CN115650235A - Preparation method of flake intercalation densification titanium carbide film - Google Patents
Preparation method of flake intercalation densification titanium carbide film Download PDFInfo
- Publication number
- CN115650235A CN115650235A CN202211435867.0A CN202211435867A CN115650235A CN 115650235 A CN115650235 A CN 115650235A CN 202211435867 A CN202211435867 A CN 202211435867A CN 115650235 A CN115650235 A CN 115650235A
- Authority
- CN
- China
- Prior art keywords
- size
- aqueous solution
- film
- titanium carbide
- intercalation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 230000002687 intercalation Effects 0.000 title claims abstract description 23
- 238000009830 intercalation Methods 0.000 title claims abstract description 23
- 238000000280 densification Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 144
- 239000002135 nanosheet Substances 0.000 claims abstract description 92
- 239000007864 aqueous solution Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000002064 nanoplatelet Substances 0.000 claims description 10
- 230000010355 oscillation Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000007888 film coating Substances 0.000 claims description 5
- 238000009501 film coating Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000002055 nanoplate Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000010410 layer Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 235000011837 pasties Nutrition 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000010884 ion-beam technique Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Images
Abstract
The invention relates to a preparation method of a flake intercalation densification titanium carbide film, which comprises the following steps of firstly, preparing large-size titanium carbide (Ti) 3 C 2 T x ) And small size Ti 3 C 2 T x Blending aqueous nanosheet solution to obtain small-size Ti 3 C 2 T x The nano-sheets are uniformly dispersed in large-size Ti 3 C 2 T x And (3) coating the mixed aqueous solution to form a small intercalated and densified titanium carbide (IDM) film. The method mainly comprises passing small-sized Ti 3 C 2 T x Nanosheet filled large-size Ti 3 C 2 T x Pores between nanosheet layers to achieve Ti 3 C 2 T x Densification of the film to promote Ti 3 C 2 T x Tensile strength, young's modulus, toughness and electrical conductivity of the film. The compactness of the IDM film is 86.7-92.2Percent, maximum tensile strength of 409MPa, corresponding Young's modulus of 13.7GPa and toughness of 4.12MJ/m 3 The conductivity was 10865S/cm.
Description
Technical Field
The invention relates to a preparation method of a flake intercalation densification titanium carbide film, belonging to the field of nano composite material preparation.
Background
Titanium carbide (Ti) 3 C 2 T x ) The nanosheet has excellent mechanical (Sci.adv.2018, 4, eaat 0491.) and electrical (appl.Phys.Lett.2016, 108, 033102.) performances, and has a wide application prospect (nat.Rev.Mater.2017, 2,16098.) in the fields of flexible electronic devices, aerospace and the like, so that Ti is required to be added 3 C 2 T x Macroscopic high-performance Ti assembled by nanosheets 3 C 2 T x A nanocomposite material.
Usually, large size Ti 3 C 2 T x The nano sheets are helpful for improving macroscopic Ti 3 C 2 T x Mechanical and electrical properties of the film. For example, razal et al (adv. Mater.2020,32,2001093.) assemble large size Ti by knife coating 3 C 2 T x Nanosheet (average transverse dimension of 10 mu m) and high-strength and high-conductivity Ti prepared 3 C 2 T x A film; however, due to the pores between the large-size nanosheets, the tensile strength and conductivity of the film are significantly reduced as the thickness of the film is increased from 0.94 μm to 2.4 μm. To this end, it is necessary to develop densification strategies to enhance large-size Ti 3 C 2 T x And (3) the performance of the film assembled by the nanosheets. More recently, cheng Qunfeng et al (sciences 2021,374, 96.) have been produced by coating Ti with a coating of Ti 3 C 2 T x Sodium carboxymethylcellulose and sodium tetraborate cross-linking agent are introduced between nanosheet layers, so that pores are effectively eliminated, and Ti is greatly improved 3 C 2 T x The mechanical property of the composite film; however, ti is hindered by the insulating crosslinking agent 3 C 2 T x Electron transfer between nanosheet layers, and thus, the resulting Ti 3 C 2 T x The electrical properties of the composite film are greatly reduced, limiting its practical application.
Therefore, there is a need to develop new densification strategies while promoting large size Ti 3 C 2 T x The mechanical and electrical properties of the film assembled by the nano-sheets. Up to now, no small-sized Ti has passed 3 C 2 T x The literature and patent reports of the preparation of a densified titanium carbide film by intercalation of a nanosheet.
Disclosure of Invention
The technical solution of the present invention is: the defects of the prior art are overcome, and the preparation method of the flake intercalation densification titanium carbide film is provided, and the prepared film has higher compactness, excellent tensile strength, young modulus, toughness and conductivity.
