Self-assembled film stabilized Ti3C2Tx oriented modified multi-protection carbon fabric liner and preparation method thereof

Abstract

The invention discloses a self-assembled film stabilized Ti3C2Tx oriented modified multi-protection carbon fabric liner and a preparation method thereof. The preparation method comprises the following steps: pretreating carbon cloth; hCl and LiF are mixed to serve as an etching agent, Ti3AlC2 powder is added, and a single-layer or few-layer original Ti3C2Tx nanosheet is prepared; the preparation method comprises the following steps: adding 1H, 1H, 2H, 2H-perfluorodecanethiol into absolute ethyl alcohol, and adding a single layer or a few layers of original Ti < 3 > C < 2 > T < x > nanosheets to obtain self-assembled film stable Ti < 3 > C < 2 > T < x >; and adding the self-assembled film-stabilized Ti3C2Tx into phenolic resin to obtain a modified resin solution, and carrying out multiple times of same-direction pulling dipping and hot-pressing curing on the pretreated carbon cloth to obtain the self-assembled film-stabilized Ti3C2Tx oriented modified multi-protection carbon fabric liner. The self-assembled film is introduced to stabilize Ti3C2Tx, so that the wear resistance of the gasket and the corrosion protection performance on the bearing are remarkably enhanced.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of composite materials and relates to a self-assembled film stabilized Ti3C2T x Oriented modified multi-protective carbon fabric liner and preparation method thereof. BACKGROUND

[0002] Joint bearing is a kind of sliding bearing with spherical structure composed of inner spherical outer ring and outer spherical inner ring, which is widely used in aerospace, rail transportation and civil life. However, there are problems of friction jam and high wear rate between metal counterparts, and it is easy to fail in harsh working conditions, which affects the flexibility and service life of the bearing. The fabric liner adopts fabric reinforced resin matrix composite technology and is mainly used as a key component of alloy joint bearing and other sliding parts. The material uses woven fiber cloth as the reinforcing framework, forms a prepreg by impregnating the resin matrix, and is cured to form a compact structure. The joint bearing has the characteristics of flexible rotation and maintenance-free, and significantly improves the durability and service life of the bearing under the condition of no liquid lubrication. However, with the continuous upgrading of high-power equipment and the rapid development of salt spray and other extreme working conditions, the joint bearing fabric liner faces more severe comprehensive performance challenges. The existing fabric liner has poor mechanical properties and cannot meet the demand of heavy load working conditions. In addition, there are void defects in the material, which limits the long-term protection of the liner to the bearing in harsh environments such as high humidity and salt spray.

[0003] The patent with authorization number CN 117661137 B discloses a preparation method of a multi-scale reinforced self-lubricating fabric liner. The method uses high-strength aramid fiber and in-situ reinforced PTFE fiber (wet spinning technology) as warp and weft threads to weave a self-lubricating fabric, and then impregnates modified resin and hot-presses and cures to obtain a composite material. This technology has a positive effect on the lubrication of the reinforced liner, and the wear rate is also reduced. However, the preparation process of this method is complex and difficult to meet the batch service needs of aviation heavy-duty joint bearings. At the same time, the corrosion resistance of aramid and PTFE fibers is poor, which affects the service life of the liner.

[0004] Patent application CN 116122049 A discloses the preparation and application of MXene-Ag co-modified PI / PTFE blended fabric composites. This method utilizes hydrogen bonding to adsorb MXene and Ag nanophases onto the surface of the PI / PTFE blended fabric, promoting interfacial interlocking and chemical bonding between the blended fabric and the phenolic resin matrix, effectively improving the interfacial adhesion performance of the fabric composite. Furthermore, the nanophases can be released to the friction interface during friction to form a friction transfer film, effectively improving the tribological properties of the composite. However, improving the interface is difficult to simultaneously address the porosity defects in the resin matrix, and it cannot effectively protect against the intrusion of corrosive media. Moreover, in humid air, some Ti atoms in MXene migrate to the lamellar surface and are easily oxidized, making it difficult to maintain its lubricating and protective functions as an additive phase in the composite material over a long period. Summary of the Invention

[0005] The purpose of this invention is to provide a self-assembled membrane stabilizing Ti3C2T x Directional modified multi-protective carbon fabric gaskets and their preparation methods address the problem of weak long-term protection capabilities for bearings in existing technologies.

