CN102320826B - Multi-case-layer structure X8R capacitor dielectric ceramic and preparation method thereof - Google Patents
Multi-case-layer structure X8R capacitor dielectric ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003990 capacitor Substances 0.000 title abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims description 67
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 57
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 30
- 239000011777 magnesium Substances 0.000 claims description 28
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 25
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 25
- 229940069446 magnesium acetate Drugs 0.000 claims description 25
- 235000011285 magnesium acetate Nutrition 0.000 claims description 25
- 239000011654 magnesium acetate Substances 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 17
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000003483 aging Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 9
- 239000003989 dielectric material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- MTZOKGSUOABQEO-UHFFFAOYSA-L barium(2+);phthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O MTZOKGSUOABQEO-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to multi-case-layer structure X8R capacitor dielectric ceramic and a preparation method thereof. The multi-case-layer structure X8R capacitor dielectric ceramic is characterized by being prepared from BaTiO3-Nb2O5-Co2O3-Sm2O3-CeO2 powder and 0.5BaTiO3-0.5Bi(Mg1/2Ti1/2)O3 powder, wherein the molar ratio of the BaTiO3-Nb2O5-Co2O3-Sm2O3-CeO2 powder to the 0.5BaTiO3-0.5Bi(Mg1/2Ti1/2)O3 powder is x/1, and x is greater than or equal to 4 but is smaller than or equal to 8. The capacitor dielectric ceramic prepared by the method has the characteristics of wide work temperature range and high stability.
Description
Technical field
The present invention relates to a kind of many shell structures X8R electrical condenser dielectric ceramic and preparation method thereof.
Background technology
The laminated ceramic capacitor of high-performance high-temperature stability (MLCC) dielectric material all is a research focus all the time.At present, and X7R (55 ℃～125 ℃, Δ C/C
25 ℃＜± 15%) prescription of MLCC material and preparation technology comparative maturity, BaTiO
3The own successful commercialization of MLCC material of base X7R type also is used widely.MLCC compares with the X7R type, and X8R (55 ℃～150 ℃, Δ C/C
25 ℃＜± 15%) operating temperature range of material is wideer, and upper limit use temperature can reach 150 ℃.But the dielectric material for the manufacture of the big capacity thermostable type of this class MLCC still mainly is with oxide-doped BaTiO such as Nb, Co
3It is main forming " shell-core " structure.Its brilliant core composition correspondence (pure BaTiO
3) the dielectric characterization peak position in～130 ℃, specific inductivity sharply descends when being higher than 130 ℃, this means that also this system is difficult to be applied to higher temperature environment.At present a lot of researchs all are devoted to how to improve the Curie temperature of " core ", as doping Na
1/2Bi
1/2TiO
3, Pb (Sn
xTi
1-x) O
3Deng the high curie point uhligite.All can promote the rate of diffusion of doping agents such as Nb but other system of solid solution in advance, particularly non-equivalence are mixed and low melting component mixes, thereby cause caving in of " shell-core " structure.
For the pottery with shell-cored structure, its dielectric properties can be regarded the stack of the dielectric characteristics of each gradient component as, and namely the chemical constitution of its crystal grain shell and core is pressed the common performance that determines of concentration factor, according to the Lichteneche experimental formula
lgε＝V
c*lgε
c+V
s*lgε
s
In the formula, V
c, V
sAnd ε
c, ε
sBe respectively volume fraction and the specific inductivity of crystal grain shell and crystal grain core.
Barium phthalate base " shell-core " structural ceramics has stable Jie's temperature characteristics usually.Can simulate BaTiO according to following formula
3Jie's temperature curve of " shell-core " structural ceramics.As seen, Jie's temperature profile that has the pottery of " shell-core " structure is formed by stacking by crystal grain shell, the two-part temperature profile of core.Shell and core volume ratio are determining the concrete shape of specific inductivity temperature curve, thereby acting in conjunction makes BaTiO
3Pottery has smooth temperature coefficient of capacitance.
Summary of the invention
The object of the present invention is to provide a kind of many shell structures X8R electrical condenser dielectric ceramic and preparation method thereof, the electrical condenser dielectric ceramic of this method preparation has the characteristics of wide working temperature, high stability.