The invention is realized by the following technical scheme: a process for preparing the compact Ti carbide film with intercalation features that the Ti film with large size is first vortex oscillated at room temp 3 C 2 T x And small size Ti 3 C 2 T x Blending the nanosheets with an aqueous solution to produce small-sized Ti 3 C 2 T x The nano-sheets are uniformly dispersed in large-size Ti 3 C 2 T x Interlayer of the nano-sheet; then adopting a blade coating method to assemble the uniform blended aqueous solution into a small-piece intercalation densification titanium carbide (IDM) film. The method comprises the following concrete steps:
a preparation method of a flake intercalation densification titanium carbide film comprises the following steps:
(1) Stirring and ultrasonic processing titanium carbide (Ti) with a first size under the condition of room temperature 3 C 2 T x ) Nanoplatelets and a second size Ti 3 C 2 T x The nano sheets are respectively prepared into uniform Ti with a first size 3 C 2 T x Aqueous solution and second size Ti 3 C 2 T x An aqueous solution; the average surface area of the first size titanium carbide nanoplates is greater than the second size Ti 3 C 2 T x The average surface area of the nanoplatelets;
(2) Subjecting said first size Ti obtained in step (1) to 3 C 2 T x Aqueous solution and second size Ti 3 C 2 T x Mixing the aqueous solution, and oscillating by vortex to obtain Ti with second size 3 C 2 T x The nano-sheets are uniformly dispersed in Ti with the first size 3 C 2 T x Obtaining a uniform mixed aqueous solution between the nanosheet layers;
(3) And (3) carrying out vacuum bubble removal on the mixed aqueous solution, and then assembling the mixed aqueous solution into a small-piece intercalation densified titanium carbide (IDM) film by adopting a blade coating method.
Wherein the first size titanium carbide (Ti) 3 C 2 T x ) The nano sheet is large-size Ti 3 C 2 T x A nanosheet; second size Ti 3 C 2 T x The nano-sheet is small-sized Ti 3 C 2 T x Nanosheets.
Further, a first size Ti 3 C 2 T x The average surface area of the nano-sheet is 25-900 mu m 2 . E.g. first dimension Ti 3 C 2 T x The nanoplatelets have an average surface area of 25, 50, 100, 150, 160, 169, 200, 250, 300, 350, 400, 450, 500, 550, 600, 700, 800 or 900 μm 2 。
Further, a second size Ti 3 C 2 T x The average surface area of the nano-sheet is 0.01-1 mu m 2 . E.g. second dimension Ti 3 C 2 T x The nanosheets have an average surface area of 0.01, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9 or 1 μm 2 。
Further, in the step (1), large-sized Ti 3 C 2 T x The aqueous solution contains large-size Ti 3 C 2 T x Nanosheets. In the step (1), small-sized Ti 3 C 2 T x The aqueous solution containing small-sized Ti 3 C 2 T x Nanosheets.
Further, in the step (1), large-sized Ti 3 C 2 T x Nanosheets and small-size Ti 3 C 2 T x The ratio of the average surface areas of the nanosheets is greater than 400.
Further, in the step (1), large-sized Ti 3 C 2 T x Aqueous solution and small size Ti 3 C 2 T x The concentration of the aqueous solution is 15-60 mg/mL.
Further, in the step (1), the stirring time is 10-20 min, the ultrasonic time is 0.5-1 min, and the ultrasonic power in the ice-water bath is 50-70W, so that Ti is not damaged 3 C 2 T x In the case of the nanosheet structure, ti is uniformly dispersed 3 C 2 T x Nanosheets.
Further, in the step (2), large-sized Ti in the aqueous solution is mixed 3 C 2 T x Nanosheets and small-size Ti 3 C 2 T x The mass ratio of the nano sheets is 3-20. For example, in the step (2), large-sized Ti in the aqueous solution is mixed 3 C 2 T x Nanosheets and small-size Ti 3 C 2 T x The nanoplatelets have a mass ratio of 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. Small size Ti 3 C 2 T x The content of the nano sheets is too low to effectively fill large-size Ti 3 C 2 T x Interlayer porosity of nanosheets, and small size Ti 3 C 2 T x The high content of the nano-sheets will interfere with the large size of Ti 3 C 2 T x The ordered arrangement structure of the nano sheets and the ordered arrangement structure of the nano sheets are not beneficial to improving the performance of the IDM film, and in order to better optimize the compactness and the performance of the IDM film, the large-size Ti film 3 C 2 T x Nanosheets and small-size Ti 3 C 2 T x The mass ratio of the nano sheets is respectively 95: 5. 90: 10. 85: 15. 80:20, the correspondingly prepared 4 IDM films are respectively marked as IDM-I, IDM-II, IDM-III and IDM-IV.
Further, in the step (2), the speed of vortex oscillation is 1000-2000 rpm, the time is 2-3 min, and not only small-size Ti is obtained 3 C 2 T x The nano-sheets are uniformly dispersed in large-size Ti 3 C 2 T x Between the nanosheet layers and ensuring Ti 3 C 2 T x The nanosheet structure is unbroken.
