A method for preparing magnéli phase titanium suboxide porous ceramics
High-purity, high-conductivity, and high-mechanical-strength Magnéli phase titanium suboxide porous ceramics were prepared by mixing dispersants, ball milling, drying, crushing, sieving, and sintering. This solved the strength and purity problems of existing materials and achieved the preparation of high-purity ceramic materials through low-temperature sintering.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- WESTERN BAODE TECH CO LTD
- Filing Date
- 2026-03-13
- Publication Date
- 2026-06-05
AI Technical Summary
Existing Magnéli phase titanium suboxide porous ceramic materials have poor mechanical strength, poor electrical conductivity and low purity, making it difficult to meet the strength and purity requirements for large-scale use.
High-purity Magnéli phase titanium suboxide porous ceramics were prepared by mixing a dispersant and a solvent, adding titanium suboxide and titanium dioxide nanoparticles, ball milling, drying, crushing, sieving, pressing into shape, and sintering under a protective atmosphere.
A porous Magnéli phase titanium suboxide ceramic with high mechanical strength, good electrical conductivity, and high purity was prepared. The sintering temperature was reduced by 200℃, and there were no other impurities remaining. The purity exceeded 99%.
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Figure CN122145190A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of conductive structural ceramic materials technology, and in particular to a method for preparing Magnéli phase sub-titanium oxide porous ceramics. Background Technology
[0002] Magnéli phase titanium suboxide (Ti n O 2n-1 These materials possess high electrical conductivity, high corrosion resistance (to strong acids and alkalis), and good electrochemical stability, and mainly include Ti3O5, Ti4O7, Ti6O9, and Ti6O. 11 It is an isotropic material that can be widely used in traditional nickel-zinc batteries and can also be used as an anode material for treating organic wastewater using advanced electrochemical oxidation methods.
[0003] Currently, there are three main methods for preparing porous titanium suboxide ceramics: the first is to react and sinter titanium dioxide powder with metallic titanium or titanium hydride powder; the second is to react and sinter titanium dioxide powder with reducing agents such as carbon; and the third is to use titanium suboxide powder with sintering aids (one or more of MnO2, SiO2, MgO, CaO, CuO, and Al2O3). However, porous titanium suboxide ceramic materials prepared by these methods have poor mechanical strength and electrical conductivity, resulting in a short service life. Moreover, the low purity due to reactant residues and the introduction of sintering aids also affects conductivity, making it difficult to simultaneously meet the strength and purity requirements for large-scale use of titanium suboxide electrodes. Summary of the Invention
[0004] This application provides a method for preparing Magnéli phase sub-titanium oxide porous ceramics, which can solve the problems of poor mechanical strength, poor electrical conductivity and low purity of sub-titanium oxide porous ceramic materials.
[0005] To achieve the above objectives, this application adopts the following technical solution: In a first aspect, this application provides a method for preparing Magnéli phase sub-titanium oxide porous ceramics, the method comprising: After adding the dispersant to the solvent and mixing thoroughly, a dispersion solution is obtained; Titanium suboxide nanopowder and titanium dioxide nanopowder were added to the dispersion solution and stirred evenly to obtain a slurry; The slurry was subjected to ball milling, drying, crushing and sieving in sequence to obtain a mixed powder; The mixed powder is pressed into a shape to obtain a green embryo; The green body was sintered under a protective atmosphere to obtain a Magnéli phase titanium suboxide porous ceramic.
[0006] In one embodiment, the solvent includes anhydrous ethanol, isopropanol, acetone, or methanol.
[0007] In one embodiment, the dispersant is at least one of polyvinylpyrrolidone or polyethylene glycol; The amount of dispersant added is 0.5-1 wt% of the total mass of the titanium suboxide nanopowder, the titanium dioxide nanopowder, and the solvent.
[0008] In one embodiment, the mass fraction of the titanium suboxide nanopowder is 80 wt.% to 98 wt.%, and the particle size of the titanium suboxide nanopowder is 20 nm to 200 nm. The titanium dioxide nanopowder has a mass fraction of 2wt.% to 20wt.% and a particle size of 20nm to 500nm.