To achieve these goals, technical scheme of the present invention is: many shell structures X8R electrical condenser dielectric ceramic is characterized in that it is by BaTiO
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder and 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3Powder preparing forms, BaTiO
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder and 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3The mol ratio of powder is x: 1,4≤x≤8.
The above-mentioned preparation method who states many shell structures X8R electrical condenser dielectric ceramic is characterized in that it comprises the steps:
1) preparation colloidal sol: press Nb
2O
5: HF: the ammonium oxalate aqueous solution: aqueous citric acid solution=50g: 250mL: 100～150mL: 100mL, choose Nb
2O
5, HF, the ammonium oxalate aqueous solution and aqueous citric acid solution; The concentration of the described ammonium oxalate aqueous solution is 0.1g/mL (the stablizer ammonium oxalate is dissolved in the deionized water); The concentration of described aqueous citric acid solution is 1g/mL;
With Nb
2O
5Be dissolved among 90 ℃ the HF, behind the reaction 10h, add the ammonium oxalate aqueous solution, splashing into ammoniacal liquor after the stirring, to regulate pH value be 10, then 80 ℃ of following ageings 12 hours, and suction filtration, throw out washes with water, obtains Nb (OH)
5White precipitate; Nb (OH)
5Be dissolved in aqueous citric acid solution after the white precipitate drying, make Nb (OH)
5White precipitate dissolves fully, obtains the Nb salt sol; Measure Nb in the Nb salt sol with ICP
5+Concentration, standby;
Press Nb in the Nb salt sol
5+, Co (NO
3)
26H
2Co among the O
2+, Sm
2O
3Middle Sm
3+, CeO
2In Ce
4+Mol ratio (3～5): (2～4): (1～3): (1～3), choose Co (NO
3)
26H
2O, Sm
2O
3And CeO
2With Co (NO
3)
26H
2O, Sm
2O
3And CeO
2Dissolve in [Co (NO in the salpeter solution
3)
26H
2O, Sm
2O
3And CeO
2Total mass: salpeter solution=1g: 1mL; Purity 〉=the 99.5wt% of salpeter solution], obtain mixing solutions; Then mixing solutions is added in the above-mentioned Nb salt sol and fully and stir, obtain Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Colloidal sol;
2) press BaTiO
3In Ba
2+With the Nb in the Nb salt sol
5+Mol ratio be 84: 1, choose BaTiO
3And Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Colloidal sol; Press BaTiO
3: ethanol=98g: 400mL, with BaTiO
3Ultra-sonic dispersion in ethanol is slowly poured above-mentioned Nb then into
2O
5-Co
2O
3-Sm
2O
3-CeO
2In the colloidal sol; Fully stir post-heating and concentrate to form gel, at 950 ℃ of calcining 2～4h, temperature rise rate is 3～4 ℃/min, obtains BaTiO again
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder, standby;
3) press 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3Stoichiometric ratio is chosen tetrabutyl titanate, barium acetate, magnesium acetate and Bismuth trinitrate; Total mass by barium acetate, magnesium acetate and Bismuth trinitrate: the volume=2g of acetic acid: 3～5mL, barium acetate, magnesium acetate and Bismuth trinitrate are dissolved in the acetic acid, obtain barium acetate, magnesium acetate and bismuth nitrate solution;
Press tetrabutyl titanate: ethanolic soln: acetic acid solution=13.022g: 24mL: 40mL, choose tetrabutyl titanate, ethanolic soln and acetic acid solution; To add stabilizer alcohol solution in the tetrabutyl titanate, behind stirring 30～35min, add solvent acetic acid solution; Under 80 ℃ of water bath condition, add barium acetate, magnesium acetate and bismuth nitrate solution subsequently, obtain 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3Sol solution; With 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3The sol solution heating concentrates to form gel, and at 650 ℃ of calcining 2h, temperature rise rate is 1～3 ℃/min, the 0.5BaTiO that obtains after the cooling
3-0.5Bi (Mg
1/2Ti
1/2) O
3Powder (being called for short the 0.5BT-0.5BMT powder);
4) with BaTiO
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder and 0.5BT-0.5BMT powder are pressed x: 1 mixed in molar ratio, and 4≤x≤8 are medium ball milling 4～8 hours with alcohol, oven dry makes the ceramic mixture powder;
5) add binding agent in the ceramic mixture powder, the add-on of binding agent is 3～5% of ceramic mixture powder quality, mixes, and compressing tablet gets the ceramic green sheet; The ceramic green sheet is warming up to 1200～1250 ℃ then in 600 ℃ of insulations 2 hours, and temperature rise rate is 5～10 ℃/min, be incubated 10～20 minutes, be cooled to 950～1050 ℃ rapidly, be incubated 1～2 hour, furnace cooling obtains many shell structures X8R electrical condenser dielectric ceramic.
