CN116813337A - Antiferroelectric ceramic and method for preparing antiferroelectric ceramic by sintering under reducing atmosphere - Google Patents
Antiferroelectric ceramic and method for preparing antiferroelectric ceramic by sintering under reducing atmosphere Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 87
- 238000005245 sintering Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims description 62
- 238000001035 drying Methods 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000003825 pressing Methods 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 13
- 229910052741 iridium Inorganic materials 0.000 claims description 11
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 11
- 229910010293 ceramic material Inorganic materials 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
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- 238000004146 energy storage Methods 0.000 abstract description 36
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- 239000013078 crystal Substances 0.000 abstract description 5
- 239000010953 base metal Substances 0.000 abstract description 4
- 238000010344 co-firing Methods 0.000 abstract description 4
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- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
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- 239000010949 copper Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
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- C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
- C04B35/491—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT
- C04B35/493—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT containing also other lead compounds
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention discloses an antiferroelectric ceramic and a method for preparing the antiferroelectric ceramic by sintering under a reducing atmosphere, which prepares an additive oxide Y by utilizing a traditional solid phase method 2 (CO 3 ) 3 The antiferroelectric ceramic of (2) is sintered in a reducing atmosphere, and the crystal structure is not changed; y is Y 2 (CO 3 ) 3 The addition of the alloy improves the compactness of the antiferroelectric ceramic, reduces the grain size, improves the breakdown field strength and the saturation polarization strength, improves the breakdown field strength of the antiferroelectric ceramic to 400kV/cm, and obtains 5J/cm 3 The energy storage density and 93% energy storage efficiency can be recovered, and the energy storage characteristic of the sample sintered under air is achieved; by optimizing the formula of the antiferroelectric component, the anti-reduction characteristic of the antiferroelectric material is improved, the co-firing requirement with the base metal inner electrode is met, and the antiferroelectric ceramic still maintains high energy storage density and energy storage efficiency in the sintering environment under the reducing atmosphere。
Description
Technical Field
The invention belongs to the technical field of electronic material preparation, and relates to antiferroelectric ceramic and a method for preparing antiferroelectric ceramic by sintering in a reducing atmosphere.
Background
The antiferroelectric material is used as a key electronic material and has important application in the fields of inverters, high-power pulse capacitors and the like. The antiferroelectric ceramic material can generate antiferroelectric-ferroelectric phase change under the action of an external electric field, the dielectric constant of the antiferroelectric-ferroelectric phase change increases with the increase of the external electric field, and the antiferroelectric ceramic material presents positive piezoelectric coefficient; in addition, the antiferroelectric material has the characteristics of small hysteresis, high energy storage density and efficiency, high pulse discharge energy and the like, is favorable for high power and miniaturization of devices, and can be used as a candidate material of a new generation of high-performance pulse capacitor.
The lead-based antiferroelectric material is the most widely used antiferroelectric material at present, and CN 111470863A discloses a strontium-doped lanthanum lead zirconium titanium stannate antiferroelectric material obtained by a thick film preparation process, and the energy storage density of the lead-doped lanthanum titanium stannate antiferroelectric material is about 3.9J/cm 3 The energy storage efficiency is about 89.5%, and the energy storage characteristic of the energy storage device still needs to be improved in practical application. The TDK company in japan has used lanthanum-doped lead zirconate titanate-based (PLZT) antiferroelectric materials in multilayer ceramic capacitor (MLCC) products, wherein copper inner electrode antiferroelectric MLCCs are sold as high-end products. But domestic manufacturers do not sell products for the following reasons: on the one hand, the sintering temperature of the lead-based antiferroelectric ceramic material is higher and is higher than the melting point (1083 ℃) of copper at 1250 ℃ or higher, so that the sintering temperature is not matched, and CN 115894019A is added with CuO in the PLZT-based antiferroelectric material, so that the sintering temperature is reduced to 1000 ℃, but the energy storage property is reduced to some extent; on the other hand, copper inner electrodes need to be sintered in a reducing atmosphere, while lead-based antiferroelectric ceramic materials need to be sintered in an oxidizing atmosphere, resulting in mismatch of sintering atmospheres.
