CN102674813B - Material for manufacturing solid-state energy storage capacitor - Google Patents
Material for manufacturing solid-state energy storage capacitor Download PDFInfo
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- CN102674813B CN102674813B CN201210127404.8A CN201210127404A CN102674813B CN 102674813 B CN102674813 B CN 102674813B CN 201210127404 A CN201210127404 A CN 201210127404A CN 102674813 B CN102674813 B CN 102674813B
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Abstract
The invention relates to a material for manufacturing a solid-state energy storage capacitor, which is made by the following main materials in percentage by weight: 54.90-57.78 percent of lead oxide, 24.29-28.21 percent of zirconium oxide, 5.62-8.86 percent of titanium oxide, 4.68-5.52 percent of lanthanum oxide, 0-4.80 percent of barium carbonate, 0.67-0.71 percent of silver oxide and 0-1.43 percent of bismuth oxide. The material has the beneficial effects that the capacitance of the capacitor prepared by the material can present a better upward trend within a wider operating temperature range (55 DEG C below zero-125 DEG C above zero), and a dielectric constant of the capacitor is larger than 1,500; moreover, the capacitance of the capacitor has a positive voltage temperature coefficient after rated voltage is applied; and particularly, the upward trend of a positive capacitance-temperature characteristic curve is basically consistent with that of a positive capacitance-voltage characteristic curve, and the requirements of the solid-state energy storage capacitor on the material are completely met.
Description
Technical field
The invention belongs to electronic functional material technical field, be specifically related to a kind of material of making solid-state energy storage capacitor.
Background technology
Divide and mainly contain by temperature characterisitic for the main material of making conventional ceramic capacitor (circular plate type, chip multilayer) at present: I class porcelain SL, KL, COG and II class porcelain X
7r, Y
5p, Y
5u and Y
5the groups such as V.Its performance parameter of the electron ceramic material of each group only meets the general large parameter of conventional ceramic capacitor needed four (dielectric constant K, dielectric loss, temperature characterisitic, voltage endurance) requirement above, and exist a common defect be exactly in normal working temperature scope (conventionally-25 ℃～+ 85 ℃) its volume change all have and liter have the characteristic of falling, and all can present decline by a relatively large margin applying its capacitance after voltage.The characteristic of above-mentioned material capacity loss in temperature rise or after applying voltage makes it can not serve as the material of making solid-state energy storage capacitor at all.Energy storage capacitor is the core components and parts that current numerous energy storage module, pulse photoelectricity, the pulse power, exploration, ignition circuit and ignition system are badly in need of.Existing energy storage capacitor adopts poly-propyl ester or mica condenser mostly, and not only volume is large, and electric property heat is dispersed large, and reliability is low.
Summary of the invention
The invention provides a kind of material of making solid-state energy storage capacitor, adopt capacitor that this material makes can be within wider operating temperature range (55 ℃～+ 125 ℃) its capacitance presents good ascendant trend and dielectric constant is greater than 1500, and there is positive voltage temperature coefficient applying its capacity after rated voltage; Particularly the ascendant trend of positive capacity～temperature characteristics and positive capacity～voltage response is basically identical, meets the requirement of solid-state energy storage capacitor to material completely.
The present invention is with lead oxide (Pb
3o
4), zirconia (ZrO
2), titanium oxide (TiO
2) be the antiferroelectric-ferroelectric material system of major ingredient composition, and add material modified lanthana (La
2o
3), brium carbonate (BaCO
3), silver oxide (Ag
2o), bismuth oxide (Bi
2o
3) make the Mixed Zone of its structure in antiferroelectric-ferroelectric mutual conversion, and then material Curie point is adjusted to more than 125 ℃, guarantee in the time of-55 ℃～+ 125 ℃ the better ascendant trend of rising Capacitance reserve with temperature in (general-25 ℃～+ 85 ℃) scope, and the internal microstructure of material is applying after electric field polarize (transformation mutually), to guarantee that Capacitance reserve rises in the time that each temperature spot applies voltage.That is to say and make it possess the speciality of microstructure generation " phase transformation ", show in material electric property it is that while not applying voltage, this material is anti-ferroelectricity characteristic (because the position relationship of Curie point has determined the positive capacity temperature characteristic of characteristic that capacity rises with temperature always), apply the phase transformation (antiferroelectric → ferroelectric) that produces due to polarization after voltage and make it possess capacity with the characteristic (being positive capacity～voltage characteristic) that applies voltage and rise.
