CN113979742A - Magneli phase titanium suboxide ceramic, preparation method thereof and inert electrode - Google Patents

Magneli phase titanium suboxide ceramic, preparation method thereof and inert electrode Download PDF

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CN113979742A
CN113979742A CN202111449739.7A CN202111449739A CN113979742A CN 113979742 A CN113979742 A CN 113979742A CN 202111449739 A CN202111449739 A CN 202111449739A CN 113979742 A CN113979742 A CN 113979742A
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phase titanium
titanium suboxide
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刘会军
杨凌旭
曾潮流
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Songshan Lake Materials Laboratory
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Abstract

The invention discloses a Malgneli-phase titanium suboxide ceramic, a preparation method thereof and an inert electrode. The preparation method is easy to realize, can quickly prepare the Magneli-phase titanium suboxide ceramic with high compactness, high mechanical strength, high conductivity and high electrochemical stability, effectively solves the problems of low density, low conductivity, poor mechanical strength, complex equipment, high cost and the like of the conventional Magneli-phase titanium suboxide ceramic, and has the advantages of quickness, high efficiency, energy conservation, environmental protection, low cost and the like; the inert electrode made of the Magneli-phase titanium suboxide ceramic can be used for landfill leachate treatment or recovery of nickel in chemical nickel plating solution and waste liquid treatment, and effectively improves the wastewater treatment efficiency.

Description

Magneli phase titanium suboxide ceramic, preparation method thereof and inert electrode
Technical Field
The invention relates to the technical field of conductive structure ceramic materials, in particular to a method for preparing Magnesli-phase titanium suboxide ceramic with high compactness, high mechanical strength, high conductivity and high electrochemical stability at low energy consumption and/or low cost, and an inert anode which can be used for recycling nickel in garbage leachate treatment or chemical nickel plating waste liquid and treating the waste liquid.
Background
The Magneli phase titanium suboxide has high conductivity, high chemical (strong acid and strong alkali resistance) and electrochemical stability, and mainly comprises Ti3O5、Ti4O7、Ti5O9And Ti6O11Etc. of Ti4O7The conductivity of (A) is best (the conductivity is 1500S cm)-1727 S.cm higher than that of graphite-1) The widest electrochemical window. Ti4O7The stable potential window of the electrode in aqueous solution reaches 3.0V, and the electrode material is the electrode material with the widest electrochemical window in the prior report. At present, the preparation of magneli-phase titanium suboxide is mainly a thermal reduction process, i.e. using reducing substances, such as H, at high temperatures2，C，NH3Ti, Zr, etc. with TiO2Reaction for preparing TinO2n-1(n is more than or equal to 3 and less than or equal to 10). However, since the sintering temperature of the thermal reduction method usually exceeds 1000 ℃, the holding time is more than 2h, and the microstructure is agglomerated and grown due to the high temperature for a long time, so that the material performance is lower than expected. In addition, the prior method has difficulty in obtaining a single-phase titanium suboxide electrode, which is mostly formed by doping a certain phase as a main phase with a small amount of other phases, such as prepared Ti4O7Often contains a certain proportion of Ti3O5And (or) Ti5O9Therefore, the conductivity, electrochemical window, etc. of the actually obtained powder are difficult to reach the above theoretical values.
The magnelli phase titanium suboxide powder is sintered into a sheet or block electrode at high temperature, and can be widely applied to an anode material for treating organic wastewater by an electrochemical advanced oxidation method. However, the currently prepared titanium suboxide sheet or block electrode is loose and porous, has low density, poor mechanical strength and poor electrical conductivity, and further has short service life, so that the titanium suboxide sheet or block electrode is difficult to meet the requirement of large-scale use of the titanium suboxide electrode.