Further, in the step (3), the step of vacuum bubble removal is realized by placing the mixed aqueous solution in a closed dryer, vacuumizing to a vacuum degree of 2000-4000 Pa, maintaining the vacuum degree for 3-5 min, then releasing air, and repeating the vacuumizing and releasing process for 7-10 times to completely remove bubbles in the mixed aqueous solution.
Further, in the step (3), a blade coating method is adopted, and the specific implementation process comprises the following steps:
(1) Dripping the mixed aqueous solution subjected to vacuum bubble removal on the surface of a substrate of a film coating machine;
(2) Adjusting the distance between the scraper and the substrate to be 0.2-3 mm, and then starting a film coating machine to carry out blade coating, wherein the speed of the scraper is 2-10 cm/s;
(3) And (3) adjusting the temperature of the substrate to 35-45 ℃, heating for 1-2 h, drying the spread mixed aqueous solution by blade coating, and obtaining the IDM film after moisture is removed.
In the step (3), the thickness of the prepared IDM film is 0.5-20 μm. For example, the thickness of the IDM film produced is 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 μm.
The principle of the invention is as follows: by mixing small-sized Ti 3 C 2 T x The nano sheet introduces large-size Ti 3 C 2 T x Between the nano-sheet layers, large-size Ti is effectively filled 3 C 2 T x Porosity between nanosheet layers to achieve Ti 3 C 2 T x Densification of the film and promotion of Ti 3 C 2 T x Mechanical and electrical properties of the film.
With the existing densified Ti 3 C 2 T x Compared with the film technology, the invention has the characteristics and advantages that:
(1) Small size Ti 3 C 2 T x The nanosheet can be large-size Ti through crushing 3 C 2 T x The nano-sheet is directly obtained, no cross-linking agent of other components is additionally used in the preparation process, and the prepared Ti is favorably used 3 C 2 T x The film can keep Ti to the maximum 3 C 2 T x Intrinsic properties of the nanoplatelets;
(2) Small size Ti 3 C 2 T x Nano sheet filled in large size Ti 3 C 2 T x Between the nano-sheet layers, not only the pores are eliminated, but also the nano-sheet layers can be used as electron transmission and stress transmission media, and meanwhile, ti is promoted 3 C 2 T x Mechanics of film andelectrical properties.
Therefore, the IDM film prepared by the invention has higher compactness (86.7-92.2%), high tensile strength (223-409 MPa), high Young modulus (12.2-14.5 GPa) and high toughness (2.57-4.12 MJ/m) 3 ) High conductivity (9998-10865S/cm).
Drawings
FIG. 1 shows A-Large size Ti 3 C 2 T x Ti assembled by nano-sheets 3 C 2 T x Scanning Electron Microscope (SEM) photographs of ion beam cut sections of (LM) film and B-IDM-II film, IDM-II film having a more dense structure than LM film.
FIG. 2 shows the A-tensile stress-strain curves and B-conductivity of LM and IDM-II films, which have higher tensile strength, young's modulus, toughness and conductivity than LM films.
Detailed Description
The present invention will be described in detail below with reference to specific examples. 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.
The parameter testing method of the following embodiment of the invention is as follows:
the method for testing the tensile strength, the toughness and the Young modulus comprises the following steps: (1) Firstly, cutting a film sample into rectangular sample strips with the size of 3 multiplied by 10 mm; (2) Then, adhering the sample strips on a paper frame with a hollow middle part by using epoxy resin, wherein the size of the paper frame is 15 multiplied by 25mm, the size of a central hollow area is 5 multiplied by 10mm, the sample strips are symmetrically fixed on the paper frame across the central position of the hollow area, and the 10mm edges of the sample strips and the 5mm edges of the hollow area are parallel to the 25mm edges of the paper frame; (3) After the epoxy resin is cured, fixing the paper frame on a clamp of a three-dimensional vertical and horizontal UTM4103 universal mechanical testing machine, wherein the span is 5mm; (4) Then, cutting off frames on two sides of a hollowed area of a paper frame by using scissors, starting software of a universal mechanical testing machine, and testing tensile mechanical properties to obtain a stress-strain curve of a sample strip, wherein the tensile rate is 1mm/min, the cross section area of the sample strip is obtained by multiplying the width (3 mm) and the thickness (the thickness of 3-5 different positions of the cross section of the sample strip is represented by a JEOL-7500F scanning electron microscope, and then the average value is obtained), and the slope of the linear range of the tensile stress, the integral area and the initial elastic deformation at the fracture point of the stress-strain curve is respectively the tensile strength, the toughness and the Young modulus of the sample strip; (5) 3-5 sample strips are tested for each film sample, and the tensile strength, toughness and Young modulus of each film sample are respectively the average values of the tensile strength, toughness and Young modulus of the corresponding 3-5 sample strips.
