CN106278281B - A kind of boronation titanium-based composite cathode material and preparation method thereof - Google Patents

A kind of boronation titanium-based composite cathode material and preparation method thereof Download PDF

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CN106278281B
CN106278281B CN201610674207.6A CN201610674207A CN106278281B CN 106278281 B CN106278281 B CN 106278281B CN 201610674207 A CN201610674207 A CN 201610674207A CN 106278281 B CN106278281 B CN 106278281B
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张翠萍
茹红强
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Northeastern University China
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Abstract

A kind of boronation titanium-based composite cathode material and preparation method thereof, belongs to technical field of ceramic material.Boronation titanium-based composite cathode material, by TiB2Powder, metal Mo powder and Si are combined；Its phase composition is TiB2、MoSi2、Si、Mo2B、Ti3B4And TiB55.Preparation method, comprising: (1) prepare TiB2- Mo mixed powder；(2) by TiB2- Mo mixed powder is uniformly mixed with binder, preparation molding material；(3) molding material is pressed and molded, obtains TiB2- Mo biscuit；(4) by TiB2- Mo biscuit carries out infiltration in vacuum as infiltrant, obtains boronation titanium-based composite cathode material as skeleton, Si.Raw material by being first pressed and molded by this method, then the high boronation titanium-based composite cathode material of consistency is made, can be used in aluminium cell without pressure vacuum siliconising；This method step is simple, sintering temperature is low, and sintering process is undeformed, preparation cost is lower, and can produce various shape complexity, large-sized product.

Description

Titanium boride-based composite cathode material and preparation method thereof
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a titanium boride-based composite cathode material and a preparation method thereof.
Background
Titanium boride (TiB)2) The ceramic has the advantages of high melting point, high hardness, wear resistance, corrosion resistance, oxidation resistance, good electrical conductivity and thermal conductivity and the like, and is widely applied to industries such as metallurgy, military, machinery, chemical engineering, electronics and the like. Especially due to TiB2Has the characteristics of excellent conductivity and no reaction with aluminum (Al) liquid and cryolite, and can be used as a cathode material of an aluminum electrolysis cell. By using TiB2The cathode can increase the yield of aluminum, improve the current efficiency (1000-2000 kWh electricity can be saved per ton of aluminum produced), reduce the pollution caused by manufacturing carbon electrodes and solve the problem of sealing the electrolytic cellIs not required.
The prior titanium boride product is mainly prepared by a pressureless sintering method and a hot-pressing sintering method, the pressureless sintering step comprises material mixing, molding and sintering, the sintering temperature is about 2000 ℃, the compactness of the titanium boride product prepared by pressureless sintering is low, so that electrolyte and aluminum liquid are easy to corrode materials during electrolysis, the service life of the materials is reduced, and the technical performance index of the titanium boride product cannot meet the requirements of the electrolytic aluminum industry; in addition, the hot-pressing sintering method is a main method for manufacturing the high-density titanium boride product, and comprises the steps of mixing materials and hot-pressing sintering; the sintering temperature is generally over 1800 ℃, the cost of the hot pressing method is higher, and products with large size and complex shape are difficult to process by adopting the hot pressing method; the problems lead the popularization and the application of the titanium boride ceramic material in the electrolytic aluminum industry to be greatly limited.
Disclosure of Invention
The invention aims to provide a titanium boride-based composite cathode material and a preparation method thereof, aiming at the problems in the existing preparation method of the titanium boride-based composite cathode material for an aluminum electrolytic cell. The method prepares the titanium boride-based composite cathode material with high density by compression molding the raw materials and then carrying out pressureless vacuum siliconizing, and can be used in an aluminum electrolytic cell; the method has the advantages of simple steps, low sintering temperature, no deformation in the sintering process, low preparation cost and capability of producing various products with complex shapes and large sizes.
The titanium boride-based composite cathode material consists of TiB2The powder, the metal Mo powder and Si are compounded; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder is (1:2) - (1: 19); the mass M of Si is:
wherein M is titanium boride-based composite cathodeThe mass of Si in the material; m1Is TiB2-the mass of the Mo biscuit; w1Is TiB2-Mo in the Mo mixed powder accounts for mass percent; ar (Ar)MoIs the relative atomic mass of Mo; ar (Ar)SiIs the relative atomic mass of Si; rhoSiIs the density of Si; v is TiB2-volume of Mo biscuit; w2Is TiB2TiB in-Mo Mixed powder2The mass percentage of the components is calculated;is TiB2(ii) a density of (d);is MoSi2The density of (c).
The phase composition of the titanium boride-based composite cathode material is TiB2、MoSi2、Si、Mo2B、Ti3B4And TiB55。
The titanium boride-based composite cathode material has the Vickers hardness of 14-21 GPa, the bending strength of 195-265 MPa and the fracture toughness of 4.0-4.6 MPa.m1/2An open porosity of 0.1 to 0.4% and a bulk density of 3.6 to 4.1g/cm3The relative density is 97.02% -98.65%, the resistivity is 1.12 multiplied by 10-7～9.67×10-7Ω·m。
TiB as described above2The purity of the powder is more than 98 percent, and the granularity is less than or equal to 0.5 mm.
The purity of the metal Mo powder is more than 99 percent, and the granularity is less than or equal to 50 mu m.
The above Si has a particle size of 0.1 to 10 mm.
The above-mentioned Si mass was calculated based on the Mo content and the pore volume.
The mass M of Si mentioned above is the theoretical mass.
The invention relates to a preparation method of a titanium boride-based composite cathode material, which comprises the following steps:
(1) according to the proportion, TiB2Preparing TiB from powder and metal Mo powder2-Mo mixed powder;
(2) according to the proportion, TiB2Uniformly mixing the-Mo mixed powder with a binder to obtain a binder; sieving the bonding material to obtain bonding material particles with the granularity of 24-80 meshes as a die pressing material, wherein the bonding agent accounts for TiB25-10% of the total mass of the-Mo mixed powder;
(3) compression molding is carried out on the molded material under the pressure of 100-350 MPa, and drying is carried out for 10-20 h at the temperature of 80-350 ℃ after compression molding, so as to obtain TiB2-a Mo biscuit;
(4) mixing TiB2Carrying out vacuum infiltration by taking the-Mo biscuit as a framework and Si as an infiltration agent to obtain a titanium boride-based composite cathode material; wherein the vacuum infiltration parameter is that the temperature is increased to 1450-1650 ℃ at the speed of 3-10 ℃/min, then the temperature is kept for 10-70 min, and the actual consumption of Si is 100-200% of the theoretical mass.
Wherein,
the method for calculating the mass of the required infiltration agent Si in the process of preparing the titanium boride-based composite cathode material comprises the following steps:
(a) measurement of TiB2Mass M of the Mo biscuit1According to TiB2W in mass percentage of Mo in-Mo mixed powder1Calculating TiB2-mass of Mo in the Mo biscuit;
(b) according to TiB2Mass and reaction equation of Mo in Mo biscuit, calculating and reacting with TiB2Mass m of silicon required for Mo reaction in Mo biscuit1With MoSi2Mass m of2；
Mo+2Si→MoSi2
(c) Calculating the volume of the air hole:
(I) measurement of TiB2Mass M of the Mo biscuit1According to TiB2Ti in-Mo Mixed powderB2Mass percentage of W2Calculating TiB2TiB in-Mo biscuit2Calculating the mass of TiB2Volume V of1；
(II) according to MoSi2Mass m of2Calculating MoSi2Volume V of2；
(III) measurement of TiB2Volume V of the Mo green body, volume V of the pores3＝V-V1-V2；
Volume of air hole V3I.e. filling TiB2-the volume of silicon required for the pores in the Mo biscuit;
(d) according to the filling of TiB2-the volume of silicon required for pores in the Mo biscuit, calculating the TiB fill2Mass m of silicon required for pores in the Mo biscuit3；
(e) Amount of actual silicon MOozing outIs 100-200% of theoretical mass M, because in the vacuum infiltration process, the temperature is higher, and the melted Si is partially evaporated;
namely MOozing out＝M×(100％～200％)＝(m1+m3)×(100％～200％)。
The specific calculation formula is as follows:
m3＝ρsi×V3；
the theoretical mass M general formula of the infiltration agent Si required in the process of preparing the titanium boride-based composite cathode material is as follows:
practical dosage M of infiltration agent Si required in the process of preparing titanium boride-based composite cathode materialOozing outThe general formula is:
wherein M isOozing outThe actual dosage of the infiltration agent Si required in the process of preparing the titanium boride-based composite cathode material; m is the theoretical mass of a required infiltration agent Si in the process of preparing the titanium boride-based composite cathode material; m1Is TiB2-the mass of the Mo biscuit; w1Is TiB2-Mo in the Mo mixed powder accounts for mass percent; ar (Ar)MoIs the relative atomic mass of Mo; ar (Ar)siIs the relative atomic mass of Si; rhosiIs the density of Si; v is TiB2-volume of Mo biscuit; w2Is TiB2TiB in-Mo Mixed powder2The mass percentage of the components is calculated;is TiB2(ii) a density of (d);is MoSi2The density of (c).
In the above (1), TiB2The preparation method of the-Mo mixed powder comprises the following steps: mixing TiB2Uniformly mixing the powder, the metal Mo powder and the absolute ethyl alcohol to obtain a mixed material, drying the mixed material to remove the absolute ethyl alcohol, and preparing the TiB2-Mo mixed powder; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder (1:2) - (1:19), metal Mo powderAnd (3) mixing the powder with absolute ethyl alcohol (1:3) - (1: 20).
The step of drying to remove the absolute ethyl alcohol is drying for 4-10 hours at the temperature of 100-300 ℃.
The described TiB2The powder, the metal Mo powder and the absolute ethyl alcohol are uniformly mixed by adopting a mechanical mixing mode.
In the step (2), the binder is polyvinyl alcohol aqueous solution, polyvinyl pyrrolidone aqueous solution or carboxymethyl cellulose aqueous solution, and the mass percentage concentration of the binder is 3-8%.
In the above (2), the TiB2the-Mo mixed powder and the adhesive are mixed by a manual mixing or mechanical mixing mode, and during the mixing process, the adhesive material naturally forms granular adhesive material.
And (3) carrying out compression molding on the molding material, wherein the compression molding temperature is normal temperature, and the pressure is maintained for 5-15 s.
In the step (4), the vacuum infiltration adopts pressureless vacuum infiltration.
In the step (4), the vacuum infiltration equipment is a graphite vacuum heating furnace.
In the step (4), the vacuum degree of the vacuum infiltration is less than or equal to 200 Pa.
In the step (4), the amount of Si is determined according to the actual amount MOozing outIs determined by the formula (c).
The principle of the invention is as follows: adopts liquid silicon with reaction activity as an impregnant and infiltrates porous TiB containing Mo under the action of capillary force2-Mo ceramic biscuit and reaction with Mo therein to MoSi2And the impregnant fills the original air holes in the biscuit to finish the densification process.
Compared with the prior art, the invention has the advantages that:
1. the method has simple steps and low temperature requirement, can obtain the titanium boride-based composite cathode material with high density under the condition of lower preparation cost, has sample size change of less than 0.5 percent in the preparation process, and belongs to net size sintering.
2. The method can produce various products with complex shapes and large sizes, and is easy to popularize and apply in the field of manufacturing titanium boride-based composite cathode materials for aluminum electrolysis cells.
3. The product prepared by the invention has excellent properties, the Vickers hardness of the product is 14-21 GPa, the bending strength of the product is 195-265 MPa, and the fracture toughness of the product is 4.0-4.6 MPa1/2An open porosity of 0.1 to 0.4% and a bulk density of 3.6 to 4.1g/cm3The relative density is 97.02% -98.65%, the resistivity is 1.12 multiplied by 10-7～9.67×10-7Ω·m。
Drawings
FIG. 1 is an X-ray diffraction pattern of a titanium boride-based composite cathode material prepared in an example of the present invention, wherein (a) is the product of example 5 and (b) is the product of example 6;
FIG. 2 is a scanning electron micrograph of a titanium boride-based composite cathode material and an EDS analysis chart of each region in example 5 of the present invention, in which (c) is a scanning electron micrograph of the titanium boride-based composite cathode material, and (d) is TiB2EDS composition analysis chart of the region, (e) MoSi2An EDS component analysis map of the region, (f) an EDS component analysis map of the Si region;
FIG. 3 is a scanning electron micrograph of a titanium boride-based composite cathode material according to example 1 of the present invention;
FIG. 4 is a scanning electron micrograph of a titanium boride-based composite cathode material according to example 2 of the present invention;
FIG. 5 is a scanning electron micrograph of a titanium boride-based composite cathode material according to example 3 of the present invention;
FIG. 6 is a scanning electron micrograph of a titanium boride-based composite cathode material according to example 4 of the present invention;
FIG. 7 is a scanning electron micrograph of a titanium boride-based composite cathode material according to example 5 of the present invention;
FIG. 8 is a scanning electron micrograph of a titanium boride-based composite cathode material according to example 6 of the present invention;
in FIGS. 3 to 8, the light gray area is TiB2Region, white region is MoSi2The region, dark gray area is the Si region.
Detailed Description
The present invention will be described in further detail with reference to examples.
TiB used in the embodiment of the invention2The powder has a purity of more than 98% and a particle size of less than 0.5 mm.
The metal Mo powder adopted in the embodiment of the invention has the purity of more than 99 percent and the particle size of less than 50 mu m.
The granularity of Si adopted in the embodiment of the invention is 0.1-10 mm.
TiB in the examples of the present invention2The powder, the metal Mo powder and the absolute ethyl alcohol are mixed in a mechanical mixing mode.
TiB in the examples of the invention2the-Mo mixed powder and the binder are mixed by a manual mixing or mechanical mixing mode, and granular materials are naturally formed in the mixing process.
The equipment adopted by the compression molding in the embodiment of the invention is a WE-10A type hydraulic universal testing machine.
The equipment adopted by infiltration in the embodiment of the invention is a graphite vacuum heating furnace.
The Vickers indentation hardness test method in the embodiment of the invention is a Vickers indentation hardness method, and a 450SVD Vickers hardness tester is adopted.
The bending strength test method in the embodiment of the invention is a three-point bending strength method and adopts an electronic universal stretcher.
The method for testing the fracture toughness in the embodiment of the invention is an SENB method, and an electronic universal stretcher is adopted.
The method for testing the open porosity in the embodiment of the invention adopts an Archimedes drainage method.
In the embodiment of the invention, a double-electric-measurement four-probe tester is adopted for testing the resistivity.
The method for drying and removing the absolute ethyl alcohol in the embodiment of the invention is drying for 4-10 hours at the temperature of 100-300 ℃.
Example 1
A titanium boride-based composite cathode material is prepared from TiB2The powder, the metal Mo powder and Si are compounded; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder is 1: 19; the Si content was calculated from the Mo content and the pore volume, and was determined specifically according to formula (1).
The preparation method of the titanium boride-based composite cathode material comprises the following steps:
(1) according to the proportion, TiB2Preparing TiB from powder and metal Mo powder2-Mo mixed powder:
mixing TiB2Uniformly mixing the powder, the metal Mo powder and the absolute ethyl alcohol to obtain a mixed material, drying the mixed material to remove the absolute ethyl alcohol, and preparing the TiB2-Mo mixed powder; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder is 1:19, metal Mo powder and absolute ethyl alcohol are 1: 20.
(2) According to the proportion, TiB2Uniformly mixing the-Mo mixed powder with a binder to obtain a binder; sieving the bonding material to obtain bonding material particles with the granularity of 24-80 meshes as a die pressing material, wherein the bonding agent accounts for TiB21 of the total mass of-Mo Mixed powder0 percent of adhesive is polyvinyl alcohol aqueous solution with the mass percentage concentration of 3 percent;
(3) putting the mould pressing material into a mould, carrying out mould pressing forming, keeping the pressure of the mould pressing forming at 100MPa and the temperature at normal temperature for 15s, drying at 350 ℃ for 10h after mould pressing forming, and obtaining TiB2-a Mo biscuit;
(4) placing silicon particles with the particle size of 0.1-10 mm in TiB in a graphite vacuum heating furnace2Upper surface of Mo biscuit, TiB2Carrying out vacuum infiltration by taking the-Mo biscuit as a framework and Si as an infiltration agent to obtain a titanium boride-based composite cathode material; wherein the vacuum infiltration parameters are as follows: the vacuum degree is less than or equal to 200Pa, the temperature is raised to 1450 ℃ at the speed of 10 ℃/min, and then the temperature is kept for 70 min.
Wherein,
the method for calculating the mass of the required infiltration agent Si in the process of preparing the titanium boride-based composite cathode material comprises the following steps:
(a) measurement of TiB2Mass M of the Mo biscuit1According to TiB2W in mass percentage of Mo in-Mo mixed powder1Calculating TiB2-mass of Mo in the Mo biscuit;
(b) according to TiB2The mass of Mo in the Mo biscuit and the formula (1.1), the calculation of the sum of the mass and the value of TiB2Mass m of silicon required for Mo reaction in Mo biscuit1With MoSi2Mass m of2；
Mo+2Si→MoSi2 (1.1)
(c) Calculating the volume of the air hole:
(I) measurement of TiB2Mass M of the Mo biscuit1According to TiB2TiB in-Mo Mixed powder2Mass percentage of W2Calculating TiB2TiB in-Mo biscuit2Calculating the mass of TiB2Volume V of1；
(II) according to MoSi2Mass m of2Calculating MoSi2Volume V of2；
(III) measurement of TiB2Volume V of the Mo green body, volume V of the pores3＝V-V1-V2；
Volume of air hole V3I.e. filling TiB2-the volume of silicon required for the pores in the Mo biscuit;
(d) according to the filling of TiB2-the volume of silicon required for pores in the Mo biscuit, calculating the TiB fill2Mass m of silicon required for pores in the Mo biscuit3；
(e) Mass M of actual siliconOozing out100-200% of theoretical mass M, because in the vacuum infiltration process, the temperature is higher, and the molten silicon is partially evaporated;
namely MOozing out＝M×(100％～200％)＝(m1+m3)×(100％～200％)。
The specific calculation formula is as follows:
m3＝ρsi×V3；
practical dosage M of infiltration agent Si required in the process of preparing titanium boride-based composite cathode materialOozing outThe general formula is:
wherein M isOozing outThe actual dosage of the infiltration agent Si required in the process of preparing the titanium boride-based composite cathode material; m is the theoretical mass of a required infiltration agent Si in the process of preparing the titanium boride-based composite cathode material; m1Is TiB2-the mass of the Mo biscuit; w1Is TiB2-Mo in the Mo mixed powder accounts for mass percent; ar (Ar)MoIs the relative atomic mass of Mo; ar (Ar)SiIs the relative atomic mass of Si; rhosiIs the density of Si; v is TiB2-volume of Mo biscuit; w2Is TiB2TiB in-Mo Mixed powder2The mass percentage of the components is calculated;is TiB2(ii) a density of (d);is MoSi2The density of (c).
The phase composition of the titanium boride-based composite cathode material prepared in this example was TiB2、MoSi2、Si、Mo2B、Ti3B4And TiB55。
The titanium boride-based composite cathode material prepared in the embodiment has the Vickers hardness of 14GPa, the bending strength of 231MPa and the fracture toughness of 4.09 MPa.m1/2The open porosity was 0.22%, and the bulk density was 3.61g/cm3The relative density was 98.01%, and the resistivity was 9.67X 10-7Ω·m。
The scanning electron micrograph of the titanium boride-based composite cathode material prepared in this example is shown in FIG. 3.
Example 2
A titanium boride-based composite cathode material is prepared from TiB2The powder, the metal Mo powder and Si are compounded; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder is 1: 9; the Si content was calculated from the Mo content and the pore volume, and was determined specifically according to formula (1).
The preparation method of the titanium boride-based composite cathode material comprises the following steps:
(1) according to the proportion, TiB2Preparing TiB from powder and metal Mo powder2-Mo mixed powder:
mixing TiB2Uniformly mixing the powder, the metal Mo powder and the absolute ethyl alcohol to obtain a mixed material, drying the mixed material to remove the absolute ethyl alcohol, and preparing the TiB2-Mo mixed powder; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder is 1: 9, metal Mo powder and absolute ethyl alcohol are 1: 10.
(2) According to the proportion, TiB2Uniformly mixing the-Mo mixed powder with a binder to obtain a binder; sieving the bonding material to obtain bonding material particles with the granularity of 24-80 meshes as a die pressing material, wherein the bonding agent accounts for TiB29% of the total mass of the Mo mixed powder, and the binder is a polyvinylpyrrolidone aqueous solution with the mass percentage concentration of 4%;
(3) putting the mould pressing material into a mould, carrying out mould pressing forming, keeping the pressure of the mould pressing forming at the normal temperature of 150MPa for 10s, drying at the temperature of 300 ℃ for 12h after mould pressing forming, and obtaining TiB2-a Mo biscuit;
(4) placing silicon particles with the particle size of 0.1-10 mm in TiB in a graphite vacuum heating furnace2Upper surface of Mo biscuit, TiB2Carrying out vacuum infiltration by taking the-Mo biscuit as a framework and Si as an infiltration agent to obtain a titanium boride-based composite cathode material; wherein the vacuum infiltration parameters are as follows: the vacuum degree is less than or equal to 200Pa, the temperature is raised to 1500 ℃ at the speed of 8 ℃/min, and then the temperature is kept for 60 min.
Wherein,
the calculation method of the required Si mass of the infiltration agent in the process of preparing the titanium boride-based composite cathode material is the same as that described in example 1.
The phase composition of the titanium boride-based composite cathode material prepared in this example was TiB2、MoSi2、Si、Mo2B、Ti3B4And TiB55；
The titanium boride-based composite cathode material prepared in the embodiment has the Vickers hardness of 15GPa, the bending strength of 195MPa and the fracture toughness of 4.14 MPa-m1/2The open porosity was 0.16%, and the bulk density was 3.63g/cm3The relative density was 97.02%, and the resistivity was 7.76X 10-7Ω·m。
The scanning electron micrograph of the titanium boride-based composite cathode material prepared in this example is shown in FIG. 4.
Example 3
A titanium boride-based composite cathode material is prepared from TiB2The powder, the metal Mo powder and Si are compounded; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder is 1: 5.67; the Si content was calculated from the Mo content and the pore volume, and was determined specifically according to formula (1).
The preparation method of the titanium boride-based composite cathode material comprises the following steps:
(1) according to the proportion, TiB2Preparing TiB from powder and metal Mo powder2-Mo mixed powder:
mixing TiB2Uniformly mixing the powder, the metal Mo powder and the absolute ethyl alcohol to obtain a mixed material, drying the mixed material to remove the absolute ethyl alcohol, and preparing the TiB2-Mo mixed powder; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder is 1: 5.67, metal Mo powder and absolute ethyl alcohol are 1: 6.67.
(2) According to the proportion, TiB2Uniformly mixing the-Mo mixed powder with a binder to obtain a binder; sieving the bonding material to obtain bonding material particles with the granularity of 24-80 meshes as a die pressing material, wherein the bonding agent accounts forTiB28% of the total mass of the Mo mixed powder, and the binder is a polyvinylpyrrolidone aqueous solution with the mass percentage concentration of 5%;
(3) putting the mould pressing material into a mould, carrying out mould pressing forming, keeping the pressure of the mould pressing forming at normal temperature for 10s, drying at 250 ℃ for 14h after mould pressing forming, and obtaining TiB2-a Mo biscuit;
(4) placing silicon particles with the particle size of 0.1-10 mm in TiB in a graphite vacuum heating furnace2Upper surface of Mo biscuit, TiB2Carrying out vacuum infiltration by taking the-Mo biscuit as a framework and Si as an infiltration agent to obtain a titanium boride-based composite cathode material; wherein the vacuum infiltration parameters are as follows: the vacuum degree is less than or equal to 200Pa, the temperature is raised to 1550 ℃ at the speed of 6 ℃/min, and then the temperature is kept for 50 min.
Wherein,
the calculation method of the required Si mass of the infiltration agent in the process of preparing the titanium boride-based composite cathode material is the same as that described in example 1.
The phase composition of the titanium boride-based composite cathode material prepared in this example was TiB2、MoSi2、Si、Mo2B、Ti3B4And TiB55；
The titanium boride-based composite cathode material prepared in the embodiment has the Vickers hardness of 17GPa, the bending strength of 202MPa and the fracture toughness of 4.05 MPa-m1/2An open porosity of 0.23% and a bulk density of 3.70g/cm3The relative density was 98.21%, and the resistivity was 1.27X 10-7Ω·m。
The scanning electron micrograph of the titanium boride-based composite cathode material prepared in this example is shown in FIG. 5.
Example 4
A titanium boride-based composite cathode material is prepared from TiB2The powder, the metal Mo powder and Si are compounded; wherein, according to the mass ratio, the metal Mo powder: TiB2Powder is 1: 4; the Si content was calculated from the Mo content and the pore volume, and was determined specifically according to formula (1).
The preparation method of the titanium boride-based composite cathode material comprises the following steps:
(1) according to the proportion, TiB2Preparing TiB from powder and metal Mo powder2-Mo mixed powder:
mixing TiB2Uniformly mixing the powder, the metal Mo powder and the absolute ethyl alcohol to obtain a mixed material, drying the mixed material to remove the absolute ethyl alcohol, and preparing the TiB2-Mo mixed powder; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder is 1: 4, metal Mo powder and absolute ethyl alcohol are 1: 5.
(2) According to the proportion, TiB2Uniformly mixing the-Mo mixed powder with a binder to obtain a binder; sieving the bonding material to obtain bonding material particles with the granularity of 24-80 meshes as a die pressing material, wherein the bonding agent accounts for TiB27% of the total mass of the Mo mixed powder, wherein the binder is a carboxymethyl cellulose aqueous solution with the mass percentage concentration of 6%;
(3) putting the mould pressing material into a mould, carrying out mould pressing forming, keeping the pressure of the mould pressing forming at the normal temperature of 250MPa for 10s, drying at the temperature of 200 ℃ for 16h after mould pressing forming, and obtaining TiB2-a Mo biscuit;
(4) placing silicon particles with the particle size of 0.1-10 mm in TiB in a graphite vacuum heating furnace2Upper surface of Mo biscuit, TiB2Carrying out vacuum infiltration by taking the-Mo biscuit as a framework and Si as an infiltration agent to obtain a titanium boride-based composite cathode material; wherein the vacuum infiltration parameters are as follows: the vacuum degree is less than or equal to 200Pa, the temperature is raised to 1600 ℃ at the speed of 5 ℃/min, and then the temperature is preserved for 40 min.
Wherein,
the calculation method of the required Si mass of the infiltration agent in the process of preparing the titanium boride-based composite cathode material is the same as that described in example 1.
The phase composition of the titanium boride-based composite cathode material prepared in this example was TiB2、MoSi2、Si、Mo2B、Ti3B4And TiB55；
The titanium boride-based composite cathode material prepared in the embodiment has the Vickers hardness of 18GPa, the bending strength of 229MPa and the fracture toughness of 4.38 MPa-m1/2An open porosity of 0.29% and a bulk density of 3.74g/cm3The relative density was 98.16%, and the resistivity was 1.12X 10-7Ω·m。
The scanning electron micrograph of the titanium boride-based composite cathode material prepared in this example is shown in FIG. 6.
Example 5
A titanium boride-based composite cathode material is prepared from TiB2The powder, the metal Mo powder and Si are compounded; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder is 1: 3; the Si content was calculated from the Mo content and the pore volume, and was determined specifically according to formula (1).
The preparation method of the titanium boride-based composite cathode material comprises the following steps:
(1) according to the proportion, TiB2Preparing TiB from powder and metal Mo powder2-Mo mixed powder:
mixing TiB2Uniformly mixing the powder, the metal Mo powder and the absolute ethyl alcohol to obtain a mixed material, drying the mixed material to remove the absolute ethyl alcohol, and preparing the TiB2-Mo mixed powder; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder is 1:3, metal Mo powder and absolute ethyl alcohol are 1: 4.
(2) According to the proportion, TiB2Uniformly mixing the-Mo mixed powder with a binder to obtain a binder; sieving the bonding material to obtain bonding material particles with the granularity of 24-80 meshes as a mould pressing material, wherein,binder in TiB26% of the total mass of the Mo mixed powder, and the binder is a polyvinyl alcohol aqueous solution with the mass percentage concentration of 7%;
(3) putting the mould pressing material into a mould, carrying out mould pressing forming, keeping the pressure of the mould pressing forming at normal temperature for 10s, drying at 150 ℃ for 18h after mould pressing forming, and obtaining TiB2-a Mo biscuit;
(4) placing silicon particles with the particle size of 0.1-10 mm in TiB in a graphite vacuum heating furnace2Upper surface of Mo biscuit, TiB2Carrying out vacuum infiltration by taking the-Mo biscuit as a framework and Si as an infiltration agent to obtain a titanium boride-based composite cathode material; wherein the vacuum infiltration parameters are as follows: the vacuum degree is less than or equal to 200Pa, the temperature is raised to 1650 ℃ at the speed of 4 ℃/min, and then the temperature is preserved for 20 min.
Wherein,
the calculation method of the required Si mass of the infiltration agent in the process of preparing the titanium boride-based composite cathode material is the same as that described in example 1.
The phase composition of the titanium boride-based composite cathode material prepared in this example was TiB2、MoSi2、Si、Mo2B、Ti3B4And TiB55；
The titanium boride-based composite cathode material prepared in the embodiment has the Vickers hardness of 18GPa, the bending strength of 238MPa and the fracture toughness of 4.54 MPa-m1/2An open porosity of 0.27% and a bulk density of 3.81g/cm3The relative density was 98.65%, and the resistivity was 1.35X 10-7Ω·m。
The scanning electron micrograph of the titanium boride-based composite cathode material prepared in this example is shown in FIG. 7; the X-ray diffraction pattern of the titanium boride-based composite cathode material prepared in this example is shown in fig. 1 (a); in the present example, a scanning electron micrograph of the titanium boride-based composite cathode material and an EDS analysis chart of each region are shown in FIG. 2, (c) is a scanning electron micrograph of the titanium boride-based composite cathode material, and (d) is TiB2An EDS compositional analysis map of a region,(e) is MoSi2EDS component analysis chart of region (f) is EDS component analysis chart of Si region.
Example 6
A titanium boride-based composite cathode material is prepared from TiB2The powder, the metal Mo powder and Si are compounded; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder is 1: 2.33; the Si content was calculated from the Mo content and the pore volume, and was determined specifically according to formula (1).
The preparation method of the titanium boride-based composite cathode material comprises the following steps:
(1) according to the proportion, TiB2Preparing TiB from powder and metal Mo powder2-Mo mixed powder:
mixing TiB2Uniformly mixing the powder, the metal Mo powder and the absolute ethyl alcohol to obtain a mixed material, drying the mixed material to remove the absolute ethyl alcohol, and preparing the TiB2-Mo mixed powder; wherein, according to the mass ratio, the metal Mo powder and the TiB2Powder is 1: 2.33, metal Mo powder and absolute ethyl alcohol are 1: 3.33.
(2) According to the proportion, TiB2Uniformly mixing the-Mo mixed powder with a binder to obtain a binder; sieving the bonding material to obtain bonding material particles with the granularity of 24-80 meshes as a die pressing material, wherein the bonding agent accounts for TiB25% of the total mass of the Mo mixed powder, and the binder is polyvinylpyrrolidone aqueous solution with the mass percentage concentration of 8%;
(3) putting the mould pressing material into a mould, carrying out mould pressing forming, keeping the pressure of the mould pressing forming at the normal temperature for 5s, drying at the temperature of 80 ℃ for 20h after mould pressing forming, and obtaining TiB2-a Mo biscuit;
(4) placing silicon particles with the particle size of 0.1-10 mm in TiB in a graphite vacuum heating furnace2Upper surface of Mo biscuit, TiB2-Mo green body as skeleton, Si asThe infiltration agent is used for carrying out vacuum infiltration to obtain the titanium boride-based composite cathode material; wherein the vacuum infiltration parameters are as follows: the vacuum degree is less than or equal to 200Pa, the temperature is raised to 1650 ℃ at the speed of 3 ℃/min, and then the temperature is preserved for 10 min.
Wherein,
the calculation method of the required Si mass of the infiltration agent in the process of preparing the titanium boride-based composite cathode material is the same as that described in example 1.
The phase composition of the titanium boride-based composite cathode material prepared in this example was TiB2、MoSi2、Si、Mo2B、Ti3B4And TiB55；
The titanium boride-based composite cathode material prepared in the embodiment has the Vickers hardness of 20GPa, the bending strength of 264MPa and the fracture toughness of 4.34 MPa-m1/2The open porosity was 0.36%, and the bulk density was 4.02g/cm3The relative density was 98.16%, and the resistivity was 8.69X 10-7Ω·m。
The scanning electron micrograph of the titanium boride-based composite cathode material prepared in this example is shown in FIG. 8; the X-ray diffraction pattern of the titanium boride-based composite cathode material prepared in this example is shown in FIG. 1 (b).
By combining the X-ray diffraction pattern and the EDS composition analysis, FIGS. 3 to 8 are scanning electron micrographs of the composite materials of examples 1 to 6 under different addition amounts of Mo, and the light gray area in the pictures is TiB2Region, white region is MoSi2The region, dark gray area is the Si region. As can be seen from FIGS. 3 to 8, as the Mo content increases, Mo reacts with Si to form MoSi2Increased amount of (i.e. MoSi in the figure)2The corresponding white area shows a more obvious increasing trend; in addition, as the Mo content increases, the dispersion uniformity of the raw material Mo powder increases.

Claims (8)

1. The preparation method of the titanium boride-based composite cathode material is characterized by comprising the following steps of:
(1) according to the proportion, TiB2Preparing TiB from powder and metal Mo powder2-Mo mixed powder;
wherein, according to the mass ratio, the metal Mo powder: TiB2Powder (1:2) to (1: 19);
(2) according to the proportion, TiB2Uniformly mixing the-Mo mixed powder with a binder to obtain a binder; sieving the bonding material to obtain the bonding material with the granularity of 24-80 meshesThe agglomerate grains are used as molding material, wherein the binder accounts for TiB25-10% of the total mass of the-Mo mixed powder;
(3) compression molding is carried out on the molded material under the pressure of 100-350 MPa, and drying is carried out for 10-20 h at the temperature of 80-350 ℃ after compression molding, so as to obtain TiB2-a Mo biscuit;
(4) mixing TiB2Carrying out vacuum infiltration by taking the-Mo biscuit as a framework and Si as an infiltration agent to obtain a titanium boride-based composite cathode material; wherein the vacuum infiltration parameter is that the temperature is increased to 1450-1650 ℃ at the speed of 3-10 ℃/min, then the temperature is kept for 10-70 min, and the actual consumption of Si is 100-200% of the theoretical mass;
wherein the Si content is calculated from the Mo content and the pore volume:
in the titanium boride-based composite cathode material, the mass M general formula of Si is as follows:
wherein, the mass of Si in the M titanium boride-based composite cathode material; m1Is TiB2-the mass of the Mo biscuit; w1Is TiB2-Mo in the Mo mixed powder accounts for mass percent; ar (Ar)MoIs the relative atomic mass of Mo; ar (Ar)SiIs the relative atomic mass of Si; rhoSiIs the density of Si; v is TiB2-volume of Mo biscuit; w2Is TiB2TiB in-Mo Mixed powder2The mass percentage of the components is calculated;is TiB2(ii) a density of (d);is MoSi2(ii) a density of (d);
the phase composition of the prepared titanium boride-based composite cathode material is TiB2、MoSi2、Si、Mo2B、Ti3B4And TiB55；
Prepared boronThe titanium-based composite cathode material has an open porosity of 0.1-0.4%, a relative density of 97.02-98.65%, and a resistivity of 1.12 × 10-7～9.67×10-7Ω·m。
2. The method for preparing the titanium boride-based composite cathode material according to claim 1, wherein the titanium boride-based composite cathode material has a Vickers hardness of 14 to 21GPa, a bending strength of 195 to 265MPa and a fracture toughness of 4.0 to 4.6 MPa-m1/2The bulk density is 3.6 to 4.1g/cm3。
3. The method for preparing a titanium boride-based composite cathode material as claimed in claim 1, wherein the TiB is2Powder of purity>98 percent and the granularity is less than or equal to 0.5 mm; the metal Mo powder has the purity>99 percent and the granularity is less than or equal to 50 mu m; the granularity of the Si is 0.1-10 mm.
4. The method for preparing a titanium boride-based composite cathode material as claimed in claim 1, wherein in the step (1), TiB2The preparation method of the-Mo mixed powder comprises the following steps: mixing TiB2Uniformly mixing the powder, the metal Mo powder and absolute ethyl alcohol to obtain a mixed material, drying the mixed material at 100-300 ℃ for 4-10 hours to remove the absolute ethyl alcohol, and preparing TiB2-Mo mixed powder; wherein, according to the mass ratio, the metal Mo powder: TiB2Powder (1:2) to (1:19), metal Mo powder: absolute ethyl alcohol (1:3) to (1: 20).
5. The titanium boride-based composite cathode material as claimed in claim 1, wherein the binder is an aqueous solution of polyvinyl alcohol, polyvinylpyrrolidone or carboxymethylcellulose, and the mass percentage concentration of the binder is 3% to 8%.
6. The method of preparing a titanium boride-based composite cathode material as claimed in claim 1, wherein the titanium boride-based composite cathode material is prepared by(2) In (1), the TiB2the-Mo mixed powder and the adhesive are mixed by a manual mixing or mechanical mixing mode, and during the mixing process, the adhesive material naturally forms granular adhesive material.
7. The method for preparing the titanium boride-based composite cathode material according to claim 1, wherein in the step (3), the compression molding material is subjected to compression molding, the compression molding temperature is normal temperature, and the pressure is maintained for 5-15 s.
8. The method for preparing titanium boride-based composite cathode material as claimed in claim 1, wherein in the step (4), the vacuum infiltration is pressureless vacuum infiltration; the equipment adopted by the vacuum infiltration is a graphite vacuum heating furnace; the vacuum degree of the vacuum infiltration is less than or equal to 200 Pa.
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