WO2017190277A1 - Doped anatase titanium dioxide material, preparation method therefor and use thereof - Google Patents

Abstract

Disclosed is a doped anatase titanium dioxide material with the general chemical formula (A_xB_y)Ti_1-3/4x-5/4yO₂, wherein A is selected from at least one of Bi, In, Ga and Al, B is selected from at least one of Nb, W, V and Ta, 0＜x＜0.10, and 0＜y＜0.10. The sintering temperature of the doped anatase titanium dioxide material mentioned above is relatively low.

Description

Doped anatase titanium dioxide material, preparation method thereof and application thereof Technical field:

The invention relates to a doped anatase titanium dioxide material, a preparation method thereof and an application thereof.

Background technique:

Studies of high-energy memory devices (such as dynamic random access memories) and super (ordinary) capacitors have shown that the dielectric materials that make up them should have both high dielectric constant, low dielectric loss, and a wide temperature range.

At present, bimetallic ion co-doped titanium dioxide is attracting widespread attention due to its unique dielectric properties. For example, indium and lanthanum co-doped titania ceramics have a dielectric constant of more than 10 ⁴ and a dielectric loss of less than 0.05. At the same time, excellent dielectric properties can be maintained over a wide temperature range (from -180 ° C to 200 ° C). Other trivalent ions and cerium co-doped titanium dioxide ceramic materials also exhibit the same dielectric properties of indium and lanthanum co-doped titanium dioxide ceramics. In addition, indium and lanthanum co-doped titanium dioxide films also have high dielectric constant and low dielectric loss over a wide frequency range. Divalent europium ions and pentavalent europium ions are also co-doped into the titanium dioxide ceramic matrix, and their dielectric properties have also received extensive attention.

However, the sintering temperature of the commonly used doped titanium dioxide dielectric material is generally around 1400 ° C, and the sintering temperature is high.

Summary of the invention:

Based on this, it is necessary to provide a doped anatase titanium dioxide material having a lower sintering temperature, a preparation method thereof, a ceramic made of the doped anatase titanium dioxide material, and a doped anatase titanium dioxide material in a ceramic capacitor. Applications.

One doping anatase titanium dioxide material, through the chemical formula of the doped anatase titanium dioxide material is _{(A x B y) Ti 1-3} / 4x-5 / 4y O 2, wherein, A is selected from Bi, At least one of In, Ga, and Al, and B is at least one selected from the group consisting of Nb, W, V, and Ta, and 0<x<0.10, 0<y<0.10.

The preparation method of the doped anatase titanium dioxide material comprises the following steps:

Mixing a titanium source containing tetravalent titanium with a reaction solvent to form a premixed liquid, wherein the concentration of Ti ⁴⁺ in the premixed solution is 0.0005 mol/L to Ti ^{4+ and} the dissolution is saturated;

The A source containing trivalent A and the B source containing pentavalent B are added to the premix and stirred until the source A and the source B are completely dissolved to form a reaction solution in which A ³⁺ and Ti ^{4+ are present.} The molar ratio is n, the molar ratio of B ⁵⁺ to Ti ⁴⁺ is m, wherein 0 < n ≤ 2, 0 < m ≤ 2; the reaction solution is fully reacted at 50 ° C to 250 ° C to obtain the blend Miscellaneous anatase titanium dioxide material.

The above doped anatase titanium dioxide material is chemically modified with anatase titanium dioxide by co-doping + trivalent and +5 valent metal ions, and the modified doped anatase titanium dioxide material has a giant dielectric property and can be directly used for A high dielectric single-layer or multi-layer ceramic capacitor is prepared, and the doped anatase titanium dioxide material is used as a raw material to directly sinter the corresponding ceramic, and the calcination temperature only needs about 1000 ° C, and the sintering temperature is low.

DRAWINGS

1 is an XRD spectrum of the doped anatase titanium dioxide material prepared in Examples 1 to 3;

2 is a Raman spectrum of the doped anatase titanium dioxide material prepared in Examples 1 to 3 at room temperature;

3 is a transmission electron micrograph of the doped anatase titanium dioxide material prepared in Example 1;

4 is an XPS diagram of the doped anatase titanium dioxide material prepared in Example 1;

5 is a room temperature dielectric spectrum diagram of a ceramic made of the doped anatase titanium dioxide material prepared in Example 1.

detailed description

The following mainly relates to the doped anatase titanium dioxide material with reference to the accompanying drawings and specific examples, and the preparation thereof The method, the ceramic made of the doped anatase titanium dioxide material and the doped anatase titanium dioxide material are further described in detail in the ceramic capacitor.

