阅读说明：本技术 一种高强高导电碳化钛复合薄膜的制备方法 (Preparation method of high-strength high-conductivity titanium carbide composite film ) 是由 程群峰 万思杰 李响 于 2020-07-30 设计创作，主要内容包括：本发明涉及一种高强高导电碳化钛复合薄膜的制备方法,首先通过海藻酸钠(SA)与碳化钛(Ti<Sub>3</Sub>C<Sub>2</Sub>T<Sub>x</Sub>)纳米片吸附构建Ti<Sub>3</Sub>C<Sub>2</Sub>T<Sub>x</Sub>-SA异质基元材料,然后将该异质基元材料通过真空抽滤组装成氢键交联的碳化钛(HBM)复合薄膜,最后将该HBM复合薄膜浸泡在氯化钙(CaCl<Sub>2</Sub>)水溶液中,制得氢键和离子键有序交联的碳化钛(SBM)复合薄膜。所述SBM复合薄膜的最高拉伸强度为436MPa,相应的杨氏模量为14.0GPa,韧性为8.4MJ/m<Sup>3</Sup>,电导率为2988S/cm；此外,所述SBM复合薄膜也具有超高的抗疲劳性能和优异的电磁屏蔽效能,例如,在215～245MPa的拉伸应力下,能耐受2.1×10<Sup>5</Sup>次周期性拉伸；对频率在0.3～18GHz的电磁波的屏蔽系数约为46.2dB。(The invention relates to a preparation method of a high-strength high-conductivity titanium carbide composite film, which comprises the steps of firstly, passing Sodium Alginate (SA) and titanium carbide (Ti) 3 C 2 T x ) Adsorption construction of Ti by nanosheet 3 C 2 T x The preparation method comprises the following steps of (1) -SA heterogeneous element materials, assembling the heterogeneous element materials into a hydrogen bond crosslinked titanium carbide (HBM) composite film through vacuum filtration, and finally soaking the HBM composite film in calcium chloride (CaCl) 2 ) In aqueous solution, hydrogen bond andan ionic bond ordered cross-linked titanium carbide (SBM) composite film. The SBM composite film has the highest tensile strength of 436MPa, the corresponding Young modulus of 14.0GPa and the toughness of 8.4MJ/m 3 The electrical conductivity is 2988S/cm, and the SBM composite film also has ultrahigh fatigue resistance and excellent electromagnetic shielding performance, for example, can resist 2.1 × 10 under the tensile stress of 215-245 MPa 5 Secondary periodic stretching; the shielding coefficient of the electromagnetic wave with the frequency of 0.3-18 GHz is about 46.2 dB.)

1. The preparation method of the high-strength high-conductivity titanium carbide composite film is characterized by comprising the following steps:

(1) titanium carbide (Ti) is stirred and ultrasonically treated at room temperature₃C₂T_x) Preparing uniform Ti₃C₂T_xAqueous solution of the Ti₃C₂T_xThe aqueous solution contains Ti₃C₂T_xNanosheets;

(2) adding Ti obtained in the step (1) under continuous stirring₃C₂T_xAdding Sodium Alginate (SA) aqueous solution dropwise into the aqueous solution, and adding Ti₃C₂T_xAnd the SA is adsorbed on the Ti by hydrogen bond in the mixed aqueous solution of the SA and the₃C₂T_xNanosheet surface to provide Ti₃C₂T_x-a dispersion of SA heterogeneous elementary material;

(3) adopting a vacuum filtration method to carry out vacuum filtration on the Ti obtained in the step (2)₃C₂T_xAssembling the SA heterogeneous basic material dispersion liquid into a hydrogen bond cross-linked titanium carbide (HBM) composite film;

(4) obtained in the step (3)Soaking the HBM composite film in calcium chloride (CaCl)₂) In the water solution, washing and drying to obtain the titanium carbide (SBM) composite film with orderly crosslinked hydrogen bonds and ionic bonds.

2. The method for preparing the high-strength high-conductivity titanium carbide composite film according to claim 1, wherein the method comprises the following steps: in the step (1), Ti₃C₂T_xThe concentration of the aqueous solution is 1-2 mg/mL, and the solution is continuously stirred and subjected to ultrasonic treatment to Ti₃C₂T_xIntroducing argon into the aqueous solution, stirring for 5-10 min, carrying out ultrasonic treatment for 2-4 min, and carrying out ultrasonic treatment in an ice-water bath at the ultrasonic power of 50-70W.