Disclosure of Invention
In view of the above-mentioned disadvantages, the present invention aims to provide a magneli-phase titanium sub-oxide ceramic, a method for preparing the same, and an inert electrode.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method of Magneli phase titanium suboxide ceramic comprises the following steps:
(1) according to the mass percentage, 97-99.9% of the Malay-phase titanium dioxide powder and the balance of the sintering aid are uniformly mixed to form a mixture, namely the mass percentage of the titanium dioxide can be 97-99.9%, the mass percentage of the sintering aid can be 0.1-3%, the Magnetiai-phase titanium dioxide powder is preferably 97-99%, and the mass percentage of the sintering aid is 1-3% correspondingly. The structural formula of the Magneli-phase titanium suboxide powder is TinO2n-1N is more than or equal to 3 and less than or equal to 10, and the grain diameter of the Magnesli-phase titanium suboxide powder and the grain diameter of the sintering aid are preferably between nanometer and micrometer. The Magneli phase titanium suboxide powder is Ti3O5、Ti4O7、Ti5O9、Ti6O11、Ti7O13、Ti8O15、Ti9O17And Ti10O19One or more selected from the group consisting of; the sintering aid is MnO2、SiO2MgO, CaO, CuO and Al2O3One or more selected from the group consisting of;
(2) putting the mixture into a mold, carrying out pressure sintering on the mixture in vacuum, reducing or inert atmosphere protection, and keeping the temperature for a certain time; and then cooling to obtain the high-density, high-conductivity and high-mechanical-property Magneli-phase titanium suboxide ceramic, and effectively solves the problems of low density, poor mechanical strength, poor conductivity, narrow electrochemical stability window, complex equipment, high cost and the like of the conventional Magneli-phase titanium suboxide electrode. The preferable pressure intensity in the pressure sintering is 10 MPa-60 MPa, the preferable sintering temperature is 900-1300 ℃, and the preferable pressure sintering time is 10-60 min.
The Magneli-phase titanium suboxide ceramic is prepared by adopting the preparation method of the Magneli-phase titanium suboxide ceramic. Not less than 97% compactness, not less than 14GPa hardness, not less than 230GPa Young modulus, Ti4O7Electrical conductivity of not less than 1120S/cm, or Ti3O5Conductivity of not less than 530S/cm, or Ti5O9The conductivity is not lower than 540S/cm, the electrode is at 1M H2SO4The electrochemical window in (a) is not less than 3.5V.
The inert anode is made of the Magnesli-phase titanium suboxide ceramic and is in a thin slice or block shape integrally. The inert anode can be installed in electrical equipment and applied to landfill leachate treatment or recovery of nickel in chemical nickel plating solution and waste liquid treatment.
The invention has the beneficial effects that: the preparation method is easy to realize, can quickly prepare the Magneli-phase titanium suboxide ceramic with high compactness, high mechanical strength, high conductivity and high electrochemical stability, effectively solves the problems of low density, low conductivity, poor mechanical strength, complex equipment, high cost and the like of the conventional Magneli-phase titanium suboxide ceramic, and has the advantages of quickness, high efficiency, energy conservation, environmental protection, low cost and the like; the inert electrode made of the Magneli-phase titanium suboxide ceramic can be used for landfill leachate treatment or recovery of nickel in chemical nickel plating solution and waste liquid treatment, and effectively improves the wastewater treatment efficiency.
The invention is further illustrated below with reference to the figures and examples.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
FIG. 2 is a view of submicron Ti used in example 14O7Raw material powder.
FIG. 3 shows Ti obtained in example 14O7XRD pattern of bulk electrode.
FIG. 4 is Ti in FIG. 24O7Sectional SEM image of the block.
FIG. 5 shows Ti in FIG. 24O7Vickers hardness test results of the blocks.
FIG. 6 shows Ti obtained in example 34O7Electrodes at 1M H2SO4The electrochemical window of (1).
FIG. 7 shows Ti obtained in example 64O7Digital photograph of the block.
FIG. 8 shows Ti obtained in example 93O5XRD pattern of bulk electrode.
FIG. 9 shows Ti in FIG. 83O5Sectional SEM image of bulk electrode.
FIG. 10 shows Ti obtained in example 115O9XRD pattern of bulk electrode.
FIG. 11 shows Ti in FIG. 105O9Sectional SEM image of the block.
FIG. 12 shows Ti in FIG. 105O9Vickers hardness test results of the blocks.
FIG. 13 shows Ti obtained in example 125O9Digital photograph of the block.
FIG. 14 shows nanoscale Ti used in example 145O9Raw material powder.
Detailed Description
Hereinafter, the method for preparing the electrode material of magneli phase titanium suboxide according to the present invention, which has high density, high mechanical strength, high conductivity and high electrochemical stability, will be described in detail with reference to the exemplary embodiments.
