CN102963928B - Barium zirconate titanate-based Y5V powder body material and preparation method thereof - Google Patents
Barium zirconate titanate-based Y5V powder body material and preparation method thereof Download PDFInfo
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- CN102963928B CN102963928B CN201210446901.4A CN201210446901A CN102963928B CN 102963928 B CN102963928 B CN 102963928B CN 201210446901 A CN201210446901 A CN 201210446901A CN 102963928 B CN102963928 B CN 102963928B
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- barium zirconate
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Abstract
The invention discloses a kind of barium zirconate titanate-based Y5V powder body material Ba (Ti
1-xzr
x) O
3+ A, it sinters the Y5V type stupalith being formed and have ultra-high dielectric coefficient and low-dielectric loss in 1200 ~ 1320 DEG C of temperature ranges.The specific inductivity of stupalith of the present invention is maximum reaches more than 22000, temperature coefficient of capacitance between-82% ~ 22%, room temperature dielectric loss & lt; 0.8%, is powder granule 20 ~ 60? within the scope of nm, ceramic crystalline grain size is less than 5 μm.The present invention is applicable to manufacture Large Copacity, small volume, high withstand voltage, high performance laminated ceramic capacitor or energy-storage battery, has wide industrial applications prospect.
Description
Technical field
The present invention relates to a kind of barium zirconate titanate-based Y5V powder body material and preparation method thereof.
Background technology
BaTiO
3series ceramic material, as a kind of important electron ceramic material, has high-k, ferroelectric, piezoelectricity, the excellent electric property such as withstand voltage, applies to the miniature capacitor that volume low capacity is large widely.Y5V type ceramic condenser is as the representative of a class ceramic condenser of high dielectric property, and be widely used in electronic circuit, particularly high-grade electronic machine is as the mobile phone in mobile computing, mobile communication, automobile telephone etc.Y5V refers to that electrical capacity within the scope of-30-85 DEG C is relative to satisfied-82%≤(C-C of velocity of variation during room temperature 25 DEG C
25)/C
25≤ 22%; C be-30-85 DEG C within the scope of the electrical capacity of certain temperature spot.
At present, prepare barium zirconate titanate-based Y5V type ceramic condenser dielectric material and mostly use solid phase method.The major advantage of solid phase method is its preparation technology simple maturation, cheaper starting materials etc.But because its preparation technology is longer, thermal treatment temp is high, and mixture homogeneity is poor, easily cause powder granule comparatively large, component easily departs from, the shortcoming such as need the consumption of sintering agent more, thus makes the penalty of pottery.Complicated process of preparation as described in US Patent No. 005361187, the particle size of powder is more than 1 μm, and ceramic crystalline grain size is greater than 10 μm, limits the reduction of ceramic layer thickness in MLCC, and the ceramic particle that medium layer comprises very little, the less reliable of electrical condenser can be caused.
The thin brilliant barium zirconate titanate-based Y5V type pottery medium powder of Liquid preparation methods mainly contains the precipitator method and hydrothermal method.At present, the people such as Wang Sheng (Journal of Inorganic Materials, 2005,20:119-126) prepare powder median size by hydrothermal method and be less than 0.3 μm, ceramic particle size is 4 μm, and room temperature dielectric constant is greater than 18000, dielectric loss is less than 0.7%, and meets (the Ba of Y5V standard
0.97ca
0.03)
1.001(Ti
0.80zr
0.20) O
3pottery.But the requirement of hydrothermal method usually for equipment is higher, temperature, pressure must strictly control, and cost is high, and yields poorly.And although the precipitator method simplify the preparation process of Y5V powder, still there is the shortcoming that complex process, the easy segregation of component etc. cannot overcome in it, and specific inductivity is only 14000.
Compared with above two kinds of wet chemistry methods, material prepared by sol-gel method single stage method can calcine synthesis at a lower temperature, thus it is contaminated to avoid material, the material that final acquisition is high-purity, homogeneous; It achieve the Homogeneous phase mixing of element at atomic level, and can the concentration of controlled doping element more accurately, thus obtain the powder of exact chemical metering ratio; It can reach the effective control to powder granularity and pattern, obtains thin brilliant nano-powder.The powder that Chinese patent 200910254653.1 uses once through method in Sol Gel process to obtain diameter of particle to be less than 100nm, but its gained ceramic dielectric constant lower (16000), the complicated [(Ba of powder composition
0.87sr
0.04ca
0.09) (Ti
0.86zr
0.08sn
0.06) O
3].
