CN114988868A - 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 the technical field of multifunctional electronic ceramic materials, and discloses a preparation method of a strontium titanate ceramic with a giant dielectric constant and low dielectric loss. Mixing the raw materials by an oxalic acid precipitation method, washing, drying and sieving after full reaction, placing the sieved powder in a muffle furnace for calcining, cooling to room temperature and taking out the powder; and pressing and molding the powder, putting the powder into a muffle furnace, and sintering for 4 hours at the temperature of 1400 ℃ and 1500 ℃ to obtain the required strontium titanate ceramic. Preparing SrTi 1‑x (Zn 1/3 Nb 2/3 ) x O 3 The dielectric ceramic has obviously improved dielectric constant and lower dielectric loss, so that the dielectric property of the ceramic is further improved, and the requirements of production and life are met to the greatest extent.
Description
Technical Field
The invention belongs to the technical field of multifunctional electronic ceramic materials, and relates to a preparation method of a strontium titanate ceramic with a 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 formats, more energy will be converted into electricity. Electrical energy storage is becoming more complex and important, and more reliable and high performance energy storage technologies are needed to achieve efficient, versatile and environmentally friendly energy utilization. Strontium titanate having a typical perovskite structure is considered a promising lead-free energy storage material due to its unique physical properties. Therefore, the improvement of the dielectric properties of the strontium titanate ceramics is imminent.
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 of the method is not easy to be completely carried out, so that the produced powder has poor purity, granularity, composition uniformity and the like.
The following two methods are generally used 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 vacancy of the strontium titanate ceramic by changing the sintering atmosphere. Wang et al doped strontium titanate based ceramics with Nb in N 2 The ceramic is calcined in an atmosphere to obtain a value of > 10 4 And a dielectric loss of < 0.05; pan et al are at O 2 And N 2 The strontium titanate-based ceramic is subjected to medium sintering to obtain the product N 2 The medium-sintered dielectric ceramic has more excellent dielectric properties. However, high dielectric constants are often accompanied by higher dielectric losses. Therefore, the search for a dielectric ceramic with a huge dielectric constant and low dielectric loss is an urgent problem to be solved in the field of electronic ceramics.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of strontium titanate ceramic with giant dielectric constant and low dielectric loss, which solves the problem of low dielectric constant of strontium titanate ceramic materialAnd dielectric loss, etc., with 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 constant of the dielectric ceramic is obviously improved, and simultaneously, the lower dielectric loss of the dielectric ceramic is ensured as much as possible, so that the dielectric property of the ceramic is further improved, and the requirements of production and life are met to the greatest extent.
The above purpose of the invention is realized by the following technical scheme:
a strontium titanate ceramic with giant dielectric constant and low dielectric loss has the chemical formula of SrTi 1-x (Zn 1/3 Nb 2/3 ) x O 3 And 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 giant dielectric constant and low dielectric loss strontium titanate ceramic, the preparation method adopts an oxalic acid precipitation method to mix the raw materials, the raw materials are washed, dried and sieved after full reaction, the sieved powder is placed in a muffle furnace to be calcined, and the powder is taken out after being cooled to room temperature; and pressing and molding the powder, putting the powder into a muffle furnace, and sintering for 4 hours at the temperature of 1400 ℃ and 1500 ℃ to obtain the required strontium titanate ceramic.
The preparation method of the strontium titanate ceramic with giant dielectric constant and low dielectric loss comprises the following specific steps:
(1) oxalic acid and SrCl 2 、TiCl 4 、Nb 2 O 5 And ZnO SrTi according to the formula 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 a titanium tetrachloride solution to form a mixed solution B; wherein the mol 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;
(3) putting the solution A in the step (2) in a water bath kettle all the time, slowly dropping the mixed solution B into the solution A, and reacting to generate a precipitate;
(4) after full reaction, 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) at 1150 ℃ for 3 h;
(6) sieving the calcined powder obtained 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) carrying out glue discharging on the green body obtained in the step (7) until the adhesive is completely removed;
(9) and (4) sintering the green body obtained in the step (8) in a reducing atmosphere, wherein the sintering temperature is 1450 ℃, and the temperature is kept for 4 hours to obtain the required strontium titanate ceramic.
Further, the temperature of the water bath in the step (3) is 40-70 ℃.