FIG. 1 is a schematic flow chart illustrating an exemplary embodiment of a method of making a Magnesli-phase titanium suboxide electrode according to the present invention having high density, high mechanical strength, high electrical conductivity, and high electrochemical stability.
As shown in fig. 1, in an exemplary embodiment of the present invention, a method for preparing a magneli-phase titanium suboxide electrode material with high compactness, high mechanical strength, high conductivity and high electrochemical stability can be achieved by the following steps:
(1) forming a raw material mixture
According to the mass percentage, 97-99.9% of Magneli-phase titanium suboxide powder and the balance of sintering aid are proportioned, first raw material powder and second raw material are directly and uniformly mixed by ball milling and other methods to form a raw material mixture, wherein the first raw material is nano-to micron-scale Magneli-phase titanium suboxide, and the structural formula of the first raw material is TinO2n-1N is more than or equal to 3 and less than or equal to 10; the second raw material is sintering aid, namely MnO with a nanometer to submicron scale2、SiO2MgO, CaO, CuO and Al2O3Selected one or more of the group consisting of.
The content of the Magneli-phase titanium dioxide powder is 97-99.9%, wherein the higher the content of the titanium dioxide is, the higher the conductivity of a sintered block is, and the content of the sintering aid is more than 3%, which can cause the conductivity of the electrode to be reduced; the particle size of the first raw material powder is nano-sized to 10 micrometers, the smaller the particle size is, the more favorable the sintering is to obtain a compact block, and the powder larger than 10 micrometers is difficult to obtain an electrode with high compactness, high mechanical strength, high conductivity and high electrochemical stability; the sintering aid can reduce the sintering temperature and improve the compactness of the electrode, and the smaller the particle size of the sintering aid is, the more beneficial the sintering temperature is to be reduced, so that the high-density and high-strength electrode can be obtained.
(2) Sintered Ti4O7Thin sheet or block electrodes
Putting the mixed powder into a mould, pressurizing and heating the mixed powder in the mould in vacuum or inert atmosphere protection by adopting a sintering method, and keeping the temperature for a certain time; and then cooling to obtain the high-density, high-conductivity and high-mechanical-property Magneli-phase titanium suboxide ceramic electrode. The sintering temperature is lower than 900 ℃, which is not beneficial to sintering and compacting; and above 1300 ℃, the crystal grains grow abnormally, and it is difficult to obtain an electrode material with high mechanical strength. The sintering cannot be compact when the heat preservation time is less than 10min, and the abnormal growth of crystal grains can be caused when the heat preservation time is more than 60min, so that the mechanical strength of the electrode is reduced.
For example, Ti with the real density of 97 percent and above of the theoretical density is prepared4O7Electrical conductivity of not less than 1120S/cm, or Ti3O5Conductivity of not less than 530S/cm, or Ti5O9An electrode having an electrical conductivity of not less than 540S/cm; the corresponding basic technical means are as follows: the particle size of the titanium dioxide powder is 20 nm-10 mu m, the content of the sintering aid is 0.1-3%, the sintering temperature is 900-1300 ℃, the heat preservation time is 10-60 min, and the pressure is 10-60 MPa.
Preparing Ti with the real density of 98.5 percent or more of theoretical density4O7The conductivity is not less than 1260S/cm, Ti3O5The conductivity is not lower than 590S/cm, Ti5O9An electrode having an electrical conductivity of not less than 580S/cm; the corresponding preferable technical means is as follows: the titanium dioxide powder has the particle size of 20 nm-2 mu m, the content of sintering aids is 0.1-1.5%, the sintering temperature is 1080-1230 ℃, the heat preservation time is 20-40 min, and the pressure is 20-60 MPa.
Preparing Ti with true density of 99.9% or more of theoretical density4O7The conductivity is not lower than 1280S/cm, Ti3O5The conductivity is not lower than 605S/cm, Ti5O9An electrode having an electrical conductivity of not less than 600S/cm; the corresponding preferable technical means is as follows: the particle size of the titanium oxide powder is 20 nm-1 μm, the content of the sintering aid is 0.5-1.0%, the sintering temperature is 1100-1200 ℃), the heat preservation time is 25-40 min, and the pressure is 35-60 MPa.
Exemplary embodiments of the present invention will be further described below with reference to specific examples.
