WO2017190277A1 - Matériau de dioxyde de titane anatase dopé, procédé pour le préparer et utilisation dudit matériau - Google Patents

Matériau de dioxyde de titane anatase dopé, procédé pour le préparer et utilisation dudit matériau Download PDF

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WO2017190277A1
WO2017190277A1 PCT/CN2016/080924 CN2016080924W WO2017190277A1 WO 2017190277 A1 WO2017190277 A1 WO 2017190277A1 CN 2016080924 W CN2016080924 W CN 2016080924W WO 2017190277 A1 WO2017190277 A1 WO 2017190277A1
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titanium dioxide
anatase titanium
dioxide material
doped
doped anatase
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PCT/CN2016/080924
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English (en)
Chinese (zh)
Inventor
刘芸
付振晓
孙庆波
威瑟斯雷蒙德·L
诺伦拉塞
周超
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广东风华高新科技股份有限公司
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Priority to PCT/CN2016/080924 priority Critical patent/WO2017190277A1/fr
Publication of WO2017190277A1 publication Critical patent/WO2017190277A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics

Definitions

  • the invention relates to a doped anatase titanium dioxide material, a preparation method thereof and an application thereof.
  • bimetallic ion co-doped titanium dioxide is attracting widespread attention due to its unique dielectric properties.
  • 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.
  • 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.
  • 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.
  • the sintering temperature of the commonly used doped titanium dioxide dielectric material is generally around 1400 ° C, and the sintering temperature is high.
  • 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:
  • 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.
  • Example 3 is a transmission electron micrograph of the doped anatase titanium dioxide material prepared in Example 1;
  • Example 4 is an XPS diagram of the doped anatase titanium dioxide material prepared in Example 1;
  • Example 5 is a room temperature dielectric spectrum diagram of a ceramic made of the doped anatase titanium dioxide material prepared in Example 1.
  • 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.
  • 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 doped anatase titanium dioxide material has a dimension in the one-dimensional direction of less than 100 nm.
  • the doped anatase titanium dioxide material contains Ti 3+ ions induced by B 5+ ion doping.
  • the ceramic prepared from the doped anatase titanium dioxide material has a dielectric loss of less than 0.15.
  • 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.
  • 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.
  • the reaction solvent is at least one selected from the group consisting of water, ethanol, methanol, isopropanol, acetone, and oleic acid.
  • the volume of the reaction solvent is greater than 5 ml.
  • 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.
  • 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.
  • 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 .
  • 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.
  • the stirring is carried out at normal temperature.
  • 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.
  • the reaction time is 4 hours or more.
  • 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.
  • 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.
  • 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.
  • the sintering temperature is below 1200 °C. More preferably, the sintering temperature is from 1000 ° C to 1200 ° C.
  • the doped anatase titanium dioxide material is pressed into a green body and the green body is sintered.
  • the sintering is carried out in a high temperature furnace
  • 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 preparation process is as follows:
  • the preparation process is as follows:
  • the preparation process is as follows:
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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Abstract

L'invention concerne un matériau de dioxyde de titane anatase dopé de formule chimique générale (AxBy)Ti1-3/4x-5/4yO2, dans laquelle A est choisi parmi au moins l'un de Bi, In, Ga et Al, B est choisi parmi au moins l'un de Nb, W, V et Ta, 0 ＜ x ＜ 0,10, et 0 ＜ y ＜ 0,10. La température de frittage du matériau de dioxyde de titane anatase dopé est relativement basse.
PCT/CN2016/080924 2016-05-03 2016-05-03 Matériau de dioxyde de titane anatase dopé, procédé pour le préparer et utilisation dudit matériau WO2017190277A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109534393A (zh) * 2018-12-01 2019-03-29 韩城市微晶电子材料有限公司 一种钨掺杂的锐钛矿型纳米二氧化钛粉体的制备方法
WO2019129463A1 (fr) * 2017-12-27 2019-07-04 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh MATÉRIAUX CONDUCTEURS À BASE DE PARTICULES TIO<sb /> DOPÉES NB
CN112678867A (zh) * 2020-12-25 2021-04-20 苏州锦艺新材料科技有限公司 一种金红石型二氧化钛及其制备方法和应用
CN116283272A (zh) * 2023-02-14 2023-06-23 哈尔滨理工大学 一种室温铁电性氧化钛陶瓷及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102471088A (zh) * 2009-07-30 2012-05-23 国立大学法人东京大学 光催化材料及其制备方法
CN103958414A (zh) * 2011-09-16 2014-07-30 澳大利亚国立大学 巨介电常数材料
CN104169080A (zh) * 2011-09-13 2014-11-26 法蒂·多甘 用于高能量密度多层陶瓷电容器的纳米结构化介电材料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102471088A (zh) * 2009-07-30 2012-05-23 国立大学法人东京大学 光催化材料及其制备方法
CN104169080A (zh) * 2011-09-13 2014-11-26 法蒂·多甘 用于高能量密度多层陶瓷电容器的纳米结构化介电材料
CN103958414A (zh) * 2011-09-16 2014-07-30 澳大利亚国立大学 巨介电常数材料

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019129463A1 (fr) * 2017-12-27 2019-07-04 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh MATÉRIAUX CONDUCTEURS À BASE DE PARTICULES TIO<sb /> DOPÉES NB
US11618690B2 (en) 2017-12-27 2023-04-04 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Conductive materials made of Nb-doped TiO2 particles
CN109534393A (zh) * 2018-12-01 2019-03-29 韩城市微晶电子材料有限公司 一种钨掺杂的锐钛矿型纳米二氧化钛粉体的制备方法
CN112678867A (zh) * 2020-12-25 2021-04-20 苏州锦艺新材料科技有限公司 一种金红石型二氧化钛及其制备方法和应用
CN112678867B (zh) * 2020-12-25 2022-01-14 苏州锦艺新材料科技股份有限公司 一种金红石型二氧化钛及其制备方法和应用
CN116283272A (zh) * 2023-02-14 2023-06-23 哈尔滨理工大学 一种室温铁电性氧化钛陶瓷及其制备方法和应用

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