[0006] To achieve the above objectives, the present invention employs the following technical solution: A self-assembled membrane stabilizes Ti3C2T x A method for preparing directionally modified multi-protective carbon fabric liners includes: Pre-treat the carbon cloth; HCl and LiF were mixed and stirred in an ice-water bath until completely cooled, serving as an etchant. Ti3AlC2 powder was then slowly added to the etchant, and the mixture was stirred and etched in a constant-temperature water bath to remove the Al layer. The crude product was centrifuged until the pH of the supernatant was neutral. After shaking and sonication in an ice-water bath, the mixture was centrifuged again to collect the dark green supernatant. The dark green supernatant was freeze-dried to obtain a monolayer or few layers of original Ti3C2T. x Nanosheets; 1H,1H,2H,2H-perfluorodecylthiol was added to anhydrous ethanol and stirred until homogeneous to obtain a reaction solution. A monolayer or few-layer layer of pristine Ti3C2T was then added. x Nanosheets were ultrasonically treated and reacted with stirring in Ti3C2T x PFDT film was formed by surface self-assembly, filtered and dried to obtain a self-assembled stable Ti3C2T film. x ; Stabilizing Ti3C2T with self-assembled membrane xUltrasonic treatment is added to the phenolic resin until it is uniformly dispersed to obtain a modified resin solution. The pretreated carbon cloth is completely immersed in the modified resin solution and subjected to multiple homodirectional pull-up impregnation. After drying, a prepreg is obtained. After hot pressing and curing, natural cooling to room temperature is performed to obtain a self-assembled film stable Ti3C2T x A directional modified multi-protective carbon fabric liner.

[0007] Further, the pretreatment method of the carbon cloth is as follows: The carbon cloth with a specification of 6-12 K is completely immersed in acetone, sealed, and soaked at room temperature for 42-54 h. Deionized water is used for repeated cleaning, and drying is performed at 60-80 ℃ to obtain a pretreated carbon cloth.

[0008] Further, the concentration of the HCl solution is 8-10 mol / L, the volume-to-mass ratio of HCl to LiF is 20-60 mL:1-4 g, and the mass-to-volume ratio of Ti3AlC2 powder to etchant is 1-4 g:20-60 mL.

[0009] Further, the constant-temperature water bath temperature for removing the Al layer is 25-35 ℃, the stirring speed is 200-600 rpm / min, and the stirring time is 40-56 h. The ultrasonic treatment time in the ice water bath is 0.5-1.5 h, the centrifugation time is 3-5 min, and the rotation speed is 4000-5000 rpm / min.

[0010] Further, the volume ratio of 1H,1H,2H,2H-perfluorodecanethiol to anhydrous ethanol is 1-3:94-102, and the mass-to-volume ratio of the monolayer or few-layer original Ti3C2T x nanosheet to the reaction solution is 2-6 g:95-105 mL.

[0011] Further, the ultrasonic treatment time of the self-assembled film stable Ti3C2T x is 5-10 min, the stirring reaction time is 9-15 h, the reaction temperature is 25-30 ℃, the stirring speed is 200-300 rpm / min, the drying temperature is 40-60 ℃, and the time is 6-8 h.

[0012] Further, the mass fraction of the self-assembled film stable Ti3C2T x in the modified resin solution is 0.1%-0.2%, and the ultrasonic treatment time is 10-15 min.

[0013] Further, during the pull-up impregnation process, each impregnation is performed for 8-10 s, drying is performed for 10-15 min after impregnation, and the process is repeated for 2-3 cycles. The drying temperature is 25-30 ℃, and the drying time is 4-8 h.

[0014] Furthermore, the hot-press curing temperature is 165~175 ℃, the pressure is 4~6 MPa, and the hot-pressing time is 10~15 min.

[0015] A self-assembled film stabilized for Ti3C2T prepared by the method described above. x Targeted modification of multi-protective carbon fabric liner.