Example 1: 9.8 Unit weight (e.g., grams) of Ti having an average particle size of about 350nm was weighed4O7The powder is shown in figure 2 and is ball milled and mixed evenly with 0.08 unit weight of CuO. Placing the mixture in a graphite mold, placing in a sintering furnace, heating to 1200 deg.C at 40MPa and flowing argon atmosphere at a speed of 10 deg.C/min, maintaining the temperature for 0.5h, and cooling to room temperature. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain Ti4O7And an electrode.
To the obtainedThe target product was tested, and the XRD pattern, SEM and vickers hardness test results are shown in fig. 3, 4 and 5, respectively. As can be seen from FIG. 3, the resulting electrode consists of a Magneli phase Ti4O7And (4) forming. As can be seen from FIG. 4, Ti4O7The electrode is composed of 1-2 mu m crystal grains, and is compact in sintering, and through further detection, the density of the obtained product is 100%, and the bulk density is 4.323g/cm3The conductivity was 1315S/cm. Ti by nanoindentation4O7The hardness of the electrode reaches 15.8GPa, and the Young modulus is 253.7 Gpa. As can be seen from FIG. 5, Ti4O7The Vickers hardness of the electrode was 1109.8HV, and the cracks were all transgranular cracks, indicating that the resulting electrode had high mechanical strength.
Example 2: ti having an average particle size of about 1.2 μm was weighed out at 5.0 unit weight (e.g., g)4O7Powder of Al in an amount of 0.07 part by weight2O3Ball milling and mixing are carried out. The mixture was placed in a graphite mold and placed in a sintering furnace. Heating to 1085 deg.C at a speed of 12 deg.C/min under 30MPa and vacuum, maintaining the temperature for 40min, and cooling to room temperature. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain Ti4O7And an electrode.
Detecting the obtained target product, wherein the density of the obtained product is 98.6%, the conductivity is 1265S/cm, and Ti is measured by a nano-indentation method4O7The hardness of the electrode reaches 15.4GPa, and the Young modulus is 249.6 Gpa.
Example 3: ti having an average particle size of about 3.5 μm was weighed out at 5.0 unit weight (e.g., g)4O7And ball milling and mixing the powder and 0.12 unit weight of MgO uniformly. The mixture was placed in a graphite mold and placed in a sintering furnace. Heating to 1050 deg.C at 10 deg.C/min under 20MPa and vacuum, maintaining the temperature for 45min, and cooling to room temperature. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain Ti4O7And an electrode.
Detecting the obtained target product to obtain compact productThe degree is 97.5%, the conductivity is 1120S/cm, and Ti is measured by a nanoindentation method4O7The hardness of the electrode reaches 14.2GPa, and the Young modulus is 241.5 Gpa. For it is at 1M H2SO4The electrochemical window test was performed, and the results are shown in fig. 6. Indicates Ti4O7The oxygen evolution potential of the electrode reaches 3.0V and the hydrogen evolution potential is about-0.5V, so that the electrode is at 1M H2SO4The electrochemical stability window in (1) reaches 3.5V.
Example 4: weighing 20.0 unit weight (e.g., gram) of Ti having an average particle size of about 100nm4O7Powder of Al in an amount of 0.07 part by weight2O3Ball milling and mixing are carried out. The mixture was placed in a graphite mold and placed in a sintering furnace. Heating to 1200 deg.C at a speed of 12 deg.C/min under 40MPa and flowing argon atmosphere, maintaining the temperature for 35min, and cooling to room temperature. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain Ti4O7And an electrode.
And detecting the obtained target product, wherein the density of the obtained product is 100%, the conductivity is 1325S/cm, and the Vickers hardness is 1142.8 HV. Ti by nanoindentation4O7The hardness of the electrode reaches 15.6GPa, and the Young modulus is 257.3 GPa.
Example 5:
60 units by weight (e.g., grams) of Ti having an average particle size of about 600nm is weighed4O7And ball milling and mixing the powder and 0.4 unit weight of MgO uniformly. The mixture was placed in a graphite mold and placed in a sintering furnace. Heating to 1200 deg.C at a speed of 15 deg.C/min under 45MPa and vacuum, maintaining the temperature for 25min, and cooling to room temperature. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain Ti4O7And an electrode.
Detecting the obtained target product, wherein the density of the obtained product is 99.6%, the conductivity is 1286S/cm, and Ti is measured by a nano indentation method4O7The hardness of the electrode reaches 14.1GPa, and the Young modulus is 235.8 GPa.