The chemical formula of the doped anatase titanium dioxide material of one embodiment is (A _x B _y )Ti _1-3/4x-5/4y O ₂ , wherein A is at least selected from the group consisting of Bi, In, Ga, and Al. In one case, B is at least one selected from the group consisting of Nb, W, V, and Ta, and 0<x<0.10, 0<y<0.10.

Preferably, the doped anatase titanium dioxide material has a dimension in the one-dimensional direction of less than 100 nm.

Preferably, the doped anatase titanium dioxide material contains Ti ³⁺ ions induced by B ⁵⁺ ion doping.

Preferably, the ceramic prepared from the doped anatase titanium dioxide material has a dielectric loss of less than 0.15.

Preferably, the ceramic prepared from the doped anatase titanium dioxide material has a dielectric constant in the range of 20 Hz to 10 ⁵ Hz of 8,000 to 150,000.

The above doped anatase titanium dioxide material is chemically modified with anatase titanium dioxide by co-doping + trivalent and +5 valent metal ions, and the modified doped anatase titanium dioxide material has a giant dielectric property and can be directly used for A high dielectric single-layer or multi-layer ceramic capacitor is prepared, and the doped anatase titanium dioxide material is used as a raw material to directly sinter the corresponding ceramic, the calcination temperature only needs about 1000 ° C, and the sintering temperature is low; the size of the doped anatase titanium dioxide material Smaller, as a raw material of ceramic capacitors, it can realize the miniaturization of electronic devices and the integration of its production process, which can reduce the calcination temperature in the molding process, reduce the thickness of each dielectric film, and increase the energy density of ceramic devices. This small nanomaterial can promote the miniaturization of multilayer ceramic capacitors with high capacitance and excellent temperature stability.

The preparation method of the above doped anatase titanium dioxide material comprises the following steps:

Step S110, mixing a titanium source containing tetravalent titanium with a reaction solvent to form a premixed solution, wherein the concentration of Ti ⁴⁺ in the premixed solution is 0.0005 mol/L to a concentration of Ti ⁴⁺ saturated.

Saturating the concentration of Ti ⁴⁺ means that the titanium source reaches saturation solubility in the reaction solvent.

Preferably, the titanium source is selected from the group consisting of Ti(NO ₃ ) ₄ , a hydrate of Ti(NO ₃ ) _{4 ,} a hydrate of TiCl ₄ , TiCl _{4 ,} a hydrate of Ti(SO ₄ ) ₂ , Ti(SO ₄ ) ₂ , Hydrate of TiOSO ₄ , TiOSO ₄ , hydrate of C ₈ H ₂₀ O ₄ Ti, C ₈ H ₂₀ O ₄ Ti, hydrate of C ₁₂ H ₂₈ O ₄ Ti, C ₁₂ H ₂₈ O ₄ Ti, C ₁₆ H At least one of a hydrate of ₃₆ O ₄ Ti and C ₁₆ H ₃₆ O ₄ Ti.

Preferably, the reaction solvent is at least one selected from the group consisting of water, ethanol, methanol, isopropanol, acetone, and oleic acid.

Preferably, the volume of the reaction solvent is greater than 5 ml.

In step S120, the A source containing trivalent A and the B source containing pentavalent B are added to the premixed solution and stirred until the source A and the source B are completely dissolved to form a reaction solution.

Wherein, in the reaction solution, the molar ratio of A ³⁺ to Ti ⁴⁺ is n, and the molar ratio of B ⁵⁺ to Ti ⁴⁺ is m, wherein 0 < n ≤ 2, 0 < m ≤ 2. In this step, the amount of the A source containing trivalent A and the B source containing pentavalent B is determined according to the preset concentration of A ³⁺ and B ⁵⁺ in the reaction solution.

Preferably, the source of A is selected from the group consisting of hydrates of A(NO ₃ ) ₃ , A(NO ₃ ) ₃ , hydrates of ACl ₃ , ACl ₃ , hydration of A ₂ (SO ₄ ) ₃ , A ₂ (SO ₄ ) ₃ At least one of a hydrate of A(C ₂ H ₃ O ₂ ) ₃ and A(C ₂ H ₃ O ₂ ) ₃ .

Preferably, the B source is selected from the group consisting of hydrates of B(NO ₃ ) ₅ , B(NO ₃ ) ₅ , hydrates of B ₂ (SO ₄ ) ₅ , B ₂ (SO ₄ ) ₅ , hydrate of BCl ₅ and BCl ₅ . At least one of the substances.

