Vanadium oxide / transition metal oxide composite film and preparation method and application thereof
By preparing vanadium oxide/transition metal oxide composite films through low-temperature steam heat treatment, the problem of uncontrollable morphology caused by high-temperature treatment was solved, complementary responses to visible and infrared light were achieved, and electrochromic performance and stability were improved.
Patent Information
- Application Number
- CN202511311278.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-15
- Publication Date
- 2025-12-16
AI Technical Summary
The morphology of existing vanadium oxide/transition metal oxide composite films is uncontrollable during high-temperature processing, and the response in the infrared region is weak, which limits the efficiency of solar light modulation.
A vanadium oxide precursor solution was coated onto a transition metal oxide thin film using a low-temperature steam heat treatment method to form a vanadium oxide/transition metal oxide composite thin film.
It improves the overall sunlight modulation capability and electrochromic cycle stability of the thin film, enhances the complementary response to visible and infrared light, and improves the electrochromic performance of the smart window.
Smart Images
Figure CN121134833A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of inorganic metal materials, and particularly relates to a vanadium oxide / transition metal oxide composite film and a preparation method and application thereof. BACKGROUND
[0002] Vanadium oxide (such as V3O7, V2O5, etc.) as a high-performance electrochromic material, its high-capacity characteristics are derived from the significant optical transmittance change caused by the valence state transition under voltage driving. However, in the application of smart windows, due to the strong response of the material to the visible light region and the weak response to the infrared light region, the overall sunlight regulation efficiency is limited.
[0003] To solve this problem, introducing a second-phase material with strong infrared response to construct a composite system becomes an effective strategy. However, when vanadium oxide is combined with transition metal oxide, under the strong interface interaction, vanadium species is easy to form vanadium-oxygen oligomers (the characteristic Raman peak is located at 1030 cm - 1) Single-layer dispersion on the surface of the oxide, only under high vanadium concentration or high temperature conditions, it can be converted into crystalline vanadium oxide. The interdiffusion phenomenon of vanadium ions and transition metal ions during high-temperature treatment not only leads to the loss of control of the morphology of vanadium oxide, but also forms a doped phase instead of an independent phase.
[0004] Therefore, it is of great significance to study a preparation method and application of a low-temperature synthesized vanadium oxide / transition metal oxide composite film. SUMMARY
[0005] The present application aims to provide a vanadium oxide / transition metal oxide composite film and a preparation method and application thereof, so as to solve the problem of uncontrolled morphology of vanadium oxide caused by high preparation temperature in the preparation process of the existing composite film.
[0006] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:
[0007] The present application provides a preparation method of a vanadium oxide / transition metal oxide composite film, and the preparation method is as follows:
[0008] The vanadium oxide precursor solution is coated on the transition metal oxide film, and then low-temperature vapor heat treatment is carried out, so as to obtain the vanadium oxide / transition metal oxide composite film.
[0009] Preferably, the vanadium oxide precursor solution comprises a vanadium oxide precursor and a solvent.
[0010] Preferably, the vanadium oxide precursor is one or more of vanadium tripropoxide, vanadium chloride, ammonium vanadate and vanadium oxide.
[0011] The solvent is one or more of oxalic acid, ethanol, isopropanol, n-butanol and water.
[0012] The ratio of the vanadium oxide precursor to the solvent is 0.05-1 mol:6 L.
[0013] Preferably, the coating is dip coating or spin coating.
[0014] Preferably, in the dip coating, the speed of pulling is 30-120 mm / s, the number of pulling is 1-5, the speed of dipping is 30-120 mm / s, and the time of each dipping is independently 2-60 s.
[0015] Preferably, in the spin coating, the speed is 500-2000 rpm, the number of spin coating is 1-6, the amount of vanadium oxide precursor solution used in each spin coating is independently 0.01-0.1 mL, the time of each spin coating is independently 20-80 s, and the interval between each spin coating is independently 10-60 s.
[0016] Preferably, the transition metal oxide film is a vanadium oxide film, a titanium oxide film, a tungsten oxide film, a nickel oxide film or a niobium oxide film.
[0017] Preferably, in the low-temperature steam heat treatment, the temperature is 70-260 ℃, and the time is 0.5-120 h, and the low-temperature steam heat treatment is carried out in a steam heat solution, and the steam heat solution is water, anhydrous ethanol, ammonia water or hydrochloric acid.
