reported MXene-based composite fiber. The rate is nearly two orders of magnitude higher.
  • orderly stacking can form an open two-dimensional channel.

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Abstract

本发明公开了纳米片有序堆叠的宏观高导电性MXene带状纤维及柔性电容器，将Ti 3AlC 2 粉末投入HF溶液中，搅拌洗涤，得到晶体；再将晶体加入四甲基氢氧化铵水溶液中，搅拌后依次经过离心处理、洗涤，然后重新分散在水中，超声处理，得到碳化钛水溶液；将碳化钛水溶液注射入凝固浴中，得到初始纤维；将初始纤维经过酸处理、洗涤，得到纳米片有序堆叠的宏观高导电性MXene带状纤维；以带状纤维为负极，与隔膜、电解质、正极组装，得到基于宏观高导电性MXene带状纤维的柔性电容器。基于Ti 3C 2 纳米片的固有金属电导率和定向堆叠结构，所制备的带状纤维具有优异的电导率（高达2458 S cm -1）。这项研究凸显了MXene作为宏观组装平台的巨大潜力，并扩大了MXene材料在可穿戴电子产品中的应用。

Description

纳米片有序堆叠的宏观高导电性MXene带状纤维及柔性电容器 技术领域
本发明属于柔性纤维状电极技术，具体涉及纳米片有序堆叠的宏观高导电性MXene带状纤维及基于宏观高导电性MXene带状纤维的柔性电容器。
 背景技术
基于最近小型化和可穿戴电子设备的爆炸性发展，开发具有高电导率和合理的电化学性能的柔性纤维状电极已变得越来越重要。近来，已经提出了厚度为几埃量级和横向尺寸在微米范围内的二维纳米片作为用于构造宏观纤维电极的理想材料。特别地，具有几乎完美有序排列的纳米片结构的纤维可以使单个纳米片的性能利用达到最大化。例如，具有亲水性表面的氧化石墨烯纳米片可以很好地分散在水性介质中，从而有助于使用可扩展的湿法纺丝方法制备连续纤维。特别是，通过精细控制纳米片的堆叠有序性，可以极大地改善纤维的机械强度和电性能。为了增强纤维电化学性能，已经通过在石墨烯或其他导电纤维基材上沉积赝电容材料（例如氧化锰，氧化钴和氧化钌）来制备混合纤维电极。或者，类似于氧化石墨烯的纺丝工艺，将分散在水性介质中的二维过渡金属氧化物纳米片直接组装到纤维电极中。有时将纳米片与作为集流体的石墨烯进行复合。应当指出，包含大量电化学活性材料的纤维通常可以提供增强的能量存储能力，但是总体倍率性能在很大程度上受到固有的低电导率的限制。因此，尽管急需具有优异能量存储能力的导电纤维状电极，但是其开发是一项艰巨的任务。
已经报道了一些开创性的实验尝试，用于生产宏观的MXene纤维，但是大多数研究不得不结合具有纤维可纺性的组分，例如还原性氧化石墨烯（rGO），导电高分子PEDOT等。纯净的MXene纤维的形成在很大程度上受到MXene尺寸的限制以及对合适的凝固浴选择的限制，与石墨和其他层状结构（通过范德华力将各层保持在一起）不同，牢固的M-A键意味着仅通过使用苛刻的化学方法对A层进行选择性刻蚀才能生成MXene。另外，在蚀刻期间M-A键的断裂会基于它们的相似键能而损坏M-X键。结果，尽管母体MAX晶体的长度为数十微米，但获得的MXenes大多仅表现出有限的横向尺寸，仅为几百纳米，从而产生了额外的晶界，这对于构造宏观的MXene纤维构成了重大障碍。尤其是，MXene的小尺寸是使薄片以宏观结构对齐的一个缺点，这可能需要精细控制薄片界面和合成参数。
 技术问题
本发明为了解决现有技术没有纯MXene宏观纤维的缺陷，公开了纳米片有序堆叠的宏观高导电性MXene带状纤维及其制备方法与应用，制备的纯MXene宏观纤维具有优异的力学性能、导电性能，为开创性研究工作。本发明称为MXene宏观纤维因其独特的物理和化学特性而在能源储能领域具有潜在应用。首先，过渡金属碳化物或氮化物中的大量自由电子赋予MXene具有出色的金属导电性；其次，二维薄片形态确保高比表面积，潜在地提供高双电层电容；第三，也是最重要的是，大量表面基团的氧化还原反应，特别是在酸性环境中，使MXene纳米片具有额外的赝电容。因此，MXene在没有任何辅助组分的帮助下具有潜在的传递优良电化学性能的潜力。
