CN111849214A - Efficient preparation of core-shell ATO @ TiO2Method for conducting whiskers - Google Patents

Efficient preparation of core-shell ATO @ TiO2Method for conducting whiskers Download PDF

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CN111849214A
CN111849214A CN202010848864.4A CN202010848864A CN111849214A CN 111849214 A CN111849214 A CN 111849214A CN 202010848864 A CN202010848864 A CN 202010848864A CN 111849214 A CN111849214 A CN 111849214A
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高强
王明序
高春霞
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Yangzhou University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3653—Treatment with inorganic compounds
    • C09C1/3661—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/40—Electric properties

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Abstract

The invention relates to a method for efficiently preparing core-shell ATO @ TiO2Mixing titanium dioxide whiskers and deionized water according to the mass concentration of 10-40% to form suspension, adding sodium ion surfactant with the mass proportion of 0.5-2% after constant temperature treatment to carry out activation pretreatment, preparing ATO precursor liquid with certain acidity according to the coating ratio and the doping ratio, mixing the ATO precursor liquid into a pretreated suspension carrier, ageing for 1-5h to complete coating of a conductive layer on the surface of a whisker carrier, filtering and washing the coated suspension, carrying out spray drying, and calcining at the temperature of 400-700 ℃ to obtain a core-shell ATO @ TiO @ with soft and fluffy texture2And (3) conductive whiskers. ATO @ TiO of the present invention2The preparation method of the conductive whisker comprises the steps of uniformly pretreating a whisker carrier before coating by using a surfactant, enabling negative ion active groups on the surface of the whisker after treatment to form an electric double layer structure, and increasing the carrier in suspensionThe dispersibility of the tin-antimony composite material, the charge attraction of the surface of the crystal whisker to metal ions of tin-antimony is enhanced, and the coating efficiency and the coating speed are improved.

Description

Efficient preparation of core-shell ATO @ TiO2Method for conducting whiskers
Technical Field
The invention relates to a process for the oxidation of carbon dioxideThe technical field of titanium conductive whisker preparation, in particular to a method for efficiently preparing core-shell ATO @ TiO by adopting a chemical deposition coating technology2A method of conductive whiskers.
Background
Conductive TiO2The whisker material is one of functional titanium dioxide, and has the advantages of high whiteness, excellent conductivity, low percolation threshold, environmental friendliness, strong stability and the like. In recent years, as a novel light-colored conductive filler, the conductive filler is widely applied to various microelectronic technical fields with conductive and antistatic requirements such as coatings, chemical fibers, papermaking, printing ink and the like and industries related to surface conductive treatment of insulator materials. A plurality of TiO2In the mode of conducting treatment of the crystal whisker, antimony-doped tin oxide (ATO) is coated on the surface of the crystal whisker in a liquid-phase coprecipitation mode to prepare light-colored ATO @ TiO2The conductive whisker is one of the best feasibility and stability, and is also one of the preparation methods of the industrialized composite conductive filler at present.
So far, many reports have been made on the preparation of composite functional powder by a coprecipitation method using a liquid phase. By searching for relevant literature in the last two years: the Chinese patent publication numbers are: CN106567128A, published as 2017, 4, 19 and entitled preparation method of conductive potassium titanate whisker, which discloses that the potassium titanate whisker is taken as a carrier raw material, deionized water is added to the carrier raw material to be dispersed into suspension slurry, nano conductive powder, a salt solution of tin and antimony, niobium pentoxide and a metal (zinc, magnesium and iron) reducing agent in a certain proportion are continuously added, and precipitation reaction is carried out after pH is adjusted by ammonia water. Finally, the required potassium titanate conductive crystal whisker is obtained through washing and drying. The Chinese patent publication numbers are: CN109851856A, published as 6.2019 and 7.7, entitled preparation method of core-shell composite conductive titanium dioxide powder, which also comprises the steps of adding the dispersed coating agent into the suspension of the matrix drop by drop, aging and washing under specific pH; calcining and dehydrating to finally obtain particle type conductive TiO2And (3) powder. Also, there are Chinese patent publications as follows: CN105271389A, published 2016, 1, 27, entitled preparation method of conductive titanium dioxide powder, and adopts similar coating process to coat tin-antimony oxideCoated in TiO2And (5) coating the surface of the powder. Read-through composite conductive TiO2The preparation method of the product comprises the following steps: the research on the coating process of liquid-phase coprecipitation is single, and the influence of the surface performance of the carrier on the ion loading process is hardly considered, so that the experimental result has certain randomness, and the fluctuation of the product performance is large. On the other hand, due to the agglomerated nature of the nanoparticles, it is difficult for the matrix to be sufficiently dispersed by simple physical methods such as sonication, stirring, etc. Agglomerated radicals generally cannot effectively contact a coating agent due to the fact that large mass is deposited at the bottom of the reaction kettle, so that coating defects are caused, ions forming a nucleation area cannot react in time, so that local concentration is too high, a crystal growth process of homogeneous nucleation is generated, and raw materials are wasted. In addition, the traditional mode lacks active regulation and control on the adsorption process of the coated ions, a part of raw materials cannot be adsorbed and grown due to the lack of active sites on the surface of the carrier, so that the use rate of the raw materials is reduced, the environment is polluted during discharge, and meanwhile, the prepared conductive whiskers have poor coating rate and coating uniformity and the conductivity of the material.
In addition, the traditional processes of thermal drying, air flow drying and the like are generally adopted in the existing patents, and a sample calcined at high temperature is agglomerated again and is difficult to disperse again, which is fatal to subsequent application, and the rod-shaped conductive whiskers cannot adopt a violent ball milling mode, so that a reasonable matching post-treatment method is also lacked.
Disclosure of Invention
Aiming at the coating defects existing in the titanium dioxide conductive whisker deposition coating technology in the prior art, the invention provides a method for efficiently preparing core-shell ATO @ TiO2The method for conducting the crystal whiskers has the advantages that the specific surfactant is used for effectively pretreating the titanium dioxide crystal whisker carrier, so that the crystal whisker suspension liquid is effectively dispersed and activated in surface performance, the ion adsorption performance is promoted, the coating agent can nucleate and grow into a film on the surface of the carrier more completely and efficiently, the coating rate is improved, the agglomeration of the coating agent is avoided, and the coating defect is overcome.
The purpose of the invention is realized by that the core-shell ATO @ TiO is efficiently prepared2A method of electrically conducting whiskers, comprising the steps of:
a) mixing titanium dioxide whisker powder with deionized water to prepare a mixed solution with the mass concentration of 10-40%, and mechanically stirring for 10-30 min at the constant temperature of 40-60 ℃ to obtain a uniformly dispersed suspension A;
b) adding a sodium salt surfactant with the mass being 0.5-2% of that of the titanium dioxide whisker powder in the step a) into the suspension A, continuously dispersing for 0.5-2 h at constant temperature, adjusting the pH value of the dispersed suspension to 1-5 by using an acid solution, and heating to 60-80 ℃ to obtain a homogeneous suspension B;
c) preparing an ATO precursor solution: respectively measuring tin tetrachloride crystals and antimony trichloride crystals according to the theoretical coating ratio of tin dioxide and the doping ratio of antimony trioxide, dissolving the tin tetrachloride crystals and the antimony trichloride crystals in a proper amount of deionized water, and adjusting the acid concentration in the solution to 1-5mol/L by using hydrochloric acid to obtain an ATO precursor solution;
d) uniformly adding the ATO precursor solution in the step c into the suspension B in the step B, simultaneously adding alkali liquor to enable the pH of the suspension to be 1-5, and carrying out aging reaction for 1-5 hours;
e) filtering and washing the suspension after the aging reaction in the step d, spray-drying, and calcining at 400-700 ℃ for 1-5h to obtain the core-shell ATO @ TiO2And (3) conductive whiskers.
Further, in the step a, the pH value of the suspension is adjusted to 6-11 by ammonia water during pretreatment of the suspension after mixing the titanium dioxide whiskers with deionized water.
In step b, sodium salt surfactant is one or more of trisodium phosphate, tetrasodium phosphate, sodium hexametaphosphate, sodium silicate and sodium lignosulfonate, and the added amount is 0.5-2% of titanium dioxide whisker powder. And c, forming a double electric layer structure to increase the dispersibility of the carrier in the suspension by the negative ion active groups on the surfaces of the whiskers after the pretreatment in the step b, and generating a charge attraction effect on metal ions of tin and antimony by the coulomb charge force to enable the coating agent in a homogeneous system to nucleate and grow on the surfaces of the carriers more completely and efficiently to form a film.
In order to accurately determine the feeding amount of the coating material, realize high-efficiency coating rate and reduce waste of the coating material, in the step c, when the ATO precursor solution is prepared, the coating ratio of the tin dioxide refers to that the mass of the titanium dioxide whisker powder in the conductive whisker is 10-20%, and the antimony trioxide doping ratio refers to that the mass of the tin dioxide is 1-10%.
In order to further accurately feed, in the step c, according to the coating ratio of tin dioxide, the adding mass of tin tetrachloride is 23-46% of the adding mass of titanium dioxide whisker powder in the step a), the adding mass of antimony trichloride is 0.67-6.7% of the adding mass of tin tetrachloride, and the mass concentration of ATO precursor liquid tin tetrachloride is 5-20%.
Further, in step d), the aging temperature is 60-80 ℃.
And step d, dropwise adding alkali liquor which is non-sodium ion alkali liquor.
In order to improve the texture of the dried conductive whiskers, in the step e, the suspension filtering and washing mode is water washing and pressure filtration to obtain a powder filter cake, and during spray drying, the material spray inlet temperature is 180-. And carrying out filter pressing on the coated conductive whisker powder, and then carrying out spray drying treatment, so that the conductive whisker is soft and fluffy in texture, free from agglomeration and reunion, and greatly improved in dispersibility in subsequent base materials.
The coating process for preparing the core-shell conductive titanium dioxide whisker, provided by the invention, comprises the following steps: the titanium dioxide whisker carrier before coating is pretreated by using the surfactant, so that metal ions in a uniform system can nucleate, grow and coat on the surface of the carrier to form a film more completely and efficiently; after the pretreatment of the method, the utilization efficiency and the coating speed of the coating raw materials are improved, the consumption of the tin-antimony raw materials is saved by 20-30%, the coating efficiency is improved by 30-50%, the tin-antimony raw materials in a uniform system basically reach 100% and are coated on the surface of a crystal whisker carrier, and an ICP test result shows that: sn and Sb ion residues in the coated waste liquid directly reach the emission standard; meanwhile, the conductivity of the conductive whisker powder is improved by 5-10 times; after the coated conductive whiskers are subjected to spray drying treatment, the coated conductive whiskers are soft and fluffy in texture and free of agglomeration, the dispersibility of the conductive whiskers in a subsequent base material is greatly improved, the conductive whiskers are favorably dispersed and bridged in a base material system to form a conductive network, and the effect of reducing the percolation threshold is achieved.
Drawings
FIG. 1 shows the efficient preparation of core-shell ATO @ TiO according to the present invention2A process flow diagram of a method of conducting whiskers.
FIG. 2 is a core-shell ATO @ TiO prepared in example 12And (3) an SEM image of the conductive whiskers.
FIG. 3 is a core-shell ATO @ TiO prepared in example 22And (3) an SEM image of the conductive whiskers.
FIG. 4 is a core-shell ATO @ TiO prepared in example 32And (3) an SEM image of the conductive whiskers.
FIG. 5 is a core-shell ATO @ TiO prepared in comparative example 12And (3) an SEM image of the conductive whiskers.
FIG. 6 is a core-shell ATO @ TiO prepared in comparative example 22And (3) an SEM image of the conductive whiskers.
FIG. 7 is a core-shell ATO @ TiO prepared in comparative example 32And (3) an SEM image of the conductive whiskers.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The efficient preparation of core-shell ATO @ TiO according to the present invention will be described in detail with reference to the following specific examples and comparative examples2A method of conductive whiskers.
Example 1
(1) Weighing 10g of titanium dioxide whisker powder, mechanically stirring and mixing the titanium dioxide whisker powder and 100ml of deionized water to form uniform suspension, adjusting the pH value of the suspension to 6, heating to 40 ℃, carrying out constant temperature treatment for 30min, then adding 0.05g of sodium hexametaphosphate surfactant for pretreatment, continuously heating to 60 ℃, and carrying out constant temperature dispersion pretreatment for 1 h; (2) dropwise adding a proper amount of hydrochloric acid solution with the concentration of 2mol/L into the pretreated suspension to adjust the pH value of the suspension to 1, and controlling the temperature of the suspension to be 60 ℃ to realize homogeneous treatment of the suspension; (3) preparing an ATO precursor solution: dissolving 2.3g of crystallized stannic chloride and 0.08g of antimony trichloride in 40ml of deionized water, and dropwise adding hydrochloric acid until the acid concentration of an ATO solution is 1 mol/L; (4) adding the prepared ATO precursor solution into the suspension subjected to the homogeneous phase treatment in the step (2) at the speed of 20ml/min, simultaneously dropwise adding a proper amount of ammonia water with the mass concentration of 10% to keep the pH value of the coating solution unchanged at 1, and after dropwise adding, continuing to perform constant-temperature aging reaction for 1 hour to complete the coating treatment; (5) and filtering and washing the suspension after the aging treatment to obtain a powder filter cake of suspended matters, then carrying out spray drying, wherein the temperature of an inlet liquid is 180 ℃ during drying, the feeding rate is 30r/min, and finally calcining the dried powder at 600 ℃ for 1h to obtain the core-shell type conductive titanium dioxide whisker of the embodiment. The SEM image is shown in figure 2, and it can be seen that the surface of the whisker is uniformly and smoothly coated, and the problem of non-uniform coating caused by agglomeration of the coating is not found on the surface; taking 0.2g of the core-shell type conductive titanium dioxide whisker powder prepared in the embodiment, tabletting for 3min under the pressure of 20MPa, and testing the surface resistivity of a sample by using a four-probe resistance tester to obtain: 78.5 +/-10 omega cm.
Example 2
(1) Weighing 10g of titanium dioxide whisker powder, mechanically stirring and mixing the titanium dioxide whisker powder and 150ml of deionized water to form uniform suspension, dropwise adding 10% by mass of potassium hydroxide solution, adjusting the pH value of the suspension to 8, heating to 60 ℃, carrying out constant temperature treatment for 10min, then adding a mixture of 0.1g of tetrasodium phosphate and 0.01g of sodium hexametaphosphate as a surfactant for pretreatment, and continuously carrying out constant temperature dispersion pretreatment for 1h at 60 ℃; (2) dropwise adding a proper amount of hydrochloric acid solution with the concentration of 2.5mol/L into the pretreated suspension to adjust the pH of the suspension to 3, and raising the temperature of the suspension to 60 ℃ to realize homogeneous treatment of the suspension; (3) preparing a precursor solution: dissolving 3.45g of crystallized tin tetrachloride and 0.162g of antimony trichloride in 40ml of deionized water, dropwise adding hydrochloric acid until the acid concentration of the ATO solution is 2.5mol/L (4), adding the prepared ATO precursor solution into the suspension subjected to the homogeneous treatment in the step (2) at the speed of 40ml/min, dropwise adding a proper amount of potassium hydroxide solution with the mass concentration of 10% to keep the pH value of the coating solution unchanged at the same time, and continuing to perform constant-temperature aging reaction for 2 hours after dropwise adding is completed to complete the coating treatment; (5) and filtering and washing the suspension after the aging treatment to obtain a powder filter cake of suspended matters, then carrying out spray drying, wherein the temperature of an inlet liquid is 220 ℃ and the feeding rate is 45r/min during drying, and finally calcining the dried powder at 400 ℃ for 5h to obtain the core-shell type conductive titanium dioxide whisker of the embodiment.
The SEM image is shown in figure 3, and it can be seen that the surface of the whisker is uniformly and smoothly coated, and the problem of non-uniform coating caused by agglomeration of the coating is not found on the surface; taking 0.2g of the core-shell type conductive titanium dioxide whisker powder prepared in the embodiment, tabletting for 3min under the pressure of 20MPa, and testing the surface resistivity of a sample by using a four-probe resistance tester to obtain: 112 +/-10 omega cm.
Example 3
(1) Weighing 10g of titanium dioxide whisker powder, mechanically stirring and mixing the titanium dioxide whisker powder and 200ml of deionized water to form uniform suspension, dropwise adding 10% by mass of potassium carbonate solution, adjusting the pH value of the suspension to 11, heating to 60 ℃, carrying out constant temperature treatment for 10min, then adding a mixture of 0.05g of sodium silicate and 0.05g of sodium lignosulphonate as a surfactant for pretreatment, and continuously carrying out constant temperature dispersion pretreatment for 1h at 60 ℃; (2) dropwise adding a proper amount of hydrochloric acid solution with the concentration of 2mol/L into the pretreated suspension to adjust the pH of the suspension to 3, and raising the temperature of the suspension to 80 ℃ to realize homogeneous treatment of the suspension; (3) preparing a precursor solution, dissolving 4.6g of crystallized stannic chloride and 0.246g of antimony trichloride in 40ml of deionized water, and dropwise adding a proper amount of hydrochloric acid solution until the acid concentration of the ATO solution is 3 mol/L; (4) adding the prepared ATO precursor solution into the suspension subjected to the homogeneous phase treatment in the step (2) at the speed of 10ml/min, continuously dropwise adding a proper amount of potassium carbonate solution with the mass concentration of 10% to keep the pH value of the coating solution unchanged, and continuously performing constant-temperature aging reaction for 3 hours after dropwise adding is completed to complete the coating treatment; (5) and filtering and washing the suspension after the aging treatment to obtain a powder filter cake of suspended matters, then carrying out spray drying, wherein the temperature of an inlet liquid during drying is 2240 ℃, the feeding rate is 50r/min, and finally calcining the dried powder at 500 ℃ for 2.5h to obtain the core-shell type conductive titanium dioxide whisker of the embodiment. The SEM image is shown in figure 4, and it can be seen that the surface of the whisker is uniformly and smoothly coated, and the problem of non-uniform coating caused by agglomeration of the coating is not found on the surface; taking 0.2g of the core-shell type conductive titanium dioxide whisker powder prepared in the embodiment, tabletting for 3min under the pressure of 20MPa, and testing the surface resistivity of a sample by using a four-probe resistance tester to obtain: 105 + -10 omega cm.
In addition, the residual tin ions and antimony ions in the waste liquid obtained after the polyester washing in the example 1-3 were measured, and the residual tin ions and antimony ions were almost absent in the waste liquid, which indicates that the coating utilization rate of the coating agent substantially reaches 100%.
Comparative example 1
(1) Taking 10g of titanium dioxide whiskers, adding 100ml of deionized water, and fully dispersing for 1h through mechanical stirring; (2) adjusting the pH value of the dispersion suspension in (1) to 1 by 2mol/L hydrochloric acid solution, and raising the temperature to 60 ℃; (3) preparing an ATO precursor solution, dissolving 2.3g of crystallized stannic chloride and 0.08g of antimony trichloride in 40ml of deionized water, and dropwise adding hydrochloric acid until the acid concentration of the ATO solution is 1 mol/L; adding the prepared ATO solution into the suspension at the speed of 20ml/min, adjusting and controlling the pH value of the suspension to keep 1 unchanged, and continuing the constant-temperature aging reaction for 1h after the dropwise addition is finished; (3) and (4) filtering and washing the sample, and spray drying. The dried sample powder was calcined at 600 ℃ for 1 hour to obtain core-shell type conductive titanium dioxide whiskers of this comparative example, whose SEM image is shown in fig. 5. As can be seen from the graph, the conductive whiskers had a surface that was not smoothly agglomerated, indicating that the coating layer of the coating agent was not uniform, and the surface resistivity of the sample was measured in the same manner as in example 1, and found to be 0.73. + -. 0.05 kOmega-cm, which was significantly higher than the resistivity of the conductive whiskers in examples 1 to 3.
Comparative example 2
(1) Taking 10g of titanium dioxide whiskers, adding 150ml of deionized water, and dispersing for 1h at room temperature by adopting ultrasonic 150 Hz; (2) dropwise adding hydrochloric acid solution to adjust the pH to 3, and controlling the temperature of the suspension to be 60 ℃; preparing an ATO precursor solution: (3) dissolving 3.45g of crystallized stannic chloride and 0.162g of antimony trichloride in 40ml of deionized water, and dropwise adding hydrochloric acid until the acid concentration of the ATO solution is 2.5 mol/L; (4) adding the prepared ATO solution into the suspension at the speed of 40ml/min, adjusting the pH of the solution to 3, keeping unchanged, and continuing to perform a constant-temperature aging reaction at 60 ℃ for 2 hours after the dropwise addition is completed; (5) and (3) carrying out suction filtration and washing on the sample, carrying out spray drying, and calcining the dried sample powder at 500 ℃ for 1.5h to obtain the core-shell type conductive titanium dioxide whisker of the comparative example.
The SEM image is shown in FIG. 6. As can be seen from the figure, the surface resistivity of the sample was measured in the same manner as in example 1, and the result was 1.24 ± 0.05k Ω · cm, although the coating agent was not uniformly coated on the surface of the whisker and agglomerated.
Comparative example 3
(1) Taking 10g of titanium dioxide whiskers, adding 200ml of deionized water, and mechanically stirring and mixing to obtain a uniform suspension; . Dropwise adding alkali liquor to adjust the pH value of the suspension to 11, heating to 60 ℃, carrying out constant temperature treatment for 10min, then adding a surfactant consisting of 0.1g of sodium silicate and 0.1g of sodium lignosulphonate, continuously heating to 40 ℃, and carrying out constant temperature dispersion treatment for 1 h; (2) dropwise adding hydrochloric acid solution to adjust the pH value of the reaction solution to 3, raising the temperature of the suspension to 80 ℃, adding the prepared ATO solution (the preparation parameters of the ATO solution are that 4.6g of crystalline stannic chloride and 0.246g of antimony trichloride are dissolved in 40ml of deionized water, dropwise adding hydrochloric acid until the acid concentration of the ATO solution is 3 mol/L) into the suspension at the speed of 10ml/min, simultaneously controlling the pH value of the solution to be 11 through potassium carbonate alkali solution, and continuing to carry out constant-temperature aging reaction for 1h after the dropwise addition is finished. (3) And (3) carrying out suction filtration and washing on the sample, then carrying out spray drying, and finally calcining the dried sample powder at 500 ℃ for 1.5h to obtain the core-shell type conductive titanium dioxide whisker of the comparative example, wherein an SEM picture of the core-shell type conductive titanium dioxide whisker is shown in FIG. 7. The surface resistivity of the sample was measured by the same method as in example one, and the result was 383 ± 20 Ω · cm.

Claims (8)

1. Efficient preparation of core-shell ATO @ TiO2The method for conducting whiskers is characterized by comprising the following steps of:
a) mixing titanium dioxide whisker powder with deionized water to prepare a mixed solution with the mass concentration of 10-40%, and mechanically stirring for 10-30 min at the constant temperature of 40-60 ℃ to obtain a uniformly dispersed suspension A;
b) adding a sodium salt surfactant with the mass of 0.5-2% of that of the titanium dioxide whisker powder in the step a) into the suspension A, continuously dispersing for 0.5-2 h under a constant temperature condition, adjusting the pH value of the dispersed suspension to 1-5 by using an acid solution, and heating to 60-80 ℃ to obtain a homogeneous suspension B;
c) preparing an ATO precursor solution: respectively measuring tin tetrachloride crystals and antimony trichloride crystals according to the theoretical coating ratio of tin dioxide and the doping ratio of antimony trioxide, dissolving the tin tetrachloride crystals and the antimony trichloride crystals in a proper amount of deionized water, and adjusting the acid concentration in the solution to 1-5mol/L by using hydrochloric acid to obtain an ATO precursor solution;
uniformly adding the ATO precursor solution in the step c into the suspension B in the step B, simultaneously adding alkali liquor to enable the pH of the suspension to be 1-5, and carrying out aging reaction for 1-5 hours;
filtering and washing the suspension after the aging reaction in the step d, spray-drying, and calcining at 400-700 ℃ for 1-5h to obtain the core-shell ATO @ TiO2And (3) conductive whiskers.
2. The efficient preparation of core-shell ATO @ TiO of claim 12The method for conducting the whiskers is characterized in that in the step a, the pH value of suspension is adjusted to 6-11 through ammonia water during pretreatment of the suspension after the titanium dioxide whiskers are mixed with deionized water.
3. The efficient preparation of core-shell ATO @ TiO of claim 12The method for conducting the crystal whisker is characterized in that in the step b, the sodium salt surfactant is one or the combination of more than one of trisodium phosphate, tetrasodium phosphate, sodium hexametaphosphate, sodium silicate and sodium lignosulphonate, and the addition mass of the sodium salt surfactant is 0.5-2% of the mass of the titanium dioxide crystal whisker powder.
4. The efficient preparation of core-shell ATO @ TiO of claim 12The method for preparing the conductive whiskers is characterized in that in the step c, when the ATO precursor solution is prepared, the coating ratio of the tin dioxide refers to that the mass of the titanium dioxide whisker powder in the conductive whiskers is 10-20%, and the antimony trioxide doping ratio refers to that the mass of the antimony trioxide is 1-10%.
5. The efficient preparation of the core-shell ATO @ TiO of claim 42The method for conducting the crystal whisker is characterized in that in the step c, according to the coating ratio of the tin dioxide, the adding mass of the tin tetrachloride crystal is the oxidation of the tin dioxide in the step a)The adding mass of the titanium whisker powder is 23-46%, the adding mass of the antimony trichloride crystal is 0.67-6.7% of the adding mass of the tin tetrachloride, and the mass concentration of the ATO precursor liquid tin tetrachloride is 5-20%.
6. The efficient preparation of core-shell ATO @ TiO of claim 12The method for conducting whiskers is characterized in that in the step d), the aging temperature is 60-80 ℃.
7. The efficient preparation of core-shell ATO @ TiO of claim 12The method for conducting the whiskers is characterized in that in the step d, the dropwise added alkali liquor is non-sodium ion alkali liquor.
8. The efficient preparation of core-shell ATO @ TiO of claim 12The method for conducting the whiskers is characterized in that in the step e, the suspension filtering and washing mode is water washing and pressure filtration to obtain a powder filter cake, and during spray drying, the temperature of a material spray inlet is 180-.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115520896A (en) * 2022-10-09 2022-12-27 南通大学 Preparation method of composite conductive powder based on photoelectric effect

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