3. The method for preparing the high-strength high-conductivity titanium carbide composite film according to claim 1, wherein the method comprises the following steps: in the step (2), the concentration of the SA water solution is 0.5-1 mg/mL, and the solution is continuously stirred towards Ti₃C₂T_xIntroducing argon into the mixed aqueous solution of the Ti and the SA, and stirring for 10-20 min to obtain Ti₃C₂T_x-Ti in the dispersion of SA heterogeneous elementary materials₃C₂T_xAnd the mass ratio of SA is 3.5-4.5.

4. The method for preparing the high-strength high-conductivity titanium carbide composite film according to claim 1, wherein the method comprises the following steps: in the step (3), the Ti obtained in the step (2) is filtered by vacuum filtration₃C₂T_xThe specific implementation process of assembling the hydrogen bond crosslinked titanium carbide (HBM) composite film by the SA heterogeneous basic material dispersion liquid is as follows:

(1) ti to be stirred uniformly₃C₂T_x-adding the SA heterogeneous elementary material dispersion into a vacuum filtration flask;

(2) starting a vacuum pump, and performing vacuum filtration, wherein the vacuum degree is 1-5 Pa;

(3) with the progress of suction filtration, Ti₃C₂T_xAssembling the-SA heterogeneous basic material into a layered structure under the action of water flow, and obtaining the hydrogen bond crosslinked titanium carbide (HBM) complex after completing suction filtrationAnd (6) combining the films.

5. The method for preparing the high-strength high-conductivity titanium carbide composite film according to claim 1, wherein the method comprises the following steps: in the step (4), CaCl₂The concentration of the aqueous solution is 0.5-9 mg/mL, wherein the preferable concentration range is 4-8 mg/mL, and the soaking time is 10-12 h.

6. The method for preparing the high-strength high-conductivity titanium carbide composite film according to claim 1, wherein the method comprises the following steps: in the step (4), the washing is realized by soaking in deionized water for 0.5-1 h, and the drying is realized by vacuum drying at 30-50 ℃ for 20-40 min.

7. The method for preparing the high-strength high-conductivity titanium carbide composite film according to claim 1, wherein the method comprises the following steps: in the step (4), the prepared SBM composite film contains calcium ions Ca²⁺The content is 0.3-2.5 wt%.

8. The method for preparing the high-strength high-conductivity titanium carbide composite film according to claim 1, wherein the method comprises the following steps: in the step (4), the prepared SBM composite film is circular, the diameter is 2-4 cm, and the thickness range is 1-10 mu m.

Technical Field

The invention relates to a preparation method of a high-strength and high-conductivity titanium carbide composite film, belonging to the field of preparation of nano composite materials.

Background

Titanium carbide (Ti)₃C₂T_x) The nanosheet has excellent mechanical (Sci.adv.2018,4, eaat0491.) and electrical (appl.Phys.Lett.2016,108,033102.) performances, and has a wide application prospect in the fields of flexible electronic devices, aerospace and the like (nat.Rev.Mater.2017,2,16098.), so that Ti is required to be added₃C₂T_xMacroscopic high-performance Ti assembled by nanosheets₃C₂T_xA nanocomposite material.

Natural abalone shells have excellent mechanical properties, mainly due to their internal regular and ordered layered structure and rich interfacial effects (nat. rev. mater.2016,1,16007.). Inspired by the above, in recent years, scientists have prepared a large amount of high-performance layered Ti by using various interfacial crosslinking strategies₃C₂T_xAnd (3) compounding the film. For example, Gogotsi et al (Proc. Natl. Acad. Sci. USA 2014,111,16676.) in Ti₃C₂T_xPolyvinyl alcohol is introduced between layers, and Ti with high strength and conductivity is prepared through hydrogen bond crosslinking₃C₂T_xCompounding a film; in Ti by Medium vibration et al (J.Mater.chem.C 2020,8,1673.)₃C₂T_xAluminum ions are introduced between layers, and Ti with high strength and high efficiency electromagnetic shielding is prepared through the ionic bond crosslinking effect₃C₂T_xCompounding a film; king et al (adv. Funct. Mater.2018,28,1801511.) in Ti₃C₂T_xBoric acid radical is introduced between layers, and rigid Ti is prepared through covalent bond crosslinking₃C₂T_xA composite membrane having excellent gas separation performance; von shinny et al (nat. commun.2019,10,2920.) reinforcement by aramid nanofibersToughening effect, and preparing the Ti with high strength and toughness integrated and high-efficiency salt difference energy power generation₃C₂T_xCompounding a film; taylor et al (Nanoscale 2019,11,20295.) prepare high-strength conductive Ti by enhancing toughening effect through montmorillonite nanosheets₃C₂T_xAnd (3) compounding the film. Although the various interfacial crosslinking strategies reported above have improved Ti to some extent₃C₂T_xMechanical properties of the composite film, however, due to the insertion of a large amount of insulating crosslinking agent into Ti₃C₂T_xInterlaminar of these Ti₃C₂T_xThe electrical properties of the composite film are greatly reduced, which greatly limits Ti₃C₂T_xThe practical application of the film. Therefore, there is a need to develop a novel interfacial crosslinking strategy for preparing Ti with high strength and high conductivity₃C₂T_xAnd (3) compounding the film. At present, no document or patent report for preparing the high-strength and high-conductivity titanium carbide composite film by utilizing hydrogen bonds and ionic bond ordered crosslinking exists.