Concrete polarization process: when added electric field, do not have the displacement polarization of opposite sign but equal magnitude in this material structure cell, overall spontaneous macroscopic polarization is zero, presents antiferroelectric characteristic.Add after electric field, can cause turning to of polarized dipole and electrical, make all consistent with the direction that applies electric field (charge storage process) of direction of all dipoles, crystal has at this moment become again the ferroelectric after polarization.This phase transformation is exactly the basic reason that after applied voltage, capacity presents rising.
The applicability factor (easily purchase on market and energy volume shipment, material purity and particle size distribution are easily controlled) that further contemplates batch production, its initial raw materials all adopts the form of oxide or carbonate to prepare burden.
Material of the present invention is made up of the major ingredient of following weight ratio:
Lead oxide (Pb
3o
4) 54.90～57.78%,
Zirconia (ZrO
2) 24.29～28.21%,
Titanium oxide (TiO
2) 5.62～8.86%,
Lanthana (La
2o
3) 4.68～5.52%,
Brium carbonate (BaCO
3) 0～4.80%,
Silver oxide (Ag
2o) 0.67～0.71%,
Bismuth oxide (Bi
2o
3) 0～1.43%.
Weight ratio by 0～1.5% in described material is added auxiliary material; Described auxiliary material is made up of the raw material of following weight ratio:
Boron oxide (B
2o
3) 4%,
Silica (SiO
2) 4%,
Aluminium oxide (Al
2o
3) 1%,
Zinc oxide (ZnO) 5%,
Cadmium oxide (CdO) 37%,
Bismuth oxide (Bi
2o
3) 24%,
Lead oxide (Pb
3o
4) 25%.
Described major ingredient mainly solves electric property problem, adjust to more than 125 ℃ by material Curie point, guarantee in the time of-55 ℃～+ 125 ℃ the better ascendant trend of rising Capacitance reserve with temperature in (general-25 ℃～+ 85 ℃) scope, and the internal microstructure of material is applying after electric field must polarize (transformation mutually), to guarantee that Capacitance reserve rises in the time that each temperature spot applies voltage.
Described auxiliary material is low temperature glass formula, mainly solves easy fired problem, makes into porcelain temperature≤1120 ℃ and can not change main material electric property.Because sintering temperature (becoming porcelain temperature)≤1120 ℃, could adapt to multilayer chip capacitor porcelain basal body and interior electrode is realized low temperature co-fired processing request; Plectane capacitor porcelain basal body carries out when different with electrode preparation, successively burns till for twice, to firing temperature no requirement (NR), generally 1200 ℃ of left and right.
The addition of described auxiliary material is according to the structure of burning kiln and temperature control method adjustment.
The advantage that the present invention compared with prior art has and effect:
1, the present invention is having or not material behavior under external electric field situation all to present phase change characteristics.Show (under rated voltage) positive capacity～voltage characteristic when thering is positive capacity～temperature characterisitic in electric property and having electric field.Concrete classical insulation is as follows:
Dielectric constant: >=1500
Dielectric loss :≤250 × 10
-4(25 ℃, 1KH)
Temperature characterisitic :+4000ppm/ ℃ ± 1000 (55 ℃～+ 25 ℃)
+3000ppm/℃±1000(+25℃～+125℃)
Voltage coefficient: >=+10% (under rated voltage)
Puncture voltage: >=7KV/mm
2, the present invention is by adding auxiliary material low temperature glass, make material become porcelain temperature to drop to smoothly below 1120 ℃, and with do not add auxiliary material and become the performance of porcelain temperature >=1120 ℃ in full accord, met multilayer chip capacitor porcelain basal body and interior electrode and realized low temperature co-fired processing request.