The conductivity test method comprises the following steps: (1) Firstly, cutting a film sample into rectangular sample strips with the size of 2 multiplied by 30 mm; (2) Then fixing the two ends of the sample strip on two electrodes of a Keithley2400 digital source meter by using conductive silver paste; (3) After the conductive silver paste is solidified, opening a Keithley2400 digital source meter, reading the resistance, and then calculating according to the length and the cross section area of the sample strip to obtain the conductivity of the sample strip; (4) Each film sample was tested for 3-5 sample strips, the conductivity of which was the average of the conductivities of the corresponding 3-5 sample strips.
The compactness testing method comprises the following steps: (1) cutting the film sample into square sample strips of 50X 50 mm; (2) Weighing the mass of the sample strip by using a Sadoris BT125D electronic microbalance, representing the thicknesses of 3-5 different positions of the section of the sample strip by using a JEOL-7500F scanning electron microscope, and then calculating the average value to obtain the thickness of the sample strip; (3) The actual density of the sample strip is obtained by dividing the mass by the thickness and the surface area, and then the actual density of the sample strip is divided by the theoretical density of the corresponding film, so that the compactness of the film sample is obtained, wherein the large-size Ti is 3 C 2 T x And small size Ti 3 C 2 T x The theoretical density of the nanosheet is obtained by the following method: first, an X-ray photoelectron spectrometer (ESCALB 220 i-XL) is used for characterizing large-size Ti 3 C 2 T x And small size Ti 3 C 2 T x Elemental composition of nanosheets, and then Ti 3 C 2 T x The nanosheets being regarded as Ti 3 AlC 2 Al in (1) by T x Obtained after substitution, furtherAccording to Ti 3 AlC 2 Theoretical density of (4.24 g/cm) 3 ) And Ti 3 C 2 T x And Ti 3 AlC 2 Relative molecular weight and unit cell volume of (A), can be calculated to obtain large-size Ti 3 C 2 T x And small size Ti 3 C 2 T x Theoretical density of nanoplatelets. Further, large-sized Ti is incorporated 3 C 2 T x And small size Ti 3 C 2 T x The mass ratio of the nano sheets can calculate the theoretical density of each film.
The preparation method of part of raw materials used in the following examples of the invention is as follows:
large size Ti 3 C 2 T x The preparation method of the nanosheet comprises the following steps: (1) Taking 15mL of concentrated hydrochloric acid (the concentration is 12 mol/L) in a polytetrafluoroethylene reagent bottle, and then adding 5mL of deionized water into the polytetrafluoroethylene reagent bottle to obtain a diluted hydrochloric acid solution; (2) Weighing 1.6g of lithium fluoride powder, adding the lithium fluoride powder into the diluted hydrochloric acid solution under continuous stirring, and continuously stirring for 5min to obtain an etching solution; (3) 1.0g of titanium aluminum carbide (Ti) was weighed 3 AlC 2 ) Adding the powder into the etching solution under continuous stirring, sealing a polytetrafluoroethylene reagent bottle, and placing the sealed polytetrafluoroethylene reagent bottle in a water bath kettle at 50 ℃ for stirring and reacting for 30 hours at constant temperature; (4) Uniformly distributing the mixed solution after the reaction is finished into 4 centrifugal tubes with the volume of 50mL, adding 30mL of deionized water into each centrifugal tube, centrifuging for 5min at the speed of 3500rpm, removing the supernatant, and repeating the processes of adding deionized water, centrifuging and removing the supernatant for 6-8 times until the supernatant is dark green and the lower layer is precipitated into pasty slurry; (5) Adding 30mL of deionized water into the pasty slurry precipitate of each centrifuge tube, performing vortex oscillation (2000 rpm) for 3min, centrifuging at 1500rpm for 20min, and collecting supernatant; (6) Further centrifuging the supernatant collected in the step (5) for 20min at the speed of 4000rpm, collecting the centrifuged precipitate, and drying the precipitate in vacuum to obtain the large-size Ti 3 C 2 T x Nanosheet powder, measured as having an average surface area of 169 μm 2 。