[0016] Compared with the prior art, the present invention has the following beneficial effects: This invention provides a self-assembled membrane-stabilized Ti3C2T x A method for preparing directionally modified multi-protective carbon fabric gaskets, using an etching method to prepare single-layer or few-layer Ti3C2T. x Nanosheets were formed, and then PFDT was adsorbed onto the surface of the sheets via hydrogen bonding and weak chemical bonds using a wet chemical method. Finally, the fluorinated chains self-aligned to form a stable coating film through the synergistic effect of van der Waals forces between fluorine molecules, resulting in a self-assembled stable Ti3C2T film. x Next, it was dispersed in a phenolic resin solution, and after thorough mixing, a preform was prepared by multiple unidirectional lifting impregnation processes. After hot pressing and curing, a multi-layer protective carbon fabric gasket was finally produced. This was achieved by stabilizing Ti3C2T using a self-assembled film. x By constructing a "labyrinth" structure within the matrix to compensate for internal defects and prevent the penetration of corrosive media, PFDT can effectively prevent Ti3C2T. x Oxidation failure, multi-tiered Ti3C2T x In synergy with PFDT, and leveraging the hydrophobicity of PFDT to reduce the surface energy of the material, Ti3C2T together delays the damage of corrosive media to the bearing. x As a lubricating phase distributed on the friction surface, PFDT and Ti3C2T together provide lubrication performance. x Nanosheets form a friction film at the friction interface, reducing the coefficient of friction and wear, and synergistically regulating the tribological properties of the composite material, thus giving the alloy bearing better rotational flexibility and a longer service life. This invention uses high-strength, high-wear-resistant carbon fabric as reinforcement to cope with harsh conditions such as high temperature and heavy load. Two-dimensional Ti3C2T is coated with a self-assembled film (PFDT) through multiple dip-coating processes. x By introducing a matrix, the "maze effect" and low surface energy characteristics are used to slow down the penetration of corrosive media. At the same time, the synergistic effect of the two is used to improve the friction and wear performance of the composite material, thereby simultaneously improving the wear resistance and corrosion protection of the fabric gasket under heavy-load, high-salt-spray harsh conditions, and fully enhancing the lubricity and service life of the carbon fabric gasket under heavy-load conditions.

[0017] The self-assembled film stabilized by this invention for Ti3C2T xThe oriented modified multi-protection carbon fabric liner has excellent mechanical properties, and in a friction process, the PFDT covers the two-dimensional Ti3C2T x The filler exists in the friction surface to play a good lubricating effect, effectively improving the service life and stability of the carbon fabric liner. In addition, Ti3C2T x By constructing a "labyrinth" structure in the matrix, the surface defects of the resin are reduced, and the penetration of the corrosion medium is blocked, and the PFDT is further stabilized in the Ti3C2T x The surface constructs a hydrophobic self-assembled film to reduce the surface energy of the material, significantly improves the protection capability of the liner for alloy bearings, and the wear rate of the liner is reduced by 13.78%, and the corrosion current density of the bearing protected by the liner is reduced from 7.43*10 -6 A / cm 2 To 3.38*10 -6 A / cm 2 , reduced by 54.51%.

[0018] The present application introduces a self-assembled film to stabilize Ti3C2T x The present application introduces a self-assembled film to stabilize Ti3C2T x The present application introduces a self-assembled film to stabilize Ti3C2T x The present application introduces a self-assembled film to stabilize Ti3C2T x The present application introduces a self-assembled film to stabilize Ti3C2T x The present application introduces a self-assembled film to stabilize Ti3C2T BRIEF DESCRIPTION OF DRAWINGS

[0019] In order to more clearly illustrate the technical scheme of the embodiments of the present application, the following will briefly introduce the drawings needed in the embodiments, and it should be understood that the following drawings only show some embodiments of the present application, and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor.

[0020] Figure 1 The scanning electron microscope morphology of Ti3C2T x prepared by etching method in embodiment 1 of the present application.

[0021] Figure 2 The micro-morphology diagram of the PFDT-coated Ti3C2T x piece prepared in embodiment 1 of the present application.

[0022] Figure 3 The polarization curve comparison diagram of the sample prepared in embodiment 1 of the present application and the contrast sample protective bearing sample, wherein 3M-CF / PF is Ti3C2T x The oriented modified liner protects the bearing sample, and 3PM-CF / PF is the self-assembled film stabilized Ti3C2T x The oriented modified liner protects the bearing sample.

[0023] Figure 4 Comparison chart of friction coefficient of the sample prepared for Example 1 of the present application and comparative samples, wherein 3M-CF / PF is Ti3C2T x Directionally modified liner protected bearing sample, 3PM-CF / PF is self-assembled film stabilized Ti3C2T x Directionally modified liner protected bearing sample.