Summary of the invention
The object of this invention is to provide the barium zirconate titanate-based Y5V powder of a kind of ultra-high dielectric coefficient low-dielectric loss ceramic condenser, its specific inductivity is maximum can reach 24000, dielectric loss (25 DEG C)≤0.8%.
Another object of the present invention is to provide an one step preparation method of above-mentioned barium zirconate titanate-based Y5V powder.
For achieving the above object, implementation procedure of the present invention is as follows:
Formula B a (Ti
1-xzr
x) O
3the barium zirconate titanate-based Y5V powder that+A represents, wherein 0.05<x<0.20, A are MnO
2, CuO, Nb
2o
5and rare earth oxide, principal crystalline phase Ba (Ti
1-xzr
x) O
3weight percent to be the weight percent of each component in 98.5-99.7wt%, A be: MnO
2for 0.01-0.05%, CuO are 0.09-0.4%, Nb
2o
5for 0.1-0.5%, rare earth oxide is 0.1-0.6%, and described rare earth oxide is the oxide compound of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium.
Above-mentioned barium zirconate titanate-based Y5V raw powder's production technology, comprises the following steps:
(1) titanic acid ester is dissolved in Glacial acetic acid and alcoholic solvent;
(2) add barium, zirconium, manganese, copper, rare earth salt aqueous solution according to stoichiometric ratio, the water-soluble complexes of niobium or alcohol niobium, stir to obtain colloidal sol;
(3) colloidal sol stirs further and obtains gel, 30 ~ 90 DEG C of dry dry gel powders;
(4) dry gel powder calcines 0.5 ~ 8.0 hour to obtain barium zirconate titanate-based Y5V powder at 750 ~ 1200 DEG C.
Described titanic acid ester general formula is Ti (OR)
4, wherein R is butyl, sec.-propyl, octyl group or n-propyl.
Described alcoholic solvent is selected from ethanol, n-propyl alcohol, Virahol, n-butyl alcohol, 2-butanols.
Barium, manganese, copper, rare-earth salts add with the form of nitrate, nitrite or acetate, and zirconium adds with the form of zirconium nitrate or Zircosol ZN, and the water-soluble complexes of niobium or alcohol niobium are Nb
2o
5superoxol, niobium hydroxide, ethanol niobium, n-propyl alcohol niobium, amylalcohol niobium.
Use powder that above-mentioned barium zirconate titanate-based Y5V powder preparation method obtains through granulation, compressing tablet, obtain Y5V pottery at 1200-1320 DEG C of sintering 1 ~ 6h.
The high dielectric constant and low dielectric loss ceramic condenser dielectric material performance that the present invention prepares reaches following index: ceramic disks sintering temperature is between 1200-1320 DEG C, grain-size is at 2-7 μm, from in the temperature range of-30 DEG C to+85 DEG C, temperature coefficient of capacitance (TCC) is in the scope of+22% ~-82%, the room temperature dielectric constant of material at 15000-22000, room temperature dielectric loss <0.8%.
The present invention adopts once through method in Sol Gel process, by optimize further material compositing formula and control preparation condition can obtain particle diameter little, be evenly distributed and the higher barium zirconate titanate-based Y5V type pottery medium powder of purity, thus for preparing high-performance, MLCC that is thin layer, miniaturization provides a new approach; In the present invention, zirconium barium titanate major ingredient, additive such as doping component and sintering agent etc. all adopt sol-gel method single stage method to add, uneven to avoid major ingredient and additive etc. to carry out causing composition to mix when secondary mixes, and the problems such as new impurity are entered in blending; The median size of powder prepared by the present invention is little, good dispersity, activity is high, purity is high; Raw material of the present invention is easy to get, and equipment is simple, and simple process, system component are controlled.
Accompanying drawing explanation
Fig. 1 is powder XRD spectra prepared by embodiment 1;
Fig. 2 is powder TEM photo prepared by embodiment 1;
Fig. 3 is the SEM photo of powder sintering pottery prepared by embodiment 1;
Fig. 4 is the dielectric properties of pottery prepared by embodiment 1;
Fig. 5 is the SEM photo of powder sintering pottery prepared by embodiment 2;
Fig. 6 is the dielectric properties of pottery prepared by embodiment 2.