3, the electric property of electric property of the present invention and current all I, II electron-like ceramic material has essential distinction, particularly the ascendant trend of positive capacity～temperature characteristics and positive capacity～voltage response is basically identical, meet the requirement of solid-state energy storage capacitor to material completely, there is good energy storage characteristic.Most critical be that the capacitor made of this material is in the time of additional rated voltage, the capacitance of the capacitance of each temperature spot during than making alive is not high, whole temperature range Capacitance reserve a complete ascendant trend, this is the foundation that this material can be used to make energy storage capacitor.
4, the present invention can be within wider operating temperature range (55 ℃～+ 125 ℃) its capacitance presents good ascendant trend and dielectric constant is greater than 1500, and there is positive voltage temperature coefficient applying its capacity after rated voltage.
Accompanying drawing explanation
Fig. 1 is the capacitor chip temperature characteristics figure that the present invention makes.Clear while showing additional rated voltage, the capacitance of the capacitance of each temperature spot during than making alive is not high, whole temperature range Capacitance reserve a complete ascendant trend.
Embodiment
Major ingredient preparation: get lead oxide, zirconia, titanium oxide, lanthana, brium carbonate, silver oxide, 10 kilograms of major ingredient raw materials of bismuth oxide configuration by formula described in table 1, by " batching-abrasive material-baking material-calcining (850 ± 5 ℃)-pulverizing-fine grinding (D
50≤ 2 μ)-dry " to prepare major ingredient stand-by for process route.
Auxiliary material preparation: get 40 grams of boron oxides, 40 grams of silica, 10 grams, aluminium oxide, 50 grams, zinc oxide, 370 grams of cadmium oxides, 240 grams of bismuth oxides, 1 kilogram of auxiliary material raw material of 250 grams of configurations of lead oxide, by " batching-abrasive material-oven dry-calcining (850 ± 5 ℃)-cold water extraction-fine grinding (D
50≤ 1 μ)-dry " to prepare auxiliary material stand-by for process route.
The present invention's preparation: after taking major ingredient and the even mixing of auxiliary material by material prescription described in table 1, granulation can obtain 10 kilograms of materials of the present invention.
Capacitor chip is made: the above-mentioned material of preparation is suppressed to green density>=5.0g/cm by Φ 11 × 1.21 (mm of unit) size
3, becoming 1092 ℃ of (± 5 ℃) roastings of porcelain temperature and be incubated 2 hours, then preparing electrode (full electrode), then carry out chip performance test.
The present invention is by adjusting by a small margin Pb, Zr, Ti, La, Ba, Ag, the ratio of Bi etc. and obtain seriation material (dielectric constant is as 1500,2000,2500), to meet the user demand of various forms (garden plate, chip), various sizes element.Under the prerequisite that guarantees positive Vcc characteristic (while applying voltage, Capacitance reserve rises) (namely possessing energy storage characteristic), its Tcc characteristic, dielectric constant, dielectric loss, withstand voltage different advantages and the feature of all having presented, used them can produce the solid energy storage capacitor that possesses energy storage characteristic that meets different use occasion different field.
All embodiment data and measuring and calculation result gather as follows (formula unit: kilogram)
Remarks:
1. embodiment 1 is applicable to making chip capacitor, and embodiment 2 is applicable to making garden plate capacitor.Temperature range is-55 ℃～+ 125 ℃.
2. embodiment 3,4,5,6-55 ℃～+ 85 ℃ Tcc characteristics be+more than 2500ppm/ ℃.