Further, the drying temperature in the step (4) and the drying temperature in the step (7) are both 40-80 ℃.
Further, the sieving in the step (4) and the sieving in the step (6) are both performed 3-5 times through a 120-mesh sieve.
Further, the washing in step (4) is carried out by suction-filtering and washing the precipitate with a buchner flask and a vacuum pump.
Further, the adhesive in the step (7) is polyvinyl alcohol with a mass ratio of 6%.
Further, the sieving in the step (7) is 2-3 times of sieving with a 140-mesh sieve.
The strontium titanate ceramic obtained by the invention has giant dielectric constant and low dielectric loss, and the dielectric constant of the strontium titanate ceramic can reach 2 multiplied by 10 5 The dielectric loss is as low as 0.008, and the dielectric property is far better than that of the common strontium titanate ceramic. The product prepared by the preparation method provided by the invention has high purity and small grain size, is a cubic phase, and can meet the requirement 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 adopts a liquid phase method to prepare SrTi 1-x (Zn 1/ 3 Nb 2/3 ) x O 3 A dielectric ceramic. The doped samples were processed in nitrogen, then the ceramic would achieve a giant dielectric constant and low dielectric losses due to fully ionized oxygen vacancies and large defect dipoles. Specific parameters are defined on the process to improve the dielectric property of the dielectric ceramic, so that the requirements in production and life are better met. The dielectric constant ε of the strontium titanate dielectric ceramic r 701-224096.5, dielectric loss tan delta is 0.008-0.1, the ceramic powder prepared by the preparation method is fine and has high purity, the dielectric property of the ceramic is excellent, the process method is simple, and the ceramic powder has very wide application prospect.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.
Example 1
1. Oxalic acid and SrCl 2 、TiCl 4 、Nb 2 O 5 And ZnO SrTi according to the formula 1-x (Zn 1/3 Nb 2/3 ) x O 3 (x is 0.015) batching;
2. weighing 76g of oxalic acid with the content of 1.0007, and dissolving in 300ml of deionized water; weigh 0.3365g Nb 2 O 5 And 0.0814g ZnO in a small beaker, adding a proper amount of deionized water, and then putting the small beaker into an ultrasonic cleaning machine for ultrasonic treatment for 30min to ensure that the doped sample is more dispersed; finally, mixing the doped sample with an oxalic acid solution;
3. 50g of SrCl with a content of 1.0626 were weighed 2 Dissolving in 200ml deionized water; 122ml of 1.6409mol/L TiCl were metered in 4 (ii) a Mixing the two solutions uniformly;
4. placing the solution in the step 2 in a water bath kettle at 40-70 ℃ and continuously stirring, and slowly and uniformly dripping the mixed solution in the step 3 for reaction for 1 h;
5. after full reaction, washing the obtained powder with deionized water, detecting whether chloride ions are cleaned by silver nitrate, drying the powder in an electric heating forced air drying oven at the temperature of 40-80 ℃, and sieving the powder with a 120-mesh sieve for 3-5 times;
6. placing the obtained powder in a muffle furnace, presintering at 1150 ℃, and keeping the temperature for 3 hours;
7. sieving the presintered powder with a 120-mesh sieve for 3-5 times, adding 6% polyvinyl alcohol adhesive in the sieved powder, drying, grinding with an agate mortar, and sieving with a 140-mesh sieve for 2-3 times;
8. pressing the obtained powder into a green body by using a hydraulic press at 200MPa, placing the green body into a muffle furnace for rubber discharge, slowly heating to 600 ℃, and keeping the temperature for 2 hours;
9. putting the green body after rubber discharge on N 2 Calcining in 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; and then the dielectric property of the prepared sample is tested by a desk type 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 Dielectric ceramics, which differ only in that the sintering atmosphere in step 9 is air, and the rest of the steps are the same as in embodiment 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 Dielectric ceramics, which differ only in that the sintering temperature in step 9 is 1400 ℃.
Example 4
Preparation method of SrTi according to traditional solid phase method 1-x (Zn 1/3 Nb 2/3 ) x O 3 Dielectric ceramicThe other points are the same as those of 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 Dielectric ceramics, which differ 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 Dielectric ceramics, which differ 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 Dielectric ceramics, which differ only in that the doping ratio x in step 1 is 0.15.