Small size Ti 3 C 2 T x The preparation method of the nano sheet comprises the following steps: (1) Taking 15mL of concentrated hydrochloric acid (the concentration is 12 mol/L) in a polytetrafluoroethylene reagent bottle, and then adding 5mL of deionized water into the polytetrafluoroethylene reagent bottle to obtain a diluted hydrochloric acid solution; (2) Weighing 1.6g of lithium fluoride powder, adding the lithium fluoride powder into the diluted hydrochloric acid solution under continuous stirring, and continuously stirring for 5min to obtain an etching solution; (3) 1.0g of titanium aluminum carbide (Ti) was weighed 3 AlC 2 ) Adding the powder into the etching solution under continuous stirring, sealing a polytetrafluoroethylene reagent bottle, and placing the sealed polytetrafluoroethylene reagent bottle in a water bath kettle at 50 ℃ for stirring and reacting for 30 hours at constant temperature; (4) Uniformly distributing the mixed solution after the reaction is finished in 4 centrifugal tubes of 50mL, adding 30mL of deionized water into each centrifugal tube, centrifuging for 5min at the speed of 3500rpm, removing the supernatant, repeating the processes of adding deionized water, centrifuging and removing the supernatant for 6-8 times until the supernatant is dark green and the lower layer precipitates to be pasty slurry; (5) Adding 30mL of deionized water into the pasty slurry precipitate of each centrifuge tube, performing vortex oscillation (2000 rpm) for 3min, centrifuging at 1500rpm for 20min, and collecting supernatant; (6) Placing the supernatant collected in the step (5) in an ice bath for 2.5 hours by ultrasonic treatment (100W) under the condition of continuously introducing nitrogen, then centrifuging the obtained solution at the speed of 9500rpm for 20min, collecting the centrifuged precipitate, and drying the precipitate in vacuum to obtain the small-size Ti 3 C 2 T x Nanosheet powder, measured to have an average surface area of 0.25 μm 2 。
Example 1
Preparing 30mg/mL of large-size Ti in advance 3 C 2 T x Nanosheets (average surface area 169 μm 2 ) Aqueous solution: 150mg of large-size Ti is weighed 3 C 2 T x Adding the nanosheets into 5mL of deionized water, mechanically stirring for 15min, and then ultrasonically dispersing in an ice-water bath (60W) for 0.75min; using the same procedure to mix small-sized Ti 3 C 2 T x 30mg/mL small-size Ti is prepared from nanosheets 3 C 2 T x Nanosheets (average surface area 0.25 μm) 2 ) An aqueous solution; then large size Ti 3 C 2 T x Aqueous solution and small size Ti 3 C 2 T x The aqueous solution was prepared according to the following ratio 95:5, mixing in a volume ratio; after vortex oscillation (1500 rpm) for 2.5min, placing the obtained uniform mixed aqueous solution in a closed dryer, vacuumizing to 3000Pa vacuum degree, maintaining the vacuum degree for 4min, then deflating, and repeating the vacuumizing and deflating processes for 8 times to completely remove bubbles in the mixed aqueous solution; then slowly dripping the mixed aqueous solution on the surface of a substrate of a coating machine close to a scraper, adjusting the distance between the scraper and the substrate to be 0.5mm, and starting the coating machine to scrape the scraper at the speed of 5 cm/s; and finally, adjusting the temperature of the substrate to 40 ℃, and heating for 1h to obtain a small-piece intercalation densification titanium carbide (IDM-I) film, wherein the thickness of the IDM-I film is 2.7 +/-0.1 mu m.
The density test shows that the compactness of the IDM-I film is 86.7 percent; the mechanical and electrical performance tests of 3-5 sample strips show that the tensile strength is 243 +/-12 MPa, the Young modulus is 12.2 +/-1.6 GPa, and the toughness is 3.16 +/-0.12 MJ/m 3 The conductivity was 10340. + -. 159S/cm.
Example 2
Preparing 30mg/mL of large-size Ti in advance 3 C 2 T x Nanosheet (average surface area 169 μm 2 ) Aqueous solution: 150mg of large-size Ti is weighed 3 C 2 T x Adding the nanosheets into 5mL of deionized water, mechanically stirring for 15min, and then ultrasonically dispersing in an ice-water bath (60W) for 0.75min; using the same procedure to mix small-sized Ti 3 C 2 T x Nanosheet prepared small-size Ti of 30mg/mL 3 C 2 T x Nanosheets (average surface area 0.25 μm) 2 ) An aqueous solution; then large size Ti 3 C 2 T x Aqueous solution and small size Ti 3 C 2 T x The aqueous solution was prepared according to a 90:10 by volume; after vortex oscillation (1500 rpm) for 2.5min, placing the obtained uniform mixed aqueous solution in a closed dryer, vacuumizing to 3000Pa vacuum degree, maintaining the vacuum degree for 4min, then deflating, and repeating the vacuumizing and deflating processes for 8 times to completely remove bubbles in the mixed aqueous solution; then slowly dripping the mixed aqueous solution on the surface of the substrate of the film coating machine close to a scraper, and adjusting the scraper toThe distance between the substrates is 0.5mm, and a coating machine is started to scrape the scraper at the speed of 5 cm/s; and finally, adjusting the temperature of the substrate to 40 ℃, and heating for 1h to obtain a small-piece intercalation densification titanium carbide (IDM-II) film, wherein the thickness of the IDM-II film is 2.8 +/-0.2 mu m.
