Modified Ti3C2TX-based oily conductive ink and preparation method thereof
By preparing modified Ti3C2TX-based oily conductive ink under electrostatic interaction at the oil-water interface, the problems of easy oxidation and difficult dispersion of Ti3C2TX were solved, enabling the widespread application of Ti3C2TX in inks and improving its conductivity and printing performance.
Patent Information
- Application Number
- CN202511836143.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-08
- Publication Date
- 2026-02-17
AI Technical Summary
Ti3C2TX is easily attacked and oxidized by oxygen and water molecules. Its surface polar functional groups make it difficult to disperse in the oil phase. Existing modification methods are complex and the content of modifiers is difficult to control, which limits its effectiveness in ink applications.
A Ti3C2TX aqueous dispersion was prepared by selective etching. An oil phase solution with a positively charged modifier was added, and a Pickering emulsion was formed through electrostatic interaction at the oil-water interface to achieve surface modification of Ti3C2TX and prepare a modified Ti3C2TX-based oily conductive ink.
The modification process was simplified, and the oxidation resistance and dispersibility of Ti3C2TX were improved. The prepared ink has excellent conductivity and printing performance, is suitable for various molding methods, and can be applied in fields such as electromagnetic shielding and infrared stealth.
Smart Images
Figure CN121537832A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of material surface modification, and relates to Ti3C2T X , and particularly relates to a modified Ti3C2T X based oil-soluble conductive ink and a preparation method. BACKGROUND
[0002] Ti3C2T X Due to high electrical conductivity, hydrophilicity and interlayer embeddability, Ti3C2T X is widely used in energy storage, sensing, electromagnetic shielding and flexible electronics. However, Ti3C2T X is easily attacked by oxygen and water molecules due to the presence of defect vacancies on the surface, resulting in oxidation deformation and loss of excellent performance, which seriously limits its application. In addition, Ti3C2T X is easily dispersed in polar solvents such as water due to the presence of polar functional groups on the surface, not only accelerating its oxidation damage, but also limiting its application in inks. By performing surface modification treatment on Ti3C2T X , oxygen and water molecules can be effectively isolated, the stability can be improved, and the dispersion phase range can be widened. However, the current modification method mainly focuses on covalent reaction and electrochemistry, and there are problems such as difficult control of reaction conditions, narrow adjustable range of modifier content, and easy damage to the structure of Ti3C2T X . Therefore, exploring a fast and simple Ti3C2T X modification method is an effective way to promote the wide application of Ti3C2T . SUMMARY
[0003] In view of the problems in the prior art, the purpose of the present application is to provide a modified Ti3C2T X based oil-soluble conductive ink and a preparation method, to solve the technical problem that the application effect of Ti3C2T X in inks in the prior art needs to be further improved.
[0004] In order to solve the above technical problems, the technical scheme is adopted as follows: A preparation method of a modified Ti3C2T X based oil-soluble conductive ink, which specifically comprises the following steps: Step one, preparing a water dispersion A of Ti3C2T X : Ti3C2T X is prepared by removing the Al layer from Ti3AlC2 by selective etching, and then Ti3C2T X is subjected to ultrasonic peeling, centrifugal cleaning and redispersion of the precipitate after centrifugal cleaning to obtain Ti3C2T XAqueous dispersion A.
[0005] Step 2, prepare oil phase solution B of the modifier: A positively charged modifier was added to the oil phase and dissolved using ultrasound to obtain an oil phase solution B of the modifier.
[0006] Step 3, Preparation of modified Ti3C2T X Oil-based conductive ink: The Ti3C2T obtained in step one X The aqueous dispersion A was added to the oil phase solution B of the modifier obtained in step two, and stirred. Surface modification was achieved at the oil-water interface through electrostatic interaction between the two solutions. Simultaneously, a stable Pickering emulsion was formed throughout the system. After standing for 1–6 hours, demulsification, centrifugal washing, and redispersion of the precipitate after centrifugal washing were performed sequentially to obtain modified Ti3C2T. X Oil-based conductive ink.