[0009] In one embodiment, the slurry is sequentially ball-milled, dried, crushed, and sieved to obtain a mixed powder, comprising: After adding grinding balls to the slurry and performing ball milling, a mixed slurry is obtained; After drying the mixed slurry, it is crushed and then sieved to obtain mixed powder.
[0010] In one embodiment, the grinding ball is made of one of zirconium oxide, aluminum oxide, or agate, and the grinding time is 10 to 30 hours.
[0011] In one embodiment, the drying temperature does not exceed 80°C; the sieve mesh size is 100~200 mesh.
[0012] In one embodiment, the compression molding method is molding or isostatic pressing; the compression molding pressure is 50~200MPa.
[0013] In one embodiment, the sintering temperature is 800~1300℃, and the sintering holding time is 1~5 hours.
[0014] In a second aspect of this application, a Magnéli phase sub-titanium oxide porous ceramic is provided, which is prepared using the preparation method of the Magnéli phase sub-titanium oxide porous ceramic of the first aspect of this application.
[0015] The beneficial effects of the technical solutions provided in this application include at least the following: The method for preparing Magnéli-phase titanium suboxide porous ceramics provided in this application involves adding a dispersant to a solvent and mixing it evenly to obtain a dispersion solution; adding titanium suboxide nanopowder and titanium dioxide nanopowder to the dispersion solution and stirring evenly to obtain a slurry; subjecting the slurry to ball milling, drying, crushing, and sieving processes sequentially to obtain a mixed powder; pressing the mixed powder into a green body to obtain a green body; and sintering the green body under a protective atmosphere to obtain Magnéli-phase titanium suboxide porous ceramics. The method for preparing Magnéli-phase titanium suboxide porous ceramics provided in this application is simple, requiring only titanium suboxide and titanium dioxide powders as reactants. Furthermore, the use of nanopowders as raw materials results in high sintering activity and effectively reduces the sintering temperature (significantly lower than other processes by 200°C). Moreover, the titanium suboxide porous ceramic material obtained after sintering has a purity exceeding 99% and is free of reactant residues introduced by other preparation methods (such as carbon in the reducing agent and impurities like Mg, Al, Si, and Ca in the sintering aid). Attached Figure Description
[0016] Figure 1 A flowchart illustrating a method for preparing Magnéli phase titanium suboxide porous ceramics provided in this application embodiment. Detailed Implementation
[0017] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0018] Hereinafter, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of embodiments of this disclosure, unless otherwise stated, "a plurality of" means two or more.
[0019] In addition, the use of “based on” or “according to” implies openness and inclusivity, because processes, steps, calculations or other actions “based on” or “according to” one or more conditions or values can in practice be based on additional conditions or values beyond those conditions.
[0020] This application relates to the field of conductive structural ceramic materials technology. The application provides a method for preparing Magnéli phase sub-titanium oxide porous ceramics, which can prepare Magnéli phase sub-titanium oxide porous ceramics with different densities and mechanical strengths, high conductivity and high electrochemical stability, as well as an anode material that can be used for sewage treatment.
[0021] This application provides a method for preparing Magnéli phase sub-titanium oxide porous ceramics, such as... Figure 1 As shown, the method includes the following steps: Step 101: Add the dispersant to the solvent and mix well to obtain a dispersion solution.
[0022] Optionally, the solvent includes: anhydrous ethanol, isopropanol, acetone or methanol; Optionally, the dispersant is at least one of polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG); the amount of the dispersant added is 0.5-1 wt% of the total mass of the titanium suboxide nanopowder, the titanium dioxide nanopowder, and the solvent.
[0023] In the preparation process, anhydrous ethanol can be weighed and added to a ball mill jar, then a dispersant can be added, and the mixture can be mechanically stirred and mixed evenly to obtain a dispersion solution.
[0024] Step 102: Add the titanium suboxide nanopowder and titanium dioxide nanopowder to the dispersion solution and stir evenly to obtain a slurry.
[0025] Optionally, the mass fraction of the titanium suboxide nanopowder is 80 wt.% to 98 wt.%, and the particle size of the titanium suboxide nanopowder is 20 nm to 200 nm; the mass fraction of the titanium dioxide nanopowder is 2 wt.% to 20 wt.%, and the particle size of the titanium dioxide nanopowder is 20 nm to 500 nm.