 技术解决方案
本发明采用如下技术方案。
纳米片有序堆叠的宏观高导电性MXene带状纤维，其制备方法包括以下步骤。
（1）将Ti 3AlC 2粉末投入HF溶液中，搅拌洗涤，得到晶体；再将晶体加入四甲基氢氧化铵水溶液中，搅拌后依次经过离心处理、洗涤，然后重新分散在水中，超声处理，得到碳化钛水溶液。
（2）将步骤（1）的碳化钛水溶液注射入凝固浴中，得到初始纤维。
（3）将步骤（2）的初始纤维经过酸处理、洗涤，得到纳米片有序堆叠的宏观高导电性MXene带状纤维。
以上述纳米片有序堆叠的宏观高导电性MXene带状纤维为负极，与电解质、正极、隔膜组装，得到高性能柔性超级电容器。
本发明中，步骤（1）中，HF溶液的浓度为8～12 wt%；四甲基氢氧化铵水溶液的浓度为22～28 wt%；碳化钛水溶液的浓度为10～30 mg/mL，碳化钛的横向尺寸为1～2.5微米，优选1.6～2微米。本发明制备的碳化钛水溶液中，纳米片具有尺寸大、尺寸分布均匀以及纳米片有序性高等特点，利于溶液可纺性以及制备连续长纤维。
本发明中，步骤（2）中，凝固浴为壳聚糖-乙酸凝固浴，优选的，壳聚糖-乙酸凝固浴中，溶剂为水，壳聚糖浓度为0.6 wt%，乙酸浓度为4 wt%；采用常规注射器进行注射，采用旋转盘进行接收，具体制备过程为现有技术，得到含有壳聚糖的Ti 3C 2初始纤维。
本发明中，步骤（3）中，酸处理为硫酸溶液浸泡，比如在1M的硫酸水溶液中浸泡3天，洗涤为醇洗，比如乙醇洗涤。
本发明中，步骤（4）中，电解质为聚乙烯醇-硫酸为电解质、正极为rGO纤维，电解质、正极为现有产品；具体组装超级电容器的方法为现有技术。
现有公开的Ti 3C 2纳米片溶液很难具有可纺性，需要在石墨烯或者其他可纺性的粘结剂辅助下才能制备得到Ti 3C 2复合纤维，而本发明得到可纺性的Ti 3C 2溶液并通过湿法纺丝工艺和酸处理的方法制备得到了纯MXene纤维；由于对Ti 3C 2溶液的制备以及纺丝参数的设计，制备的纯Ti 3C 2纤维宏观呈现带状结构，微观内部具有Ti 3C 2纳米片高度有序堆叠的结构，这种纳米片有序堆叠的结构有利于最大化纤维的力学强度（30 Mpa）和最小化纳米片与纳米片之间的电阻（电导率高达2458 S cm -1）；本发明酸处理纤维使得纤维内部具有开放的二维离子传输通道，纤维具有高的电化学性能（电流密度为1 A g -1时容量达309 F g -1,电流密度为10 A g -1时，容量为231 F g -1，循环10000圈后容量保持率为97.24%）；本发明纯Ti 3C 2纤维与还原氧化石墨烯纤维（rGO）匹配组装了非对称超级电容器，组装的非对称电容器具有高的体积能量密度（58.4 mW h cm -3）。
附图说明
图1为纤维的制备示意图以及初始纤维以及纯碳化钛纤维的结构图。
图2为碳化钛纳米片的原子力显微镜图以及纳米片尺寸分布统计，说明优选后的溶液中纳米片尺寸普遍在1.6-2.0μm之间，且尺寸分布范围窄。
图3为不同浓度下的碳化钛溶液的偏光显微镜图，说明随着浓度的增加，溶液中纳米片有序性在增加。
图4为溶液中纳米片的间距模拟图与计算，说明本发明的溶液中纳米片的自由体积减小，受约束力度变大而更加有序。
图5为（a）湿纺设备的示意图以及所得纤维的结构示意图，（b）Ti 3C 2薄板的典型原子力显微镜（AFM）图像，（c）在不同阶段的原始纤维的横截面和俯视图的光学显微镜图像，距针出口的距离：I（1厘米），II（11厘米），III（21厘米），IV（31厘米），（d）连续的长宏观纤维的照片。
图6为初始纤维与纯碳化钛薄膜的热重数据，从数据图中可以看出，初始纤维中含有少量的絮凝剂壳聚糖。