Based on the above background, in order to meet the requirement of co-firing atmosphere matching of the lead-based antiferroelectric material and the copper inner electrode, the lead-based antiferroelectric material needs to be sintered in a reducing atmosphere and still has high performance, namely, the reduction resistance of the lead-based antiferroelectric material needs to be improved.
Disclosure of Invention
In order to overcome the defects existing in the prior art, the invention provides a method for improving the anti-reduction characteristic of a lead-based antiferroelectric material, and the invention firstly designs a high-energy-storage antiferroelectric material which is chemically connected withIs (Pb) 0.92 La 0.02 Sr 0.06 )(Zr 0.50 Sn 0.40 Ti 0.10 )O 3 -0.4wt% bbsk and introducing Y 2 (CO 3 ) 3 As an anti-reduction auxiliary agent, the anti-reduction characteristic of the ceramic matrix is effectively improved, and the ceramic matrix has high energy storage characteristic.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a method for preparing antiferroelectric ceramic by sintering in a reducing atmosphere comprises the following steps:
step 1, a lead source, a strontium source, a lanthanum source, a zirconium source, a tin source and a titanium source are mixed according to (Pb) 0.92 La 0.02 Sr 0.06 )(Zr 0.50 Sn 0.40 Ti 0.10 )O 3 Weighing and adding iridium source into the mixture in sequence, mixing, ball milling by a wet method, drying and calcining to obtain presintered powder;
step 2, weighing BaCO 3 -B 2 O 3 -SiO 2 -K 2 CO 3 Uniformly mixing the glass material compound and the presintered powder obtained in the step 1 according to the stoichiometric ratio, and drying to obtain dry mixed powder;
step 3, adding a granulating auxiliary agent into the dry mixed powder obtained in the step 2 for granulating, and then sieving to obtain ceramic powder with uniform particle size, wherein the particle size is 0.18-0.25 mm;
step 4, obtaining a ceramic green body by the ceramic powder obtained in the step 3 in a single-shaft pressing mode;
and 5, sintering the ceramic green body obtained in the step 4 in air and reducing atmosphere to obtain the antiferroelectric ceramic finished product material.
In the step 1, the lead source is PbO and the strontium source is SrCO 3 Lanthanum source is La 2 O 3 Zirconium source is ZrO 2 The tin source is SnO 2 The titanium source is TiO 2 The iridium source is Y 2 (CO 3 ) 3 。
In the step 1, the ball milling time is 12 hours, and the drying condition is 80 ℃; in step 2, baCO 3 -B 2 O 3 -SiO 2 -K 2 CO 3 Glass material compound and presintered powder obtained in step 1Ball milling and mixing are carried out on the mixture, the ball milling time is 12 hours, and the drying condition is 80 ℃.
In the step 2, the calcination temperature is 750-800 ℃ and the heat preservation time is 2h.
In the step 1, the addition amount of the iridium source is not more than 0.6% of the mass of the antiferroelectric ceramic material.
In the step 2, the addition amount of the sintering aid BBSK accounts for 0.4% of the mass of the antiferroelectric ceramic material.
In the step 3, the addition amount of the granulating auxiliary agent accounts for 20% of the mass of the antiferroelectric ceramic material, and the granulating auxiliary agent adopts a polyvinyl alcohol solution or a polyvinyl butyral solution.
In the step 4, the pressure of single-axis compression molding is 40MPa, and the dwell time is not less than 1 minute.
In the step 5, the sintering atmosphere is air atmosphere, the temperature in the sintering process is 1000-1020 ℃, the heat preservation time is 2 hours, the heating rate is 5 ℃/min, and the ceramic is cooled to the room temperature at the speed of 5 ℃/min.