Disclosure of Invention

The technical problem of the invention is solved: the defects of the prior art are overcome, and the preparation method of the high-strength high-conductivity titanium carbide composite film is provided.

The invention is realized by the following technical scheme: a process for preparing high-strength and-conductivity composite titanium carbide film includes such steps as stirring at room temp to make Sodium Alginate (SA) adsorbed on Ti by hydrogen bond₃C₂T_xConstructing Ti on the surface of the nanosheet₃C₂T_x-SA heterogeneous elementary material; then Ti is filtered by vacuum filtration₃C₂T_xAssembling SA heterogeneous basic materials into a hydrogen bond cross-linked titanium carbide (HBM) composite film; finally, soaking the HBM composite film in calcium chloride (CaCl)₂) In water solution, the titanium carbide (SBM) composite film with orderly crosslinked hydrogen bonds and ionic bonds is prepared, and the specific implementation steps are as follows:

(1) mixing Ti by ultrasonic method₃C₂T_xPreparing uniform Ti₃C₂T_xAn aqueous solution;

(2) under continuous stirring, adding Ti₃C₂T_xAdding dropwise aqueous SA solution into the aqueous solution to make SA adsorbed on Ti by hydrogen bond₃C₂T_xNanosheet surface to provide Ti₃C₂T_x-a dispersion of SA heterogeneous elementary material;

(3) vacuum filtering the Ti₃C₂T_xAssembling the SA heterogeneous basic material dispersion liquid into the HBM composite film;

(4) soaking the HBM composite film in CaCl₂And (4) washing and drying in the aqueous solution to obtain the SBM composite film.

In the step (1), Ti₃C₂T_xThe concentration of the aqueous solution is 1-2 mg/mL, and the solution is continuously stirred and subjected to ultrasonic treatment to Ti₃C₂T_xIntroducing argon into the aqueous solution to prevent Ti₃C₂T_xOxidized; stirring time is 5-10 min, ultrasonic time is 2-4 min, and ultrasonic power in ice-water bath is 50-70W, so that Ti is not damaged₃C₂T_xIn the case of the nanosheet structure, Ti is uniformly dispersed₃C₂T_xNanosheets.

In the step (2), the concentration of the SA water solution is 0.5-1 mg/mL, and the solution is continuously stirred towards Ti₃C₂T_xIntroducing argon into the mixed solution of the SA and the Ti to prevent the Ti₃C₂T_xOxidized; the stirring time is 10-20 min, so that SA is fully adsorbed on Ti₃C₂T_xThe surface of the nanosheet; obtained Ti₃C₂T_xIn a dispersion of SA heterogeneous elementary materials, Ti₃C₂T_xThe mass ratio of the SA to the Ti is 3.5-4.5, and too little SA cannot completely coat Ti₃C₂T_xNanosheets, too much SA will be at Ti₃C₂T_xExcessive deposition on the surface of the nanosheet, both of which are not conducive to subsequent Ca²⁺With SA and Ti₃C₂T_xAnd crosslinking the nanosheets.

In the step (3), a vacuum filtration method is adopted, and the specific implementation process is as follows:

(1) firstly, evenly stirring Ti₃C₂T_x-adding the SA heterogeneous elementary material dispersion into a vacuum filtration flask;

(2) starting a vacuum pump, and performing vacuum filtration, wherein the vacuum degree is 1-5 Pa;

(3) with the progress of suction filtration, Ti₃C₂T_xAssembling the SA heterogeneous basic materials into a layered structure under the action of water flow, and obtaining the HBM composite film after suction filtration is completed.