图7为（a）初始纤维和纯碳化钛纤维的XPS数据,初始纤维内部含有壳聚糖，酸处理后得到的纯碳化钛纤维中无壳聚糖，说明壳聚糖被去除了;(b) 初始纤维与纯碳化钛纤维的红外数据, 初始纤维中含有壳聚糖的特征吸收峰NH 2，而酸处理后得到的纯碳化钛纤维中壳聚糖的峰已经没有了，说明壳聚糖被去除了。
图8为与原始的Ti 3C 2-壳聚糖纤维相比，酸处理的纯Ti 3C 2纤维的XRD图谱，（b）经酸处理的纯Ti 3C 2纤维的低倍和（c）高放大倍数截面SEM图像，（d）酸处理的Ti 3C 2纤维的截面HRTEM晶格图像。 插图：FFT生成的模式。
图9为纤维超薄切片后透射电子显微镜下的元素分析。
图10为初始纤维与纯碳化钛纤维的力学强度；酸处理后，壳聚糖被去除，导致纤维的力学强度轻微下降，但是依然具有良好的力学强度。
图11为缠绕在玻璃棒上的纯Ti 3C 2纤维的照片和紧密打结的纤维的SEM图像，得到的纯碳化钛纤维具有良好的柔性。
图12为同样的测试方法下，与其他报告的基于MXene的纤维相比，纯净的Ti 3C 2纤维的电导率，本发明得到的纯碳化钛纤维具有高的电导率。
图13为初始纤维与纯碳化钛纤维的电阻比较，（a）11厘米长的初始纤维的电阻，计算得到电导率为767 S cm -1，（b）11厘米长纯碳化钛纤维的电阻，计算得到的电导率为2458 S cm -1，（c）初始纤维与纯碳化钛纤维的电阻随长度变化关系，呈线性关系，说明纤维是均匀的，（d）纯碳化钛纤维在不同弯曲角度下的电阻，说明纯碳化钛纤维在弯曲下电阻也是稳定的。
图14为纯净的纯碳化钛纤维在三电极系统中的电化学性能。（a）三电极设置的示意图。（b）以不同扫描速率记录的CV曲线。（c）在不同电流密度下记录的GCD曲线。（d）在不同扫描速率下的比电容和相应的长度电容。 插图：在不同的电流密度下，基于MXene的光纤超级电容器的电容保持能力的比较。（e）10 4个循环的循环稳定性。插图：第一个和最后一个循环的GCD曲线。
图15为纯碳化钛纤维在10 A g -1下循环10000圈后的截面SEM图；纯碳化钛纤维具有良好的电极工作稳定性。
图16为初始纤维与酸处理后的纯碳化钛纤维的性能差别，A为初始碳化钛纤维与纯碳化钛纤维的电化学性能数据，B为电化学阻抗数据，纯碳化钛纤维具有更小的离子扩散电阻。
图17为通过阻抗数据计算H +的扩散系数。
图18为GCD使酸处理的不同长度的纯Ti 3C 2纤维弯曲。
图19为非对称纤维超级电容器的电化学性能。（a）柔性非对称设备的示意图。（b）纯Ti 3C 2纤维和rGO纤维在相同扫描速率下的CV曲线。（c）不同扫速下的非对称器件的CV曲线和（d）不同电流密度下的GCD曲线。（e）组装后的非对称器件的体积能量密度、功率密度与其他纤维超级电容器和纤维电池相比。（f）由串联连接的三个柔性设备驱动的蓝色LED徽标纤维的照片，以及（g）编织成手套以照明电子手表的两条串联纤维的照片。
图20为（a）氧化还原石墨烯纤维的SEM表面图；（b）氧化还原石墨烯纤维的截面图。
图21为氧化还原石墨烯纤维在不同扫速下的循环伏安曲线（CV）。
图22为组装的器件工作区间，工作电压为0-1.5 V。
图23为组装的器件在电流密度为10 A g -1下循环工作10000次数据，内嵌图为：器件循环工作前第一与最后一次恒电流充放电数据。
图24为（a）本发明碳化钛纳米片，凝固浴为壳聚糖-乙酸水溶液；效果：能成连续的纤维且力学强度高；（b）本发明碳化钛纳米片，凝固浴为5%氯化钙的水-异丙醇（体积比3:1）；效果：只能得到短纤维且很脆，几乎无强度；（c）小纳米片，凝固浴为壳聚糖-乙酸水溶液；效果：短纤维，有一定的强度。
图25为10 mg mL -1碳化钛溶液在壳聚糖-乙酸溶液中纺丝效果，只能得到短纤维，得不到连续的纤维。
本发明的实施方式