[0007] The present invention also has the following technical features: Specifically, in step two, the positively charged modifier includes one or more of the following: water-soluble cocoyl methyl monoethanolamide, dodecyltrimethylammonium chloride, alkyl quaternary ammonium salt, and alkylamine.
[0008] The alkylamines include one or more of octadecylamine and n-butylamine.
[0009] In step two, the oil phase includes one or more of toluene, chloroform, cyclohexane, and n-hexane.
[0010] Specifically, in step three, the Ti3C2T... X Aqueous dispersion A was prepared using Ti3C2T X The mass ratio between the amount of the modifier added and the amount of the positively charged modifier added during the preparation of the oil phase solution B of the modifier is (0.1~49):1.
[0011] Specifically, in step three, the stirring speed is 50-800 r / min, and the stirring time is 1-60 min.
[0012] Specifically, in step three, the redispersed phase includes one or more of toluene, chloroform, cyclohexane, and n-hexane.
[0013] In step three, the modified Ti3C2T X The concentration of the base oil-based conductive ink is 1–300 g / L.
[0014] This invention also protects a modified Ti3C2T XA base oil-based conductive ink, which uses the modified Ti3C2T as described above. X The method for preparing a base oil-based conductive ink is as follows: the conductivity of the film after molding is 200-500 S / cm, the electromagnetic shielding is 35-40 dB, and the infrared emissivity is 17.2%-18.3%.
[0015] Compared with the prior art, the present invention has the following technical effects: (I) This invention is aimed at Ti3C2T X The problems of easy oxidation and difficulty in dispersing in nonpolar oil phases, and the existing modification methods for modifying Ti3C2T. X To address the complexities of the process and the difficulty in controlling the loading, the oil-water interface is used as a reaction platform, utilizing negatively charged Ti3C2T in the aqueous phase. X The electrostatic interaction between the nanosheets and the positively charged modifier molecules in the oil phase enables the realization of Ti3C2T. X Surface modification of nanosheets, modified Ti3C2T X The preparation method of the basic oil-based conductive ink is simple and it exhibits excellent conductivity. (Ti3C2T) X Its antioxidant properties are significantly improved.
[0016] (II) This invention allows for simple and efficient replacement of the type and molecular weight of the modifier, enabling the selection of suitable modifiers based on application requirements; furthermore, Ti3C2T X The modification process is simple and requires no heating or other treatments.
[0017] (III) The modified Ti3C2T prepared in this invention X The base oil-based conductive ink has good printing performance and can be used for molding methods with a wide viscosity range, such as vacuum filtration, scraping, screen printing and direct ink writing. The molded film can be used in electromagnetic shielding or infrared stealth applications. Attached Figure Description
[0018] Figure 1 This is a photograph of the Pickering emulsion formed after stirring in Example 1 of the present invention.
[0019] Figure 2 The unmodified Ti3C2T obtained in Example 1 of this invention X ( Figure 2 (a) and the modified Ti3C2T X ( Figure 2 Transmission electron micrographs of (b) after being placed at room temperature for 1 month.
[0020] Figure 3 The unmodified Ti3C2T obtained in Example 1 of this invention X Compared with modified Ti3C2TX The X-ray diffraction pattern.
[0021] Figure 4 The modified Ti3C2T prepared using a vacuum filtration device in Example 5 of this invention X Cross-sectional scanning electron microscope image of the thin film.
[0022] Figure 5 The modified Ti3C2T in Example 5 of this invention X The images show the physical results of the preparation of base oil-based conductive inks by various molding methods: (a) vacuum filtration, (b) scraping coating, (c) screen printing, and (d) direct ink writing.
[0023] The specific content of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Detailed Implementation
[0024] It should be noted that, unless otherwise specified, all methods and raw materials in this invention are adopted from the prior art and commonly used methods and raw materials in the art. For example, water-soluble coconut oil methyl monoethanolamide is a known water-soluble coconut oil methyl monoethanolamide, alkyl quaternary ammonium salt is a known alkyl quaternary ammonium salt, alkylamine is a known alkylamine, chloroform is a known chloroform, cyclohexane is a known cyclohexane, and n-hexane is a known n-hexane.