Preferably, the stirring is carried out at normal temperature.

Preferably, the stirring time is from 0 hours to 10 hours, preferably 1.5 hours.

Step S130, the reaction solution is sufficiently reacted at 50 ° C to 250 ° C to obtain a doped anatase titanium dioxide material.

Preferably, the reaction time is 4 hours or more.

Preferably, the reaction solution is sufficiently reacted at 50 ° C to 250 ° C to be separated and purified to obtain a doped anatase titanium dioxide material. The separation and purification operation is specifically: separately washing the obtained reaction product with water and ethanol and centrifuging.

Preferably, the reaction solution is contained in a sealed reaction vessel, and the reaction vessel is heated in a heating apparatus at 50 ° C to 250 ° C. Further preferably, the heating device is at least one of an oven, a water bath, and an oil bath. Kind.

Synthesis-doped anatase titanium dioxide material is simple, mild reaction conditions; non-toxic raw materials and reaction by-products, more environmentally friendly; doped anatase titanium dioxide material prepared has a smaller particle size; and by changing the A ³⁺ The concentration of B ⁵⁺ ions in the reaction solvent can be adjusted to the co-doping concentration in the doped anatase titanium dioxide material.

The ceramic of one embodiment is formed by sintering the above-doped anatase titanium dioxide material.

Preferably, the sintering temperature is below 1200 °C. More preferably, the sintering temperature is from 1000 ° C to 1200 ° C.

Preferably, the doped anatase titanium dioxide material is pressed into a green body and the green body is sintered.

Preferably, the sintering is carried out in a high temperature furnace,

Preferably, the sintering time is from 0.5 hours to 60 hours.

The above ceramics have high dielectric properties and a low sintering temperature.

The above doped anatase titanium dioxide material can be applied in the fields of ceramic capacitors, biosensors, dye-sensitized cells, and organic-inorganic hybrid materials.

The doped anatase titanium dioxide material particles directly as a raw material of a single-layer or multi-layer ceramic capacitor can also effectively increase the number of laminations per unit thickness, thereby increasing the storage density of the capacitor device.

The details are described below in conjunction with specific embodiments.

Example 1

The structure of the doped anatase titanium dioxide material of Example 1 is: (A _x B _y )Ti _1-3/4x-5/4y O ₂ , where x=y=0.05, A=In, B=Nb The preparation process is as follows:

(1) 0.68 ml of titanium tetrachloride is added to 120 ml of ethanol solution to form a solution A;

(2) adding 0.092 grams of antimony pentachloride and 1.64 grams of indium acetate to solution A to form a solution B;

(3) Solution B is stirred at room temperature for 1.5 hours;

(4) The stirred solution B is transferred to the reaction vessel and the reaction kettle is sealed;

(5) The reaction kettle was placed in an oven at 200 ° C for 15 hours;

(6) After cooling the reaction vessel, the reaction product was washed with water and ethanol, and after centrifugation, the desired nanomaterial was obtained.

Example 2

The structure of the doped anatase titanium dioxide material of Example 2 is: (A _x B _y )Ti _1-3/4x-5/4y O ₂ , where x=y=0.03, A=In, B=Nb The preparation process is as follows:

(1) 0.68 ml of titanium tetrachloride is added to 120 ml of ethanol solution to form a solution A;

(2) adding 0.053 g of antimony pentachloride and 0.8553 g of indium acetate to solution A to form a solution B;

(3) Solution B is stirred at room temperature for 1.5 hours;

(4) The stirred solution B is transferred to the reaction vessel and the reaction kettle is sealed;

(5) The reaction kettle was placed in an oven at 200 ° C for 15 hours;

(6) After cooling the reaction vessel, the reaction product was washed with water and ethanol, and after centrifugation, the desired nanomaterial was obtained.

Example 3

The structure of the doped anatase titanium dioxide material of Example 3 is: (A _x B _y )Ti _1-3/4x-5/4y O ₂ , where x=y=0.01, A=In, B=Nb The preparation process is as follows:

(1) 0.68 ml of titanium tetrachloride is added to 120 ml of ethanol solution to form a solution A;

(2) adding 0.0388 g of antimony pentachloride and 0.446 g of indium acetate to solution A to form solution B;

(3) Solution B is stirred at room temperature for 1.5 hours;

(4) The stirred solution B is transferred to the reaction vessel and the reaction kettle is sealed;

(5) The reaction kettle was placed in an oven at 200 ° C for 15 hours;

(6) After cooling the reaction vessel, the reaction product was washed with water and ethanol, and after centrifugation, the desired nanomaterial was obtained.