In the step 5, the sintering atmosphere is a reducing atmosphere formed by mixing nitrogen and hydrogen, and the volume ratio of the nitrogen to the hydrogen is N 2 :H 2 The temperature of the sintering process is 1000-1020 ℃, the heat preservation time is 2 hours, the heating rate is 5 ℃/min, and the ceramic is cooled to room temperature at the speed of 5 ℃/min.
Compared with the prior art, the invention has the following beneficial effects: the invention is realized by adding Y 2 (CO 3 ) 3 So that the antiferroelectric ceramic still has high energy storage density and energy storage efficiency when sintered in a reducing atmosphere, Y 2 (CO 3 ) 3 The addition of the alloy leads the grain size of the antiferroelectric ceramic to be obviously reduced, the defect quantity to be reduced, the breakdown field intensity and the discharge energy density to be increased, the anti-reduction characteristic of the antiferroelectric ceramic to be improved, the atmosphere condition required by co-firing with the base metal inner electrode is met, noble metal is not needed to be used as the inner electrode, and the cost of the antiferroelectric ceramic is reduced; the antiferroelectric component used in the invention can be prepared at a lower sintering temperature, has excellent performance and high energy storage density and energy storage efficiency; the antiferroelectric ceramic of the invention has the advantages of cheap raw materials, simple preparation method and suitability forAnd (5) industrialized production.
Furthermore, the ceramic green body is obtained by adopting a single-axis pressing mode, the obtained ceramic green body is more compact, and the powder combination is more compact.
Further, the lead source is PbO, and the strontium source is SrCO 3 Lanthanum source is La 2 O 3 Zirconium source is ZrO 2 The tin source is SnO 2 The titanium source is TiO 2 The iridium source is Y 2 (CO 3 ) 3 The prepared powder is purer and has no other sundries.
Furthermore, the preparation method of the invention can improve the breakdown field strength of the antiferroelectric ceramic to 400kV/cm to obtain 5J/cm 3 The energy storage density and 93% energy storage efficiency can be recovered, the energy storage characteristic of the sample sintered under air is achieved, and the leakage current density under the sintering of the reducing atmosphere is reduced.
Drawings
The following drawings depict only certain embodiments of the invention and are not therefore to be considered limiting of its scope.
Fig. 1 is a scanning electron microscope image of the natural plane of the antiferroelectric ceramics in example 1 and example 2.
Fig. 2 is an X-ray diffraction pattern of the antiferroelectric ceramics in comparative example, example 2, example 3, and example 4.
FIG. 3 is a scanning electron microscope image of a cross section of the antiferroelectric ceramic in comparative example, example 2, example 3, and example 4;
fig. 4 is a graph of the hysteresis loop of the antiferroelectric ceramics in comparative example, example 2, example 3, and example 4.
Fig. 5 is a graph showing energy storage properties of antiferroelectric ceramics in comparative examples, example 2, example 3, and example 4.
Detailed Description
The present invention is described in further detail below:
a method for improving anti-reduction characteristics of antiferroelectric ceramics comprises the following specific steps:
step one, a lead source, a strontium source, a lanthanum source, a zirconium source, a tin source and a titanium source are mixed according to stoichiometric ratio (Pb 0.92 La 0.02 Sr 0.06 )(Zr 0.50 Sn 0.40 Ti 0.10 )O 3 (Sr-PLZST) weighing, and sequentially mixing, ball milling, drying and calcining an iridium source according to the mass ratio to obtain presintered powder; wherein the zirconium source is PbO and the strontium source is SrCO 3 Lanthanum source is La 2 O 3 Zirconium source is ZrO 2 The tin source is SnO 2 The titanium source is TiO 2 The iridium source is Y 2 (CO 3 ) 3 The ball milling time is 12 hours, the drying condition is 80 ℃, the calcining temperature is 800 ℃, the heat preservation time is 2 hours, the addition amount of the iridium source accounts for 0,0.2 percent, 0.4 percent and 0.6 percent of the mass of Sr-PLZST, and the iridium source is called Y0, Y2, Y4 and Y6 for short.