材料：Ti 3AlC 2粉末（98％，325目）购自上海布汉化工科技有限公司；氢氟酸水溶液（HF，40％，> 98％）和四甲基氢氧化铵水溶液（TMAOH，25％）购自J＆K Scientific Co.，Ltd；.盐酸（HCl，≥98％）和硫酸（H 2SO 4，≥98）从阿拉丁购买；壳聚糖（99％）和乙酸（99.5％）由国药集团化学试剂有限公司提供；聚乙烯醇（PVA，Mw = 1788）从阿拉丁工业公司（中国上海）购买；氧化石墨烯（GO）从J＆K Scientific，Ltd.购买；隔膜购自Nippon Kodoshi Corporation(日本高度纸工业株式会社)。
三电极测试方法：以电极夹夹住纤维直接作为工作电极，Ag/AgCl作为参比电极，Pt作为对电极，在1M的硫酸电解液中进行电化学测试。（测试设备CHI660E电化学工作站）。
两电极测试：采用CHI660E电化学工作站对其进行电化学性能测试，纤维器件的正负极分别与电化学工作站相连接，直接测试。
电导率测试：采用欧姆表测定11厘米长的纤维的电阻，然后通过SEM计算纤维的截面面积，通过公式σ=L/RS计算得到电导率。
力学强度计算：采用SEM截面内图计算纤维截面积，采用Instron 3365万能材料拉伸仪测定纤维的力学强度。
本发明纳米片有序堆叠的宏观高导电性MXene带状纤维的制备方法如下。
（1）将Ti 3AlC 2粉末投入HF溶液中，搅拌洗涤，得到晶体；再将晶体加入四甲基氢氧化铵水溶液中，搅拌后依次经过离心处理、洗涤，然后重新分散在水中，超声处理，得到碳化钛水溶液；优选的，在超声处理后进行离心处理，得到碳化钛水溶液。
（2）将步骤（1）的碳化钛水溶液注射入凝固浴中，得到初始纤维。
（3）将步骤（2）的初始纤维经过酸处理、洗涤，得到纳米片有序堆叠的宏观高导电性MXene带状纤维。
以步骤（3）的纳米片有序堆叠的宏观高导电性MXene带状纤维为负极，与电解质、正极、隔膜组装，得到高性能柔性超级电容器。
本发明原料都为市购，涉及的测试方法都为本领域常规测试方法。
实施例一   碳化钛胶体水溶液的制备：Ti 3AlC 2粉末（1g）投入HF溶液中（10 wt%，30 mL），搅拌10分钟后，用蒸馏水离心洗涤3次，然后在真空烘箱中80℃干燥24小时。将干燥后的粉末置于四甲基氢氧化铵水溶液中（25 wt%, 10 mL）持续搅拌24小时；所得悬浮液以5000rpm离心10分钟，取底部沉淀用去离子水洗涤并干燥；然后再重新分散在去离子水中，在室温下超声15分钟，以3500rpm离心15分钟，取上层悬浮液以8000rpm离心15分钟，取下层悬浮液即可得到碳化钛胶体水溶液，浓度为20 mg/mL。
将碳化钛胶体水溶液装入带有旋转喷嘴（直径为500 μm的常规不锈钢纺丝针头）的塑料注射器中，并注入（40 mL h -1）凝固浴中，通过旋转磁盘接收；凝固浴是含有4 wt％乙酸的壳聚糖水溶液（壳聚糖 0.6 wt％），旋转磁盘的速度设置为560 rph，从喷嘴到旋转磁盘中心的距离：6 cm；当碳化钛胶体水溶液与凝结浴接触，立即形成连续初始纤维；将初始纤维在凝固浴中静置15分钟后，将其用水和乙醇洗涤；然后将初始纤维浸入1 M 硫酸水溶液中3 d；酸处理过的纤维用去离子水和乙醇分别洗涤5次，并在环境条件下干燥，得到纳米片有序堆叠的宏观高导电性MXene带状纤维，称为纯Ti 3C 2纤维。
将初始纤维用去离子水和乙醇分别洗涤5次，并在环境条件下干燥，得到Ti 3C 2-壳聚糖纤维，作为对比纤维，称为初始Ti 3C 2纤维。
本发明将包含Ti 3C 2片（20 mg mL -1）的溶液通过注射泵由针头（直径为500 μm）挤出到置于转盘上的凝固浴中，通过在质子化壳聚糖的凝固浴中湿纺Ti 3C 2溶液并随后在酸中去除壳聚糖，制备了宏观的纯Ti 3C 2纤维，如图1所示。
制备的纳米片的横向尺寸为1.6～2 µm，平均厚度约为1.6 nm（图2），基于纳米片之间的排斥力，即使当浓度增加至20mg mL -1时，溶液也显示出高稳定性，基于＞10 3的纳米片的纵横比（宽度/厚度），计算出形成液晶相的理论临界浓度为10.88mg mL -1，但是，对具有接近临界浓度（20 mg mL -1）两倍的溶液的偏振光学显微镜表征，并没有揭示液晶相的典型双折射特征（图3），20 mg mL -1的溶液中纳米片之间的平均间距估计约为170 nm（图4），用于连续纤维制造。
