CN1397957A - Multi-layer ceramic capacitor material with ultrahigh dielectric constant and temp stability and its preparing process - Google Patents
Multi-layer ceramic capacitor material with ultrahigh dielectric constant and temp stability and its preparing process Download PDFInfo
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- CN1397957A CN1397957A CN 02125720 CN02125720A CN1397957A CN 1397957 A CN1397957 A CN 1397957A CN 02125720 CN02125720 CN 02125720 CN 02125720 A CN02125720 A CN 02125720A CN 1397957 A CN1397957 A CN 1397957A
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 7
- 239000000654 additive Substances 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 16
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 13
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims description 34
- 230000000996 additive effect Effects 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 239000000428 dust Substances 0.000 claims description 13
- 239000004615 ingredient Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 206010013786 Dry skin Diseases 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 5
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 5
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- YWJHUQQPWSXFTC-UHFFFAOYSA-H barium(2+) oxalate titanium(4+) Chemical compound [Ti+4].[Ba++].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O YWJHUQQPWSXFTC-UHFFFAOYSA-H 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910001422 barium ion Inorganic materials 0.000 claims description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- GEZAXHSNIQTPMM-UHFFFAOYSA-N dysprosium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Dy+3].[Dy+3] GEZAXHSNIQTPMM-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims 5
- 239000002671 adjuvant Substances 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 30
- 239000000919 ceramic Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 8
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
This invention discloses a multi-layer ceramic capacitor material with superhigh dielectric constant and stable temp and its preparation method with the main components of barium titanate, metal powder and secondary additives of Co oxide, Nb oxide and rare earth oxide. Barium titanate is prepared by solid phase synthesis and chemical synthesis mixed with metal powders and secondary additives, formed under pressure and sintered to multi-layer ceramic capacitor materials greatly reducing temp of synthesis and finish without adding combustion adjuvant with the controlled room temp dielectric constant of the material of 4000-42000, tolerant variety of less than and equal to minus or plus 15% and sintered temp under 128 deg.C.
Description
Technical field
The invention belongs to the capacitor material preparing technical field, particularly have a kind of ultra-high dielectric coefficient, temperature-stable multilayer ceramic capacitor material of ultra-high dielectric coefficient, temperature stabilization and preparation method thereof.
Technical background
Multilayer ceramic capacitor is that electrode material is replaced in parallel being superimposed together with ceramic body with multilayer, and burns till an integral body simultaneously.According to the international EIA of Electronic Industries Association standard.Its capacitance is meant that the capacitance with 25 ℃ is a benchmark, within the scope of from-55 to+125 ℃ of temperature, and temperature coefficient of capacitance＜± 15%, dielectric loss (DF)≤2.5%.Multilayer ceramic capacitor is divided into two big classes by composition: a class is made up of leaded ferroelectric, and is another kind of with BaTiO
3The ferroelectric of the non-plumbous system of base is formed.And the latter is because environmentally safe, and mechanical strength and reliability be better than the former, and therefore non-lead is BaTiO
3Base has broad application prospects.Traditional non-lead is that the composition of multi-layer ceramic capacitor material mainly is with BaTiO
3Be base-material, suitably adding niobium (Nb), tantalum (Ta), magnesium (Mg), transition elements cobalt (Co), manganese (Mn) etc. and other element is modifier (secondary additive), and general sintering temperature height is all more than 1300 ℃.Some also adds silica (SiO
2), bismuth oxide (Bi
2O
3) wait sintering aid to reduce sintering temperature.Preparation technology passes through solid-phase synthesis.Processing step comprise weighing-batch mixing-high temperature synthetic-pulverizing-secondary interpolation-screening-moulding-sintering etc.There is the component skewness in this technology, and the synthesis temperature height is subject to contaminating impurity, shortcomings such as reproducibility difference.And the sintering temperature height, the energy consumption height is unfavorable for technology controlling and process.Room temperature dielectric constant with the ceramic material of barium phthalate base multilayer ceramic capacitor does not surpass 5000.Comparatively Cheng Shu product is as United States Patent (USP), U.S Pat.No5571767, (Wilson) the Wilson invention with BaTiO
3Be major ingredient, add neodymia, with Bi
2O
3, TiO
2And glassy phase PbO, Bi
2O
3, SiO
2, TiO
2, Al
2O
3Be sintering aid, under 1100 ℃, the multi-layer ceramic capacitor material of sintering preparation, dielectric constant is 3200 to the maximum.U.S. material is researched and analysed the BaTiO that the low fever has been reported in the laboratory
3Quito layer ceramic capacitor material, its dielectric constant reaches 4400, but the sintering process complexity, needs strict control, burns till sintering temperature～1110 ℃ for three times.