In the step (4), CaCl₂The concentration of the aqueous solution is 0.5-9 mg/mL, and the concentration of CaCl is too low₂Is not compatible with SA and Ti₃C₂T_xThe nanosheets being fully cross-linked with an excessive concentration of CaCl₂Will react with SA and Ti₃C₂T_xThe nanosheets are excessively crosslinked, the nanosheets and the SBM composite film are not beneficial to improving the mechanical property of the SBM composite film, the preferable concentration range is 4-8 mg/mL, and CaCl is used for better optimizing the property of the SBM composite film₂The concentration of the aqueous solution is respectively selected to be 1mg/mL, 2mg/mL, 4mg/mL and 8mg/mL, and the corresponding prepared 4 SBM composite films are respectively marked as SBM-I, SBM-II, SBM-III and SBM-IV; in CaCl₂The soaking time in the aqueous solution is 10 to 12 hours, so that Ca is added²⁺Sufficient penetration into the film occurs for crosslinking.

In the step (4), the washing method comprises soaking in deionized water for 0.5-1 h to remove non-crosslinked Ca²⁺Completely removing; the drying procedure is vacuum drying at 30-50 ℃ for 20-40 min, so that the free water molecules adsorbed in the film are completely removed.

Calcium ion (Ca) of the SBM composite film prepared in the step (4)²⁺) The content is 0.3-2.5 wt%.

In the step (4), the prepared SBM composite film is circular, the diameter of the SBM composite film is 2-4 cm, the thickness range is 1-10 mu m, an excessively thin film is not easy to prepare, and an excessively thick film is easy to introduce excessive defects in the preparation process, so that the mechanical property of the excessively thin film is not facilitated.

The inventionProcessing: through the evolution of hundreds of millions of years, the natural abalone shell has excellent mechanical properties, mainly because of a regular layered structure and a fine multi-scale interface structure, and the characteristic is that the mechanical properties can be greatly improved by a small amount of interface cross-linking agents. Inspired by the above, the invention utilizes the hydrogen bond and ionic bond ordered crosslinking strategy to greatly promote Ti under the condition of introducing a small amount of insulating interface crosslinking agent₃C₂T_xInterfacial strength between layers and effective retention of Ti₃C₂T_xInterlayer electron conduction is carried out, thus preparing Ti with high strength and high conductivity₃C₂T_xComposite film, and conventional Ti₃C₂T_xCompared with the technology of the composite film, the invention has the characteristics and advantages that:

(1) the SA molecular chain contains a large amount of hydroxyl which can be reacted with Ti₃C₂T_xthe-F, -OH and-O functional groups on the surface of the nano sheet are subjected to hydrogen bond crosslinking to promote Ti₃C₂T_xInterlayer interface strength; further, Ca²⁺Can be in SA and SA, SA and Ti₃C₂T_x、Ti₃C₂T_xWith Ti₃C₂T_xForm stronger ionic bond between the Ti and the Ti₃C₂T_xInterlayer interfacial strength, in addition, Ca²⁺Crosslinking induces Ti₃C₂T_xThe lamina is regularly oriented and is beneficial to Ti₃C₂T_xThe mechanical and electrical properties of the composite film are improved, therefore, the hydrogen bond and ionic bond ordered crosslinking strategy can introduce small amount of SA and Ca²⁺In the case of (3), Ti is greatly elevated₃C₂T_xThe mechanical property of the composite film is effectively maintained, and Ti is effectively maintained₃C₂T_xThe intrinsic high conductivity of the conductive material;

(2) the double interface crosslinking function of the hydrogen bond and the ionic bond is also beneficial to inhibiting cracks in Ti₃C₂T_xThe interlayer expansion, thereby greatly improving Ti₃C₂T_xThe fatigue resistance of the composite film;

thus, prepared by the present inventionThe SBM composite film not only has ultrahigh tensile strength (303-436 MPa), high Young modulus (9.8-14.0 GPa) and high toughness (6.32-8.39 MJ/m)³) High conductivity (2892-3125S/cm), and ultrahigh fatigue resistance (fatigue life up to 2.1 × 10)⁵Second) and excellent electromagnetic shielding effectiveness (44.6-49.1 dB).

Drawings

Fig. 1 shows a preparation process of a high-strength and high-conductivity SBM composite film, which includes: firstly, SA molecules are adsorbed on Ti by stirring₃C₂T_xConstructing Ti on the surface of the nanosheet₃C₂T_x-SA heterogeneous elementary material; then vacuum filtering is adopted to obtain the Ti₃C₂T_xAssembling the SA heterogeneous basic element materials into the HBM composite film; finally, soaking the HBM composite film in CaCl₂Washing and drying in water solution to obtain SBM composite film;

FIG. 2 shows A) uncrosslinked Ti₃C₂T_x(MXene), B) Ionically bonded Ti₃C₂T_x(IBM), C) HBM, D) Wide angle X-ray diffraction (WAXS) pattern of SBM-III film with corresponding 002 peak azimuth scan curve;