The density test shows that the compactness of the IDM-II film is 90.9 percent; the mechanical and electrical performance tests of 3-5 sample strips show that the tensile strength is 409 +/-26 MPa, the Young modulus is 13.7 +/-1.0 GPa, and the toughness is 4.12 +/-0.56 MJ/m 3 The conductivity was 10865. + -. 203S/cm.
Example 3
Preparing 30mg/mL of large-size Ti in advance 3 C 2 T x Nanosheets (average surface area 169 μm 2 ) Aqueous solution: weighing 150mg of large-size Ti 3 C 2 T x Adding the nanosheets into 5mL of deionized water, mechanically stirring for 15min, and then ultrasonically dispersing in an ice-water bath (60W) for 0.75min; using the same procedure to mix small-sized Ti 3 C 2 T x 30mg/mL small-size Ti is prepared from nanosheets 3 C 2 T x Nanosheets (average surface area 0.25 μm) 2 ) An aqueous solution; then large size Ti 3 C 2 T x Aqueous solution and small size Ti 3 C 2 T x The aqueous solution was prepared as follows: 15 in a volume ratio; after vortex oscillation (1500 rpm) for 2.5min, placing the obtained uniform mixed aqueous solution in a closed dryer, vacuumizing to 3000Pa vacuum degree, maintaining the vacuum degree for 4min, then deflating, and repeating the vacuumizing and deflating processes for 8 times to completely remove bubbles in the mixed aqueous solution; then slowly dripping the mixed aqueous solution on the surface of a substrate of a coating machine close to a scraper, adjusting the distance between the scraper and the substrate to be 0.5mm, and starting the coating machine to scrape the scraper at the speed of 5 cm/s; and finally, adjusting the temperature of the substrate to 40 ℃, and heating for 1h to obtain a small-piece intercalation densification titanium carbide (IDM-III) film, wherein the thickness of the IDM-III film is 2.7 +/-0.2 mu m.
The density test shows that the compactness of the IDM-III film is 91.5 percent; the mechanical and electrical properties of 3-5 sample strips are tested, and the results show that the tensile strength is328 +/-21 MPa, young's modulus of 14.0 +/-1.3 GPa, toughness of 3.42 +/-0.38 MJ/m 3 The conductivity is 10422 +/-185S/cm.
Example 4
Preparing 30mg/mL of large-size Ti in advance 3 C 2 T x Nanosheet (average surface area 169 μm 2 ) Aqueous solution: 150mg of large-size Ti is weighed 3 C 2 T x Adding the nanosheets into 5mL of deionized water, mechanically stirring for 15min, and then ultrasonically dispersing in an ice-water bath (60W) for 0.75min; using the same procedure to mix small-sized Ti 3 C 2 T x 30mg/mL small-size Ti is prepared from nanosheets 3 C 2 T x Nanosheets (average surface area 0.25 μm) 2 ) An aqueous solution; then large size Ti 3 C 2 T x Aqueous solution and small size Ti 3 C 2 T x The aqueous solution was prepared according to 80:20 by volume; after vortex oscillation (1500 rpm) for 2.5min, placing the obtained uniform mixed aqueous solution in a closed dryer, vacuumizing to 3000Pa vacuum degree, maintaining the vacuum degree for 4min, then deflating, and repeating the vacuumizing and deflating processes for 8 times to completely remove bubbles in the mixed aqueous solution; then slowly dripping the mixed aqueous solution on the surface of a substrate of a coating machine close to a scraper, adjusting the distance between the scraper and the substrate to be 0.5mm, and starting the coating machine to scrape the scraper at the speed of 5 cm/s; and finally, regulating the temperature of the substrate to be 40 ℃, and heating for 1h to obtain a small-piece intercalation densification titanium carbide (IDM-IV) film, wherein the thickness of the IDM-IV film is 2.6 +/-0.1 mu m.
The density test shows that the compactness of the IDM-IV film is 92.2 percent; the mechanical and electrical performance tests of 3-5 sample strips show that the tensile strength is 223 +/-19 MPa, the Young modulus is 14.5 +/-1.1 GPa, and the toughness is 2.57 +/-0.30 MJ/m 3 The conductivity is 9998 +/-108S/cm.