3. embodiment 3 is applicable to the occasion of firing condition poor (temperature is difficult to be controlled), can be used to make temperature range at the capacitor (garden plate, chip) of-55 ℃～+ 85 ℃.
4. embodiment 4,5,6 are applicable to making temperature range at-55 ℃～+ 85 ℃, the less withstand voltage higher capacitor of loss (garden plate, chip).
The capacitor core chip size that described embodiment 1 makes and test data, be calculated as follows:
Remarks: under 1092 ℃ of roasting conditions, shrinkage is 11.89%.
Dielectric constant K=14.4HC/ Φ
2=14.4 × 0.105 × 1256 ÷ 0.978
2=1985 (C is 25 ℃, capacity under 1KHz condition, and H is chip thickness, Φ is chip diameter)
Dielectric loss tg
6=35 × 10
-1
Temperature characterisitic Tcc calculated data is as follows
| Temperature (℃) | -55 | -25 | 0 | 25 | 50 | 85 | 125 |
| Capacity (PF) | 1015 | 1221 | 1291 | 1330 | 1520 | 1679 | 1743 |
Tcc=(1330-1015) ÷ 80 ÷ 1015=3879ppm/ ℃-55 ℃～+ 25 ℃ time
Tcc=(1743-1330) ÷ 100 ÷ 1330=3105ppm/ ℃+25 ℃～125 ℃ time
Voltage coefficient Vcc=Cv-Co/Co × 100% >=10%
Puncture voltage Vj >=9KV/mm
Above five parameters are the result of embodiment 1 roasting at 1092 ℃, meet the processing request of capacitor (plectane and multiple-layer sheet ceramic capacitor), also meet the requirement of this invention completely.
Above-described embodiment is preferred embodiment of the present invention, is not used for limiting practical range of the present invention, and the equivalence of being done with content described in the claims in the present invention therefore all changes, within all should being included in the claims in the present invention scope.
Claims (1)
1. make the material of solid-state energy storage capacitor, it is characterized in that described material is made up of major ingredient and the auxiliary material of following weight ratio: major ingredient 98.5～99.5%, auxiliary material 0.5～1.5%;
Described major ingredient is made up of the raw material of following weight ratio:
Pb
3O
4 54.90～57.78%，
ZrO
2 24.29～28.21%，
TiO
2 5.62～8.86%，
La
2O
3 4.68～5.52%，
BaCO
3 0～4.80%，
Ag
2O 0.67～0.71%，
Bi
2O
3 0.99～1.43%；
Described auxiliary material is made up of the raw material of following weight ratio:
B
2O
3 4%，
SiO
2 4%，
Al
2O
3 1%，
ZnO 5%，
CdO 37%，
Bi
2O
3 24%，
Pb
3O
4 25%。
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|---|---|---|---|
| CN201210127404.8A CN102674813B (en) | 2012-04-27 | 2012-04-27 | Material for manufacturing solid-state energy storage capacitor |
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| CN102674813B true CN102674813B (en) | 2014-05-21 |
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Denomination of invention: A material for solid state energy storage capacitor Effective date of registration: 20210624 Granted publication date: 20140521 Pledgee: Xi'an investment and financing Company limited by guarantee Pledgor: SHAANXI HUAXING ELECTRONIC DEVELOPMENT Co.,Ltd. Registration number: Y2021610000162 |
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Date of cancellation: 20220729 Granted publication date: 20140521 Pledgee: Xi'an investment and financing Company limited by guarantee Pledgor: SHAANXI HUAXING ELECTRONIC DEVELOPMENT Co.,Ltd. Registration number: Y2021610000162 |
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Denomination of invention: A material for making solid-state energy storage capacitors Effective date of registration: 20220908 Granted publication date: 20140521 Pledgee: Shaanxi SME financing Company limited by guarantee Pledgor: SHAANXI HUAXING ELECTRONIC DEVELOPMENT Co.,Ltd. Registration number: Y2022980014865 |