CN1256299C - Energy accumulating dielectric ceramic and its prepn process - Google Patents

Energy accumulating dielectric ceramic and its prepn process Download PDF

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CN1256299C
CN1256299C CN 200410061202 CN200410061202A CN1256299C CN 1256299 C CN1256299 C CN 1256299C CN 200410061202 CN200410061202 CN 200410061202 CN 200410061202 A CN200410061202 A CN 200410061202A CN 1256299 C CN1256299 C CN 1256299C
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sro
mgo
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CN1636931A (en
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刘韩星
余洪滔
吴朝晖
尧中华
曹明贺
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Abstract

The present invention relates to energy accumulating dielectric ceramics and a preparing method thereof. The ceramics comprise the chemical constitution of SrO-Bi2O3-TiO2, and the molar ratio of SrO to Bi2O3 to TiO2 is 1 to x to y, wherein x is from 0.02 to 0.15, and y is from 1.02 to 1.12; ZnO, MgO and ZrO2 whose purity is greater than 99% are doped. In the preparing method, SrCO3, Bi2O3 and TiO2 whose purity is greater than 99% are used as initial raw materials, and the chemical ratio of the SrO to the Bi2O3 to the TiO2 is 1 to x to y, wherein x is from 0.02 to 0.15, and y is from 1.02 to 1.12; after deionized water is added the raw materials which are ground by a ball mill for 11 to 13 hours, the raw materials are dried; the raw materials are presintered at 800 to 1200 DEG C for 3 to 5 hours; ZnO, MgO and ZrO2 whose purity is greater than 99% are added, and deionized water is added the mixing materials which are ground by a ball mill, and are mixed; then the mixed materials are baked in an air atmosphere; after baking, polyvinyl alcohol water solution whose concentration is 0.5 to 2.0 wt% is added to the materials for granulation; the energy accumulating dielectric ceramics are obtained by pressed moulding and sintering. The obtained energy accumulating dielectric ceramics have the advantages of high dielectric constant, low loss and high breakdown strength.