[0024] Figure 5 Comparison chart of wear rate of the sample prepared for Example 1 of the present application and comparative samples, wherein 3M-CF / PF is Ti3C2T x Directionally modified liner protected bearing sample, 3PM-CF / PF is self-assembled film stabilized Ti3C2T x Directionally modified liner protected bearing sample. DETAILED DESCRIPTION

[0025] To enable persons skilled in the art to understand the features and effects of the present application, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used in the text are the usual meanings understood by those skilled in the art of the present application, and in the event of conflict, the definition in the specification shall prevail.

[0026] Theories or mechanisms described and disclosed herein, whether correct or not, should not be considered limiting on the scope of the present application, i.e., the present application can be practiced without regard to any particular theory or mechanism.

[0027] In this text, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents and concentrations, are for the sake of brevity and convenience. Therefore, the description of numerical ranges or percentage ranges should be considered to have encompassed and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions).

[0028] In this text, unless otherwise specified, "comprise", "include", "contain", "have" or similar terms encompass the meaning of "consist of" and "consist essentially of", for example, "A comprises a" encompasses the meaning of "A comprises a and other" and "A comprises only a".

[0029] In this text, for the sake of brevity, all possible combinations of the technical features in each embodiment or example are not described. Therefore, as long as the combinations of the technical features do not conflict, the technical features in each embodiment or example can be combined arbitrarily, and all possible combinations should be considered as the scope disclosed in the specification.

[0030] The application will be further described in connection with the following specific embodiments. It needs to be understood that these embodiments are only used for illustrating the application and not for limiting the scope of the application. Furthermore, it needs to be understood that those skilled in the art can make various alterations or modifications to the application after reading the content taught by the application, and these equivalent forms also fall within the scope defined by the appended claims of the application.

[0031] The following examples use the instruments and equipment that are conventional in the art. The experimental methods in the following examples, unless otherwise specified, are generally carried out according to the conventional conditions, or according to the conditions suggested by the manufacturers. The following examples use various raw materials, unless otherwise specified, all use conventional commercially available products, and the specifications are conventional specifications in the art. In the specification of the application and the following examples, unless otherwise specified, "%" means weight percent, "parts" means weight parts, and the ratio means weight ratio.

[0032] The application will be further described in connection with the following specific embodiments. It needs to be understood that these embodiments are only used for illustrating the application and not for limiting the scope of the application. Furthermore, it needs to be understood that those skilled in the art can make various alterations or modifications to the application after reading the content taught by the application, and these equivalent forms also fall within the scope defined by the appended claims of the application. The application provides a self-assembled film stabilized Ti3C2T x The preparation method of the oriented modified multi-protection carbon fabric liner specifically comprises the following steps: Step 1: pretreat the carbon cloth to remove impurities and sizing agent on the surface.

[0033] The specification of the carbon cloth is 6-12 K.

[0034] The pretreatment method of the carbon cloth is: completely immerse the carbon cloth in acetone, seal and soak at room temperature for 42-54 h. Then, repeatedly wash with deionized water and dry at 60-80 ℃ to obtain the pretreated carbon cloth.

[0035] Step 2: prepare the original Ti3C2T x nanosheets: add HCl and LiF into a polytetrafluoroethylene solvent bottle, seal and stir in an ice water bath for 5-15 min until completely cooled, as an etching agent; then slowly add Ti3AlC2 powder into the etching agent, and stir to etch in a constant temperature water bath to remove the Al layer. After etching, repeatedly centrifuge the crude product until the pH of the upper liquid is neutral, at which time the Ti3C2T x nanosheets begin to spontaneously delaminate; then, after manual shaking of the solution and ultrasonic treatment in an ice water bath, centrifugal treatment is performed to collect the ink green supernatant on the upper layer of the solution. Finally, freeze-dry the ink green supernatant to obtain single-layer or few-layer original Ti3C2T x nanosheets.

[0036] Preferably, the concentration of the HCl solution is 8-10 mol / L, and the volume-mass ratio of HCl to LiF is 20-60 mL:1-4 g.

[0037] The mass-volume ratio of Ti3AlC2 powder to etchant is 1-4:20-60, and the duration is 5-15 min.

[0038] The temperature of the constant-temperature water bath for removing the Al layer is 25-35 ℃, the magnetic stirring speed is 200-600 rpm / min, and the stirring time is 40-56 h.