Described binding agent is polyvinyl alcohol or water glass.
Relation according to " shell-core " structure and system dielectric properties, the present invention designs a kind of many shell structures, by coating the different multicomponent of Curie temperature and in system, embodying the dielectric properties of each component simultaneously, to obtain to have in wideer temperature range the dielectric material of high-temperature stability, as accompanying drawing 2.The present invention selects X7R type MLCC dielectric material BaTiO
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2As matrix, coat the 0.5BaTiO of high-temperature temperature good stability again at skin
3-0.5Bi (Mg
1/2Ti
1/2) O
3Layer then can embody 0.5BaTiO in this structure simultaneously
3-0.5Bi (Mg
1/2Ti
1/2) O
3With the performance of X7R dielectric material, has excellent temperature stability thereby be implemented in more in the wide temperature range.
The invention has the beneficial effects as follows:
1, meet the wide operating temperature range of X8R, high-temperature stability is good: by coating two-layer different ceramic dielectric layer, make BaTiO
3The based capacitor stupalith has stable capacitance temperature factor, temperature coefficient of capacitance in-55～155 ℃ of temperature ranges do not exceed ± 15% scope (characteristics with wide working temperature, high stability), the specific inductivity that room temperature is 25 ℃ about 1800, meet the requirement of X8R type high temperature multi-layer capacitor material, be expected to be applied to eco-friendly high-temperature stable ceramic condenser of new generation as stupalith.
2, low-dielectric loss: have lower dielectric loss (＜4.2%) in-55～156 ℃ of temperature ranges, and dielectric loss descends gradually with the rising of temperature, wherein the dielectric loss of 25 ℃ of room temperatures only is 1.4%.
3, sintering temperature and low: rise to 1200～1250 ℃ from room temperature, temperature rise rate is 5～10 ℃/min, is incubated 10～20 minutes, is cooled to 950～1050 ℃ rapidly, is incubated 1～2 hour, cools to room temperature with the furnace and namely finishes sintering.
Description of drawings
Fig. 1 is desirable many shell structures dielectric structures synoptic diagram.Nucleus is BaTiO
3, first shell is the BaTiO that is rich in additives such as Nb, Co
3Zone, second shell are 0.5BT-0.5BMT.
Fig. 2 is the XRD figure spectrum of many shell structures X8R electrical condenser dielectric ceramic of embodiment 1 preparation.Second shell has a small amount of dephasign, but keeps perovskite structure, according to sosoloid statement convention, with chemical formula 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3Explain it and form, it is second shell composition of many shell structures.First shell and many shell structures test result all are the perovskite structure main peak, and wherein many shell structures test result is the test result of (being product) after all layers coating.
Fig. 3 is that specific inductivity and the loss of many shell structures X8R electrical condenser dielectric ceramic of embodiment 1 preparation varies with temperature figure.The two dielectrics peak phenomenon that has occurred nucleocapsid structure as we can see from the figure, wherein 130 ℃ of corresponding BaTiO in peak
3Main peak, be the nucleus part component of many shell structures.
Fig. 4 for many shell structures X8R electrical condenser dielectric ceramic of embodiment 1 preparation when 1kHz temperature coefficient of capacitance (be benchmark with 25 ℃) with variation of temperature figure, frame of broken lines is the temperature coefficient of capacitance claimed range of X8R electrical condenser.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.The component of the many shell structures of different embodiment is consistent, mainly is that first shell is different with the molar ratio of second shell.