[0018] The concentration of the ammonia water is 0.02-4 mol / L, and the concentration of the hydrochloric acid is 0.5-2 mol / L.
[0019] The application also provides a vanadium oxide / transition metal oxide composite film prepared by the preparation method.
[0020] The application also provides an application of the vanadium oxide / transition metal oxide composite film in the field of electrochromism.
[0021] According to the technical solution, compared with the prior art, the application has the following beneficial effects:
[0022] The preparation method coats a solution containing a vanadium oxide precursor on the surface of a transition metal oxide film, and then performs a low-temperature steam heat treatment process to obtain a vanadium oxide / transition metal oxide composite film, the obtained film has outstanding total sunlight modulation capacity and excellent electrochromic cycle stability, and effectively improves the electrochromic performance of a traditional V2O5 film for intelligent windows. BRIEF DESCRIPTION OF DRAWINGS
[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.
[0024] Figure 1 The images shown are SEM images of the composite films obtained in Example 1 and Comparative Example 1, where a is the composite film obtained in Example 1 and b is the film obtained in Comparative Example 1. Detailed Implementation
[0025] This invention provides a method for preparing vanadium oxide / transition metal oxide composite thin films, the method comprising:
[0026] A vanadium oxide precursor solution is coated onto a transition metal oxide film, followed by low-temperature steam heat treatment to obtain a vanadium oxide / transition metal oxide composite film.
[0027] In this invention, the vanadium oxide precursor solution includes a vanadium oxide precursor and a solvent.
[0028] In this invention, the vanadium oxide precursor is preferably one or more of tripropanol vanadium oxide, vanadium chloride, ammonium vanadate, and vanadium oxide;
[0029] The solvent is preferably one or more of oxalic acid, ethanol, isopropanol, n-butanol, and water;
[0030] The preferred ratio of vanadium oxide precursor to solvent is 0.05–1 mol:6 L, more preferably 0.1–0.8 mol:6 L, and even more preferably 0.2–0.5 mol:6 L.
[0031] In this invention, the coating is preferably applied by dip coating or spin coating.
[0032] In this invention, during the immersion and lifting process, the lifting speed is preferably 30-120 mm / s, more preferably 40-100 mm / s, and even more preferably 50-80 mm / s; the number of lifting cycles is preferably 1-5, more preferably 2-4, and even more preferably 3; the immersion speed is preferably 30-120 mm / s, more preferably 50-100 mm / s, and even more preferably 60-80 mm / s; and the immersion time for each cycle is preferably 2-60 s, more preferably 10-50 s, and even more preferably 20-30 s.
[0033] In this invention, during spin coating, the rotation speed is preferably 500–2000 rpm, more preferably 800–1600 rpm, and even more preferably 1000–1200 rpm. The number of spin coatings is preferably 1–6, more preferably 2–5, and even more preferably 3–4. The amount of vanadium oxide precursor solution used in each spin coating is preferably 0.01–0.1 mL, more preferably 0.02–0.08 mL, and even more preferably 0.05–0.06 mL. The spin coating time is preferably 20–80 s, more preferably 30–70 s, and even more preferably 40–60 s. The interval between each spin coating is preferably 10–60 s, more preferably 20–50 s, and even more preferably 30–40 s.
[0034] In this invention, the transition metal oxide thin film is preferably a vanadium oxide thin film, a titanium oxide thin film, a tungsten oxide thin film, a nickel oxide thin film, or a niobium oxide thin film.
[0035] In this invention, the temperature of the low-temperature steam heat treatment is preferably 70-260°C, more preferably 100-200°C, and even more preferably 150-180°C. The treatment time is preferably 0.5-120h, more preferably 24-96h, and even more preferably 48-64h. The low-temperature steam heat treatment is carried out in a steam thermal solution, which is preferably water, anhydrous ethanol, ammonia, or hydrochloric acid.
[0036] The concentration of the ammonia water is preferably 0.02-4 mol / L, more preferably 0.5-3 mol / L, and even more preferably 1-2 mol / L. The concentration of the hydrochloric acid is preferably 0.5-2 mol / L, more preferably 1-1.8 mol / L, and even more preferably 1.2-1.5 mol / L.