Comparative example 1
Compared to example 1, except that small size Ti was not formulated and added 3 C 2 T x Except the aqueous solution of the nano-sheet, the other conditions are the same, the thickness of the prepared titanium carbide film (LM film) is 2.7 +/-0.1 mu m, and the compactness is 83.9 percentThe tensile strength is 185 +/-6 MPa, the Young modulus is 9.5 +/-0.7 GPa, and the toughness is 2.36 +/-0.02 MJ/m 3 The conductivity was 9822. + -. 133S/cm. FIG. 1A-shows a large size Ti3C prepared in comparative example 1 2 T x Ti3C assembled by nano-sheets 2 T x (LM) Scanning Electron Microscope (SEM) photograph of ion beam cut section of the film. FIG. 1B is a Scanning Electron Microscope (SEM) photograph of an ion beam cut cross section of the IDM-II film prepared in example 2, which has a more dense structure than the LM film. FIG. 2 shows the A-tensile stress-strain curves and B-conductivity of LM and IDM-II films, which have higher tensile strength, young's modulus, toughness and conductivity than LM films. It can be seen that, ti is large in size 3 C 2 T x More pores exist among the nano-sheet layers, and Ti obtained by assembling the nano-sheet layers 3 C 2 T x The mechanical and electrical properties of the film are poor; thereby reducing the size of Ti 3 C 2 T x Nanosheet inserted large-size Ti 3 C 2 T x After the nano-sheet layers are arranged, the pores can be effectively eliminated, and Ti is promoted at the same time 3 C 2 T x Mechanical and electrical properties of the film.
In conclusion, the chip intercalation densified titanium carbide film obtained by the invention has higher compactness (90.9%), high tensile strength (409 MPa), high Young modulus (13.7 GPa) and high toughness (4.12 MJ/m) 3 ) And high conductivity (10865S/cm). The densified high-performance titanium carbide film has wide application in the fields of flexible electronic devices, aerospace and the like.
It should be noted that, according to the above embodiments of the present invention, those skilled in the art can fully implement the full scope of the present invention as defined by the independent claims and the dependent claims, and implement the processes and methods as the above embodiments; and the invention has not been described in detail so as not to obscure the present invention.
The above description is only a partial embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention.
Claims (8)
1. A preparation method of a flake intercalation densification titanium carbide film is characterized by comprising the following steps:
(1) Stirring and ultrasonic processing titanium carbide (Ti) with a first size under the condition of room temperature 3 C 2 T x ) Nanoplatelets and a second size Ti 3 C 2 T x The nano sheets are respectively prepared into uniform Ti with a first size 3 C 2 T x Aqueous solution and second size Ti 3 C 2 T x An aqueous solution; the average surface area of the first size titanium carbide nanoplates is greater than the second size Ti 3 C 2 T x The average surface area of the nanoplatelets;
(2) Subjecting the first size Ti obtained in the step (1) to 3 C 2 T x Aqueous solution and second size Ti 3 C 2 T x Mixing the aqueous solution, and oscillating by vortex to obtain Ti with second size 3 C 2 T x The nano-sheets are uniformly dispersed in Ti with the first size 3 C 2 T x Obtaining a uniform mixed aqueous solution between the nanosheet layers;
(3) And (3) carrying out vacuum bubble removal on the mixed aqueous solution obtained in the step (2), and then assembling the mixed aqueous solution into a small-piece intercalation densification titanium carbide (IDM) film by adopting a blade coating method.
2. The method for preparing the flake intercalation densified titanium carbide film according to claim 1, wherein: in the step (1), the first size Ti 3 C 2 T x Nanoplatelets and a second size Ti 3 C 2 T x The ratio of the average surface areas of the nanosheets is greater than 400;
preferably, in the step (1), the first size Ti 3 C 2 T x Aqueous solution and second size Ti 3 C 2 T x The concentration of the aqueous solution is 15-60 mg/mL;
preferably, in the step (1), the stirring time is 10-20 min, the ultrasonic time is 0.5-1 min, the ultrasonic power is 50-70W, and the ultrasound is performed in an ice-water bath.
3. The method for preparing a platelet-intercalated densified titanium carbide film according to claim 1, wherein: in the step (2), ti with the first size in the mixed aqueous solution 3 C 2 T x Nanoplatelets and a second size Ti 3 C 2 T x The mass ratio of the nano sheets is 3-20;
preferably, in the step (2), the speed of the vortex oscillation is 1000-2000 rpm, and the time is 2-3 min.
4. The method for preparing the flake intercalation densified titanium carbide film according to claim 1, wherein: in the step (3), the step of vacuum bubble removal comprises the steps of placing the mixed aqueous solution in a closed dryer, vacuumizing to the vacuum degree of 2000-4000 Pa, keeping the vacuum degree for 3-5 min, then deflating, and repeating the vacuumizing and deflating processes for 7-10 times.
5. The method for preparing the flake intercalation densified titanium carbide film according to claim 1, wherein: in the step (3), the specific implementation process of assembling the IDM film by adopting the blade coating method from the mixed aqueous solution after vacuum bubble removal comprises the following steps:
(1) Dripping the mixed aqueous solution subjected to vacuum bubble removal on the surface of a substrate of a film coating machine;
(2) Adjusting the distance between the scraper and the substrate to be 0.2-3 mm, and then starting a film coating machine to carry out blade coating, wherein the speed of the scraper is 2-10 cm/s;
(3) And (3) adjusting the temperature of the substrate to 35-45 ℃, heating for 1-2 h, drying the spread mixed aqueous solution by blade coating, and obtaining the IDM film after moisture is removed.