Step two, weighing BaCO 3 -B 2 O 3 -SiO 2 -K 2 CO 3 Mixing (BBSK for short) glass material compound and presintered powder in the first step according to the stoichiometric ratio, ball milling and drying to obtain dry mixed powder; wherein the ball milling time is 12h, the drying condition is 80 ℃, and the adding amount of BBSK accounts for 0.4% of the mass of the pre-sintered powder of the antiferroelectric ceramic in the step one.
Step three, mixing 20wt% of polyvinyl alcohol solution with the ceramic powder in the step two, granulating, and then passing through a 60-mesh screen to obtain ceramic powder with uniform particle size;
step four, pressing and forming by a single-axis pressing method to obtain a ceramic green body; wherein, the pressure adopted by the compression molding is 40MPa, and the pressure maintaining time is 1 minute.
Step five, sintering the ceramic green body in the step four under air or reducing atmosphere respectively to obtain an antiferroelectric ceramic finished product material; wherein the sintering atmosphere is air atmosphere, the temperature in the sintering process is 1020 ℃ (marked as Y0A), the heat preservation time is 2 hours, the heating rate is 5 ℃/min, and the temperature is reduced to the room temperature at the speed of 5 ℃/min; the sintering atmosphere is a reducing atmosphere, and the reducing atmosphere is specifically N 2 And H 2 ，N 2 And H 2 The volume ratio is 500:1, the temperature in the sintering process is 1010-1020 ℃ (marked as Y0H, Y2H, Y4H and Y6H), the heat preservation time is 2 hours, the heating rate is 5 ℃/min, and the temperature is reduced to the room temperature at the speed of 3 ℃/min.
The present invention will be described in detail below with reference to examples and drawings, so that those skilled in the art will more fully understand the present invention, but the present invention is not limited to the scope of all examples. All other embodiments obtained without making inventive efforts are within the scope of the invention.
Comparative example
In this example, the chemical formula is (Pb) 0.92 La 0.02 Sr 0.06 )(Zr 0.50 Sn 0.40 Ti 0.10 )O 3 0.4wt% BBSK (Sr-PLZST) without Y addition 2 (CO 3 ) 3 The sample of the antiferroelectric material sintered in air atmosphere, designated Y0A, is prepared by the following steps:
step 1, selecting a high-purity raw material PbO and SrCO 3 、La 2 O 3 、ZrO 2 、SnO 2 、TiO 2 Weighing according to the stoichiometric ratio of Sr-PLZST, adding ethanol and zirconium dioxide balls, mixing for 12 hours in a ball milling tank, drying, grinding, and sieving with a 60-80 mesh sieve to obtain uniformly mixed raw material powder;
step 2, heating the mixed raw material powder to 800 ℃ in an air atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 2h, and grinding the mixed raw material powder into fine powder;
step 3, weighing the fine powder in the step 2 and BBSK glass powder according to the mass ratio, mixing, performing secondary ball milling for 20 hours, and then drying at 80 ℃ to obtain Y0A presintered powder;
step 4, adding 20wt% PVA solution into the presintered powder for granulation, and pressing the mixture into a ceramic green body through a single-shaft pressing method after passing through a 60-80-mesh screen, wherein the pressure is 40MPa, and the pressure is maintained for 1 minute;
and 5, placing the ceramic green compact in a crucible, burying a proper amount of presintering powder, sintering in a muffle furnace at 1000-1020 ℃ for 2 hours, and obtaining the Y0A antiferroelectric ceramic body.