[0026] During the preparation process, titanium suboxide nanoparticles and titanium dioxide nanoparticles can be weighed separately and added to the dispersion solution in small amounts multiple times, while being mechanically stirred and mixed evenly to obtain a slurry.
[0027] Step 103: The slurry is subjected to ball milling, drying, crushing and sieving in sequence to obtain mixed powder.
[0028] Optionally, the process of sequentially ball milling, drying, crushing and sieving the slurry to obtain mixed powder can be as follows: after adding grinding balls to the slurry for ball milling, a mixed slurry is obtained; after drying the mixed slurry, it is crushed and then sieved to obtain mixed powder.
[0029] Optionally, the grinding balls are made of zirconium oxide, alumina, or agate, and the grinding time is 10-30 hours. The drying temperature does not exceed 80°C; the sieve mesh size is 100-200 mesh.
[0030] During the preparation process, grinding balls can be added to the slurry, and then the mixture can be placed on a ball mill and mixed evenly. The mixed slurry can then be dried in an oven, crushed, and sieved to obtain a uniformly mixed powder.
[0031] Step 104: Press the mixed powder into shape to obtain a green embryo.
[0032] Optionally, the mixed powder can be loaded into a mold and pressed into shape to obtain a green body.
[0033] Optionally, the pressing method is compression molding or isostatic pressing; the pressing pressure is 50~200MPa.
[0034] Step 105: Under a protective atmosphere, the green body is sintered to obtain Magnéli phase titanium suboxide porous ceramic.
[0035] During the preparation process, the green blank can be placed in a sintering furnace and sintered in a hydrogen atmosphere. After sintering, cooling yields Magnéli phase titanium suboxide porous ceramic.
[0036] Optionally, the sintering temperature is 800~1300℃, and the sintering holding time is 1~5 hours.
[0037] The method for preparing Magnéli-phase titanium suboxide porous ceramics provided in this application involves adding a dispersant to a solvent and mixing it evenly to obtain a dispersion solution; adding titanium suboxide nanopowder and titanium dioxide nanopowder to the dispersion solution and stirring evenly to obtain a slurry; subjecting the slurry to ball milling, drying, crushing, and sieving processes sequentially to obtain a mixed powder; pressing the mixed powder into a green body to obtain a green body; and sintering the green body under a protective atmosphere to obtain Magnéli-phase titanium suboxide porous ceramics. The method for preparing Magnéli-phase titanium suboxide porous ceramics provided in this application is simple, requiring only titanium suboxide and titanium dioxide powders as reactants. Furthermore, this application uses nanoscale powders as raw materials, resulting in high sintering activity and effectively reducing the sintering temperature (significantly lower than other processes by 200°C). Moreover, the titanium suboxide porous ceramic material obtained after sintering has a purity exceeding 99% and is free of reactant residues introduced by other preparation methods (such as carbon in the reducing agent and impurity elements like Mg, Al, Si, and Ca in the sintering aid).
[0038] The method for preparing Magnéli phase titanium suboxide porous ceramics is based on the above embodiments. This application also provides some specific embodiments. The following embodiments describe the technical solutions of this application in more detail. These embodiments are for illustrative purposes only, as various modifications and variations within the scope of the disclosure of this application will be apparent to those skilled in the art. The reagents and raw materials used in the embodiments are commercially available or synthesized using conventional methods and can be used directly without further processing. The instruments and apparatus used in the embodiments are also commercially available.
[0039] Example 1: Weigh 300g of anhydrous ethanol and add it to a ball mill jar with a volume of 1.5 liters. Then weigh 2.5g of PVP and stir to mix evenly to obtain a dispersion solution. Weigh out 180g of titanium suboxide nanoparticles and 20g of titanium dioxide nanoparticles respectively, and add them in small amounts several times to the well-mixed anhydrous ethanol of PVP. Stir evenly to obtain a slurry. Add 1500g of zirconia grinding balls to the slurry, seal it and place it on a ball mill, mix at 300rpm for 20h to obtain a well mixed slurry; The mixed slurry is placed in a container and dried in an oven at 70°C. It is then crushed and passed through a 200-mesh sieve to obtain a uniformly mixed powder. The mixed powder is loaded into a φ20mm mold and pressed into shape under a pressure of 100MPa to obtain a green body. The green blank is placed in a sintering furnace and sintered at 1100℃ for 2 hours under a hydrogen atmosphere. After sintering, it is cooled to obtain cylindrical Magnéli phase sub-titanium oxide porous ceramic.