Summary of the invention
The purpose of this invention is to provide a kind of ultra-high dielectric coefficient, temperature-stable multilayer ceramic capacitor material and preparation method thereof, described multi-layer ceramic capacitor material mainly is made up of barium titanate, metal dust and secondary additive.Described multi-layer capacity modulator material is to be major ingredient with the barium titanate, adds to be used to improve the metal powder of dielectric property, and the secondary additive that is used to improve temperature performance, with the prescription of mol ratio is:
X ([100-(a+b+c)] BaTiO
3+ a Nb
2O
5+ b Co
3O
4+ c Re
2O
3+ d MnO
2The Me of)+(1-x), 0.5≤x≤1.0 wherein, 0.1≤a≤3.0,0.1≤b≤1.5,0.1≤c≤1.2,1.0≤a/b≤5.0, Me represents argent (Ag), palladium (Pd), silver palladium alloy (Ag-Pd), Re represents yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), dysprosium (Dy), erbium (Er) and ytterbium (Yb), wherein manganese oxide (MnO
2) add in right amount or do not add and all can.
Described major ingredient BaTiO
3Shared molal quantity is 50-99%; The shared molal quantity of described metal dust is 0-49%; Be the 1-3 kind of silver, palladium, silver palladium alloy, the consumption of secondary additive accounts for the 0.5-4mol% of total amount of material.Its secondary additive comprises niobium oxide (Nb
2O
5), cobalt sesquioxide (Co
2O
3) or cobaltosic oxide (Co
3O
4) and rare earth oxide yittrium oxide (Y
2O
3), cerium oxide (CeO
2), praseodymium oxide (Pr
2O
3), neodymia (Nd
2O
3), samarium oxide (Sm
2O
3), dysprosia (Dy
2O
3), ytterbium oxide (Yb
2O
3) in the 1-3 kind.
Described ultra-high dielectric coefficient, temperature-stable multilayer ceramic capacitor preparation methods are: preparation major ingredient BaTiO
3, again by prescription x ([100-(a+b+c)] BaTiO
3+ a Nb
2O
5+ b Co
3O
4+ c Re
2O
3+ dMnO
2The Me of)+(1-x), ball milling, drying, moulding, sintering formed after proportioning was mixed.
Step of preparation process is as follows:
1. solid phase method synthesizes BaTiO
3Material: with initial feed TiO
2, and BaCO
3By the stoichiometric proportion weighing, be medium mixing and ball milling 24 hours with water, reach its granularity less than 1 μ m after, under 70～120 ℃ of temperature, dry by the fire 6 hours, again under 1200 ℃ of temperature, solid phase reaction is synthesized BaTiO in 6 hours
3
2. also pressing formula rate and add metal dust, secondary additive mixing, is medium ball milling 24-72 hour with water;
3. under 70～120 ℃ of temperature, dry moulding in 6 hours;
4 sintering are 1150～1300 ℃ temperature range, and sintering 30～240 minutes promptly gets multi-layer ceramic capacitor material behind the natural cooling.
Described barium titanate BaTiO
3Be to adopt butyl titanate (Ti (OC
4H
9)
4), barium nitrate (Ba (NO
3)
2), barium acetate (Ba (CH
3COO)
2) chemically synthetic.Its synthesis technique is: by the stoichiometric proportion wiring solution-forming, Ti or Ba ion concentration are between 0.1～5M in the solution with three kinds of raw materials; With oxalic acid is that precipitation reagent carries out co-precipitation, forms the barium titanium oxalate white depositions, 10～80 ℃ of precipitation reaction temperature, and the reaction time is 2～4 hours; Sediment earlier with behind the deionized water wash several, is washed for several times with ethanol again, under 70～120 ℃, dried through 10～24 hours; And 700～1100 ℃ of calcinings down, be incubated after 0.5～2 hour, obtain the material B aTiO of superfine powder
3With secondary additive, metal dust and its even mixing, be medium ball milling 24～72 hours then with water; Under 70～120 ℃ after 10～24 hours dryings, extrusion forming, sintering, natural cooling promptly get ultra-high dielectric coefficient, temperature-stable multilayer ceramic capacitor material.