[0039] The repeated centrifugation is performed by a centrifuge, the number of centrifugation is 7-9, the speed is 3000-4000 rpm / min, and the time is 3-5 min.

[0040] The manual shaking time is 20-60 min, the ultrasonic time in an ice water bath is 0.5-1.5 h, and the centrifugation time is 3-5 min at a speed of 4000-5000 rpm / min.

[0041] The freeze-drying is performed by a freeze-drying machine, and the time is 48-60 h.

[0042] Step 3: Ti3C2T x Surface PFDT film self-assembly: 1H, 1H, 2H, 2H-perfluorodecanethiol (PFDT) is added to anhydrous ethanol to prepare a reaction solution, and after stirring uniformly, monolayer or few-layer original Ti3C2T x nanosheets are added and ultrasonic treatment is performed, the stirring reaction is performed on the Ti3C2T x surface to form a PFDT film. After completion, suction filtration is performed and drying is performed to obtain self-assembled film stabilized Ti3C2T x .

[0043] Preferably, the volume ratio of 1H, 1H, 2H, 2H-perfluorodecanethiol to anhydrous ethanol is 1-3:94-102, and the mass-volume ratio of monolayer or few-layer original Ti3C2T x nanosheets to the reaction solution is 2-6:95-105.

[0044] The ultrasonic time after adding monolayer or few-layer original Ti3C2T x nanosheets is 5-10 min.

[0045] The stirring reaction is performed by a magnetic stirrer, the reaction time is 9-15 h, the reaction temperature is 25-30 ℃, and the stirring speed is 200-300 rpm / min.

[0046] The drying temperature is 40-60 ℃, and the time is 6-8 h.

[0047] Step 4: The self-assembled film stabilized Ti3C2T xThe phenolic resin is added into ultrasonic to be uniformly dispersed to obtain a modified resin solution, then the treated carbon cloth is fully immersed in the modified resin solution for multiple times of same direction pulling and dipping, and then drying is performed to obtain a prepreg.

[0048] Preferably, the self-assembled film in the modified resin solution stabilizes Ti3C2T x The mass fraction of the phenolic resin is 0.1% to 0.2%, and the ultrasonic time is 10 to 15 min.

[0049] The solvent of the phenolic resin is acetone, and the mass ratio of acetone to phenolic resin is 4:1 to 3:1.

[0050] In the pulling and dipping process, each dipping is performed for 8 to 10 s, and after the dipping, drying is performed for 10 to 15 min, and the process is performed for 2 to 3 cycles, and then the drying temperature is 25 to 30 DEG C, and the drying time is 4 to 8 h.

[0051] Step 5: The prepreg is cured by a vulcanizing machine, and after natural cooling to room temperature, a self-assembled film stabilized Ti3C2T x is obtained.

[0052] Preferably, the curing by hot pressing is performed by using a vulcanizing machine, the hot pressing temperature is 165 DEG C to 175 DEG C, the pressure is 4 MPa to 6 MPa, and the hot pressing time is 10 min to 15 min.

[0053] The application will be further described in detail below in combination with specific embodiments: Embodiment 1: Step 1: 6K carbon cloth is fully immersed in acetone, sealed and soaked at room temperature for 48 h. Then, the carbon cloth is repeatedly washed with deionized water and dried in an oven at 60 DEG C to obtain a pretreated carbon cloth.

[0054] Step 2: The original Ti3C2T x nanosheet is prepared by etching: 40 mL of 9M HCl and 2g of LiF are added into a polytetrafluoroethylene solvent bottle, sealed and stirred in an ice water bath for 10 min until completely cooled, as an etching agent; then 2g of Ti3AlC2 powder is slowly added into the etching agent within 15 min, and stirred in a 30 DEG C constant temperature water bath at a speed of 200 rpm / min for 48 h to remove the Al layer. After etching, the centrifuge is used to repeatedly centrifuge the crude product at a speed of 3000 rpm / min until the pH of the upper liquid is neutral, at which time the Ti3C2T x starts to spontaneously delaminate; then the solution is manually shaken for 20 min and ultrasonically treated in an ice water bath for 0.5 h, and then centrifuged at a speed of 5000 rpm / min for 5 min to collect the ink green supernatant on the solution. Finally, the above ink green supernatant is freeze-dried for 48 h to obtain a single-layer or few-layer original Ti3C2Tx nanosheets.