在质子化壳聚糖凝固浴中进行较大横向尺寸的纳米片纺丝可得到连续的纤维且强度很好，将Ti 3C 2溶液通过狭窄的纺丝喷嘴（直径为500 µm）以一定速度注入凝固浴中时，立即发生了絮凝，其横截面与注射针头的横截面相同，当从针头出口拉出纤维时，圆柱纤维逐渐转变为带状纤维，如图5c所示，所获得纤维的横截面图和俯视图的形态演变，表明带状纤维的异常形成是由于形成密集取向的片材堆叠而引起的，计算出四个阶段的横截面积，并显示出逐渐减小的趋势，制备的纤维实物如图5d，纤维长度仅取决于进料，原料足够多可纺出足够长的连续纤维，通过热重数据（TGA）分析可以得到初始Ti 3C 2纤维与纯Ti 3C 2纤维的区别，参见图6；纳米片之间的壳聚糖可通过在硫酸中处理而完全去除，图7，得到的纯MXene纤维密度为3.26 g cm -3，与商业碳纤维相当。
分析了酸处理前后Ti 3C 2纤维的结构和形态特征。图8a中显示的X射线粉末衍射（XRD）曲线在两个样品的低角度状态下均显示出反射峰，这意味着这两个结构的规则薄片堆积。酸处理后，纳米片之间的间距从原始的Ti 3C 2-壳聚糖纤维间距1.43 nm减小到1.33 nm，清楚地检测到与Ti 3C 2层的面内特征相关的衍射（110），这表明经过酸处理后，Ti 3C 2纳米片的主体结构得到了很好的保存。使用扫描电子显微镜（SEM）对获得的纤维的形态进行表征，结果显示出清晰的带状结构和规则的片对片面部堆叠（图8b和8c），验证了光学显微镜和XRD的结果。重要的是，在对原始纤维和酸处理过的纤维进行横截面观察时，没有发现大差异，这表明酸处理不会引起结构劣化，并且可以成功地继承有序堆叠结构。在高分辨率透射电子显微镜（HRTEM）图像中可以更清楚地观察到这种结构。在图8d中，可以清楚地看到对应于堆叠层的平行条纹。条纹距离测得为1.33 nm，与XRD结果一致。进行傅立叶变换（FFT）模式显示出良好排列的衍射斑，进一步证实了Ti 3C 2纳米片的有序堆积。元素Mapping结果表明，Ti，C，O和S元素分布均匀（图9）。
基于定向的堆叠结构和二维纳米片的柔韧性，上述获得的宏观纯净的Ti 3C 2纤维的拉伸强度达到30 MPa，见图10，小图为本发明纯碳化钛纤维可吊起钥匙而不断，因此，基于定向片材堆叠结构的继承，酸处理在机械性能方面不会引起明显的劣化。如图11所示，这些纤维具有足够的强度和柔韧性，可以在Φ5 mm的玻璃棒上弯曲并打结而没有任何断裂的迹象，因此对于柔性储能装置而言是令人满意的。此外，由金属Ti 3C 2薄片提供的薄片和电子通道之间的二维开放纳米通道有助于离子和电子的快速传输。测得纯Ti 3C 2纤维的电导率为2458 S cm -1，比MXene基复合纤维的值大几个数量级，见图12，现有纤维右上角的数字为参考文献编号。由于其紧凑的堆叠结构和出色的机械柔韧性，纤维的电导率值随弯曲角度的变化很小，见图13。因此，Ti 3C 2纳米片的异常高度定向的堆叠结构可产生出色的离子传导性，晶格内快速的离子扩散以及可接受的机械强度，这为实现柔性储能装置提供了坚实的基础。电导率的测试方法，测定11cm长的纤维电阻，然后通过SEM截面图计算出纤维的横截面积，通过公式：电导率σ=L/RS 计算得到电导率。
考虑到上面讨论的本发明纯碳化钛纤维定向纳米片堆叠和高电导率，首先在1 M H 2SO 4电解质中以标准的三电极配置表征获得的纤维的电化学性能，其中长纤维的一端直接夹在电极上作为工作电极，Ag/AgCl为参比电极，Pt片为对电极（图14a）。这种设置对光纤电极来说是苛刻的条件，因为光纤电极一端的电子必须先经过很长的一段距离才能穿过光纤，然后才能到达集电器。酸处理过的纯Ti 3C 2纤维在-0.6至0.2 V的电位范围内在不同扫描速率下的循环伏安（CV）曲线如图14b所示。