Described BaTiO
3Major ingredient directly and metal dust, additive mix, be medium ball milling 24-72 hour with the absolute ethyl alcohol; Under 50～70 ℃, after 10～24 hours dryings, extrusion forming, and under 1150～1300 ℃, through 30～240 minutes sintering, natural cooling promptly got ultra-high dielectric coefficient, temperature-stable multilayer ceramic capacitor material.
Described BaTiO
3Salt, additive that major ingredient and metal oxide or other easily are decomposed into metal mix, and are medium ball milling 24～72 hours with the absolute ethyl alcohol; Under 50～70 ℃, through 10～24 hours dryings; Under 300 ~ 500 ℃, this kind of pre-burning powder makes wherein metal oxide or slaine decomposite metal dust, extrusion forming then; Under 1150～1300 ℃, through 30～240 minutes sintering, natural cooling promptly got multi-layer ceramic capacitor material.Described metal dust is that metal oxide or other labile slaine are silver oxide (Ag
2O), silver carbonate (Ag
2CO
3), silver nitrate (AgNO
3).
The invention has the beneficial effects as follows, use technology of the present invention to need not to add any sintering agent, just can go out ultra-high dielectric coefficient, the temperature-stable multilayer ceramic capacitor material of excellent performance at≤1280 ℃ sintering temperature, the room temperature dielectric constant of material can be controlled between 4400～42000, temperature coefficient of capacitance＜± 15% in-55 ℃～+ 125 ℃ scopes, and have 10
12～10
13The high insulation resistivity of Ω CM, stable performance, puncture voltage is greater than 5KV/mm, and dielectric loss is little, and mechanical strength is big, characteristics such as reliability height, good uniformity.Preparation technology of the present invention is easy, utilizes the advantage of material self to reduce sintering temperature, and firing range is wide, and it is simply adjustable to fill a prescription, and sintering process is easily controlled.
Description of drawings
Fig. 1 is the characteristic curve corresponding to the sample dielectric constant with temperature variation of embodiment 1.
Fig. 2 is the temperature variant characteristic curve of sample percentage of capacitance variation with temperature corresponding to embodiment 1.
Fig. 3 is the characteristic curve corresponding to the sample dielectric constant with temperature variation of embodiment 2.
Fig. 4 is the temperature variant characteristic curve of sample percentage of capacitance variation with temperature corresponding to embodiment 2.
Fig. 5 is the characteristic curve corresponding to the sample dielectric constant with temperature variation of embodiment 3.
Fig. 6 is the temperature variant characteristic curve of sample percentage of capacitance variation with temperature corresponding to embodiment 3.
Fig. 7 is the characteristic curve corresponding to the sample dielectric constant with temperature variation of embodiment 4.
Fig. 8 is the temperature variant characteristic curve of sample percentage of capacitance variation with temperature corresponding to embodiment 4.
Fig. 9 is the characteristic curve corresponding to the sample dielectric constant with temperature variation of embodiment 5.
Figure 10 is the temperature variant characteristic curve of sample percentage of capacitance variation with temperature corresponding to embodiment 5.