[0037] In this invention, the amount of steam heat treatment solution used is preferably 0.1-5 mL / 100 mL of the vessel volume, more preferably 1-4 mL / 100 mL of the vessel volume, and even more preferably 2-3 mL / 100 mL of the vessel volume.
[0038] The present invention also provides a method for preparing vanadium oxide / transition metal oxide composite thin films, resulting in vanadium oxide / transition metal oxide composite thin films.
[0039] The present invention also provides the application of vanadium oxide / transition metal oxide composite thin films in the field of electrochromism.
[0040] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0041] Example 1
[0042] Vanadium tripropanol oxide and isopropanol were mixed at a ratio of 0.1 mol: 6 L to obtain a vanadium oxide precursor solution.
[0043] A vanadium oxide precursor solution was composited onto a titanium oxide film by dip-coating to obtain a preliminary composite film. The relevant parameters for dip-coating were: dipping speed of 60 mm / s, dipping speed of 60 mm / s, number of dips of 1, and dipping time of 5 s.
[0044] The preliminary composite film is subjected to low-temperature steam heat treatment in a steam-heated reactor to obtain the composite film. The relevant process parameters for low-temperature steam heat treatment are: treatment temperature of 180℃, treatment time of 12h, steam heat solution of water, and water volume of 5mL / 100mL reactor volume.
[0045] Example 2
[0046] Ammonium vanadate and water were mixed at a ratio of 0.2 mol: 6 L to obtain a vanadium oxide precursor solution.
[0047] A vanadium oxide precursor solution was composited onto a titanium oxide film by dip-coating to obtain a preliminary composite film. The relevant parameters for dip-coating were: dipping speed of 60 mm / s, dipping speed of 60 mm / s, number of dips of 1, and dipping time of 5 s.
[0048] The preliminary composite film is subjected to low-temperature steam heat treatment in a steam-heated reactor to obtain the composite film. The relevant process parameters for low-temperature steam heat treatment are: treatment temperature of 180℃, treatment time of 12h, steam heat solution of water, and water volume of 5mL / 100mL reactor volume.
[0049] Example 3
[0050] Vanadium chloride and anhydrous ethanol were mixed at a ratio of 0.5 mol: 6 L to obtain a vanadium oxide precursor solution.
[0051] A vanadium oxide precursor solution was composited onto a titanium oxide film by dip-coating to obtain a preliminary composite film. The relevant parameters for dip-coating were: dipping speed of 70 mm / s, dipping speed of 70 mm / s, number of dips of 1, and dipping time of 30 s.
[0052] The preliminary composite film is subjected to low-temperature steam heat treatment in a steam-heated reactor to obtain the composite film. The relevant process parameters for low-temperature steam heat treatment are: treatment temperature of 140℃, treatment time of 48h, steam heat solution of 0.02mol / L ammonia water, and ammonia water volume of 5mL / 100mL reactor volume.
[0053] Comparative Example 1
[0054] Vanadium tripropanol oxide and isopropanol were mixed at a ratio of 0.1 mol: 6 L to obtain a vanadium oxide precursor solution.
[0055] A vanadium oxide precursor solution was composited onto a titanium oxide film by dip-coating to obtain a preliminary composite film. The relevant parameters for dip-coating were: dipping speed of 60 mm / s, dipping speed of 60 mm / s, number of dips of 1, and dipping time of 5 s.
[0056] The preliminary composite film was calcined at 300℃ for 2 hours to obtain the composite film.
[0057] The composite films obtained in Examples 1-3 and Comparative Example 1 were subjected to the following performance tests.
[0058] SEM images of the composite films obtained in Example 1 and Comparative Example 1 are shown below. Figure 1 As shown, a is the composite film obtained in Example 1, and b is the film obtained in Comparative Example 1. Figure 1 It is evident that the sample treated with low-temperature steam heat generated needle-shaped vanadium oxide nanoparticles in situ within the macropores of titanium oxide, while the sample treated with calcination only showed macroporous structures.
[0059] Optical modulation test:
[0060] The composite films obtained in Example 2 and Comparative Example 1 were subjected to electrochromic optical modulation tests (test conditions: ±1.5V, pressure applied for 40s, transmittance difference in the wavelength range of 380~1100nm), and the results are shown in Table 1.
[0061] Table 1. Optical modulation test results of the composite films obtained in Example 2 and Comparative Example 1.