Embodiment 1:
The preparation method of many shell structures X8R electrical condenser dielectric ceramic, it comprises the steps:
1) preparation colloidal sol: with the Nb of 50g
2O
5Be dissolved among 90 ℃ the HF of 250mL, treat that 10h fully reacts the stablizer ammonium oxalate aqueous solution (concentration of the described ammonium oxalate aqueous solution is 0.1g/mL) that the back adds 100mL, splashing into ammoniacal liquor after fully stirring, to regulate pH value be that 10[generates Nb (OH)
5White precipitate], 80 ℃ of following ageings 12 hours, suction filtration, throw out washed with water [to remove NH then
4 +, C
2O
4 2-, F
-], obtain Nb (OH)
5White precipitate; Nb (OH)
5Be dissolved in 100mL aqueous citric acid solution (concentration of described aqueous citric acid solution is 1g/mL) after the white precipitate drying, make Nb (OH)
5White precipitate dissolves fully, namely gets stable Nb salt sol; Measure Nb in the Nb salt sol with ICP
5+Concentration, standby;
Press Nb in the Nb salt sol
5+, Co (NO
3)
26H
2Co among the O
2+, Sm
2O
3Middle Sm
3+, CeO
2In Ce
4+Mol ratio 4: 3: 2: 2, choose Co (NO
3)
26H
2O, Sm
2O
3And CeO
2With Co (NO
3)
26H
2O, Sm
2O
3And CeO
2Dissolve in (Co (NO in the salpeter solution that purity is 99.5wt%
3)
26H
2O, Sm
2O
3And CeO
2Total mass: nitric acid=1g: 1mL), obtain mixing solutions; Then mixing solutions is added in the above-mentioned Nb salt sol and fully and stir, after stablizing, obtain Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Colloidal sol;
2) press BaTiO
3In Ba
2+With the Nb in the Nb salt sol
5+Mol ratio be 84: 1, choose BaTiO
3And Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Colloidal sol; BaTiO with 98g
3Ultra-sonic dispersion in the ethanol of 400mL is slowly poured above-mentioned Nb then into
2O
5-Co
2O
3-Sm
2O
3-CeO
2In the colloidal sol; Fully stir post-heating and concentrate to form gel, at 950 ℃ of calcining 3h, temperature rise rate is 3 ℃/min, obtains BaTiO again
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder, standby;
3) press 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3Stoichiometric ratio is chosen tetrabutyl titanate, barium acetate, magnesium acetate and Bismuth trinitrate; Barium acetate, magnesium acetate and Bismuth trinitrate are dissolved in the acetic acid (acetic acid of 24mL, just dissolving is just; When tetrabutyl titanate was got 13.022g, the total mass of barium acetate, magnesium acetate and Bismuth trinitrate was 15.27g at this moment), obtain barium acetate, magnesium acetate and bismuth nitrate solution;
Get the 13.022g tetrabutyl titanate, slowly add the stabilizer alcohol solution (purity 〉=99.5wt%), behind the stirring 30min, slowly add the solvent acetic acid solution (purity is greater than 99.5wt%) of 40mL of 24mL; Under 80 ℃ of water bath condition, add barium acetate, magnesium acetate and bismuth nitrate solution subsequently, obtain water white 0.5BaTiO after stablizing
3-0.5Bi (Mg
1/2Ti
1/2) O
3Sol solution; With 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3The sol solution heating concentrates to form gel, and at 650 ℃ of calcining 2h, temperature rise rate is 2 ℃/min, the 0.5BaTiO that obtains after the cooling
3-0.5Bi (Mg
1/2Ti
1/2) O
3Powder (being called for short the 0.5BT-0.5BMT powder);
4) with BaTiO
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder and 0.5BT-0.5BMT powder are pressed 6: 1 mixed in molar ratio, are medium ball milling 6 hours with alcohol, and oven dry makes the ceramic mixture powder;
5) add polyvinyl alcohol (binding agent) in the ceramic mixture powder, the add-on of polyvinyl alcohol is 4% of ceramic mixture powder quality, mixes, and compressing tablet gets the ceramic green sheet; The ceramic green sheet is warming up to 1200 ℃ then in 600 ℃ of insulations 2 hours, and temperature rise rate is 10 ℃/min, is incubated 10 minutes, is cooled to 950 ℃ rapidly, is incubated 1 hour, and furnace cooling obtains many shell structures X8R electrical condenser dielectric ceramic.