[0025] In this invention, room temperature refers to the ambient temperature during the production process, which is typically within the range of 20±10℃.
[0026] In this invention, Ti3C2T X It is a known two-dimensional transition metal carbide, in which T X This indicates surface functional groups, specifically -O, -F, and -OH. Ti3C2T X Ti3C2T is a commonly used material in this field. X .
[0027] Following the above technical solution, specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent modifications made on the basis of the technical solution of the present invention fall within the protection scope of the present invention.
[0028] Example 1: This embodiment provides a modified Ti3C2T X A method for preparing a base oil-based conductive ink, the method specifically includes the following steps: Step 1, Preparation of Ti3C2T X Aqueous dispersion A: Ti3C2T was prepared by selective etching to remove the Al layer from Ti3AlC2. X Then for Ti3C2T X Ultrasonic stripping, centrifugal washing, and redispersion of the precipitate after centrifugal washing were performed to obtain 1 g / L Ti3C2T. X Aqueous dispersion A.
[0029] In this embodiment, the selective etching method is a commonly known selective etching method in the art; the ultrasonic stripping method is a commonly known ultrasonic stripping method in the art; and the centrifugal cleaning method is a commonly known centrifugal cleaning method in the art.
[0030] In this embodiment, Ti3AlC2 is titanium aluminum carbide, and the Ti3AlC2 used is the commonly known Ti3AlC2 in the art.
[0031] Step 2, prepare oil phase solution B of the modifier: Octadecylamine was added to toluene and dissolved using ultrasound to obtain a 1 g / L toluene solution B containing octadecylamine.
[0032] In this embodiment, octadecylamine is octadecylamine, which is commonly known in the art, and toluene is toluene, which is commonly known in the art.
[0033] In this embodiment, the ultrasound-assisted dissolution method employs a method commonly known in the art.
[0034] Step 3, Preparation of modified Ti3C2T X Oil-based conductive ink: The Ti3C2T obtained in step one X Aqueous dispersion A was added to toluene solution B of octadecylamine obtained in step two, and stirred at 300 r / min for 10 min. Surface modification was achieved at the oil-water interface through electrostatic interaction between the two solutions, while a stable Pickering emulsion was formed throughout the system. The mixture was then allowed to stand at room temperature for 1 h, followed by demulsification, centrifugal washing with toluene, and redispersing of the precipitate after centrifugation with toluene to obtain modified Ti3C2T with a concentration of 1–300 g / L. X Oil-based conductive ink.
[0035] In this embodiment, a Pickering emulsion is an emulsion stabilized by solid particles adsorbed on the interface between the aqueous and oil phases. Typically, emulsions are water-in-oil or oil-in-water emulsions. The concept of a Pickering emulsion is a commonly known concept in the art.
[0036] In this embodiment, the demulsification method adopts a method commonly known in the art; the centrifugal washing method adopts a method commonly known in the art.
[0037] This embodiment also provides a modified Ti3C2T X The base oil-based conductive ink uses the modified Ti3C2T as described in this embodiment. X The method for preparing base oil-based conductive ink.
[0038] Figure 1 This is a photograph of the Pickering emulsion formed after stirring in Example 1. Figure 1 As can be seen, the entire system forms a stable Pickering emulsion.
[0039] Figure 2 The unmodified Ti3C2T obtained in step one X ( Figure 2 (a) in the text is different from the modified Ti3C2T obtained in step three. X ( Figure 2 Transmission electron microscopy (TEM) images of (b) after being placed at room temperature for one month. Figure 2 It can be observed that unmodified Ti3C2T X Significant oxidation occurred, and the nanosheets were destroyed, while the modified Ti3C2T... X The structure remains intact.
[0040] Figure 3 The unmodified Ti3C2T obtained in step one X Compared with the modified Ti3C2T obtained in step three X The X-ray diffraction pattern. (From...) Figure 3 As can be seen from this, the modified Ti3C2T X The 002 peak shifted significantly, indicating the presence of modifiers between the nanosheets.