可以观察到显示宽氧化还原峰的电流响应，这清楚地证明了纤维的赝电容行为；此外，即使在100 mV s -1的扫描速率下，CV曲线也没有表现出明显的失真，表明其优异的速率性能。图14c显示了恒电流充放电（GCD）曲线，该曲线明显偏离完美的三角形，表明Ti 3C 2纳米片的表面氧化还原反应，这与CV分析结果相符，即使在10 A g -1的高电流密度下也没有明显的欧姆降，表明纤维电极的高电导率，纤维以1 A g -1的电流密度下具有309 F g -1（52.38 mF cm -1）的比电容。当电流密度增加到10 A g -1时，电容保持在231 F g -1（39.16 mF cm -1），这表示电容保持率为74.76％。相反，同样的测试下，其他基于MXene的纤维超级电容器随着电流密度的增加显示出较低的电容保持率（图14d）。Ti 3C 2纤维的高倍率性能可归因于基于纳米片定向堆叠的快速离子嵌入和脱嵌，快速的电子转移以及Ti 3C 2层状结构中离子传输的短路径。另外，酸处理的Ti 3C 2纤维电极在10 A g -1的电流密度下也表现出出色的循环稳定性，如图14e所示，经过10 4个循环的长期循环后，其电容保持率约为97.24％。此外，没有明显的形变，表明本发明制备的纤维电极的结构稳定性（图15）。
同样的测方法下，初始Ti 3C 2纤维作为电极替换纯Ti 3C 2纤维，在10 A g -1的电流密度下没有表现出出色的循环稳定性，经过10 4个循环后，其电容保持率约为91.38％。
图16A为初始碳化钛纤维与纯碳化钛纤维的电化学性能数据（CV数据），在10 mV s -1扫速下，碳化钛-壳聚糖纤维的容量要明显小于纯碳化钛纤维。进行了电化学阻抗谱（EIS）分析，以深入了解Ti 3C 2纤维的电荷转移和离子传输特性。Ti 3C 2纤维电极在高频下显示出较短的Warburg区域，表明电子传输速率快，而在低频下显示出近乎垂直的曲线，表明具有理想的电容特性（图16）。还从动力学角度分析了纤维的优异离子传输性能，其扩散系数估计为9.2×10 -7 cm 2 s -1，与原始Ti 3C 2壳聚糖纤维的值为1.43×10 -7 cm 2 s -1（图17），证实了设计的Ti 3C 2纤维具有有序堆叠结构和预浸通道的结构优势。为了突出所获得的Ti 3C 2纤维的优异的导电性网络，还以2 A g -1的电流密度测试了长度延伸5倍至15 cm的纤维的GCD曲线，如图18所示。即使在这样的长度下，也没有观察到明显的欧姆降，并且曲线几乎全部重叠。所有这些结果提供了明确的证据，即所制备的具有Ti 3C 2薄片定向堆叠的纤维电极和层之间提供了优异的离子和电子传输性能，从而产生了优异的整体电化学性能。
实施例二 以实施例一的纳米片有序堆叠的宏观高导电性MXene带状纤维为负极，与聚乙烯醇-硫酸电解质、正极rGO纤维组装，得到高性能柔性超级电容器。
采用实施例一的方法，将碳化钛胶体水溶液替换为浓度为10 mg/mL的市售GO水溶液（GO片层厚度约1nm，横向尺寸3～5 µm），得到GO初始纤维，再将其浸入90℃的氢碘酸（57wt％）水溶液中5小时，然后水洗，得到rGO纤维，作为正极。
在搅拌下将1 g PVA粉末在90°C下溶解于10 mL蒸馏水中，直到获得澄清溶液，加入1g 硫酸搅拌后将澄清溶液冷却至室温，从而获得聚乙烯醇-硫酸电解质。
将正极和负极分别用银浆与铜线集流体连接后平行放入热缩管，加入现有聚合物隔膜和聚乙烯醇-硫酸电解质，加热密封组装成高性能柔性超级电容器；具体组装方式为现有技术。