Example 1
In this example, the chemical formula is (Pb) 0.92 La 0.02 Sr 0.06 )(Zr 0.50 Sn 0.40 Ti 0.10 )O 3 (Sr-PLZST) without addition of Y 2 (CO 3 ) 3 The sample of the antiferroelectric material sintered in the reducing atmosphere is denoted as Y0H, and the specific preparation method is as follows:
step 1, selecting a high-purity raw material PbO and SrCO 3 、La 2 O 3 、ZrO 2 、SnO 2 、TiO 2 Weighing according to the stoichiometric ratio of Sr-PLZST, adding ethanol and zirconium dioxide balls, mixing for 12 hours in a ball milling tank, drying, grinding, and sieving with a 60-80 mesh sieve to obtain uniformly mixed raw material powder;
step 2, heating the mixed raw material powder to 800 ℃ in an air atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 2h, and grinding the mixed raw material powder into fine powder;
step 3, weighing the fine powder in the step 2 and BBSK glass powder according to the mass ratio, mixing, performing secondary ball milling for 20 hours, and then drying at 80 ℃ to obtain Y0H presintered powder;
step 4, adding 20wt% PVA solution into the presintered powder for granulation, pressing into ceramic green bodies through a 60-mesh screen by a single-shaft pressing method, wherein the pressure is 40MPa, and maintaining the pressure for 1 minute;
and 5, placing the ceramic green compact in a crucible, embedding a proper amount of presintering powder, and sintering in an atmosphere furnace at 1010 ℃ for 2 hours to obtain the Y0H antiferroelectric ceramic body.
Step 4, introducing a reducing atmosphere into the reactor to be N 2 And H 2 The volume ratio is 500:1.
Example 2
In this example, the chemical formula is (Pb) 0.92 La 0.02 Sr 0.06 )(Zr 0.50 Sn 0.40 Ti 0.10 )O 3 (Sr-PLZST) 0.2wt% Y 2 (CO 3 ) 3 The sample of the antiferroelectric material sintered in the reducing atmosphere is denoted as Y2H, and the specific preparation method is as follows:
step 1, selecting a high-purity raw material PbO and SrCO 3 、La 2 O 3 、ZrO 2 、SnO 2 、TiO 2 Weighting according to the stoichiometric ratio of Sr-PLZST, and then adding ethanol and zirconium dioxideMixing the balls in a ball milling tank for 12 hours, then drying, grinding and sieving with a 60-80 mesh sieve to obtain uniformly mixed raw material powder;
step 2, heating the mixed raw material powder to 800 ℃ in an air atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 2h, and grinding the mixed raw material powder into fine powder;
step 3, weighing the fine powder in the step 2 and BBSK glass powder according to the mass ratio, mixing, performing secondary ball milling for 20 hours, and then drying at 80 ℃ to obtain Y2H presintered powder;
step 4, adding 20wt% polyvinyl alcohol (PVA) solution into the presintered powder for granulating, and pressing into ceramic green bodies through a 60-mesh screen by a single-shaft pressing method, wherein the pressure is 40MPa, and the pressure is maintained for 1 minute;
and 5, placing the ceramic green compact into a crucible, embedding a proper amount of presintered powder, and sintering in an atmosphere furnace at the sintering temperature of 1000 ℃ for 2 hours to obtain the Y2H antiferroelectric ceramic body.
Step 4, introducing a reducing atmosphere into the reactor to be N 2 And H 2 The volume ratio is 500:1.
Example 3
In this example, the chemical formula is (Pb) 0.92 La 0.02 Sr 0.06 )(Zr 0.50 Sn 0.40 Ti 0.10 )O 3 (Sr-PLZST) 0.4wt% Y 2 (CO 3 ) 3 The sample of the antiferroelectric material sintered in the reducing atmosphere, designated as Y4H, is prepared by the following steps:
step 1, selecting a high-purity raw material PbO and SrCO 3 、La 2 O 3 、ZrO 2 、SnO 2 、TiO 2 Weighting according to the stoichiometric ratio of Sr-PLZST, and obtaining high-purity Y 2 (CO 3 ) 3 Weighing materials according to the mass ratio, adding ethanol and zirconium dioxide balls, mixing for 12 hours in a ball milling tank, drying, grinding, and sieving with a 70-mesh sieve to obtain uniformly mixed raw material powder;
step 2, heating the mixed raw material powder to 750 ℃ in an air atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 2h, and grinding the mixed raw material powder into fine powder;
step 3, weighing the fine powder in the step 2 and BBSK glass powder according to the mass ratio, mixing, performing secondary ball milling for 20 hours, and then drying at 80 ℃ to obtain Y4H presintered powder;
step 4, adding 20wt% polyvinyl alcohol (PVA) solution into the presintered powder for granulating, pressing into ceramic green bodies through a single-shaft pressing method after passing through a 80-mesh screen, wherein the pressure is 40MPa, and maintaining the pressure for 1 minute;
and 5, placing the ceramic green compact in a crucible, embedding a proper amount of presintering powder, and sintering in an atmosphere furnace at 1020 ℃ for 2 hours to obtain the Y4H antiferroelectric ceramic body.