[0062]
[0063] Table 1 uses optical modulation amplitude to characterize the ability of the thin film to regulate solar irradiance. It reflects the degree of regulation after modulation; the higher the value, the stronger the ability to regulate solar irradiance. As shown in Table 1, the composite thin film obtained in Example 2, due to the two-phase composite structure, allows vanadium oxide and titanium oxide to complement each other in visible and infrared light, respectively, greatly enhancing the optical modulation amplitude to 40.3%, corresponding to a solar energy regulation amplitude of 36.7%. In contrast, the composite thin film obtained in Comparative Example 1 only achieved 14.6% and 15.1% respectively.
[0064] Stability test:
[0065] The composite films obtained in Example 3 and Comparative Example 1 were subjected to electrochromic cycle stability tests. The test conditions were: a voltage of ±1.5V was applied at a wavelength of 400nm for 40s, and the results were statistically analyzed after 50 cycles. The test results are shown in Table 2.
[0066] Table 2 shows the cycle stability test results of the composite films obtained in Example 3 and Comparative Example 1.
[0067]
[0068] Table 2 uses the rate of change of optical contrast to characterize cycling stability. It is equal to the ratio of the optical contrast value at the 50th cycle to the optical contrast value at the 1st cycle, reflecting the degree of performance stability after cycling. The higher the value, the better the cycling stability. As can be seen from Table 2, the cycling stability of the composite film obtained in Example 3 is better than that of the composite film obtained in Comparative Example 1.
[0069] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing a vanadium oxide / transition metal oxide composite thin film, characterized in that, The preparation method is as follows: A vanadium oxide precursor solution is coated onto a transition metal oxide film, followed by low-temperature steam heat treatment to obtain a vanadium oxide / transition metal oxide composite film.
2. The method for preparing a vanadium oxide / transition metal oxide composite thin film according to claim 1, characterized in that, The vanadium oxide precursor solution includes a vanadium oxide precursor and a solvent.
3. The method for preparing a vanadium oxide / transition metal oxide composite thin film according to claim 2, characterized in that, The vanadium oxide precursor is one or more of tripropanol vanadium oxide, vanadium chloride, ammonium vanadate, and vanadium oxide. The solvent is one or more of oxalic acid, ethanol, isopropanol, n-butanol, and water; The ratio of vanadium oxide precursor to solvent is 0.05–1 mol: 6 L.
4. The method for preparing a vanadium oxide / transition metal oxide composite thin film according to claim 1, characterized in that, The coating is applied by dip coating or spin coating.
5. The method for preparing a vanadium oxide / transition metal oxide composite thin film according to claim 4, characterized in that, In the immersion and lifting process, the lifting speed is 30-120 mm / s, the number of lifting times is 1-5, the immersion speed is 30-120 mm / s, and the immersion time for each time is 2-60 s.
6. The method for preparing a vanadium oxide / transition metal oxide composite thin film according to claim 4, characterized in that, In the spin coating process, the rotation speed is 500-2000 rpm, the number of spin coatings is 1-6, the amount of vanadium oxide precursor solution used in each spin coating is 0.01-0.1 mL, the spin coating time is 20-80 s, and the interval between each spin coating is 10-60 s.
7. The method for preparing a vanadium oxide / transition metal oxide composite thin film according to claim 1, characterized in that, The transition metal oxide thin film is a vanadium oxide thin film, a titanium oxide thin film, a tungsten oxide thin film, a nickel oxide thin film, or a niobium oxide thin film.
8. The method for preparing a vanadium oxide / transition metal oxide composite thin film according to claim 1, characterized in that, In the aforementioned low-temperature steam heat treatment, the treatment temperature is 70–260°C, the treatment time is 0.5–120 h, and the low-temperature steam heat treatment is carried out in a steam thermal solution, which is water, anhydrous ethanol, ammonia, or hydrochloric acid. The concentration of the ammonia water is 0.02–4 mol / L, and the concentration of the hydrochloric acid is 0.5–2 mol / L.
9. The vanadium oxide / transition metal oxide composite thin film prepared by the method for preparing a vanadium oxide / transition metal oxide composite thin film according to any one of claims 1 to 8.
10. The application of the vanadium oxide / transition metal oxide composite thin film of claim 9 in the field of electrochromism.