Embodiment
Fig. 1～Figure 10 shows that is according to each sample (shown in the table 1-table 5) temperature characteristics of dielectric constant and the temperature curve that electric capacity varies with temperature rate of the embodiment 1～5 that preparation method of the present invention did.Its probe temperature is-60 ℃～130 ℃.ε is the dielectric constant of material in the table; TCC: temperature coefficient of capacitance;
Tg δ (25 ℃): dielectric loss during room temperature;
TCC(T)％＝100×(ε(T)-ε(25℃))/ε(25℃)。
In conjunction with top test curve figure, exemplify following embodiment and respectively the present invention illustrated:
Embodiment 1, is example with Nh, Co, Nd element doping.Fixedly additive Nb, Co consumption are 1.0mol%.Nb∶Co＝2.5。Barium titanate BaTiO
3Major ingredient adopts chemical synthesis process to produce its initial feed butyl titanate (Ti (OC
4H
9)
4) 102.1g is dissolved in ethanol, barium acetate (Ba (CH
3COO)
2) be that 76.64g is water-soluble, oxalic acid (H
2C
2O
42H
2O) be dissolved in ethanol for 83.2g.Earlier the butyl titanate ethanolic solution is added in the oxalic acid ethanolic solution, stir, then the barium acetate aqueous solution is slowly added, form the white precipitate of barium titanium oxalate.Sediment is earlier with the washed with de-ionized water several, and with after the ethanol cleaning for several times, drying is calcined, and obtains white barium carbonate powder material again.In barium carbonate powder material 20g, add secondary additive by prescription respectively, the content of niobium oxide and cobalt oxide is 1.0mol% in the prescription, the content of neodymia is respectively 0.3,0.5,0.7,0.8,0.9 and 1.0mol%, is designated as 1-1,1-2,1-3,1-4,1-5,1-6.Batching is mixed through ball milling, after the drying, and compression moulding under 2MPa pressure, diameter is 10mm, thickness is 1mm.In 1240 ℃ of sintering 4h.Programming rate is 6 ℃/min.The ceramics that burns till is measured its dielectric property behind the silver ink firing up and down.The dielectric property parameter of the ceramic print that is obtained sees Table 1.What Fig. 1 curve provided is the dielectric temperature characteristic curve of sample.Fig. 2 provides the temperature coefficient of capacitance curve of sample.
Embodiment 2: fixing prescription major ingredient barium titanate is 98mol%, and the content of niobium oxide and cobalt oxide is 1.0mol%, and neodymia is 1.0mol%.Barium titanate adopts the chemical synthesis of embodiment 1 to produce.Press embodiment 1 prescription respectively and add secondary additive in barium carbonate powder material 20g, batching is mixed through ball milling, after the drying, and compression moulding under 2MPa pressure, diameter is 10mm, thickness is 1mm.Respectively at 1200 ℃, 1220 ℃, 1240 ℃, 1250 ℃, 1260 ℃, 1280 ℃ of sintering 2h.Programming rate is 6 ℃/min.Measure its dielectric property behind the ceramics upper and lower surface silver ink firing that burns till.The dielectric property parameter of the ceramic print that is obtained sees Table 2.What Fig. 3 curve provided is the dielectric temperature characteristic curve of sample.Fig. 4 provides the temperature coefficient of capacitance curve of sample.
Embodiment 3: use three groups of 20g barium titanates of weighing, add secondary additive according to embodiment 1 prescription, add 0.2g, 1.0g, 2.0g silver powder then respectively, be designated as 3-, 3-2,3-3, batching is mixed through the alcohol ball milling, after the drying, behind the 2MPa forming under the pressure, at 1240 ℃ of sintering, temperature retention time is 2 hours.Its dielectric property of test behind the ceramics sample silver ink firing that is obtained.Table 3 is listed under 1240 ℃ of sintering, the dielectric property parameter of different metal Ag powder addition ceramics sample.Fig. 5 and Fig. 6 are respectively the dielectric temperature characteristic curve and the temperature coefficient of capacitance curve of sample.
Embodiment 4: use the pure barium titanate powder of embodiment 2 preparations, three groups of 20g barium titanates of weighing add secondary additive according to embodiment 1 prescription, add 4.72g, 6.30g, 7.24g silver nitrate (AgNO then respectively
3), being designated as 4-1,4-2,4-3, batching is mixed through the alcohol ball milling, after the drying, heat-treats under 350 ℃, and temperature retention time is 2 hours.Silver nitrate is decomposed into argent simple substance after the preliminary treatment.Then with this powder behind the 2MPa forming under the pressure, at 1250 ℃ of sintering, temperature retention time is 2 hours.Its dielectric property of test behind the ceramics sample silver ink firing that is obtained.Table 4 is listed under 1250 ℃ of sintering, the dielectric property parameter of different silver nitrate addition ceramics samples.Fig. 7 and Fig. 8 are respectively the dielectric temperature characteristic curve and the temperature coefficient of capacitance curve of sample.