FIG. 3 shows X-ray photoelectron spectroscopy (XPS) for MXene, IBM, HBM, SBM-III films A) X-ray diffraction (XRD) curves and B) Infrared Spectroscopy (FTIR) for SBM-III composite films C) Ca 2p, D) Ti 2p, E) C1 s; the interlayer spacing of the IBM composite film was reduced compared to the MXene film, mainly due to Ca²⁺The cross-linking effect is realized, and the interlayer spacing of the HBM composite film is increased mainly due to the insertion of larger SA molecular chains into Ti₃C₂T_xInterlamination; compared with MXene film (3432 cm)^-1) the-OH peaks of HBM and IBM composite films were red-shifted to 3420cm, respectively^-1And 3424cm^-1Mainly due to hydrogen bond and ionic bond crosslinking; compared with HBM (1593 cm)^-1) -COO of SBM-III^-Peak red shift to 1584cm^-1This indicates Ca²⁺and-COO^-Coordination crosslinking between groups; the presence of Ca 2p peak in the SBM-III composite film indicates that Ca is present therein²⁺Crosslinking; compared with HBM (455.8eV, 457.1eV, 288 eV)9eV), SBM-III of Ti²⁺2p_3/2、Ti³⁺2p_3/2Further, the peaks of O-C ═ O were shifted down to 455.5eV, 456.8eV and 288.4eV, respectively, and it was confirmed that Ca was contained in the solution²⁺and-COO^-The groups are subjected to coordination crosslinking;

FIG. 4 shows the A) tensile stress-strain curve, B) tensile strength, Young' S modulus, toughness, electrical conductivity, shielding coefficient against electromagnetic waves with frequency of 0.3 to 18GHz, C) electromagnetic shielding coefficient versus frequency curve, and D) fatigue life (S-N) curve of MXene, IBM, HBM, SBM-III films;

FIG. 5 shows an SBM-III film and a literature report of Ti₃C₂T_xTensile strength and conductivity of the composite film are compared to a scatter plot.

Detailed Description

The invention is described in detail below with reference to the figures and the embodiments. The following examples are only for explaining the present invention, the scope of the present invention shall include the full contents of the claims, and the full contents of the claims of the present invention can be fully realized by those skilled in the art through the following examples.

As shown in fig. 1, the method of the present invention is implemented as: stirring at room temperature to adsorb SA to Ti via hydrogen bond₃C₂T_xConstructing Ti on the surface of the nanosheet₃C₂T_x-SA heterogeneous elementary material; then Ti is filtered by vacuum filtration₃C₂T_xAssembling the SA heterogeneous basic element materials into the HBM composite film; finally, soaking the HBM composite film in CaCl₂And (4) preparing the SBM composite film in an aqueous solution. By changing CaCl₂The concentration of the aqueous solution can regulate and control Ca in the SBM composite film²⁺To optimize the performance of the SBM composite film. When Ca is present²⁺When the content of (A) is 1.24 wt%, the performance of the SBM composite film is optimal and is marked as SBM-III, the tensile strength of the SBM composite film is up to 436MPa, the corresponding Young modulus is 14.0GPa, and the toughness is 8.4MJ/m³The conductivity is 2988S/cm; in addition, the SBM composite film also has ultra-high fatigue resistance and excellent electromagnetic shielding performance, for example, at 215 ℃; e.g., aCan endure 2.1 × 10 under the tensile stress of 245MPa⁵Secondary periodic stretching; the shielding coefficient of the electromagnetic wave with the frequency of 0.3-18 GHz is about 46.2 dB.

The Ti₃C₂T_xThe surface of the two-dimensional nano sheet contains functional groups such as-F, -OH and ═ O and the like, and the two-dimensional nano sheet is easy to dissolve in water; the biomacromolecule is SA, and the molecular chain of the biomacromolecule contains a large number of hydroxyl and carboxylate radicals which can be reacted with Ti₃C₂T_xThe functional groups on the surface of the nano-sheet are subjected to hydrogen bond crosslinking and can be linked with Ca²⁺Ionic bond crosslinking is carried out; the metal ion is Ca²⁺，Ca²⁺Can be in SA and SA, SA and Ti₃C₂T_x、Ti₃C₂T_xWith Ti₃C₂T_xForm stronger ionic bonds between the two.

The titanium carbide composite film with the orderly crosslinked hydrogen bonds and ionic bonds is circular, the corresponding diameter is 2-4 cm, and the thickness range is 1-10 mu m.