6. The method for preparing the flake intercalation densified titanium carbide film according to claim 1, wherein: in the step (3), the thickness of the prepared IDM film is 0.5-20 μm.
7. According to claim1, the preparation method of the flake intercalation densification titanium carbide film is characterized by comprising the following steps: in the step (1), the first size Ti 3 C 2 T x The average surface area of the nano-sheet is 25-900 mu m 2 。
8. The method for preparing the flake intercalation densified titanium carbide film according to claim 1, wherein: in the step (1), the second size Ti 3 C 2 T x The average surface area of the nano-sheet is 0.01-1 mu m 2 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211435867.0A CN115650235A (en) | 2022-11-16 | 2022-11-16 | Preparation method of flake intercalation densification titanium carbide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211435867.0A CN115650235A (en) | 2022-11-16 | 2022-11-16 | Preparation method of flake intercalation densification titanium carbide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115650235A true CN115650235A (en) | 2023-01-31 |
Family
ID=85019373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211435867.0A Pending CN115650235A (en) | 2022-11-16 | 2022-11-16 | Preparation method of flake intercalation densification titanium carbide film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115650235A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252768A (en) * | 2020-01-20 | 2020-06-09 | 北京航空航天大学 | Preparation method and application of titanium carbide MXene functionalized graphene nanocomposite film |
| CN113582591A (en) * | 2021-08-11 | 2021-11-02 | 北京航空航天大学 | Preparation method of densified titanium carbide composite film |
-
2022
- 2022-11-16 CN CN202211435867.0A patent/CN115650235A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252768A (en) * | 2020-01-20 | 2020-06-09 | 北京航空航天大学 | Preparation method and application of titanium carbide MXene functionalized graphene nanocomposite film |
| CN113582591A (en) * | 2021-08-11 | 2021-11-02 | 北京航空航天大学 | Preparation method of densified titanium carbide composite film |
Non-Patent Citations (1)
| Title |
|---|
| XIAOJIE SHEN ET: "All-MXene-Based Integrated Membrane Electrode Constructed using Ti3C2Tx as an Intercalating Agent for High-Performance Desalination", 《ENVIRONMENT SCIENCE & TECHNOLOGY》, vol. 54, no. 7, pages 4554 - 4563 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6956641B2 (en) | Composite electrolyte | |
| EP3623441A1 (en) | Thermal interface material, and preparation and application thereof | |
| CN110128792B (en) | Thermal interface composite material and preparation method and application thereof | |
| KR102184847B1 (en) | Silicon particles for battery electrodes | |
| WO2019112643A1 (en) | Composite comprising silicon carbide and carbon particles | |
| KR20190082818A (en) | Manufacturing method of anode slurry for secondary battery | |
| KR20190082819A (en) | Anode slurry for secondary battery | |
| CN112552681B (en) | Functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film and preparation method thereof | |
| CN111777841B (en) | Lamellar anisotropy-based graphene/epoxy resin composite material and preparation method thereof | |
| CN106450335B (en) | A kind of siliceous graphene composite material and preparation method thereof and the application in flexible lithium battery | |
| WO2007072745A1 (en) | Separator material for solid polymer electrolyte fuel cell and process for producing the same | |
| Gueon et al. | Si nanoparticles-nested inverse opal carbon supports for highly stable lithium-ion battery anodes | |
| CN104844066A (en) | Boron nitride paper and preparation method therefor | |
| Din et al. | Role of filler content and morphology in LLZO/PEO membranes | |
| Conrado et al. | A continuous 3D-graphene network to overcome threshold issues and contact resistance in thermally conductive graphene nanocomposites | |
| CN115850968A (en) | MXene-based high-thermal-conductivity fireproof composite film and preparation method and application thereof | |
| Wu et al. | Dielectric properties and thermal conductivity of polyvinylidene fluoride synergistically enhanced with silica@ multi-walled carbon nanotubes and boron nitride | |
| EP4084060A1 (en) | Boron nitride sintered body, composite body, method for producing said boron nitride sintered body, method for producing said composite body, and heat dissipation member | |
| CN115650235A (en) | Preparation method of flake intercalation densification titanium carbide film | |
| CN110105756A (en) | A kind of high tenacity high thermal conductivity PBONF based coextruded film and preparation method thereof | |
| Weng et al. | Improved thermal conductivities of epoxy resins containing surface functionalized BN nanosheets | |
| CN112250996A (en) | Micro-nano epoxy resin electronic packaging material and preparation method and application thereof | |
| CN114539716B (en) | Epoxy composite dielectric material and preparation method thereof | |
| CN107910554A (en) | A kind of lithium ion battery SiOC composite negative pole materials and preparation method thereof | |
| Fu et al. | Improved dielectric stability of epoxy composites with ultralow boron nitride loading |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |