CN114988868B - Preparation method of strontium titanate ceramic with giant dielectric constant and low dielectric loss - Google Patents
Preparation method of strontium titanate ceramic with giant dielectric constant and low dielectric loss Download PDFInfo
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Abstract
The invention belongs to a multifunctional deviceThe technical field of electronic ceramic materials, and discloses a preparation method of strontium titanate ceramic with giant dielectric constant and low dielectric loss. Mixing raw materials by an oxalic acid precipitation method, washing, drying and sieving after full reaction, placing the sieved powder in a muffle furnace for calcination, and taking out the powder after cooling to room temperature; and (3) after the powder is pressed and formed, putting the powder into a muffle furnace, and sintering the powder for 4 hours at 1400-1500 ℃ to obtain the required strontium titanate ceramic. Preparation of SrTi 1‑x (Zn 1/3 Nb 2/3 ) x O 3 The dielectric ceramic has obviously raised dielectric constant and low dielectric loss, and has further improved dielectric performance, so as to meet the requirement of production and life.
Description
Technical Field
The invention belongs to the technical field of multifunctional electronic ceramic materials, and relates to a preparation method of strontium titanate ceramic with giant dielectric constant and low dielectric loss. In particular to a method for synthesizing niobium and zinc doped strontium titanate ceramic powder by a liquid phase method.
Background
In future new energy patterns, more energy will be converted into electrical energy. Electrical energy storage is becoming more complex and important, and thus more reliable and high performance energy storage technologies are needed to achieve efficient, multi-functional and environmentally friendly energy utilization. Strontium titanate having a typical perovskite structure is considered to be a lead-free energy storage material with good prospects due to its unique physical properties. Therefore, improvement of the dielectric properties of strontium titanate ceramics is an urgent issue.
The preparation method of the strontium titanate powder mainly comprises the following steps: solid phase method, hydrothermal method, liquid phase method, sol-gel method, alkali fusion method, etc. The most traditional method is a solid phase method, but the reaction is not easy to complete, so the produced powder is poor in purity, granularity, composition uniformity and the like.
The following two methods are generally employed to increase the dielectric constant of strontium titanate ceramics: one is to change the defect concentration of the strontium titanate ceramic by doping modification, and the other is to change the oxygen vacancies of the strontium titanate ceramic by changing the sintering atmosphere. Wang et al doped strontium titanate-based ceramics with Nb and N 2 Calcining the ceramic in the atmosphere to obtain the product with the particle diameter of more than 10 4 A dielectric constant and a dielectric loss of < 0.05; pan et al at O respectively 2 And N 2 Middle sintering strontium titanate base ceramic to obtain the product in N 2 The medium sintered dielectric ceramic has more excellent dielectric properties. But high dielectric constants are often accompanied by higher dielectric losses. Therefore, the exploration of dielectric ceramics with huge dielectric constant and low dielectric loss is an urgent problem to be solved in the current electronic ceramic field.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of strontium titanate ceramics with huge dielectric constant and low dielectric loss, solves the related technical problems of low dielectric constant, high dielectric loss and the like of strontium titanate ceramic materials, and uses oxalic acid and SrCl 2 、TiCl 4 、Nb 2 O 5 And ZnO as raw materials, and preparing SrTi by doping modification and adopting a liquid phase method 1-x (Zn 1/3 Nb 2/3 ) x O 3 The dielectric ceramic has obviously raised dielectric constant and low dielectric loss, and has further improved dielectric performance, so as to meet the requirement of production and life.
The above object of the present invention is achieved by the following technical solutions:
a strontium titanate ceramic with giant dielectric constant and low dielectric loss has the chemical equation SrTi 1-x (Zn 1/3 Nb 2/3 ) x O 3 X is more than or equal to 0.009 and less than or equal to 0.015. From oxalic acid, srCl 2 、TiCl 4 、Nb 2 O 5 And ZnO as raw materials.
The invention also claims a preparation method of the strontium titanate ceramic with the giant dielectric constant and the low dielectric loss, which adopts an oxalic acid precipitation method to mix raw materials, washes, dries and sieves after full reaction, and then the sieved powder is placed in a muffle furnace to be calcined, and is cooled to room temperature and then taken out; and (3) after the powder is pressed and formed, putting the powder into a muffle furnace, and sintering the powder for 4 hours at 1400-1500 ℃ to obtain the required strontium titanate ceramic.
The preparation method of the strontium titanate ceramic with the giant dielectric constant and the low dielectric loss comprises the following specific steps:
(1) Oxalic acid, srCl 2 、TiCl 4 、Nb 2 O 5 And ZnO according to the chemical formula SrTi 1-x (Zn 1/3 Nb 2/3 ) x O 3 X is more than or equal to 0.009 and less than or equal to 0.015;
(2) Dissolving oxalic acid in deionized water, adding niobium pentoxide and zinc oxide to form a solution A, dissolving strontium chloride in the deionized water, and adding titanium tetrachloride solution to form a mixed solution B; wherein the molar ratio of oxalic acid, niobium pentoxide, zinc oxide, strontium chloride and titanium tetrachloride is 3:0.001-0.005:0.001-0.005:1:1, a step of;
(3) Placing the solution A in the step (2) in a water bath, slowly dripping the mixed solution B into the solution A, and reacting to generate precipitate;
(4) After the reaction is fully carried out, washing, drying and sieving the precipitate obtained in the step (3) to obtain powder with uniform particles;
(5) Calcining the powder obtained in the step (4) for 3 hours at 1150 ℃;
(6) Sieving the powder calcined in the step (5) to obtain strontium titanate powder with uniform particles;
(7) Adding an adhesive into the strontium titanate powder obtained in the step (6), drying, grinding, sieving, and pressing a ceramic green body;
(8) Discharging the adhesive from the green body obtained in the step (7) until the adhesive is completely removed;
(9) Sintering the green body obtained in the step (8) in a reducing atmosphere at 1450 ℃ for 4 hours to obtain the required strontium titanate ceramic.
Further, the water bath temperature in the step (3) is 40-70 ℃.
Further, the drying temperature in the step (4) and the step (7) is 40-80 ℃.
Further, the screening in the step (4) and the step (6) is carried out 3-5 times by 120-mesh screening.
Further, the precipitate is washed in step (4) by a buchner flask and a vacuum pump for filtration.
Further, the binder in the step (7) is polyvinyl alcohol with a mass ratio of 6%.
Further, the screening in the step (7) is to pass through a 140 mesh screen 2 to 3 times.
The strontium titanate ceramic obtained by the invention has giant dielectric constant and low dielectric loss, and the dielectric constant can reach 2 multiplied by 10 5 And the dielectric loss is as low as 0.008, and the dielectric property is far better than that of common strontium titanate ceramics. The product prepared by the preparation method provided by the invention has high purity, small particle size and cubic phase, and can meet the requirements of preparing high-performance ceramics. The invention has high practical value in production and life. Can be widely applied to industries such as electronics, machinery and the like.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses oxalic acid and SrCl 2 、TiCl 4 、Nb 2 O 5 And ZnO as raw materials, and preparing SrTi by adopting a liquid phase method 1-x (Zn 1/ 3 Nb 2/3 ) x O 3 A dielectric ceramic. The doped sample is treated in nitrogen and then the ceramic will achieve a giant dielectric constant and low dielectric loss due to fully ionized oxygen vacancies and large defect dipoles. Specific parameters are defined in the process to improve the dielectric property of the material, so that the production and life requirements are better met. Dielectric constant epsilon of the strontium titanate dielectric ceramic r The dielectric loss tan delta is 0.008-0.1, the ceramic powder prepared by the preparation method is fine, high in purity, excellent in dielectric property of ceramic, simpler in process method and wide in application prospect.
Detailed Description
The present invention is described in detail below by way of specific examples, but the scope of the present invention is not limited thereto. Unless otherwise specified, the experimental methods used in the present invention are all conventional methods, and all experimental equipment, materials, reagents, etc. used can be obtained from commercial sources.
Example 1
1. Oxalic acid, srCl 2 、TiCl 4 、Nb 2 O 5 And ZnO according to the chemical formula SrTi 1-x (Zn 1/3 Nb 2/3 ) x O 3 (x=0.015);
2. 76g of oxalic acid with the content of 1.0007 is weighed and dissolved in 300ml of deionized water; 0.3365g Nb is weighed 2 O 5 Adding 0.0814g ZnO into a small beaker, adding a proper amount of deionized water, and then putting the small beaker into an ultrasonic cleaner for ultrasonic treatment for 30min to enable the doped sample to be more dispersed; finally, mixing the doped sample with oxalic acid solution;
3. 50g of SrCl with a content of 1.0626 are weighed 2 Dissolving in 200ml deionized water; 122ml of TiCl having a concentration of 1.6409mol/L are measured out 4 The method comprises the steps of carrying out a first treatment on the surface of the Mixing the two materials uniformly;
4. placing the solution in the step 2 in a water bath kettle at 40-70 ℃ and continuously stirring, slowly and uniformly dripping the mixed solution in the step 3, wherein the reaction time is 1h;
5. after the full reaction, washing the obtained powder with deionized water, checking whether chloride ions are cleaned or not with silver nitrate, putting the powder into an electrothermal blowing drying oven, drying at 40-80 ℃ and sieving with a 120-mesh sieve for 3-5 times;
6. placing the obtained powder in a muffle furnace, presintering at 1150 ℃ and preserving heat for 3h;
7. the presintered powder is screened by a 120-mesh sieve for 3 to 5 times, then the polyvinyl alcohol adhesive with the mass fraction of 6 percent is added into the screened powder, and the powder is ground by an agate mortar and screened by a 140-mesh sieve for 2 to 3 times after being dried;
8. the obtained powder is used for pressing a ceramic green body, a hydraulic press is used for pressing the ceramic green body into a green body under 200MPa, the ceramic green body is put into a muffle furnace for glue discharging, the temperature is slowly increased to 600 ℃, and the heat preservation time is 2 hours;
9. placing the green body after glue discharge in N 2 Calcining under atmosphere at 1450 deg.C for 4 hr to obtain SrTi 1-x (Zn 1/3 Nb 2/3 ) x O 3 A ceramic;
10. silver plating the ceramic obtained in the step 9; the dielectric properties of the resulting samples were then tested by bench LCR digital bridge.
Example 2
SrTi was prepared according to the preparation method of example 1 1-x (Zn 1/3 Nb 2/3 ) x O 3 The dielectric ceramic was different only in that the sintering atmosphere in step 9 was air, and the rest of the steps were the same as in example 1.
Example 3
SrTi was prepared according to the preparation method of example 1 1-x (Zn 1/3 Nb 2/3 ) x O 3 The dielectric ceramic differs only in that the sintering temperature in step 9 is 1400 ℃.
Example 4
SrTi is prepared according to the traditional solid phase method 1-x (Zn 1/3 Nb 2/3 ) x O 3 The dielectric ceramic was the same as in example 1.
Example 5
SrTi was prepared according to the preparation method of example 1 1-x (Zn 1/3 Nb 2/3 ) x O 3 The dielectric ceramic differs only in that the doping ratio x in step 1 is 0.009.
Example 6
SrTi was prepared according to the preparation method of example 1 1-x (Zn 1/3 Nb 2/3 ) x O 3 The dielectric ceramic differs only in that the doping ratio x in step 1 is 0.006.
Example 7
SrTi was prepared according to the preparation method of example 1 1-x (Zn 1/3 Nb 2/3 ) x O 3 The dielectric ceramic differs only in that the doping ratio x in step 1 is 0.15.