Embodiment 5: to the pure barium titanate powder of the embodiment of the invention two preparations, three groups of 20g barium titanates of weighing add secondary additive according to prescription, add 6.39g, 7.16g, 7.67g silver carbonate (Ag then respectively
2CO
3), being designated as 5-1,5-2,5-3, batching is mixed through the alcohol ball milling, after the drying, heat-treats under 300 ℃, and temperature retention time is 2 hours.Silver carbonate is decomposed into argent simple substance after the preliminary treatment.Then with this powder behind the 2MPa forming under the pressure, at 1240 ℃ of sintering, temperature retention time is 2 hours.Its dielectric property of test behind the ceramics sample silver ink firing that is obtained.Table 5 is listed under 1240 ℃ of sintering, the dielectric property parameter of different silver carbonate addition ceramics samples.Fig. 9 and Figure 10 are respectively the dielectric temperature characteristic curve and the temperature coefficient of capacitance curve of sample.
In addition, the insulation resistance of ceramic material and puncture voltage test result see Table 6.
Above-mentioned experimental result explanation by the adjustment of prescription, technology and metal addition, at 1200 ~ 1250 ℃, does not add under the condition of sintering aid, can obtain the barium phthalate base multi-layer ceramic capacitor material of ultra-high dielectric coefficient (up to 42000) temperature-stable.
The room temperature dielectric constant of sample can be controlled between 4000 to 42000, and temperature coefficient of capacitance is less than ± 15%, and dielectric loss is less than 2.5%.Insulation resistivity is 10
12~ 10
13Ω CM, puncture voltage is greater than 5KV/mm.Utilize prescription of the present invention and technology, chemical method preparation technology particularly, it is low to obtain sintering temperature, and performance is adjustable, and sintering range is wide, the multi-layer ceramic capacitor material of the barium phthalate base that stability and reproducibility are good.And the uniform crystal particles of material, particle diameter is less than 1 micron, and mechanical strength is good, the reliability height, anti-breakdown characteristics is strong, can be applied to big capacity multilayer ceramic capacitor, is a kind of ultra-high dielectric coefficient, temperature-stable multilayer ceramic capacitor material with wide application prospect.
Table 1
| ??SAMPLE | ??CONDITION | ????E | ????TCC(％) | ????E ??(25℃) | ????E | ????T ??CC(％) | ????TGδ ????(25 ??℃)(％) |
| ??????????-55℃ | ???????????125℃ | ||||||
| ????1-1 | ?1240℃/4h | ????2981 | ????-13.9 | ????3462 | ????4213 | ????21.7 | ????2.76 |
| ????1-2 | ?1240℃/4h | ????4053 | ????-2.33 | ????4150 | ????4601 | ????10.9 | ????1.31 |
| ????1-3 | ?1240℃/4h | ????4488 | ????2.61 | ????4374 | ????4366 | ????-0.18 | ????1.50 |
| ????1-4 | ?1240℃/4h | ????4356 | ????2.93 | ????4232 | ????3946 | ????-6.75 | ????1.55 |
| ????1-5 | ?1240℃/4h | ????4290 | ????0.92 | ????4251 | ????4186 | ????-1.53 | ????1.38 |
| ????1-6 | ?1240℃/4h | ????4273 | ????2.10 | ????4185 | ????3783 | ????-9.60 | ????1.32 |
Table 2
| ?SAMPLE | ?CONDITION | ????E | ??TCC(％) | ????E ??(25℃) | ????E | ?TCC(％) | ????TGΔ (25℃)(％) |
| ?????????-55℃ | ???????????125℃ | ||||||
| ??2-1 | ?1200℃/2h | ????2557 | ????-11.8 | ????2901 | ????3226 | ????11.2 | ????6.18 |
| ??2-2 | ?1220℃/2h | ????3147 | ????-7.69 | ????3409 | ????3843 | ????12.7 | ????1.91 |