[0055] Step 3: Ti3C2T x Surface PFDT film self-assembly: 1 mL of 1H, 1H, 2H, 2H-Perfluorodecanethiol (PFDT) was added to 94 mL of anhydrous ethanol to prepare the reaction solution, and 2 g of single-layer or few-layer pristine Ti3C2T x nanosheets were added and ultrasonically treated for 5 min, and then stirred at a speed of 200 rpm / min and a temperature of 25 °C for 12 h using a magnetic stirrer, and then the Ti3C2T x nanosheets were placed in a 60 °C oven and dried for 6 h to obtain self-assembled film-stabilized Ti3C2T x .

[0056] Step 4: The self-assembled film-stabilized Ti3C2T x was ultrasonically treated for 10 min to obtain a 0.15% mass fraction of modified phenolic resin solution. The treated carbon cloth was completely immersed in the modified phenolic resin for 10 s, vertically lifted and placed in a 30 °C oven for drying, and the lifting and immersion was repeated 3 times, and then dried for 8 h to obtain a prepreg.

[0057] Step 5: The prepreg was hot-pressed and cured at a temperature of 170 °C and a pressure of 5 MPa for 10 min by a vulcanizing machine, and after natural cooling to room temperature, the self-assembled film-stabilized Ti3C2T x directionally modified multi-protection carbon fabric liner.

[0058] Example 2: Step 1: A 6 K carbon cloth was completely immersed in acetone, sealed and soaked at room temperature for 42 h. Subsequently, it was repeatedly washed with deionized water and dried in an oven at 60 °C to obtain a pretreated carbon cloth.

[0059] Step 2: Etching method for preparing pristine Ti3C2T x nanosheets: 20 mL of 8M HC1 and 1 g of LiF were added to a polytetrafluoroethylene solvent bottle, sealed and stirred in an ice water bath for 5 min until completely cooled, as an etching agent; then 1 g of Ti3AlC2 powder was slowly added to the etching agent within 5 min, and stirred at a constant temperature of 25 °C for 40 h at a stirring speed of 200 rpm / min to remove the Al layer. After etching, the crude product was repeatedly centrifuged at a speed of 3000 rpm / min until the pH of the upper liquid was neutral, at which time the Ti3C2T xThe solution initially separated spontaneously; then, it was manually agitated for 20 min and sonicated in an ice-water bath for 0.5 h, followed by centrifugation at 4000 rpm / min for 3 min to collect the dark green supernatant. Finally, the dark green supernatant was freeze-dried for 48 h to obtain a monolayer or few-layer original Ti3C2T. x Nanosheets.

[0060] Step 3: Ti3C2T x Surface PFDT film self-assembly: 1 mL of 1H,1H,2H,2H-perfluorodecylthiol (PFDT) was added to 94 mL of anhydrous ethanol to prepare a reaction solution. After stirring thoroughly, 2 g of monolayer or few-layer original Ti3C2T was added. x Nanosheets were ultrasonically treated for 5 min, and then stirred with a magnetic stirrer at 200 rpm / min and 25 °C for 9 h in Ti3C2T. x A PFDT film was formed by surface self-assembly. After the reaction was complete, the solution was filtered and dried in an oven at 40 °C for 6 h to obtain a stable self-assembled Ti3C2T film. x .

[0061] Step 4: Stabilize the self-assembled Ti3C2T membrane x Add 25% phenolic resin and sonicate for 10 min until uniformly dispersed to prepare a 0.10% modified phenolic resin solution. Completely immerse the pretreated carbon cloth in the modified phenolic resin for 8 s, lift it vertically and place it in a 25 ℃ oven to dry. Repeat the lifting and immersion process twice, and then dry for 4 h to obtain the prepreg.

[0062] Step 5: The prepreg is hot-pressed and cured for 10 min at 165 ℃ and 4 MPa using a vulcanizing machine. After natural cooling to room temperature, a self-assembled film stabilized Ti3C2T is obtained. x Targeted modification of multi-protective carbon fabric liner.

[0063] Example 3: Step 1: Completely immerse 12K carbon cloth in acetone, seal it, and soak it at room temperature for 54 hours. Then, wash it repeatedly with deionized water and dry it in an oven at 80 °C to obtain the pretreated carbon cloth.