The products prepared in examples 1 to 7 were subjected to dielectric properties and the results are shown in Table 1
TABLE 1 dielectric Properties of the products prepared in example 1-example 7
The test results above show that: the sintering atmosphere is N 2 When the oxygen vacancies are completely ionized and the huge defect dipole generates giant dielectric constant and low dielectric loss, the ionization and the movement of the oxygen vacancies lead to N 2 Dielectric properties of dielectric ceramics calcined in an atmosphere are far superior to those of dielectric ceramics calcined in O 2 Dielectric ceramic calcined in atmosphere. At a sintering temperature of 1400 ℃, the doped sample is not fully doped due to the temperature decrease, resulting in a decrease in the dielectric constant compared to 1450 ℃. When the doping proportion is x=0.006, the dielectric constant modification is not obvious due to the smaller doping content; when the doping ratio is x=0.15, the dielectric properties of the dielectric ceramic are deteriorated due to incomplete doping and generation of impurity phases caused by excessive doping amount; when the preparation method is a traditional solid phase method, the raw materials are difficult to mix uniformly, and the reaction temperature is high and difficult to complete, so that the dielectric property of the ceramic cannot meet the requirements of high-grade electronic ceramics. When the doping ratio is 0.009 less than or equal to x less than or equal to 0.015, the dielectric constant epsilon of the ceramic is 7746-224096.5, and the dielectric loss tan delta is 0.02-0.10. At dielectric constant > 10 5 And when the dielectric loss is smaller than 0.02, the dielectric property is excellent, and the application requirements of the modern technology can be met.
The above-described embodiments are only preferred embodiments of the invention, and not all embodiments of the invention are possible. Any obvious modifications thereof, which would be apparent to those skilled in the art without departing from the principles and spirit of the present invention, should be considered to be included within the scope of the appended claims.
Claims (1)
1. A process for preparing the dielectric strontium titanate ceramic with high dielectric constant and low dielectric loss features that,
1. oxalic acid, srCl 2 、TiCl 4 、Nb 2 O 5 And ZnO according to the chemical formula SrTi 1-x (Zn 1/3 Nb 2/3 ) x O 3 (x=0.015);
2. 76g of oxalic acid with the content of 1.0007 is weighed and dissolved in 300ml of deionized water; 0.3365g Nb is weighed 2 O 5 Adding 0.0814g ZnO into a small beaker, adding a proper amount of deionized water, and then putting the small beaker into an ultrasonic cleaner for ultrasonic treatment for 30min to enable the doped sample to be more dispersed; finally, mixing the doped sample with oxalic acid solution;
3. 50g of SrCl with a content of 1.0626 are weighed 2 Dissolving in 200ml deionized water; 122ml of TiCl having a concentration of 1.6409mol/L are measured out 4 The method comprises the steps of carrying out a first treatment on the surface of the Mixing the two materials uniformly;
4. placing the solution in the step 2 in a water bath kettle at 40-70 ℃ and continuously stirring, slowly and uniformly dripping the mixed solution in the step 3, wherein the reaction time is 1h;
5. after the full reaction, washing the obtained powder with deionized water, checking whether chloride ions are cleaned or not with silver nitrate, putting the powder into an electrothermal blowing drying oven, drying at 40-80 ℃ and sieving with a 120-mesh sieve for 3-5 times;
6. placing the obtained powder in a muffle furnace, presintering at 1150 ℃ and preserving heat for 3h;
7. the presintered powder is screened by a 120-mesh sieve for 3 to 5 times, then the polyvinyl alcohol adhesive with the mass fraction of 6 percent is added into the screened powder, and the powder is ground by an agate mortar and screened by a 140-mesh sieve for 2 to 3 times after being dried;
8. the obtained powder is used for pressing a ceramic green body, a hydraulic press is used for pressing the ceramic green body into a green body under 200MPa, the ceramic green body is put into a muffle furnace for glue discharging, the temperature is slowly increased to 600 ℃, and the heat preservation time is 2 hours;
9. placing the green body after glue discharge in N 2 Calcining under atmosphere at 1450 deg.C for 4 hr to obtain SrTi 1-x (Zn 1/ 3 Nb 2/3 ) x O 3 And (3) ceramics.
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