[0041] In this embodiment, Ti3C2T X The 002 peak is a commonly used peak known in this field.
[0042] In this embodiment, unmodified Ti3C2T X The Ti3C2T obtained in step one X Ti3C2T in aqueous dispersion A X Modified Ti3C2T X The modified Ti3C2T obtained in step three X Ti3C2T in basic oil-based conductive ink X .
[0043] Example 2: This embodiment provides a modified Ti3C2T XThe preparation method of the base oil-based conductive ink is basically the same as that in Example 1, except that in step two, the concentration of the octadecylamine toluene solution B is changed from 1 g / L to 10 g / L.
[0044] This embodiment also provides a modified Ti3C2T X The base oil-based conductive ink uses the modified Ti3C2T as described in this embodiment. X The method for preparing base oil-based conductive ink.
[0045] Example 3: This embodiment provides a modified Ti3C2T X The preparation method of the base oil-based conductive ink is basically the same as that in Example 1, except that in step two, octadecylamine is replaced with dodecyltrimethylammonium chloride.
[0046] In this embodiment, the dodecyltrimethylammonium chloride used is the commonly known dodecyltrimethylammonium chloride in the art.
[0047] This embodiment also provides a modified Ti3C2T X The base oil-based conductive ink uses the modified Ti3C2T as described in this embodiment. X The method for preparing base oil-based conductive ink.
[0048] Example 4: This embodiment provides a modified Ti3C2T X The preparation method of the base oil-based conductive ink is basically the same as that in Example 1, except that in step two, octadecylamine is replaced with n-butylamine.
[0049] In this embodiment, the n-butylamine used is the commonly known n-butylamine in the art.
[0050] This embodiment also provides a modified Ti3C2T X The base oil-based conductive ink uses the modified Ti3C2T as described in this embodiment. X The method for preparing base oil-based conductive ink.
[0051] Example 5: This embodiment presents the modified Ti3C2T obtained in Example 1. X Molding methods and applications of base oil-based conductive inks. The molding methods specifically include the following four approaches: First, take 5 g / L of modified Ti3C2T. X 10 mL of basic oil-based conductive ink was added to a vacuum filtration apparatus to prepare a thin film. The resulting film was designated as modified Ti3C2T. X film.
[0052] Second, take 20 g / L of modified Ti3C2T X 10 mL of basic oil-based conductive ink was used to prepare a thin film by a blade coating method.
[0053] Third, take 50 g / L of modified Ti3C2T X 10 mL of basic oil-based conductive ink was screen-printed.
[0054] Fourth, take 80 g / L of modified Ti3C2T X 10 mL of basic oil-based conductive ink was formed using direct ink writing technology.
[0055] The conductivity, electromagnetic shielding performance, and infrared performance of the samples obtained by the above four molding methods were measured respectively.
[0056] In this invention, the vacuum filtration device is a commonly used vacuum filtration device known in the art, and the method for preparing the thin film using the vacuum filtration device is a commonly used method known in the art.
[0057] In this invention, the methods for measuring conductivity, electromagnetic shielding performance, and infrared performance are commonly known in the art.
[0058] In this embodiment, the methods of coating by scraping, screen printing, and direct ink writing are all commonly known methods in the art.
[0059] Figure 4 Modified Ti3C2T prepared using a vacuum filtration device X Scanning electron microscope (SEM) image of the cross-section of the thin film. The cross-sectional image shows that the nanosheets are tightly packed, forming a dense thin film, indicating the modified Ti3C2T. X The good formability of oil-based conductive inks.
[0060] Modified Ti3C2T in Example 5 X Physical images of the results of preparing base oil-based conductive inks through various molding methods are shown below. Figure 5 As shown. Figure 5 Examples (a) to (d) show the molding results of vacuum filtration, blade coating, screen printing, and direct ink writing, respectively, with the ink viscosity increasing sequentially for each of the four molding methods. Figure 5 It can be seen that the modified Ti3C2T X Oil-based conductive inks can be adapted to a variety of molding methods.