Embodiment
Embodiment 1
By 1.00molBa (Ti
1-xzr
x) O
3+ A, ZrO in powder
2content (x) be respectively 5.1mol%, 5.4mol%, 5.7mol%, A are the fixing MnO of composition
2, CuO, Nb
2o
5and rare earth oxide.Adopt once through method in Sol Gel process synthesis BaTiO
3based Y 5 V nano-powder.Concrete steps are as follows:
A) stoichiometrically take tetrabutyl titanate 50.00g, add Glacial acetic acid and the 29ml dehydrated alcohol of 45ml under stirring, fully stir; Barium acetate 43.70g, holmium nitrate 0.4931g, manganese acetate 0.0848g is added, neutralized verdigris 0.2762g, niobium oxides 0.1838g(Nb according to stoichiometric ratio
2o
5the form that adds be Nb
2o
5superoxol C
nb5+=0.01141g/ml, 16.11ml), the quality of zirconium nitrate is 8.4427g, constantly stirs, and temperature of reaction is room temperature, and the reaction times is 2 hours, obtains blue-greenish colour vitreosol; Abundant stirring obtains the barium phthalate base presoma of homogeneous transparent, overnightly leaves standstill, 80 DEG C of dry dry gel powders.
B) xerogel obtains nano-powder in 2 hours 900 DEG C of calcinings, and as shown in Figure 1, Fig. 2 is shown in by TEM photo to its XRD figure spectrum.
C) powder adds water formation slurry, and be that mill Jie carries out ball milling with zirconia ball, Ball-milling Time is 6 ~ 48h.By dried for ball milling sample through granulation, make the base substrate disk of diameter 8mm and thickness 1.5mm in 6MPa pressure, carry out sintering and being incubated 2h in 1300 DEG C, make disk stupalith, Fig. 3 is shown in by SEM photo.
The dielectric properties of ceramics sample are shown in Fig. 4 and table 1, and as seen from Table 1, prepared material meets the requirement of EIA-Y5V standard.
Embodiment 2
By 1.00molBa (Ti
1-xzr
x) O
3+ A, ZrO in powder
2the fixing MnO of content (x) to be 5.4mol%, A be composition
2, CuO, Nb
2o
5and rare earth oxide.Adopt once through method in Sol Gel process to synthesize barium zirconate titanate-based Y5V powder, the sintering temperature of pottery is respectively 1300 DEG C, 1260 DEG C and 1240 DEG C (being designated as #2-1, #2-2 and #2-3 successively), and concrete steps are as follows:
A) stoichiometrically take tetrabutyl titanate 50.00g, add appropriate Glacial acetic acid and dehydrated alcohol under stirring, fully stir; Barium acetate 43.70g, holmium nitrate 0.4931g, zirconium nitrate 8.4427g, manganese acetate 0.0848g is added, neutralized verdigris 0.2762g, Nb according to stoichiometric ratio
2o
50.1838g(Nb
2o
5the form that adds be Nb
2o
5superoxol C
nb5+=0.01141g/ml, 16.11ml), and constantly stir, temperature of reaction is room temperature, and the reaction times is 2 hours, obtains blue-greenish colour vitreosol; Abundant stirring obtains the barium zirconate titanate-based presoma of homogeneous transparent, overnightly leaves standstill, 80 DEG C of dry dry gel powders.
B) xerogel obtains powder in 2 hours 900 DEG C of calcinings.
C) powder adds water formation slurry, and be that mill Jie carries out ball milling with zirconia ball, Ball-milling Time is 6 ~ 48h.By dried for ball milling sample through granulation, make the base substrate disk of diameter 8mm and thickness 1.5mm in 6MPa pressure, in 1300 DEG C, carry out respectively at 1260 DEG C and 1240 DEG C sintering and being incubated 2h, make disk stupalith, Fig. 5 is shown in by SEM photo.
Fig. 6 and table 2 is the dielectric properties of the ceramics sample sintered under differing temps.As seen from Table 2, prepared material meets the requirement of EIA-Y5V standard.
Embodiment 3
By 1.00molBa (Ti
1-xzr
x) O
3+ A, ZrO in powder
2the fixing MnO of content (x) to be 5.4mol%, A be composition
2, CuO, Nb
2o
5and rare earth oxide.Adopt once through method in Sol Gel process to synthesize barium zirconate titanate-based Y5V powder, change MnO in A
2, CuO, Nb
2o
5or one or several quality of rare earth oxide, concrete steps are as follows:
A) stoichiometrically take tetrabutyl titanate 50.00g, add appropriate Glacial acetic acid and dehydrated alcohol under stirring, fully stir; Barium acetate 43.70g, zirconium nitrate 8.4427g and the MnO changing different amount is respectively added according to stoichiometric ratio
2, CuO, Nb
2o
5or one or several of rare earth oxide, detailed parameter is followed successively by #3-1 in Table 3(, #3-2 ..., #3-18), and constantly stir, temperature of reaction is room temperature, and the reaction times is 2 hours, obtains blue-greenish colour vitreosol; Abundant stirring obtains the barium zirconate titanate-based presoma of homogeneous transparent, overnightly leaves standstill, 80 DEG C of dry dry gel powders.