In the step 4), the reducing atmosphere is introduced into N 2 And H 2 The volume ratio is 500:1.
Example 4
In this example, the chemical formula is (Pb) 0.92 La 0.02 Sr 0.06 )(Zr 0.50 Sn 0.40 Ti 0.10 )O 3 (Sr-PLZST) 0.6wt% Y was added 2 (CO 3 ) 3 The sample of the antiferroelectric material sintered in the reducing atmosphere is denoted as Y6H, and the specific preparation method is as follows:
step 1, selecting a high-purity raw material PbO and SrCO 3 、La 2 O 3 、ZrO 2 、SnO 2 、TiO 2 Weighting according to the stoichiometric ratio of Sr-PLZST, and obtaining high-purity Y 2 (CO 3 ) 3 Weighing materials according to the mass ratio, adding ethanol and zirconium dioxide balls, mixing for 12 hours in a ball milling tank, drying, grinding, and sieving with a 70-mesh sieve to obtain uniformly mixed raw material powder;
step 2, heating the mixed raw material powder to 780 ℃ in an air atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 2h, and grinding the mixed raw material powder into fine powder;
step 3, weighing the fine powder in the step 2 and BBSK glass powder according to the mass ratio, mixing, performing secondary ball milling for 20 hours, and then drying at 80 ℃ to obtain Y6H presintered powder;
step 4, adding 20wt% of polyvinyl butyral (PVB) solution into the presintered powder for granulating, and pressing into ceramic green bodies through a 60-80 mesh screen by a single-shaft pressing method, wherein the pressure is 40MPa, and the pressure is maintained for 1 minute;
and 5, placing the ceramic green compact in a crucible, embedding a proper amount of presintering powder, and sintering in an atmosphere furnace at 1020 ℃ for 2 hours to obtain the Y6H antiferroelectric ceramic body.
In the step 4, the reducing atmosphere is introduced into N 2 And H 2 The volume ratio is 500:1.
Fig. 1 is a natural-surface scanning electron microscope image of examples 1 and 2. As shown in FIG. 2, the sample of example 1 (Y0H) showed spherical particles on its natural surface, which were metallic lead as compared with the literature and as shown by the energy spectrum analysis, whereas the sample of example 2 had a normal surface morphology, which indicated that when Y was not added 2 (CO 3 ) 3 When the sample is sintered in a reducing atmosphere, the ceramic body is decomposed and Pb 2+ The ions being reduced to the elemental metal Pb, and Y 2 (CO 3 ) 3 The addition of (3) significantly improves its anti-reduction properties.
Fig. 2 is an X-ray diffraction pattern of comparative examples 2 to 4. As can be seen from FIG. 2, the diffraction peaks of the comparative example and the example both form a pure perovskite structure, and no second phase exists, indicating Y 3+ The ions diffuse completely into the lattice; the cleavage peak at 44.5 ° indicates that the crystal structure is tetragonal perovskite structure; with Y 3+ The amount of ion doping increases and the diffraction peak moves to a low angle, which can be explained from the angle of ion radius, Y 3+ The ion radius of (a) is larger than that of the B-site ion, and the occupied lattice B site causes the lattice volume to be increased, so that the diffraction peak moves to a low angle according to the Bragg formula. The diffraction peaks of comparative example and example 1 are not significantly different, indicating that the reducing atmosphere sintering does not change the crystal structure of the antiferroelectric material.