[0061] Example 6: This embodiment presents the modified Ti3C2T obtained in Example 4. X The molding method and application of base oil-based conductive inks specifically include the following steps: Step 1: Take 5 g / L of modified Ti3C2T X 10 mL of basic oil-based conductive ink was added to a vacuum filtration device to prepare a thin film.
[0062] Step 2: Measure the conductivity, electromagnetic shielding performance, and infrared performance of the thin film obtained in Step 1.
[0063] Table 1 shows the test results of the conductivity, electromagnetic shielding, and infrared stealth properties of the films prepared using the vacuum filtration device in Examples 5 and 6, respectively. As can be seen from Table 1, the smaller the molecular weight of the modifier, the better the performance of Ti3C2T. X The more conductivity is retained, the more suitable it is for use in high conductivity scenarios.
[0064] Table 1. Conductivity, electromagnetic shielding, and infrared stealth properties of the thin films in Examples 5 and 6.
Claims
1. A modified Ti3C2T X A method for preparing a base oil-based conductive ink, characterized in that, The method specifically includes the following steps: Step 1, Preparation of Ti3C2T X Aqueous dispersion A: Ti3C2T was prepared by selective etching to remove the Al layer from Ti3AlC2. X Then for Ti3C2T X Ultrasonic peeling, centrifugal washing, and redispersion of the precipitate after centrifugal washing were performed to obtain Ti3C2T. X Aqueous dispersion A; Step 2, prepare oil phase solution B of the modifier: A positively charged modifier was added to the oil phase and dissolved using ultrasound to obtain an oil phase solution B of the modifier. Step 3, Preparation of modified Ti3C2T X Oil-based conductive ink: The Ti3C2T obtained in step one X The aqueous dispersion A was added to the oil phase solution B of the modifier obtained in step two, and stirred. Surface modification was achieved at the oil-water interface through electrostatic interaction between the two solutions. Simultaneously, a stable Pickering emulsion was formed throughout the system. After standing for 1–6 hours, demulsification, centrifugal washing, and redispersion of the precipitate after centrifugal washing were performed sequentially to obtain modified Ti3C2T. X Oil-based conductive ink.
2. The modified Ti3C2T as described in claim 1 X A method for preparing a base oil-based conductive ink, characterized in that, In step two, the positively charged modifier includes one or more of the following: water-soluble coconut oil methyl monoethanolamide, dodecyltrimethylammonium chloride, alkyl quaternary ammonium salt, and alkylamine. The alkylamines include one or more of octadecylamine and n-butylamine; In step two, the oil phase includes one or more of toluene, chloroform, cyclohexane, and n-hexane.
3. The modified Ti3C2T as described in claim 1 X A method for preparing a base oil-based conductive ink, characterized in that, In step three, the Ti3C2T X Aqueous dispersion A was prepared using Ti3C2T X The mass ratio between the amount of the modifier added and the amount of the positively charged modifier added during the preparation of the oil phase solution B of the modifier is (0.1~49):
1.
4. The modified Ti3C2T as described in claim 1 X A method for preparing a base oil-based conductive ink, characterized in that, In step three, the stirring speed is 50-800 r / min, and the stirring time is 1-60 min.
5. The modified Ti3C2T as described in claim 1 X A method for preparing a base oil-based conductive ink, characterized in that, In step three, the redispersed phase includes one or more of toluene, chloroform, cyclohexane, and n-hexane. In step three, the modified Ti3C2T X The concentration of the base oil-based conductive ink is 1–300 g / L.
6. A modified Ti3C2T X Oil-based conductive ink, characterized in that, The ink uses the modified Ti3C2T as described in any one of claims 1 to 5. X The method for preparing a base oil-based conductive ink is as follows: the conductivity of the film after molding is 200-500 S / cm, the electromagnetic shielding is 35-40 dB, and the infrared emissivity is 17.2%-18.3%.