The XRD figure of many shell structures X8R electrical condenser dielectric ceramic is composed as shown in Figure 2, and second shell has a small amount of dephasign, but keeps perovskite structure, according to sosoloid statement convention, with chemical formula 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3Explain it and form, it is second shell composition of many shell structures.First shell and many shell structures test result all are the perovskite structure main peak, and wherein many shell structures test result is the test result of (being product) after all layers coating.
Many shell structures X8R electrical condenser dielectric ceramic sample that embodiment 1 obtains, last its dielectric properties of silver slurry test, obtain its specific inductivity and dielectric loss with variation of temperature figure (see figure 3) and its temperature coefficient of capacitance (be benchmark with 25 ℃) with variation of temperature figure (see figure 4).This has illustrated that many shell structures X8R electrical condenser dielectric ceramic that present embodiment obtains is under 1kHz, has stable capacitance temperature factor, temperature coefficient of capacitance does not exceed ± 15% scope in-55～150 ℃ temperature range, 25 ℃ of specific inductivity of room temperature are 1800, meet the requirement of X8R type high temperature multi-layer capacitor material; Have lower dielectric loss (＜4.2%)-55～156 ℃ of temperature ranges, wherein the dielectric loss of 25 ℃ of room temperatures only is 1.4%.Illustrate that the electrical condenser dielectric ceramic of this embodiment preparation has the characteristics of wide working temperature, high stability.
Embodiment 2:
The preparation method of many shell structures X8R electrical condenser dielectric ceramic, it comprises the steps:
1) preparation colloidal sol: with the Nb of 50g
2O
5Be dissolved among 90 ℃ the HF of 250mL, treat that 10h fully reacts the ammonium oxalate aqueous solution (concentration of the described ammonium oxalate aqueous solution is 0.1g/mL) that the back adds 120mL, splashing into ammoniacal liquor after fully stirring, to regulate pH value be that 10[generates Nb (OH)
5White precipitate], 80 ℃ of following ageings 12 hours, suction filtration, throw out washed with water [to remove NH then
4 +, C
2O
4 2-, F
-], obtain Nb (OH)
5White precipitate; Nb (OH)
5Be dissolved in 100mL aqueous citric acid solution (concentration of described aqueous citric acid solution is 1g/mL) after the white precipitate drying, make Nb (OH)
5White precipitate dissolves fully, namely gets stable Nb salt sol; Measure Nb in the Nb salt sol with ICP
5+Concentration, standby;
Press Nb in the Nb salt sol
5+, Co (NO
3)
26H
2Co among the O
2+, Sm
2O
3Middle Sm
3+, CeO
2In Ce
4+Mol ratio 3: 2: 1: 1, choose Co (NO
3)
26H
2O, Sm
2O
3And CeO
2With Co (NO
3)
26H
2O, Sm
2O
3And CeO
2Dissolve in (Co (NO in the salpeter solution of 99.5wt%
3)
26H
2O, Sm
2O
3And CeO
2Total mass: nitric acid=1g: 1mL), obtain mixing solutions; Then mixing solutions is added in the above-mentioned Nb salt sol and fully and stir, after stablizing, obtain Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Colloidal sol;
2) press BaTiO
3In Ba
2+With the Nb in the Nb salt sol
5+Mol ratio be 84: 1, choose BaTiO
3And Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Colloidal sol; BaTiO with 98g
3Ultra-sonic dispersion in the ethanol of 400mL is slowly poured above-mentioned Nb then into
2O
5-Co
2O
3-Sm
2O
3-CeO
2In the colloidal sol; Fully stir post-heating and concentrate to form gel, at 950 ℃ of calcining 2h, temperature rise rate is 3 ℃/min, obtains BaTiO again
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder, standby;