FIG. 3 is a scanning electron microscope image of a cross section of comparative example 2 to 4. As shown in fig. 3, no second phase grains were found in all samples, consistent with the results of fig. 1; the grains of example 2 were loosely packed and porous, the grains of examples 3 and 4 were densely packed, and the grains of examples 2 to 4 were smaller in size with Y, as compared with the comparative example 2 (CO 3 ) 3 The grain size is slightly increased, which indicates that the sintering in the reducing atmosphere is unfavorable for the crystallizationGrain growth, and Y 2 (CO 3 ) 3 The addition of (3) promotes the growth of crystal grains and improves the densification degree of the ceramic body.
Fig. 4 is a hysteresis loop of comparative examples 2 to 4. Examples 2 to 4 all show the same hysteresis loop characteristics with increasing electric field. The comparative example (Y0A) had a breakdown field of 415kV/cm and a maximum polarization of 29. Mu.C/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The breakdown field of example 2 (Y2H) was 320kV/cm, and the maximum polarization intensity was 23. Mu.C/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Example 3 (Y4H) the breakdown field was 380kV/cm and the maximum polarization was 28. Mu.C/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Example 4 (Y6H) the breakdown field was 400kV/cm and the maximum polarization was 32. Mu.C/cm 2 It is shown that sintering in a reducing atmosphere results in a ceramic body with a different degree of reduction in breakdown field strength and maximum polarization strength, with Y 2 (CO 3 ) 3 The addition amount is increased, the breakdown field strength and the maximum polarization intensity are improved, and the loop is thinner, which indicates Y 2 (CO 3 ) 3 The reduction resistance of the ceramic body is improved.
Fig. 5 is a graph of energy storage density and energy storage efficiency calculated for the hysteresis loops of examples 2 to 4 according to the comparative example. As can be seen from the figure, when Y is not added 2 (CO 3 ) 3 When the energy storage density and the energy storage efficiency of the sample sintered in the reducing atmosphere are obviously reduced, which is related to the poor density of the ceramic body; with Y 2 (CO 3 ) 3 The addition amount is increased, the density of the ceramic body is increased, the breakdown field strength and the polarization strength are increased, and the energy storage density is also increased. The recoverable storage density of comparative example (Y0A) was 4.5J/cm 3 The energy storage efficiency is 87.7%; example 3 (Y6H) recoverable energy storage Density of 5J/cm 3 The energy storage efficiency was 93%, indicating that when 0.6wt% Y was added 2 (CO 3 ) 3 When the anti-ferroelectric ceramic is sintered in the reducing atmosphere, the energy storage characteristic of the anti-ferroelectric ceramic can reach the energy storage characteristic of air sintering, and the anti-reduction characteristic is obviously improved.
In conclusion, the invention prepares the additive oxide Y by utilizing the traditional solid phase method 2 (CO 3 ) 3 Is a non-ferroelectric ceramic. Sintering ceramic body under reducing atmosphereThe crystal structure is not changed; y is Y 2 (CO 3 ) 3 The addition of the alloy improves the compactness of the antiferroelectric ceramic, reduces the grain size, improves the breakdown field strength and the saturation polarization strength, and when the addition amount is 0.6wt%, the breakdown field strength of the antiferroelectric ceramic is improved to 400kV/cm, and 5J/cm is obtained 3 The energy storage density and the energy storage efficiency of 93 percent reach the energy storage characteristic of the sample sintered under the air; by optimizing the formula of the antiferroelectric component, the anti-reduction characteristic of the antiferroelectric material is improved, the co-firing requirement of the antiferroelectric material and the internal electrode of the base metal is met, and compared with the prior art, the invention ensures that the antiferroelectric ceramic still maintains high energy storage density and energy storage efficiency in the sintering environment under the reducing atmosphere, and has important significance for promoting the industrialized mass production of the pulse power capacitor of the internal electrode of the base metal.