Description

Energy-storing dielectric ceramic and preparation method thereof
Technical field
The present invention relates to a kind of energy-storing dielectric ceramic and preparation method thereof, be specifically related to a kind of SrO-Bi 2O 3-TiO 2Base energy storage medium ceramic and preparation method.
Background technology
The pulse formation technology is the important topic in the research of high-voltage pulse power, and for adapting to the development that solid state pulse forms line, the direction of pulse formation technology forward low-resistance high current, miniaturization develops.This just requires energy-storing dielectric ceramic to satisfy the requirement of following dielectric and voltage endurance: the relative permittivity ε that (1) is high r(2) low dielectric loss tg η; (3) high disruptive strength E bAt present, the research system of energy-storing dielectric ceramic has TiO 2And BaTiO 3TiO 2Pottery has high disruptive strength, its E b〉=35kv/mm, but TiO 2The ceramic dielectric constant has certain limitation; BaTiO 3Pottery has high specific inductivity, but BaTiO 3The pottery disruptive strength is on the low side, E b=5 ~ 8kv/m, dielectric loss is bigger than normal, and has electrostriction phenomena.SrTiO 3Base ceramic dielectric constant is higher relatively, high-frequency loss is little, electrostriction is little, and disruptive strength E bRelative TiO 2Pottery is lower.Traditional SrO-Bi 2O 3-TiO 2Capacitance ceramic dielectric loss under high frequency is big, and specific inductivity is big with the variation of frequency, and disruptive strength is on the low side, must improve to satisfy the requirement of energy-storing dielectric ceramic dielectric and voltage endurance
Summary of the invention
The purpose of this invention is to provide a kind of energy-storing dielectric ceramic, a kind of preparation method of this media ceramic is provided simultaneously with high-k, low-loss, higher disruptive strength.
The objective of the invention is to realize with following technical proposals:
A kind of energy-storing dielectric ceramic is characterized in that: its main chemical constitution is SrO-Bi 2O 3-TiO 2, SrO, Bi 2O 3And TiO 2Molar ratio be: 1: x: y, x=0.02 ~ 0.15 wherein, y=1.02 ~ 1.12, and be mixed with 0.05 ~ 0.5wt%ZnO, 0.05 ~ 0.5wt%MgO and 1 ~ 10wt%ZrO therein 2
The preparation process of this energy-storing dielectric ceramic is:
1st, with purity greater than 99% SrCO 3, Bi 2O 3And TiO 2Be starting raw material, in strict accordance with SrO: Bi 2O 3: TiO 2=1: x: y (wherein x=0.02 ~ 0.15, y=1.02 ~ 1.12) chemistry adds in ball mill and grinds oven dry after 11-13 hour in the deionized water than batching, in 800 ~ 1200 ℃ of insulations pre-burning in 3-5 hour:
2nd, get the resulting SrO-Bi of step 1 2O 3-TiO 2Powder adds purity greater than 99% ZnO, MgO and ZrO 2, in ball mill, adding in the deionized water ground and mixed 22-26 hour, air atmosphere is oven dry down;
3rd, add the polyvinyl alcohol water solution granulation, compression moulding, sintering in the High Temperature Furnaces Heating Apparatus air atmosphere is made energy-storing dielectric ceramic;
The ZnO of wherein said adding, MgO and ZrO 2Amount accounts for 0.05 ~ 0.5wt%, 0.05 ~ 0.5wt% and the 1 ~ 10wt% of mixed powder total amount respectively; Described polyvinyl alcohol water solution concentration is 0.5 ~ 2.0wt%, and add-on is 5 ~ 10wt% of mixed powder total amount; The pressure of described compression moulding is 160 ~ 200Mpa; Described sintering temperature is 1350 ~ 1450 ℃, and described sintering time is 2 ~ 6 hours.
At this SrO-Bi 2O 3-TiO 2=1: x: in the preparation of y (wherein x=0.02 ~ 0.12, y=1.02 ~ 1.12) energy-storing dielectric ceramic, our test-results is: work as Bi 2O 3Mixed ratio surpass at 0.15 o'clock, the dielectric loss tg η of media ceramic will significantly increase to 90 * 10 -3More than; Work as Bi 2O 3Mixed ratio less than 0.02 o'clock, the relative permittivity ε of media ceramic rBe decreased to 430; Work as TiO 2Mixed ratio less than 1.02 o'clock, the specific inductivity of material is lower; Work as TiO 2Mixed ratio surpass at 1.12 o'clock, the loss of media ceramic significantly increases; If polyvinyl alcohol (PVA) aqueous solution that adds is less than 5wt%, sample is difficult to dry-pressing formed; If the PVA aqueous solution mass concentration that adds is greater than 10wt%, the media ceramic surface is easy to generate evil mind, and its withstand voltage properties is worsened; When sintering temperature was lower than 1350 ℃, the media ceramic density can significantly descend, and when sintering temperature was higher than 1450 ℃, then fusion phenomenon overbumt can appear in sample, and its dielectric and withstand voltage properties are worsened; If soaking time is lower than 2 hours, sample media loss meeting is risen, if soaking time surpasses 6 hours, the sample withstand voltage properties can descend.
The present invention is by control SrO-Bi 2O 3-TiO 2=1: x: Bi among the y (wherein x=0.02 ~ 0.15, y=1.02 ~ 1.12) 2O 3And TiO 2Incorporation, and mix ZnO, MgO and ZrO therein 2Further improve performance, overcome SrTiO 3The ceramic dielectric constant is little, and the shortcoming that disruptive strength is not high has obtained a kind of energy-storing dielectric ceramic with high-k, low-loss, higher disruptive strength.The present invention can be used for the manufacturing of various high-voltage energy storage media.
Embodiment
The embodiment of the invention adopts solid reaction process to prepare SrO-Bi 2O 3-TiO 2=1: x: y (wherein x=0.02 ~ 0.15, y=1.02 ~ 1.12) media ceramic.
Concrete implement as follows: with purity greater than 99% SrCO 3, Bi 2O 3And TiO 2Be starting raw material, in strict accordance with SrO: Bi 2O 3: TiO 2=1: x: y (wherein x=0.02 ~ 0.15, y=1.02 ~ 1.12) chemistry adds deionized water and grinds oven dry after 12 hours than batching in ball mill, in 800 ~ 1200 ℃ of insulations pre-burning in 4 hours, adds purity again greater than 99% ZnO, MgO and ZrO 2, in ball mill, added the deionized water ground and mixed 24 hours, air atmosphere oven dry down.It is that polyvinyl alcohol water solution granulation, its add-on of 0.5 ~ 2.0wt% is powder total amount 5 ~ 10wt% that material after the oven dry adds concentration, uses the pressure compression moulding of 160 ~ 200Mpa then, in 1350 ~ 1450 ℃ of sintering 2 ~ 6 hours, makes media ceramic.This preparation method can be used as the manufacturing of various high-voltage energy storage media.