[0064] Step 2: Preparation of pristine Ti3C2T by etching method xNanosheets: 60 mL of 10 M HCl and 4 g of LiF were added into a polytetrafluoroethylene solvent bottle sealed and stirred in an ice water bath for 15 min to complete cooling as an etchant; then 4 g of Ti3AlC2 powder was slowly added into the etchant within 15 min, and the etching was carried out at 600 rpm / min for 56 h in a constant temperature water bath at 35 ℃ to remove the Al layer. After etching, the crude product was repeatedly centrifuged at 4000 rpm / min to neutralize the pH of the upper liquid, at which time the Ti3C2T x spontaneous delamination started; then the solution was manually shaken for 60 min and ultrasonically treated in an ice water bath for 1.5 h, and then the ink green supernatant in the upper layer of the solution was collected by centrifugation at 5000 rpm / min for 5 min. Finally, the ink green supernatant was freeze-dried for 60 h to obtain monolayer or few-layer pristine Ti3C2T x nanosheets.

[0065] Step 3: Ti3C2T x Surface PFDT film self-assembly: 3 mL of 1H, 1H, 2H, 2H-perfluorodecanethiol (PFDT) was added into 102 mL of anhydrous ethanol to prepare a reaction solution, and 6 g of monolayer or few-layer pristine Ti3C2T x nanosheets were added and ultrasonically treated for 10 min, and then the reaction was stirred at 300 rpm / min and 30 ℃ for 15 h by using a magnetic stirrer, and a PFDT film was self-assembled on the surface of Ti3C2T x nanosheets. After the reaction was completed, the solution was suction filtered, and the self-assembled film stabilized Ti3C2T x .

[0066] Step 4: The self-assembled film stabilized Ti3C2T x was ultrasonically treated for 15 min until it was uniformly dispersed to prepare a 0.20% mass fraction modified phenolic resin solution. The pretreated carbon cloth was completely immersed in the modified phenolic resin for 10 s, vertically lifted and then placed in a 30 ℃ oven for drying, and the lifting and immersion were repeated for 3 times, and then dried for 8 h to obtain a prepreg.

[0067] Step 5: The prepreg was hot-pressed and cured by a vulcanizing machine at a temperature of 175 ℃ and a pressure of 6 MPa for 15 min, and after natural cooling to room temperature, the self-assembled film stabilized Ti3C2T x directionally modified multi-protection carbon fabric pad.

[0068] The Ti3C2T x and PFDT coated Ti3C2T x nanosheets prepared in Example 1 of the present application had a micro-morphology as shown in Figure 1and Figure 2 As shown in FIG. 1, Figure 1 As shown in FIG. 2, the Ti3C2T x x surface is smooth and free of impurities, Figure 2 As shown in FIG. 3, the Ti3C2T x x sheets have slight overlap and present a multi-layer state, and the surface is coated with a modified substance.

[0069] As shown in FIG. 4, Figure 3 As shown in FIG. 4, the self-assembled film prepared in Example 1 of the present application stabilizes Ti3C2T x The corrosion potential of the protective bearing sample of the oriented modified liner is right-shifted, compared with the Ti3C2T x The corrosion current density of the protective bearing sample of the oriented modified liner is reduced, compared with the Ti3C2T x The protective effect of the oriented modified liner on the metal substrate is enhanced.

[0070] As shown in FIG. 4, Figure 4 As shown in FIG. 4, the self-assembled film prepared in Example 1 of the present application stabilizes Ti3C2T x The corrosion potential of the protective bearing sample of the oriented modified liner is right-shifted, compared with the Ti3C2T x The friction coefficient of the protective bearing sample of the oriented modified liner is obviously reduced from 0.193 to 0.171, the stability is also improved, and the wear rate is reduced by 13.78%.