Example 6: weighing 70 unit weight(e.g., grams) Ti having an average particle size of about 800nm4O7And the powder is ball-milled and mixed evenly with CaO and MgO with the unit weight of 0.6. The mixture was placed in a graphite mold and placed in a sintering furnace. Heating to 1080 ℃ at the speed of 15 ℃/min under the conditions of 55MPa and vacuum, preserving the heat for 35min at the temperature, and then cooling to room temperature along with the furnace. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain Ti4O7Electrodes as shown in fig. 7.
XRD analysis is carried out on the obtained target product, and the result shows that the obtained electrode consists of magneli phase Ti4O7And (4) forming. SEM results show that the electrode is sintered and dense, and further detection shows that the obtained electrode has the density of 98.8%, the conductivity of 1116S/cm and the Vickers hardness of 1021.3 HV. Ti by nanoindentation4O7The hardness of the electrode reaches 14.1GPa, and the Young modulus is 241.6 Gpa.
Example 7: 100 unit weight (e.g., gram) of Ti having an average particle size of about 150nm is weighed4O7(90％)+Ti5O9(10%) powder was mixed with 0.2 unit weight of CuO + SiO2Ball milling and mixing are carried out. The mixture was placed in a graphite mold and placed in a sintering furnace. Heating to 1150 deg.C at a speed of 15 deg.C/min under 20MPa and vacuum, maintaining the temperature for 35min, and cooling to room temperature. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain Ti4O7And Ti5O9The composite electrode of (1).
XRD analysis is carried out on the obtained target product, and the result shows that the obtained electrode consists of magneli phase Ti4O7And Ti5O9And (4) forming. SEM results show that the electrode is composed of 1-2 μm crystal grains, is sintered and compact, and further detection shows that the obtained electrode has the density of 99.7% and the bulk density of 4.307g/cm3The conductivity was 1159S/cm and the Vickers hardness was 1079.8 HV. The hardness of the electrode is 15.3GPa and the Young modulus is 247.5Gpa measured by a nano indentation method.
Example 8: weigh 100 units by weight (e.g., grams) of an average particle size of about2.8 μm of Ti3O5Powder of MnO 2.5 unit weight2Ball milling and mixing are carried out. The mixture was placed in a graphite mold and placed in a sintering furnace. Heating to 1200 deg.C at a speed of 10 deg.C/min under 15MPa and flowing argon, maintaining the temperature for 25min, and cooling to room temperature. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain Ti3O5And an electrode.
The obtained target product is detected, and the density of the obtained product is 97.6 percent, and the bulk density is 4.269g/cm3The conductivity was 530S/cm. Ti by nanoindentation3O5The hardness of the electrode reaches 14.4GPa, and the Young modulus is 228.2 Gpa. The electrochemical test result shows that the electrochemical test result is 1M H2SO4The electrochemical stability window in (1) reaches 3.85V.
Example 9: weighing 120 units (e.g., grams) of Ti having an average particle size of about 700nm3O5And ball-milling and uniformly mixing the powder with 0.8 unit weight of CaO. The mixture was placed in a graphite mold and placed in a sintering furnace. Heating to 1180 ℃ at the speed of 8 ℃/min in 45MPa flowing argon, preserving the heat for 30min at the temperature, and then cooling to the ambient room temperature along with the furnace. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain Ti3O5And an electrode.
The obtained target product was tested, and the XRD spectrum and SEM test results are shown in fig. 8 and 9, respectively. As can be seen from FIG. 8, the resulting electrode was made of λ -Ti3O5Phase composition. As can be seen from FIG. 9, Ti3O5The electrode is composed of 1-2 μm crystal grains, and is sintered densely. Through further detection, the density of the obtained product is 99.9%, and the bulk density is 4.347g/cm3The conductivity was 608S/cm. Ti by nanoindentation3O5The hardness of the electrode reaches 15.5GPa, and the Young modulus is 249.6 Gpa. The electrochemical test result shows that the electrochemical test result is 1M H2SO4The electrochemical stability window in (1) reaches 3.8V.