Preparation SrO-Bi 2O 3-TiO 2Prescription and the following embodiment of condition, the product dielectric properties in the 0.5MHz-50MHz range of frequency and DC break down voltage performance test results under room temperature environment are listed table 1 in.
SrO-Bi 2O 3-TiO 2The powder synthesis condition: 800 ~ 1200 ℃, 4 hours.
Forming pressure: 160 ~ 200Mpa.
Example 1:
SrO+Bi 2O 3+TiO 2+ZnO+MgO+ZrO 2＝41.16wt％+22.09wt％+34.26wt％+0.2wt％+0.2wt％+2.09wt％，
PVA solution incorporation is 5wt%, 1350 ℃ of sintering temperatures, sintering time 2 hours.
Example 2:
SrO+Bi 2O 3+TiO 2+ZnO+MgO+o＝47.28wt％+12.02wt％+37.80wt％+0.1wt％+0.2wt％+2.6wt％，
PVA solution incorporation is 8wt%, 1350 ℃ of sintering temperatures, sintering time 3 hours.
Example 3:
SrO+Bi 2O 3+TiO 2+ZnO+MgO+ZrO 2＝43.15+18.82+35.42+0.3+0.1+2.21
PVA solution incorporation is 10wt%, 1350 ℃ of sintering temperatures, sintering time 2 hours.
Example 4:
SrO+Bi 2O 3+ TiO 2+ ZnO+MgO+ZrO 2=39.68+23.86+33.56+0.1+0.1+2.7PVA solution incorporation is 5wt%, 1350 ℃ of sintering temperatures, sintering time 2 hours.
Example 5:
SrO+Bi 2O 3+ TiO 2+ ZnO+MgO+ZrO 2=41.49+21.02+34.39+0.2+0.2+2.7PVA solution incorporation is 6wt%, 1350 ℃ of sintering temperatures, sintering time 6 hours.
Example 6:
SrO+Bi 2O 3+ TiO 2+ ZnO+MgO+ZrO 2=44.08+16.37+35.90+0.10+0.05+3.5PVA solution incorporation is 10wt%, 1400 ℃ of sintering temperatures, sintering time 2 hours.
Example 7:
SrO+Bi 2O 3+ TiO 2+ ZnO+MgO+ZrO 2=45.30+13.62+36.45+0.08+0.05+4.5PVA solution incorporation is 10wt%, 1400 ℃ of sintering temperatures, sintering time 4 hours.
Example 8:
SrO+Bi 2O 3+ TiO 2+ ZnO+MgO+ZrO 2=42.60+16.94+34.76+0.05+0.05+5.6PVA solution incorporation is 8wt%, 1425 ℃ of sintering temperatures, sintering time 2 hours.
More than each example all carry out according to described proportioning.
Table 1
Example 9:
A kind of energy-storing dielectric ceramic, its main chemical constitution is SrO-Bi 2O 3-TiO 2, SrO, Bi 2O 3And TiO 2Molar ratio be: 1: 0.02: 1.02, and be mixed with 0.05wt%ZnO, 0.05wt%MgO and 1wt%ZrO therein 2
The preparation process of this energy-storing dielectric ceramic is:
1), with purity greater than 99% SrCO 3, Bi 2O 3And TiO 2Be starting raw material, in strict accordance with SrO: Bi 2O 3: TiO 2=1: 0.02: 1.02 chemistry adds in ball mill and grinds oven dry after 11 hours in the deionized water, in 800 ℃ of insulations pre-burning in 3 hours than batching;
2), get the resulting SrO-Bi of step 1 2O 3-TiO 2Powder adds purity greater than 99% ZnO, MgO and ZrO 2, add ZnO, MgO and ZrO 2Amount accounts for 0.05wt%, 0.05wt% and the 1wt% of mixed powder total amount respectively; Added in the deionized water ground and mixed 22 hours in ball mill, air atmosphere is oven dry down;
3), add the polyvinyl alcohol water solution granulation, described polyvinyl alcohol water solution concentration is 0.5wt%, add-on is the 5wt% of mixed powder total amount; Compression moulding, pressure are 160 ~ 200Mpa, sintering in the High Temperature Furnaces Heating Apparatus air atmosphere, and sintering temperature is 1350 ℃; Described sintering time is 2 hours, makes SrO-Bi 2O 3-TiO 2Energy-storing dielectric ceramic.
Example 10:
A kind of energy-storing dielectric ceramic, its main chemical constitution is SrO-Bi 2O 3-TiO 2, SrO, Bi 2O 3And TiO 2Molar ratio be: 1: 0.15: 1.12, and be mixed with 0.5wt%ZnO, 0.5wt%MgO and 10wt%ZrO therein 2
The preparation process of this energy-storing dielectric ceramic is:
1), with purity greater than 99% SrCO 3, Bi 2O 3And TiO 2Be starting raw material, in strict accordance with SrO: Bi 2O 3: TiO 2=1: 0.15: 1.12 chemistry adds in ball mill and grinds oven dry after 13 hours in the deionized water, in 1200 ℃ of insulations pre-burning in 5 hours than batching;
2), get the resulting SrO-Bi of step 1 2O 3-TiO 2Powder adds purity greater than 99% ZnO, MgO and ZrO 2, the ZnO of adding, MgO and ZrO 2Amount accounts for 0.5wt%, the 0.5wt% of mixed powder total amount and 10wt% respectively and added in the deionized water ground and mixed 26 hours in ball mill, and air atmosphere is dried down;
3), add the polyvinyl alcohol water solution granulation, polyvinyl alcohol water solution concentration is 2.0wt%, add-on is the 10wt% of mixed powder total amount; Compression moulding, the pressure of compression moulding are 200Mpa; Sintering in the High Temperature Furnaces Heating Apparatus air atmosphere, sintering temperature are 1450 ℃, and sintering time is 6 hours; Make SrO-Bi 2O 3-TiO 2Energy-storing dielectric ceramic.
Example 11:
A kind of energy-storing dielectric ceramic, its main chemical constitution is SrO-Bi 2O 3-TiO 2, SrO, Bi 2O 3And TiO 2Molar ratio be: 1: 0.08: 1.0, and be mixed with 0.2wt%ZnO, 0.3wt%MgO and 6wt%ZrO therein 2
The preparation process of this energy-storing dielectric ceramic is:
1), with purity greater than 99% SrCO 3, Bi 2O 3And TiO 2Be starting raw material, in strict accordance with SrO: Bi 2O 3: TiO 2=1: 0.08: 1.0 chemistry adds in ball mill and grinds oven dry after 12 hours in the deionized water, in 1000 ℃ of insulations pre-burning in 4 hours than batching;
2), get the resulting SrO-Bi of step 1 2O 3-TiO 2Powder adds purity greater than 99% ZnO, MgO and ZrO 2, the ZnO of adding, MgO and ZrO 2Amount accounts for 0.2wt%, 0.3wt% and the 6wt% of mixed powder total amount respectively; Added in the deionized water ground and mixed 24 hours in ball mill, air atmosphere is oven dry down;
3), add the polyvinyl alcohol water solution granulation, polyvinyl alcohol water solution concentration is 1.0wt%, add-on is the 7wt% of powder total amount; Compression moulding, the pressure of compression moulding are 180Mpa; Sintering in the High Temperature Furnaces Heating Apparatus air atmosphere, sintering temperature are 1400 ℃, and described sintering time is 4 hours; Make SrO-Bi 2O 3-TiO 2Energy-storing dielectric ceramic.