| ??2-3 | ?1240℃/2h | ????3677 | ????-0.59 | ????3799 | ????4080 | ????7.4 | ????1.86 |
| ??2-4 | ?1250℃/2h | ????3908 | ????0.51 | ????3850 | ????4273 | ????10.2 | ????1.70 |
| ??2-5 | ?1260℃/2h | ????4571 | ????2.21 | ????4472 | ????4306 | ????-3.7 | ????1.68 |
| ??2-6 | ?1280℃/2h | ????4470 | ????-2.57 | ????4588 | ????4262 | ????-7.1 | ????1.45 |
Table 3
| ?SAMPLE | ??CONDITION | ????E | ????TCC(％) | ????E ??(25℃) | ????E | ??TCC(％) | ????TGΔ (25℃)(％) |
| ?????????????-55℃ | ?????????????125℃ | ||||||
| ??3-1 | ??1240℃/2h | ????4154 | ????-5.65 | ????4403 | ????4649 | ??5.58 | ????0.84 |
| ??3-2 | ??1240℃/2h | ????4750 | ????-7.52 | ????5136 | ????5222 | ??1.67 | ????0.869 |
| ??3-3 | ??1240℃/2h | ????5825 | ????-10.40 | ????6501 | ????6286 | ??3.30 | ????1.21 |
Table 4
| ?SAMPLE | ??CONDITION | ????E | ????TCC(％) | ????E ??(25℃) | ????E | ??TCC(％) | ????TGΔ (25℃)(％) |
| ??????????????-55℃ | ????????????125℃ | ||||||
| ??4-1 | ??1250℃/2h | ????7202 | ??-12.53 | ????8234 | ??7694 | ??-6.56 | ????1.48 |
| ??4-2 | ??1250℃/2h | ????10140 | ??-14.50 | ????11860 | ??10760 | ??-9.27 | ????2.06 |
| ??4-3 | ??1250℃/2h | ????16590 | ??-15.62 | ????19710 | ??17540 | ??-11.01 | ????1.97 |
Table 5
| ?SAMPLE | ??CONDITION | ????E | ??TCC(％) | ????E ??(25℃) | ????E | ??TCC(％) | ????TGΔ (25℃)(％) |
| ????????????-55℃ | ?????????????125℃ | ||||||
| ??5-1 | ??1240℃/2h | ????15630 | ??-15.65 | ????18530 | ??16420 | ??-11.38 | ????1.91 |
| ??5-2 | ??1240℃/2h | ????29160 | ??-15.72 | ????34600 | ??29730 | ??-14.07 | ????2.28 |
| ??5-3 | ??1240℃/2h | ????35800 | ??-14.25 | ????41750 | ??35630 | ??-14.65 | ????2.21 |
Table 6
| ?Sample | ??Sintering?Condition | ????ρ ??(×10 12Ω·cm) | ????Breaking?Down?Voltage ????(Kv/mm) |
| ??1-3 | ????1240℃-4h | ????14.5 | ????11.6 |
| ??1-4 | ????1240℃-4h | ????20.3 | ????11.0 |
| ??4-2 | ????1240℃-2h | ????12.7 | ????5.8 |
Claims (7)
1. a ultra-high dielectric coefficient, temperature-stable multilayer ceramic capacitor material, mainly form by barium titanate, metal dust and secondary additive, it is characterized in that: described multi-layer capacity modulator material is to be major ingredient with the barium titanate, add the metal powder that is used to improve dielectric property, and the secondary additive that is used to improve temperature performance, with the prescription of mol ratio be:
X ([100-(a+b+c)] BaTiO
3+ a Nb
2O
5+ b Co
3O
4+ c Re
2O
3+ d MnO
2The Me of)+(1-x), 0.5≤x≤1.0 wherein, 0.1≤a≤3.0,0.1≤b≤1.5,0.1≤c≤1.2,1.0≤a/b≤5.0, Me represents argent (Ag), palladium (Pd), silver palladium alloy (Ag-Pd), Re represents yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), dysprosium (Dy), erbium (Er) and ytterbium (Yb), wherein manganese oxide (MnO
2) add in right amount or do not add and all can.
2. according to the described ultra-high dielectric coefficient of claim 1, temperature-stable multilayer ceramic capacitor material, it is characterized in that: described major ingredient BaTiO
3Shared molal quantity is 50-99%; The shared molal quantity of described metal dust is 0-49%, and it comprises the 1-3 kind of silver, palladium, silver palladium alloy; The consumption of secondary additive accounts for the 0.5-4mol% of total amount of material, and its secondary additive comprises niobium oxide (Nb
2O
5), cobalt sesquioxide (Co
2O
3) or cobaltosic oxide (Co
3O
4) and rare earth oxide yittrium oxide (Y
2O
3), cerium oxide (CeO
2), praseodymium oxide (Pr
2O
3), neodymia (Nd
2O
3), samarium oxide (Sm
2O
3), dysprosia (Dy
2O
3), ytterbium oxide (Yb
2O
3) in the 1-3 kind.