Example 10: an average particle size of about 1 is weighed out to 60 unit weights (e.g., grams).6 μm of Ti3O5Powder of SiO 0.7 unit weight2Ball milling and mixing are carried out. The mixture was placed in a graphite mold and placed in a sintering furnace. Heating to 1100 deg.C at a speed of 10 deg.C/min under 30MPa and flowing argon, maintaining the temperature for 30min, and cooling to room temperature. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain Ti3O5And an electrode.
The obtained target product was tested, and the obtained product had a density of 98.5% and a bulk density of 4.286g/cm3The conductivity was 592S/cm. Ti by nanoindentation3O5The hardness of the electrode reaches 14.9GPa, and the Young modulus is 237.9 Gpa.
Example 11: weighing T with an average particle size of about 80nm at a weight of 80 units (e.g., grams)5O9And ball milling and mixing the powder and 0.6 unit weight of MgO uniformly. The mixture was placed in a graphite mold and placed in a sintering furnace. Heating to 1140 deg.C at the speed of 10 deg.C/min under 40MPa and flowing argon atmosphere, maintaining the temperature for 0.5h, and cooling to room temperature. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain T5O9And an electrode.
The obtained target product was tested, and the XRD pattern, SEM and vickers hardness test results are shown in fig. 10, 11 and 12, respectively. As can be seen from FIG. 10, the resulting electrode consists of a Magneli phase Ti5O9And (4) forming. As can be seen from FIG. 11, Ti5O9The electrode is composed of 1-2 mu m crystal grains, and is compact in sintering, and through further detection, the density of the obtained product is 99.9%, and the bulk density is 4.285g/cm3The conductivity was 614S/cm. Ti by nanoindentation5O9The hardness of the electrode reaches 15.3GPa, and the Young modulus is 247.9 Gpa. As can be seen in FIG. 12, Ti5O9The Vickers hardness of the electrode was 1116.1HV, and all the cracks in the cross section after breaking were transgranular cracks, indicating that the resulting Ti was obtained5O9The electrode has high mechanical strength.
Example 12: weigh 120 units (e.g., grams)T with an average particle diameter of about 65nm5O9Powder of 1.0 unit weight MnO2Ball milling and mixing are carried out. The mixture was placed in a graphite mold and placed in a sintering furnace. Heating to 1200 deg.C at a speed of 10 deg.C/min under 50MPa and flowing argon atmosphere, maintaining the temperature for 25min, and cooling to room temperature. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain T5O9Electrodes as shown in fig. 13.
XRD analysis is carried out on the obtained target product, and the result shows that the obtained electrode consists of magneli phase Ti5O9And (4) forming. SEM results show that the electrode is sintered and compact, and further detection shows that the obtained electrode has the density of 99.9%, the conductivity of 608S/cm and the Vickers hardness of 1029.3 HV. Ti by nanoindentation4O7The hardness of the electrode reaches 15.7GPa, and the Young modulus is 256.1 Gpa.
Example 13: weighing 85 units by weight (e.g., grams) of T having an average particle size of about 600nm5O9Powder of Al and 1.2 unit weight of Al2O3Ball milling and mixing are carried out. The mixture was placed in a graphite mold and placed in a sintering furnace. Heating to 1210 deg.C at 13 deg.C/min under 45MPa and flowing argon atmosphere, maintaining the temperature for 35min, and cooling to room temperature. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain T5O9And an electrode.
XRD analysis is carried out on the obtained target product, and the result shows that the obtained electrode consists of magneli phase Ti5O9And (4) forming. SEM results show that the electrode is sintered and compact, and further detection shows that the obtained electrode has the density of 98.9%, the conductivity of 587S/cm and the Vickers hardness of 1029.3 HV. Ti by nanoindentation4O7The hardness of the electrode reaches 14.5GPa, and the Young modulus is 245.6 Gpa.
Example 14: weighing a T having an average particle size of about 50nm at a weight of 100 units (e.g., grams)5O9The powder is shown in FIG. 14, and mixed with 2.6 unit weight of Al2O3Ball milling and mixing are carried out. Placing the mixture on graphiteThe mold is placed in a sintering furnace. Heating to 950 deg.C at a speed of 10 deg.C/min under 20MPa and flowing argon atmosphere, maintaining the temperature for 40min, and cooling to room temperature. Taking out the obtained sample, and removing graphite paper adhered to the surface to obtain T5O9And an electrode.