Claims (10)
1. A method for preparing antiferroelectric ceramic by sintering in a reducing atmosphere, which is characterized by comprising the following steps:
step 1, a lead source, a strontium source, a lanthanum source, a zirconium source, a tin source and a titanium source are mixed according to (Pb) 0.92 La 0.02 Sr 0.06 )(Zr 0.50 Sn 0.40 Ti 0.10 )O 3 Weighing and adding iridium source into the mixture in sequence, mixing, ball milling by a wet method, drying and calcining to obtain presintered powder;
step 2, weighing BaCO 3 -B 2 O 3 -SiO 2 -K 2 CO 3 Uniformly mixing the glass material compound and the presintered powder obtained in the step 1 according to the stoichiometric ratio, and drying to obtain dry mixed powder;
step 3, adding a granulating auxiliary agent into the dry mixed powder obtained in the step 2 for granulating, and then sieving to obtain ceramic powder with uniform particle size, wherein the particle size is 0.18-0.25 mm;
step 4, obtaining a ceramic green body by the ceramic powder obtained in the step 3 in a single-shaft pressing mode;
and 5, sintering the ceramic green body obtained in the step 4 in air and reducing atmosphere to obtain the antiferroelectric ceramic finished product material.
2. The method for preparing antiferroelectric ceramic according to claim 1, wherein in step 1, the lead source is PbO and the strontium source is SrCO 3 Lanthanum source is La 2 O 3 Zirconium source is ZrO 2 The tin source is SnO 2 The titanium source is TiO 2 The iridium source is Y 2 (CO 3 ) 3 。
3. The method for preparing antiferroelectric ceramic according to claim 1, wherein in step 1, the ball milling time is 12 hours and the drying condition is 80 ℃; in step 2, baCO 3 -B 2 O 3 -SiO 2 -K 2 CO 3 Ball milling and mixing the glass material compound and the presintered powder obtained in the step 1 for 12 hours under the drying condition of 80 ℃.
4. The method for preparing antiferroelectric ceramic according to claim 1, wherein in step 2, the calcining temperature is 750-800 ℃ and the holding time is 2h.
5. The method for preparing antiferroelectric ceramic according to claim 1, wherein the iridium source is added in an amount of not more than 0.6% by mass of the antiferroelectric ceramic material in step 1.
6. The method for preparing antiferroelectric ceramic according to claim 1, wherein in step 2, the addition amount of the sintering aid BBSK is 0.4% of the antiferroelectric ceramic material by mass.
7. The method for preparing antiferroelectric ceramic according to claim 1, wherein in step 3, the addition amount of the granulating aid is 20% of the mass of antiferroelectric ceramic material, and the granulating aid is polyvinyl alcohol solution or polyvinyl butyral solution.
8. The method for preparing antiferroelectric ceramic according to claim 1, wherein in step 4, the pressure of the single-axis pressing is 40MPa, and the dwell time is not less than 1 minute.
9. The method for preparing antiferroelectric ceramic according to claim 1, wherein in step 5, the sintering atmosphere is an air atmosphere, the temperature of the sintering process is 1000-1020 ℃, the heat preservation time is 2 hours, the heating rate is 5 ℃/min, and the ceramic is cooled to room temperature at a speed of 5 ℃/min.
10. The method for preparing antiferroelectric ceramic according to claim 1, wherein in step 5, the sintering atmosphere is a reducing atmosphere formed by mixing nitrogen and hydrogen, and the volume ratio of nitrogen to hydrogen is N 2 :H 2 The temperature of the sintering process is 1000-1020 ℃, the heat preservation time is 2 hours, the heating rate is 5 ℃/min, and the ceramic is cooled to room temperature at the speed of 5 ℃/min.
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