B) xerogel obtains nano-powder in 2 hours 900 DEG C of calcinings.
C) powder adds water formation slurry, and be that mill Jie carries out ball milling with zirconia ball, Ball-milling Time is 6 ~ 48h.By dried for ball milling sample through granulation, make the base substrate disk of diameter 8mm and thickness 1.5mm in 6MPa pressure, carry out sintering and being incubated 2h in 1300 DEG C, make disk stupalith.
Table 3 is doping different mass A(MnO
2, CuO, Nb
2o
5and rare earth oxide) ceramic powder composition.Table 4 is the dielectric properties of the made pottery of corresponding different powder in table 3.As seen from Table 4, prepared material meets the requirement of EIA-Y5V standard.
Claims (7)
1. Formula B a (Ti
1-xzr
x) O
3the barium zirconate titanate-based Y5V powder that+A represents, wherein 0.05<x<0.20, A are MnO
2, CuO, Nb
2o
5and rare earth oxide, principal crystalline phase Ba (Ti
1-xzr
x) O
3weight percent be 98.5-99.7wt%,
In A, the weight percent of each component is: MnO
2for 0.01-0.05%, CuO are 0.09-0.4%, Nb
2o
5for 0.1-0.5%, rare earth oxide is 0.1-0.6%, and described rare earth oxide is Holmium trioxide.
2. barium zirconate titanate-based Y5V raw powder's production technology described in claim 1, comprises the following steps:
(1) titanic acid ester is dissolved in Glacial acetic acid and alcoholic solvent;
(2) add barium, zirconium, manganese, copper, rare earth salt aqueous solution according to stoichiometric ratio, the water-soluble complexes of niobium or alcohol niobium, stir to obtain colloidal sol;
(3) colloidal sol stirs further and obtains gel, and gel 30 ~ 90 DEG C is dry obtains dry gel powder;
(4) dry gel powder calcines 0.5 ~ 8.0 hour to obtain barium zirconate titanate-based Y5V powder at 750 ~ 1200 DEG C.
3. barium zirconate titanate-based Y5V raw powder's production technology according to claim 2, is characterized in that: described titanic acid ester general formula is Ti (OR)
4, wherein R is butyl, sec.-propyl, octyl group or n-propyl.
4. barium zirconate titanate-based Y5V raw powder's production technology according to claim 2, is characterized in that: described alcoholic solvent is selected from ethanol, n-propyl alcohol, Virahol, n-butyl alcohol, 2-butanols.
5. barium zirconate titanate-based Y5V raw powder's production technology according to claim 2, it is characterized in that: barium, manganese, copper, rare-earth salts add with the form of nitrate, nitrite or acetate, zirconium adds with the form of zirconium nitrate or Zircosol ZN.
6. barium zirconate titanate-based Y5V raw powder's production technology according to claim 2, is characterized in that: the water-soluble complexes of described niobium or alcohol niobium are Nb
2o
5superoxol, ethanol niobium, n-propyl alcohol niobium, amylalcohol niobium.
7. a Y5V pottery, is characterized in that the powder using one of any described barium zirconate titanate-based Y5V powder preparation method of claim 2 to 6 to obtain is through granulation, compressing tablet, obtains at 1200-1320 DEG C of sintering 1 ~ 6h.
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| CN108558399A (en) * | 2018-06-01 | 2018-09-21 | 西北大学 | A kind of low-temperature sintering high dielectric property Y5V type ceramic capacitor dielectric materials and preparation method thereof |
| CN110642620A (en) * | 2019-10-15 | 2020-01-03 | 宝鸡文理学院 | Low-sintering high-dielectric ceramic material and preparation method thereof |
| CN112225559A (en) * | 2020-09-25 | 2021-01-15 | 陕西科技大学 | Zr-doped high-entropy perovskite oxide ceramic material with high energy storage and high efficiency, and preparation method and application thereof |
| CN114409402B (en) * | 2022-02-24 | 2022-10-14 | 江苏科技大学 | Capacitor dielectric porcelain and preparation method thereof |
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