XRD analysis is carried out on the obtained target product, and the result shows that the obtained electrode consists of magneli phase Ti5O9And (4) forming. SEM results show that the electrode is sintered compactly, and further detection shows that the obtained electrode has the compactness of 97.3%, the conductivity of 546S/cm and the Vickers hardness of 1029.3 HV. Ti by nanoindentation4O7The hardness of the electrode reaches 14.2GPa, and the Young modulus is 241.2 Gpa.
Table 1 shows the true density, porosity, hardness, elastic modulus and conductivity of the electrodes obtained by the different processes. It can be seen that for Ti4O7Theoretical density of 4.232g/cm3. The electrode prepared by the method has the density not lower than 97.5%, the hardness not lower than 14GPa, the Young modulus not lower than 235Gpa and the conductivity not lower than 1120S/cm. For Ti3O5Theoretical density of 4.351g/cm3. The electrode prepared by the method has the density not lower than 97.5%, the hardness not lower than 14.4GPa, the Young modulus not lower than 225GPa and the conductivity not lower than 530S/cm. For Ti5O9Theoretical density of 4.289g/cm3. The electrode prepared by the method has the density not lower than 97.3%, the hardness not lower than 14.2GPa, the Young modulus not lower than 240Gpa and the conductivity not lower than 540S/cm.
TABLE 1
Figure BDA0003385504940000121
The above examples are only preferred embodiments of the present invention, and the present invention is not limited to all embodiments, and any technical solution using one of the above examples or equivalent changes made according to the above examples is within the scope of the present invention.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. Other materials and methods of making the same, using the same or similar procedures as described in the above examples of the invention, are within the scope of the invention.

Claims (10)

1. The preparation method of the Magneli-phase titanium suboxide ceramic is characterized by comprising the following steps of:
(1) uniformly mixing the Magneli-phase titanium suboxide powder and a sintering aid to form a mixture, wherein the mass percent of the Magneli-phase titanium suboxide powder is 97-99.9%, the mass percent of the sintering aid is 0.1-3%, and the structural formula of the Magneli-phase titanium suboxide powder is TinO2n-1N is more than or equal to 3 and less than or equal to 10, and the sintering aid is MnO2、SiO2MgO, CaO, CuO and Al2O3One or more selected from the group consisting of;
(2) and (3) carrying out pressure sintering on the mixture in vacuum, reducing or inert atmosphere protection to obtain the Magnesli-phase titanium suboxide ceramic.
2. The preparation method of the Magneli-phase titanium dioxide ceramic according to claim 1, wherein the pressure in the pressure sintering in the step (2) is 10MPa to 60MPa, the sintering temperature is 900 ℃ to 1300 ℃, and the pressure sintering time is 10min to 60 min.
3. The method for preparing the Malgnelii-phase titanium suboxide ceramic according to claim 1 or 2, wherein the Malgnelii-phase titanium suboxide powder is Ti3O5、Ti4O7、Ti5O9、Ti6O11、Ti7O13、Ti8O15、Ti9O17And Ti10O19Selected one or more of the group consisting of.
4. The preparation method of the Magneli-phase titanium dioxide ceramic, according to claim 1, is characterized in that the mass percent of the Magneli-phase titanium dioxide powder is 97-99%, and the mass percent of the sintering aid is 1-3%.
5. The method of claim 2, wherein the mixture is loaded into a mold prior to the pressure sintering of step (2).
6. The method for preparing the Magneli-phase titanium suboxide ceramic according to claim 1, wherein the particle sizes of the Magneli-phase titanium suboxide powder and the sintering aid are between nanometer and micrometer.
7. A magneli-phase titania ceramic produced by the method of any one of claims 1 to 6.
8. Inert anode, characterized in that it is made of a ceramic of magneli-phase titanium suboxide according to any of claims 1 to 6 or 7.
9. An inert anode application method, characterized in that the inert anode in claim 8 is used for landfill leachate treatment or recovery of nickel in chemical nickel plating solution and waste liquid treatment.
10. An electrical device comprising an inert anode as claimed in claim 8.
CN202111449739.7A 2021-11-30 2021-11-30 Magneli phase titanium suboxide ceramic, preparation method thereof and inert electrode Pending CN113979742A (en)

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CN117682651A (en) * 2024-02-01 2024-03-12 北京赛科康仑环保科技有限公司 Titanium dioxide reactive electrochemical active film and preparation method and application thereof

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