基于Ti 3C 2纤维电极的出色电化学性能，使用聚乙烯醇-硫酸为电解质、以酸处理过的Ti 3C 2纤维为负极，rGO纤维为正极组装了非对称固体纤维超级电容器，如图19a所示。带状结构的rGO纤维也可以通过湿纺获得（图20为其SEM图），并表现出典型的电容特性（图21），rGO纤维在–0.1至0.9 V的电势窗口中具有宽的伏安响应，而经酸处理的Ti 3C 2纤维的电势窗口在-0.6至0.2 V范围内（图19b）。因此，该电极对可以提供高达1.5 V的有效电压而不会出现极化现象（图22）。如图19c和19d所示，非对称纤维超级电容器的CV和GCD曲线在相似的电压下呈现出曲率，在不同的扫描速率和电流密度下具有理想的电化学行为。非对称纤维超级电容器在5 mV s -1的扫描速率下可提供88.67 F g -1（256 F cm -3）的电容，可与典型的纤维超级电容器的值相比。此外，非对称纤维超级电容器具有92.4％的电容保持率，具有长期循环稳定性（图23）。图19e给出了比较不同纤维超级电容器和纤维电池之间的体积能量和功率密度的Ragone图。本发明在1679 mW cm -3时可提供58.38 mW h cm -3的高体积密度，在17.63 mW h cm -3时可提供约7466 mW cm -3的高体积功率密度。这些能量密度可与现有典型的非对称光纤超级电容器相媲美，而能量密度却接近现有光纤电池。基于非对称纤维超级电容器的出色储能性能，建立了一个实际应用，它使用三个串联的柔性设备为3.5 V蓝色发光二极管（LED）徽标光纤或电子表供电。由本发明非对称纤维超级电容器点亮的LED和电子手表在弯曲设备的过程中没有显示出明显的亮度暗淡，证明了本发明设备的机械强度和灵活性（图19f和19g）。
对比例 在实施例一的基础上，采用现有小尺寸碳化钛纳米片水溶液，见图24c，同样的纺丝方法，无法得到连续宏观纤维。
在实施例一的基础上，采用现有无机离子凝固浴（5wt%氯化钙水-异丙醇溶液，其中水与异丙醇体积比为3:1），见图24b，同样的纺丝方法，无法得到连续宏观纤维。
在实施例一的基础上，采用10 mg/mL碳化钛纳米片水溶液，同样的纺丝方法，无法得到连续宏观纤维，见图25。
在实施例一的基础上，采用400 rph的磁盘转速，其余同样，无法得到连续宏观纤维。
在实施例一的基础上，采用现有大尺寸碳化钛纳米片水溶液（横向尺寸3～4微米），同样的纺丝、酸浸泡方法，得到的宏观连续的Ti 3C 2纤维经过同样的测试计算，纤维以1 A g -1的电流密度下具有283 F g -1的比电容。
结论：本发明中，通过在质子化壳聚糖的凝固浴中湿纺Ti 3C 2溶液，然后在酸中去除壳聚糖，成功制备了带状结构的纯Ti 3C 2纤维（宽度1.1～1.3毫米，厚度3～5微米），具有高度取向的纳米片堆叠结构。Ti 3C 2是MXene系列的典型成员，此后将Ti 3C 2用于指代此类材料的特定材料。酸处理壳聚糖过程中，纳米片的有序堆叠结构没有被破坏，对纤维的机械性能无损害。获得的纯净的Ti 3C 2带表现出三个重要的优点。首先，纤维中的纳米片具有高有序的堆叠结构，这意味着每一片纳米片的机械性能都得到了有效整合。这种纯净的Ti 3C 2纤维可提供30.0 MPa的拉伸强度，足以用于实际的设备应用。其次，每一片纳米片都是极好的导体，并且纳米片紧密连接，有助于构建连续的导电网络，并提供2458 S cm -1的电导率，这比先前报道的MXene基复合纤维的电导率大了近两个数量级。第三，有序堆叠可形成开放的二维通道，即使在较高电流密度下，可有效减少离子传输阻碍，从而缩短了离子扩散路径的长度并促进了电极的反应（231.0 F g -1或39.2 mF cm -1，在电流密度为10 A g -1的条件下）。基于所设计的纤维Ti 3C 2电极的优异电化学行为，采用rGO纤维为正极材料，组装了非对称超级电容器。在1A g -1电流密度下，能量密度达到了58.4 m Wh cm -3（20.0 W h Kg -1），对应的体积功率密度为1679.0 mW cm -3（581.0 W Kg -1）。这项工作证明了MXene的可接受的可加工性，并为MXene材料在未来可穿戴电子产品中的应用打开了新的窗口。

Claims (10)

  1. 纳米片有序堆叠的宏观高导电性MXene带状纤维，其特征在于，所述纳米片有序堆叠的宏观高导电性MXene带状纤维的制备方法包括以下步骤：
    （1）将Ti 3AlC 2粉末投入HF溶液中，搅拌洗涤，得到晶体；再将晶体加入四甲基氢氧化铵水溶液中，搅拌后依次经过离心处理、洗涤，然后重新分散在水中，超声处理，得到碳化钛水溶液；