3) press 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3Stoichiometric ratio is chosen tetrabutyl titanate, barium acetate, magnesium acetate and Bismuth trinitrate; Barium acetate, magnesium acetate and Bismuth trinitrate are dissolved in the acetic acid (acetic acid of 30mL, just dissolving is just; When tetrabutyl titanate was got 13.022g, the total mass of barium acetate, magnesium acetate and Bismuth trinitrate was 15.27g at this moment), obtain barium acetate, magnesium acetate and bismuth nitrate solution;
Get the 13.022g tetrabutyl titanate, slowly add the stabilizer alcohol solution (purity is greater than 99.5wt%) of 24mL, behind the stirring 30min, slowly add the solvent acetic acid solution (purity is greater than 99.5wt%) of 40mL; Under 80 ℃ of water bath condition, add barium acetate, magnesium acetate and bismuth nitrate solution subsequently, obtain water white 0.5BaTiO after stablizing
3-0.5Bi (Mg
1/2Ti
1/2) O
3Sol solution; With 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3The sol solution heating concentrates to form gel, and at 650 ℃ of calcining 2h, temperature rise rate is 1 ℃/min, the 0.5BaTiO that obtains after the cooling
3-0.5Bi (Mg
1/2Ti
1/2) O
3Powder;
4) with BaTiO
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder and 0.5BT-0.5BMT powder are pressed 4: 1 mixed in molar ratio, are medium ball milling 4 hours with alcohol, and oven dry makes the ceramic mixture powder;
5) add polyvinyl alcohol (binding agent) in the ceramic mixture powder, the add-on of polyvinyl alcohol is 3% of ceramic mixture powder quality, mixes, and compressing tablet gets the ceramic green sheet; The ceramic green sheet is warming up to 1200 ℃ then in 600 ℃ of insulations 2 hours, and temperature rise rate is 5 ℃/min, is incubated 10 minutes, is cooled to 950 ℃ rapidly, is incubated 1 hour, and furnace cooling obtains many shell structures X8R electrical condenser dielectric ceramic.
The XRD figure spectrum of many shell structures X8R electrical condenser dielectric ceramic is identical with embodiment 1.
Many shell structures X8R electrical condenser dielectric ceramic sample that present embodiment is obtained, last its dielectric properties of silver slurry test, obtain its specific inductivity and dielectric loss with variation of temperature figure (slightly, identical with embodiment 1) and its temperature coefficient of capacitance (be benchmark with 25 ℃) is with variation of temperature figure (slightly, identical with embodiment 1), experimental result illustrates that the electrical condenser dielectric ceramic of this embodiment preparation has the characteristics of wide working temperature, high stability.
Embodiment 3:
The preparation method of many shell structures X8R electrical condenser dielectric ceramic, it comprises the steps:
1) preparation colloidal sol: with the Nb of 50g
2O
5Be dissolved among 90 ℃ the HF of 250mL, treat that 10h fully reacts the ammonium oxalate aqueous solution (concentration of the described ammonium oxalate aqueous solution is 0.1g/mL) that the back adds 150mL, splashing into ammoniacal liquor after fully stirring, to regulate pH value be that 10[generates Nb (OH)
5White precipitate], 80 ℃ of following ageings 12 hours, suction filtration, throw out washed with water [to remove NH then
4 +, C
2O
4 2-, F
-], obtain Nb (OH)
5White precipitate; Nb (OH)
5Be dissolved in 100mL aqueous citric acid solution (concentration of described aqueous citric acid solution is 1g/mL) after the white precipitate drying, make Nb (OH)
5White precipitate dissolves fully, namely gets stable Nb salt sol; Measure Nb in the Nb salt sol with ICP
5+Concentration, standby;
Press Nb in the Nb salt sol
5+, Co (NO
3)
26H
2Co among the O
2+, Sm
2O
3Middle Sm
3+, CeO
2In Ce
4+Mol ratio 5: 4: 3: 3, choose Co (NO
3)
26H
2O, Sm
2O
3And CeO
2With Co (NO
3)
26H
2O, Sm
2O
3And CeO
2Dissolve in (Co (NO in the salpeter solution that purity is 99.5wt%
3)
26H
2O, Sm
2O
3And CeO
2Total mass: nitric acid=1g: 1mL), obtain mixing solutions; Then mixing solutions is added in the above-mentioned Nb salt sol and fully and stir, after stablizing, obtain Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Colloidal sol;