[0040] Example 2: Weigh 300g of anhydrous ethanol and add it to a ball mill jar with a volume of 1.5 liters. Then weigh 5g of PEG, stir and mix evenly to obtain a dispersion solution. Weigh out 160g of titanium suboxide nanoparticles and 40g of titanium dioxide nanoparticles respectively, and add them in small amounts several times to the well-mixed anhydrous ethanol of PEG. Stir evenly to obtain a slurry. Add 1500g of alumina grinding balls to the slurry, seal it and place it on a ball mill, mix at 350rpm for 30h to obtain a well mixed slurry; The mixed slurry is placed in a container and dried in an oven at 60°C. It is then crushed and passed through a 100-mesh sieve to obtain a uniformly mixed powder. The mixed powder is loaded into an isostatic pressing mold and pressed under a pressure of 160 MPa to obtain a green body. The green body was placed in a sintering furnace and sintered at 1000℃ for 4 hours under a hydrogen atmosphere. After sintering, it was cooled to obtain tubular Magnéli phase sub-titanium oxide porous ceramic.
[0041] Furthermore, this application also provides a Magnéli phase sub-titanium oxide porous ceramic, which is prepared using the preparation method of the Magnéli phase sub-titanium oxide porous ceramic described in this application.
[0042] For the limitations of Magnéli phase titanium suboxide porous ceramics, please refer to the limitations of the preparation method of Magnéli phase titanium suboxide porous ceramics in this application, which will not be repeated here.
[0043] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0044] The above embodiments merely illustrate several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.
Claims
1. A method for preparing a Magnéli phase sub-titanium porous ceramic, characterized in that, The method includes: After adding the dispersant to the solvent and mixing thoroughly, a dispersion solution is obtained; Titanium suboxide nanopowder and titanium dioxide nanopowder were added to the dispersion solution and stirred evenly to obtain a slurry; The slurry was subjected to ball milling, drying, crushing and sieving in sequence to obtain a mixed powder; The mixed powder is pressed into a shape to obtain a green embryo; The green body was sintered under a protective atmosphere to obtain a Magnéli phase titanium suboxide porous ceramic.
2. The method according to claim 1, characterized in that, The solvents include anhydrous ethanol, isopropanol, acetone, or methanol.
3. The method according to claim 1, characterized in that, The dispersant is at least one of polyvinylpyrrolidone or polyethylene glycol; The amount of dispersant added is 0.5-1 wt% of the total mass of the titanium suboxide nanopowder, the titanium dioxide nanopowder, and the solvent.
4. The method according to claim 1, characterized in that, The titanium suboxide nanopowder has a mass fraction of 80 wt.% to 98 wt.% and a particle size of 20 nm to 200 nm. The titanium dioxide nanopowder has a mass fraction of 2wt.% to 20wt.% and a particle size of 20nm to 500nm.
5. The method according to claim 1, characterized in that, After the slurry is sequentially subjected to ball milling, drying, crushing, and sieving, a mixed powder is obtained, comprising: After adding grinding balls to the slurry and performing ball milling, a mixed slurry is obtained; After drying the mixed slurry, it is crushed and then sieved to obtain mixed powder.
6. The method according to claim 5, characterized in that, The grinding balls are made of one of zirconium oxide, aluminum oxide, or agate, and the grinding time is 10 to 30 hours.
7. The method according to claim 1, characterized in that, The drying temperature does not exceed 80℃; the sieve mesh size is 100~200 mesh.
8. The method according to claim 1, characterized in that, The pressing method is either molding or isostatic pressing; the pressing pressure is 50~200MPa.
9. The method according to claim 1, characterized in that, The sintering temperature is 800~1300℃, and the sintering holding time is 1~5 hours.
10. A Magnéli phase sub-titanium oxide porous ceramic, characterized in that, It was prepared using the method for preparing Magnéli phase sub-titanium porous ceramics according to any one of claims 1-9.