    （2）将步骤（1）的碳化钛水溶液注射入凝固浴中，得到初始纤维；
    （3）将步骤（2）的初始纤维经过酸处理、洗涤，得到纳米片有序堆叠的宏观高导电性MXene带状纤维。
  2. 根据权利要求1所述纳米片有序堆叠的宏观高导电性MXene带状纤维，其特征在于，步骤（1）中，HF溶液的浓度为8～12 wt%；四甲基氢氧化铵水溶液的浓度为22～28 wt%；碳化钛水溶液的浓度为10～30 mg/mL。
  3. 根据权利要求2所述纳米片有序堆叠的宏观高导电性MXene带状纤维，其特征在于，碳化钛水溶液的浓度为15～25 mg/mL。
  4. 根据权利要求1所述纳米片有序堆叠的宏观高导电性MXene带状纤维，其特征在于，步骤（2）中，凝固浴为壳聚糖-乙酸凝固浴。
  5. 根据权利要求4所述纳米片有序堆叠的宏观高导电性MXene带状纤维，其特征在于，壳聚糖-乙酸凝固浴中，溶剂为水，壳聚糖浓度为0.6 wt%，乙酸浓度为4 wt%。
  6. 根据权利要求1所述纳米片有序堆叠的宏观高导电性MXene带状纤维，其特征在于，步骤（3）中，酸处理为硫酸溶液浸泡。
  7. 根据权利要求6所述纳米片有序堆叠的宏观高导电性MXene带状纤维，其特征在于，酸处理为1M的硫酸水溶液中浸泡3天。
  8. 基于宏观高导电性MXene带状纤维的柔性电容器，其特征在于，所述基于宏观高导电性MXene带状纤维的柔性电容器的制备方法包括以下步骤：
    （1）将Ti 3AlC 2粉末投入HF溶液中，搅拌洗涤，得到晶体；再将晶体加入四甲基氢氧化铵水溶液中，搅拌后依次经过离心处理、洗涤，然后重新分散在水中，超声处理，得到碳化钛水溶液；
    （2）将步骤（1）的碳化钛水溶液注射入凝固浴中，得到初纺纤维；
    （3）将步骤（2）的初纺纤维经过酸处理、洗涤，得到纳米片有序堆叠的宏观高导电性MXene带状纤维；
    （4）以步骤（3）的纳米片有序堆叠的宏观高导电性MXene带状纤维为负极，与隔膜、电解质、正极组装，得到基于宏观高导电性MXene带状纤维的柔性电容器。
  9. 根据权利要求8所述基于宏观高导电性MXene带状纤维的柔性电容器，其特征在于，碳化钛水溶液中，碳化钛的横向尺寸为1～2.5微米。
  10. 权利要求1所述纳米片有序堆叠的宏观高导电性MXene带状纤维在制备高性能柔性超级电容器中的应用；权利要求8所述基于宏观高导电性MXene带状纤维的柔性电容器在制备柔性电子设备中的应用。
PCT/CN2020/098348 2020-05-26 2020-06-27 纳米片有序堆叠的宏观高导电性MXene带状纤维及柔性电容器 Ceased WO2021237862A1 (zh)

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CN115214201A (zh) * 2022-06-15 2022-10-21 北京理工大学 一种碳纤维/环氧树脂层合板及其制备方法
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CN115593039A (zh) * 2022-10-28 2023-01-13 中国科学院重庆绿色智能技术研究院（Cn） 一种高灵敏三明治叠层结构柔性传感器及其制备方法
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CN116178800A (zh) * 2023-02-09 2023-05-30 山东大学 一种复合光热材料及其制备方法与应用
CN116313550A (zh) * 2023-03-16 2023-06-23 江苏科技大学 一种MXene/氮掺杂碳材料/苞叶纤维三明治状网络结构柔性膜及其制法与应用
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