The dielectric properties of the products prepared in examples 1 to 7 were measured and the results are detailed in Table 1
Table 1 dielectric properties of the products prepared in examples 1-7
The test results show that: sintering atmosphere of N 2 The ionization and movement of oxygen vacancies then cause N to form due to the giant dielectric constant and low dielectric loss created by the fully ionized oxygen vacancies and the giant defect dipoles 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 an atmosphere. At a sintering temperature of 1400 deg.C, the doped sample is not fully doped due to the temperature reduction, resulting in a reduction in dielectric constant over 1450 deg.C. When the doping ratio is x equal to 0.006, the modification of the dielectric constant is not obvious due to the small doping content; when the doping ratio is 0.15, the doping amount is largeIncomplete doping and impurity phase generation caused by excessive doping, so that the dielectric property of the dielectric ceramic is deteriorated; when the preparation method is a traditional solid phase method, the dielectric property of the ceramic can not meet the requirements of high-grade electronic ceramics because the raw materials are difficult to be mixed uniformly and the reaction temperature is high and difficult to be carried out completely. When the doping proportion is more than or equal to 0.009 and 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 a dielectric constant > 10 5 In the process, the dielectric loss can be less than 0.02, so that the dielectric property is excellent, and the application requirement of the modern technology can be met.
The embodiments described above are only preferred embodiments of the invention, and are not all possible embodiments for the practical implementation of the invention. Any obvious modifications thereof, which would occur to one skilled in the art without departing from the principles and spirit of the invention, are to be considered as included within the scope of the following claims.
Claims (10)
1. A strontium titanate dielectric ceramic with giant dielectric constant and low dielectric loss is characterized in that the chemical formula is SrTi 1-x (Zn 1/3 Nb 2/3 ) x O 3 ，0.009≤x≤0.015。
2. The giant dielectric constant, low dielectric loss strontium titanate dielectric ceramic of claim 1, formed from oxalic acid, SrCl 2 、TiCl 4 、Nb 2 O 5 And ZnO as raw materials.
3. A method for preparing a giant dielectric constant and low dielectric loss strontium titanate dielectric ceramic as claimed in any one of claims 1-2, which is carried out by the steps of:
(1) oxalic acid and SrCl 2 、TiCl 4 、Nb 2 O 5 And ZnO SrTi in accordance with the formula 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 a titanium tetrachloride solution to form a mixed solution B; wherein the mol 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;
(3) putting the solution A in the step (2) in a water bath kettle all the time, and slowly dropping the mixed solution B into the solution A;
(4) after full reaction, washing, drying and sieving the powder obtained in the step (3) to obtain powder with uniform particles;
(5) calcining the powder obtained in the step (4) at 1150 ℃ for 3 h;
(6) sieving the calcined powder obtained in the step (5) to obtain strontium titanate powder with uniform particles;
(7) adding an adhesive into the powder obtained in the step (6), drying, grinding, sieving, and pressing a ceramic green body;
(8) carrying out glue discharging on the green body obtained in the step (7) until the adhesive is completely removed;
(9) and (4) sintering the green body obtained in the step (8) in a reducing atmosphere, wherein the sintering temperature is 1450 ℃, and the temperature is kept for 4 hours to obtain the required strontium titanate ceramic.
4. The method of claim 3, wherein the oxalic acid in the step (2) is in excess of 50%.
5. The method for preparing a giant dielectric constant and low dielectric loss strontium titanate dielectric ceramic according to claim 3, wherein the temperature of the water bath in step (3) is 40-70 ℃.
6. The method for preparing a strontium titanate dielectric ceramic having a giant dielectric constant and low dielectric loss according to claim 3, wherein the baking temperature in step (4) and step (7) is 40-80 ℃.
7. The method for preparing a giant dielectric constant and low dielectric loss strontium titanate dielectric ceramic according to claim 3, wherein the sieves in step (4) and step (6) are sieved 3-5 times through a 120-mesh sieve.
8. The method of claim 3, wherein the washing in step (4) is performed by suction filtration using a Buchner flask and a vacuum pump to clean the precipitate.
9. The method of claim 3, wherein the binder in the step (7) is polyvinyl alcohol in an amount of 6% by mass.
10. The method for preparing a giant dielectric constant and low dielectric loss strontium titanate dielectric ceramic according to claim 3, wherein the sieving in step (7) is performed 2-3 times through a sieve of 140 mesh.
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