Please refer to FIG. 1. FIG. 1 is an embodiment 1 (5 at.% In ³⁺ and 5 at.% Nb ⁵⁺ ), Example 2 (3 at.% In ³⁺ and 3 at.% Nb ⁵⁺ ), and Example 3 ( XRD patterns of doped anatase titanium dioxide materials prepared by 1 at. % In ^{3 +} and 1 at. % Nb ⁵⁺ ). It can be seen from Fig. 1 that the synthesized indium and cerium ion co-doped TiO 2 nanomaterials have an anatase crystal structure, and also demonstrate that the doped anatase titanium dioxide materials prepared in Examples 1-3 have a single phase characteristic and do not contain other Impurities.

Please refer to FIG. 2. FIG. 2 is Embodiment 1 (5 at.% In ³⁺ and 5 at.% Nb ⁵⁺ ), Example 2 (3 at.% In ³⁺ and 3 at.% Nb ⁵⁺ ), and Example 3 ( Raman spectra of doped anatase titanium dioxide material prepared at 1 at.%In ³⁺ and 1 at.% Nb ⁵⁺ ) at room temperature. It can be seen from Fig. 2 that the synthesized indium and cerium ion co-doped TiO 2 nanomaterials have an anatase crystal structure.

Please refer to FIG. 3. FIG. 3 is a transmission electron micrograph of the doped anatase titanium dioxide material prepared in Example 1. It can be seen from Fig. 3 that the synthesized indium and cerium ion co-doped TiO 2 nanomaterials have a particle size of about 10 nm.

Please refer to FIG. 4. FIG. 4 is an XPS diagram of the doped anatase titanium dioxide material prepared in Example 1. It can be seen from Fig. 4 that the synthesized indium and cerium ion co-doped titanium dioxide nanomaterials contain Ti ³⁺ ions.

The doped anatase titanium dioxide material prepared in Example 1 was pressed into a cylindrical green body having a diameter of 1.1 cm, and the green body was sintered at 1200 ° C for 20 hours to obtain a ceramic. Please refer to FIG. 5. FIG. 5 is a room temperature dielectric spectrum diagram of a ceramic made of the doped anatase titanium dioxide material prepared in Example 1. The room temperature dielectric spectrum indicates that the ceramic prepared using the nanopowder has a high dielectric constant (8000-150000) in the range of 20 Hz to 10 ⁵ Hz and a dielectric loss of less than 0.15.

Please refer to Table 1. Table 1 shows the energy spectrum (EDS) of the doped anatase titanium dioxide materials prepared in Examples 1 to 3. The EDS results were directly tested by scanning electron microscopy.

Table 1

sample	Ti(at.%)	Nb (at.%)	In(at.%)	Nb:Ti	In:Ti
Example 1	32.66	0.33	0.35	1.01:100	1.07:100
Example 2	31.43	1.00	0.89	3.19:100	2.81:100
Example 3	30.25	1.54	1.55	5.09:100	5.11:100

It can be seen from Table 1 that indium and antimony doped ions are indeed present in the doped anatase titanium dioxide material prepared in Examples 1 to 3, and the concentration of the doping ions can be regulated in the sample.

The above-mentioned embodiments are merely illustrative of one or more embodiments of the present invention, and the description thereof is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the protection of the patent of the present invention The scope of protection shall be subject to the appended claims.

Claims (19)

1. A doped anatase titanium dioxide material, characterized in that the doped anatase titanium dioxide material has a chemical formula of (A _x B _y )Ti _1-3/4x-5/4y O ₂ , wherein A At least one selected from the group consisting of Bi, In, Ga, and Al, and B is at least one selected from the group consisting of Nb, W, V, and Ta, and 0<x<0.10, 0<y<0.10.
2. The doped anatase titanium dioxide material according to claim 1, wherein the doped anatase titanium dioxide material has a size in a one-dimensional direction of less than 100 nm.
3. The doped anatase titanium dioxide material according to claim 1, wherein the doped anatase titanium dioxide material contains Ti ³⁺ ions induced by B ⁵⁺ ion doping.
4. The doped anatase titanium dioxide material according to claim 1, wherein the ceramic prepared from the doped anatase titanium dioxide material has a dielectric loss of less than 0.15.
5. The doped anatase titanium dioxide material according to claim 1, wherein the ceramic prepared from the doped anatase titanium dioxide material has a dielectric constant in the range of 20 Hz to 10 ⁵ Hz of 8,000 to 150,000.
6. The method for preparing a doped anatase titanium dioxide material according to any one of claims 1 to 5, comprising the steps of:

   Mixing a titanium source containing tetravalent titanium with a reaction solvent to form a premixed liquid, wherein the concentration of Ti ⁴⁺ in the premixed solution is 0.0005 mol/L until the dissolution of Ti ⁴⁺ reaches saturation;

   The A source containing trivalent A and the B source containing pentavalent B are added to the premix and stirred until the source A and the source B are completely dissolved to form a reaction solution in which A ³⁺ and Ti ^{4+ are present.} The molar ratio is n, the molar ratio of B ⁵⁺ to Ti ⁴⁺ is m, wherein 0 < n ≤ 2, 0 < m ≤ 2; the reaction solution is fully reacted at 50 ° C to 250 ° C to obtain the blend Miscellaneous anatase titanium dioxide material.
7. The method for preparing a doped anatase titanium dioxide material according to claim 6, wherein the titanium source is selected from the group consisting of Ti(NO ₃ ) ₄ , Ti(NO ₃ ) ₄ hydrate, TiCl ₄ , TiCl _{4 .} Hydrate, hydrate of Ti(SO ₄ ) ₂ , Ti(SO ₄ ) ₂ , hydrate of TiOSO ₄ , TiOSO ₄ , hydrate of C ₈ H ₂₀ O ₄ Ti, C ₈ H ₂₀ O ₄ Ti, C At least one of a hydrate of ₁₂ H ₂₈ O ₄ Ti, C ₁₂ H ₂₈ O ₄ Ti, a hydrate of C ₁₆ H ₃₆ O ₄ Ti and C ₁₆ H ₃₆ O ₄ Ti.
8. The method for preparing an anatase titanium dioxide material according to claim 6, characterized in that The reaction solvent is at least one selected from the group consisting of water, ethanol, methanol, isopropanol, acetone, and oleic acid.
9. The method for preparing an anatase titanium dioxide material according to claim 6, wherein the source A is selected from the group consisting of A(NO ₃ ) ₃ , A(NO ₃ ) ₃ hydrate, ACl ₃ , and ACl _{3 .} a hydrate, at least one of a hydrate of A ₂ (SO ₄ ) ₃ , A ₂ (SO ₄ ) _{3 ,} a hydrate of A(C ₂ H ₃ O ₂ ) ₃ and A(C ₂ H ₃ O ₂ ) ₃ One.
10. The method for preparing anatase titanium dioxide doped material according to claim 6, wherein the source of B is selected from _{B (NO 3) 5, B} (NO 3) hydrate _5, B ₂ (SO ₄ ) _5, B ₂ (SO ₄ hydrate) _5, BCl _5, and at least one of BCl _{hydrates. 5.}
11. The method for preparing a doped anatase titanium dioxide material according to claim 6, wherein the reaction solution has a reaction time of 4 hours or more in the step of sufficiently reacting at 50 ° C to 250 ° C.
12. The method for preparing an anatase titanium dioxide material according to claim 6, wherein the reaction solution is sufficiently reacted at 50 ° C to 250 ° C to be separated and purified to obtain the doped anatase titanium dioxide material. The separation and purification operation is specifically: sequentially washing the obtained reaction product with water and ethanol and centrifuging.
13. The method for preparing a doped anatase titanium dioxide material according to claim 6, wherein in the step of fully reacting the reaction solution at 50 ° C to 250 ° C, the reaction solution is placed in a sealed reaction vessel. The reaction vessel is placed in a heating apparatus at 50 ° C to 250 ° C for heating.
14. The method for preparing an anatase titanium dioxide material according to claim 13, wherein the heating device is at least one of an oven, a water bath, and an oil bath.
15. A ceramic characterized in that the ceramic is obtained by sintering the doped anatase titanium dioxide material according to any one of claims 1 to 5.
16. The ceramic according to claim 15, wherein the sintering temperature is lower than 1200 °C.
17. The ceramic according to claim 15, wherein when the doped anatase titanium dioxide material of any one of claims 1 to 4 is sintered, the doped anatase titanium dioxide material is pressed into The green body is then sintered.
18. The ceramic according to claim 15, wherein the sintering time is from 0.5 hours to 60 hours.
19. Use of the doped anatase titanium dioxide material according to any one of claims 1 to 5 in the field of ceramic capacitors, biosensors, dye-sensitized cells, and organic-inorganic hybrid materials.

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