2) press BaTiO
3In Ba
2+With the Nb in the Nb salt sol
5+Mol ratio be 84: 1, choose BaTiO
3And Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Colloidal sol; BaTiO with 98g
3Ultra-sonic dispersion in the ethanol of 400mL is slowly poured above-mentioned Nb then into
2O
5-Co
2O
3-Sm
2O
3-CeO
2In the colloidal sol; Fully stir post-heating and concentrate to form gel, at 950 ℃ of calcining 4h, temperature rise rate is 4 ℃/min, obtains BaTiO again
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder, standby;
3) press 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3Stoichiometric ratio is chosen tetrabutyl titanate, barium acetate, magnesium acetate and Bismuth trinitrate; Barium acetate, magnesium acetate and Bismuth trinitrate are dissolved in the acetic acid (acetic acid of 36mL, just dissolving is just; When tetrabutyl titanate was got 13.022g, the total mass of barium acetate, magnesium acetate and Bismuth trinitrate was 15.27g at this moment), obtain barium acetate, magnesium acetate and bismuth nitrate solution;
Get the 13.022g tetrabutyl titanate, slowly add the stabilizer alcohol solution (purity is greater than 99.5wt%) of 24mL, behind the stirring 35min, slowly add the solvent acetic acid solution (purity is greater than 99.5wt%) of 40mL; Under 80 ℃ of water bath condition, add barium acetate, magnesium acetate and bismuth nitrate solution subsequently, obtain water white 0.5BaTiO after stablizing
3-0.5Bi (Mg
1/2Ti
1/2) O
3Sol solution; With 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3The sol solution heating concentrates to form gel, and at 650 ℃ of calcining 2h, temperature rise rate is 3 ℃/min, the 0.5BaTiO that obtains after the cooling
3-0.5Bi (Mg
1/2Ti
1/2) O
3Powder;
4) with BaTiO
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder and 0.5BT-0.5BMT powder are pressed 8: 1 mixed in molar ratio, are medium ball milling 8 hours with alcohol, and oven dry makes the ceramic mixture powder;
5) add water glass (binding agent) in the ceramic mixture powder, the add-on of water glass is 5% of ceramic mixture powder quality, mixes, and compressing tablet gets the ceramic green sheet; The ceramic green sheet is warming up to 1250 ℃ then in 600 ℃ of insulations 2 hours, and temperature rise rate is 10 ℃/min, is incubated 20 minutes, is cooled to 1050 ℃ rapidly, is incubated 2 hours, and furnace cooling obtains many shell structures X8R electrical condenser dielectric ceramic.
The XRD figure spectrum of many shell structures X8R electrical condenser dielectric ceramic is identical with embodiment 1.
Many shell structures X8R electrical condenser dielectric ceramic sample that present embodiment is obtained, last its dielectric properties of silver slurry test, obtain its specific inductivity and dielectric loss with variation of temperature figure (slightly, identical with embodiment 1) and its temperature coefficient of capacitance (be benchmark with 25 ℃) is with variation of temperature figure (slightly, identical with embodiment 1), experimental result illustrates that the electrical condenser dielectric ceramic of this embodiment preparation has the characteristics of wide working temperature, high stability.
Each cited raw material of the present invention can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention, bound value and the interval value of processing parameter of the present invention (as temperature, time etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (4)
1. many shell structures X8R electrical condenser dielectric ceramic is characterized in that it is by BaTiO
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder and 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3Powder preparing forms, BaTiO
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder and 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3The mol ratio of powder is x: 1,4≤x≤8.