[0071] The above only describes the preferred embodiments of the present application and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A self-assembled film stabilized Ti3C2T x A method for producing a directional modified multi-shielded carbon fabric gasket, characterized by, The application relates to a method for preparing a carbon cloth lithium ion battery electrode. The method comprises the following steps: HCl was mixed with LiF, stirred in an ice water bath until completely cooled, as an etchant, then Ti3AlC2 powder was slowly added into the etchant, stirring etching in a constant temperature water bath to remove the Al layer, the crude product was centrifuged until the pH of the upper liquid was neutral, after oscillation and ultrasonic treatment in an ice water bath, centrifugal treatment was carried out to collect the ink green supernatant on the solution, the ink green supernatant was freeze-dried to obtain single-layer or few-layer original Ti3C2T x nanosheets; To prepare the reaction solution, 1H, 1H, 2H, 2H-perfluorodecanethiol was added to anhydrous ethanol and stirred until uniform, and a single or few-layer pristine Ti3C2T x nanosheet was added and sonicated, and the reaction was stirred. x The PFDT film was self-assembled on the surface of Ti3C2T x nanosheet, and the self-assembled film was obtained by suction filtration and drying. Stable ti3c2t with self-assembled film x The phenolic resin is ultrasonically dispersed into a modified resin solution. The pretreated carbon cloth is fully immersed in the modified resin solution and impregnated by multiple same-direction pulling and dipping. After drying, a prepreg is obtained. After hot pressing and curing, and natural cooling to room temperature, a stable Ti3C2T with a self-assembled film is obtained x Directionally modified multi-protected carbon fabric liner 2. A self-assembled film stabilized Ti3C2T x Process for the preparation of a directional modified multi-shielded carbon fabric gasket, characterized in that, The carbon cloth is pretreated by the following method: The carbon cloth of 6-12 K is completely immersed in acetone, sealed, soaked at normal temperature for 42-54 h, repeatedly cleaned with deionized water and dried at 60-80 DEG C to obtain the pretreated carbon cloth.

3. A self-assembled film stabilized Ti3C2T x Process for the preparation of a directional modified multi-shielded carbon fabric gasket, characterized in that, The concentration of the HCl solution is 8-10 mol / L, the volume / mass ratio of the HCl to LiF is (20-60 mL):(1-4 g), and the mass / volume ratio of the Ti3AlC2 powder to the etchant is (1-4 g):(20-60 mL).

4. A self-assembled film stabilized Ti3C2T x Process for the preparation of a directional modified multi-shielded carbon fabric gasket, characterized in that, The temperature of the constant-temperature water bath for removing the Al layer is 25-35 DEG C, the stirring speed is 200-600 rpm / min, and the stirring time is 40-56 h. The ultrasonic treatment time in the ice water bath is 0.5-1.5 h, the centrifugal time is 3-5 min, and the speed is 4000-5000 rpm / min.

5. A self-assembled film stabilized Ti3C2T x Process for the preparation of a directional modified multi-shielded carbon fabric gasket, characterized in that, The volume ratio of the 1H, 1H, 2H, 2H-perfluorodecanethiol to anhydrous ethanol is (1~3):(94~102), and the monolayer or few-layer original Ti3C2T x The mass volume ratio of the nanosheet to the reaction solution is (2~6 g):(95~105 mL).

6. A self-assembled film stabilized Ti3C2T x Process for the preparation of a directional modified multi-shielded carbon fabric gasket, characterized in that, The self-assembled film stabilizes Ti3C2T x The ultrasonic treatment time is 5-10 min, the stirring reaction time is 9-15 h, the reaction temperature is 25-30 DEG C, the stirring speed is 200-300 rpm / min, the drying temperature is 40-60 DEG C, and the time is 6-8 h.

7. A self-assembled film stabilized Ti3C2T x The preparation method of the directional modified multi-protective carbon fabric pad is characterized by comprising the following steps: The self-assembled film in the modified resin solution stabilizes Ti3C2T x The mass fraction is 0.1%-0.2%, and the ultrasonic time is 10-15 min.

8. A self-assembled film stabilized Ti3C2T x Process for the preparation of a directional modified multi-shielded carbon fabric gasket, characterized in that, In the pulling and dipping process, each dipping time is 8-10 s, the drying time after dipping is 10-15 min, 2-3 cycles are carried out, the drying temperature is 25-30 DEG C, and the drying time is 4-8 h.

9. A self-assembled film stabilized Ti3C2T x Process for the preparation of a directional modified multi-shielded carbon fabric gasket, characterized in that, The hot-pressing curing temperature is 165-175 DEG C, the pressure is 4-6 MPa, and the hot-pressing time is 10-15 min.

10. A self-assembled film of Ti3C2T prepared by the method of any one of claims 1-9. x A directional modified multi-shielded carbon fabric gasket.

Images