3. one kind prepares the described ultra-high dielectric coefficient of claim 1, temperature-stable multilayer ceramic capacitor preparation methods, it is characterized in that: the preparation method of described multi-layer ceramic capacitor material is to prepare major ingredient BaTiO earlier
3, again by prescription x ([100-(a+b+c)] BaTiO
3+ a Nb
2O
5+ b Co
3O
4+ c Re
2O
3+ d MnO
2Ball milling, drying, forming and sintering formed after the Me of)+(1-x) proportioning was mixed, and its step of preparation process is as follows:
1). solid phase method synthesizes BaTiO
3, with initial feed TiO
2, and BaCO
3By the stoichiometric proportion weighing, be medium mixing and ball milling 24 hours with water, reach its granularity less than 1 μ m, dry by the fire 6 hours under 70～120 ℃ of temperature the back, again under 1200 ℃ of temperature, solid phase reaction is synthesized BaTiO in 6 hours
3
2). pressing formula rate and add metal dust, secondary additive mixing, is medium ball milling 24-72 hour with water;
3). under 70～120 ℃ of temperature, dry moulding in 6 hours;
4). sintering is in 1150～1300 ℃ of temperature ranges, and sintering 30～240 minutes promptly gets multi-layer ceramic capacitor material behind the natural cooling.
4. one kind prepares the described ultra-high dielectric coefficient of claim 1, temperature-stable multilayer ceramic capacitor preparation methods, it is characterized in that: described barium titanate BaTiO
3Be to adopt butyl titanate (Ti (OC
4H
9)
4), barium nitrate (Ba (NO
3)
2), barium acetate (Ba (CH
3COO)
2) chemically synthetic; Its synthesis technique is: by the stoichiometric proportion wiring solution-forming, make in the solution Ti or Ba ion concentration between 0.1～5M three kinds of raw materials; Add precipitation reagent oxalic acid and carry out co-precipitation, form the barium titanium oxalate white depositions, 10～80 ℃ of precipitation reaction temperature, the reaction time is 2～4 hours; Sediment earlier with behind the deionized water wash several, is washed for several times with ethanol again, under 70～120 ℃, dried through 10～24 hours; And 700～1100 ℃ of calcinings down, be incubated after 0.5～2 hour, promptly obtain the material B aTiO of superfine powder
3Then secondary additive, metal dust being pressed prescription and its even mixing, is medium ball milling 24～72 hours with water; Under 70～120 ℃ after 10～24 hours dryings, extrusion forming is sintered into multi-layer ceramic capacitor material.
5. one kind prepares the described ultra-high dielectric coefficient of claim 1, temperature-stable multilayer ceramic capacitor preparation methods, it is characterized in that: described BaTiO
3Major ingredient directly and metal dust, secondary additive mix, be medium ball milling after 24-72 hour with the absolute ethyl alcohol, under 50～70 ℃, after 10～24 hours dryings, extrusion forming, be sintered into multi-layer ceramic capacitor material.
6. one kind prepares the described ultra-high dielectric coefficient of claim 1, temperature-stable multilayer ceramic capacitor preparation methods, it is characterized in that: described BaTiO
3Major ingredient and metal oxide or other labile slaine, secondary additive mix, with the absolute ethyl alcohol is medium ball milling 24～72 hours, under 50～70 ℃, through 10～24 hours dryings, and under 300～500 ℃, this kind of pre-burning powder makes wherein metal oxide or slaine decomposite metal dust, extrusion forming then, is sintered into multi-layer ceramic capacitor material.
7. according to the described ultra-high dielectric coefficient of claim 6, temperature-stable multilayer ceramic capacitor preparation methods, it is characterized in that: described metal oxide or other labile slaine are silver oxide (Ag
2O), silver carbonate (Ag
2CO
3), silver nitrate (AgNO
3).
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