2. the preparation method of many shell structures X8R electrical condenser dielectric ceramic as claimed in claim 1 is characterized in that it comprises the steps:
1) preparation colloidal sol: press Nb
2O
5: HF: the ammonium oxalate aqueous solution: aqueous citric acid solution=50g: 250mL: 100～150mL: 100mL, choose Nb
2O
5, HF, the ammonium oxalate aqueous solution and aqueous citric acid solution; The concentration of the described ammonium oxalate aqueous solution is 0.1g/mL; The concentration of described aqueous citric acid solution is 1g/mL;
With Nb
2O
5Be dissolved among 90 ℃ the HF, behind the reaction 10h, add the ammonium oxalate aqueous solution, splashing into ammoniacal liquor after the stirring, to regulate pH value be 10, then 80 ℃ of following ageings 12 hours, and suction filtration, throw out washes with water, obtains Nb (OH)
5White precipitate; Nb (OH)
5Be dissolved in aqueous citric acid solution after the white precipitate drying, make Nb (OH)
5White precipitate dissolves fully, obtains the Nb salt sol; Measure Nb in the Nb salt sol with ICP
5+Concentration, standby;
Press Nb in the Nb salt sol
5+, Co (NO
3)
26H
2Co among the O
2+, Sm
2O
3Middle Sm
3+, CeO
2In Ce
4+Mol ratio (3～5): (2～4): (1～3): (1～3), choose Co (NO
3)
26H
2O, Sm
2O
3And CeO
2With Co (NO
3)
26H
2O, Sm
2O
3And CeO
2Dissolve in the salpeter solution, obtain mixing solutions; Then mixing solutions is added in the above-mentioned Nb salt sol and stirring, obtain Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Colloidal sol;
2) press BaTiO
3In Ba
2+With the Nb in the Nb salt sol
5+Mol ratio be 84: 1, choose BaTiO
3And Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Colloidal sol; Press BaTiO
3: ethanol=98g: 400mL, with BaTiO
3Ultra-sonic dispersion in ethanol is slowly poured above-mentioned Nb then into
2O
5-Co
2O
3-Sm
2O
3-CeO
2In the colloidal sol; Fully stir post-heating and concentrate to form gel, at 950 ℃ of calcining 2～4h, temperature rise rate is 3～4 ℃/min, obtains BaTiO again
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder, standby;
3) press 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3Stoichiometric ratio is chosen tetrabutyl titanate, barium acetate, magnesium acetate and Bismuth trinitrate; Total mass by barium acetate, magnesium acetate and Bismuth trinitrate: the volume=2g of acetic acid: 3～5mL, barium acetate, magnesium acetate and Bismuth trinitrate are dissolved in the acetic acid, obtain barium acetate, magnesium acetate and bismuth nitrate solution;
Press tetrabutyl titanate: ethanolic soln: acetic acid solution=13.022g: 24mL: 40mL, choose tetrabutyl titanate, ethanolic soln and acetic acid solution; To add stabilizer alcohol solution in the tetrabutyl titanate, behind stirring 30～35min, add solvent acetic acid solution; Under 80 ℃ of water bath condition, add barium acetate, magnesium acetate and bismuth nitrate solution subsequently, obtain 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3Sol solution; With 0.5BaTiO
3-0.5Bi (Mg
1/2Ti
1/2) O
3The sol solution heating concentrates to form gel, and at 650 ℃ of calcining 2h, temperature rise rate is 1～3 ℃/min, the 0.5BaTiO that obtains after the cooling
3-0.5Bi (Mg
1/2Ti
1/2) O
3Powder;
4) with BaTiO
3-Nb
2O
5-Co
2O
3-Sm
2O
3-CeO
2Powder and 0.5BT-0.5BMT powder are pressed x: 1 mixed in molar ratio, and 4≤x≤8 are medium ball milling 4～8 hours with alcohol, oven dry makes the ceramic mixture powder;
5) add binding agent in the ceramic mixture powder, the add-on of binding agent is 3～5% of ceramic mixture powder quality, mixes, and compressing tablet gets the ceramic green sheet; The ceramic green sheet is warming up to 1200～1250 ℃ then in 600 ℃ of insulations 2 hours, and temperature rise rate is 5～10 ℃/min, be incubated 10～20 minutes, be cooled to 950～1050 ℃ rapidly, be incubated 1～2 hour, furnace cooling obtains many shell structures X8R electrical condenser dielectric ceramic.
3. the preparation method of many shell structures X8R electrical condenser dielectric ceramic according to claim 2 is characterized in that: described binding agent is polyvinyl alcohol or water glass.
4. the preparation method of many shell structures X8R electrical condenser dielectric ceramic according to claim 2 is characterized in that: Co (NO in the step 1)
3)
26H
2O, Sm
2O
3And CeO
2Total mass: salpeter solution=1g: 1mL; Purity 〉=the 99.5wt% of salpeter solution.
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| CN110304916B (en) * | 2019-04-25 | 2022-01-04 | 武汉理工大学 | Anti-reduction BaTiO3Base medium ceramic and preparation method thereof |
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