Claims (2)

1, a kind of energy-storing dielectric ceramic is characterized in that: its main chemical constitution is SrO-Bi 2O 3-TiO 2, SrO, Bi 2O 3And TiO 2Molar ratio be: 1: x: y, x=0.02 ~ 0.15 wherein, y=1.02 ~ 1.12, and be mixed with 0.05 ~ 0.5wt%ZnO, 0.05 ~ 0.5wt%MgO and 1 ~ 10wt%ZrO therein 2
2, a kind of method for preparing the described energy-storing dielectric ceramic of claim 1 is characterized in that preparation process is:
1st, with purity greater than 99% SrCO 3, Bi 2O 3And TiO 2Be starting raw material, in strict accordance with SrO: Bi 2O 3: TiO 2=1: x: y chemistry is than batching, x=0.02 ~ 0.15 wherein, and y=1.02 ~ 1.12 add deionized water and grind oven dry after 11-13 hour in ball mill, in 800 ~ 1200 ℃ of insulations pre-burning in 3-5 hour;
2nd, get the resulting SrO-Bi of step 1 2O 3-TiO 2Powder, and adding purity is greater than 99% ZnO, MgO and ZrO 2, in ball mill, adding in the deionized water ground and mixed 22-26 hour, air atmosphere is oven dry down;
3rd, add the polyvinyl alcohol water solution granulation, compression moulding, sintering in the High Temperature Furnaces Heating Apparatus air atmosphere is made energy-storing dielectric ceramic;
The ZnO of wherein said adding, MgO and ZrO 2Amount accounts for 0.05 ~ 0.5wt%, 0.05 ~ 0.5wt% and the 1 ~ 10wt% of mixed powder total amount respectively; Described polyvinyl alcohol water solution concentration is 0.5 ~ 2.0wt%, and add-on is 5 ~ 10wt% of mixed powder total amount; The pressure of described compression moulding is 160 ~ 200Mpa; Described sintering temperature is 1350 ~ 1450 ℃, and described sintering time is 2 ~ 6 hours.
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CN100404461C (en) * 2006-11-13 2008-07-23 武汉理工大学 High-energy-storage density solid energy-storage medium ceramics and its preparing process
CN103922726B (en) * 2014-04-11 2015-11-25 云南云天化股份有限公司 A kind of microwave dielectric ceramic powder and preparation method thereof
CN106187168A (en) * 2016-07-13 2016-12-07 西安电子科技大学 A kind of preparation method of low-loss high energy storage density bismuth titanates sodio pottery
CN111925187A (en) * 2020-07-03 2020-11-13 成都宏科电子科技有限公司 Lead-free high-pressure medium-temperature sintered strontium bismuth titanium-based dielectric material and preparation method thereof

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