CN1688004A - Dielectric nonlinear capacitor ceramic material and its making technique - Google Patents
Dielectric nonlinear capacitor ceramic material and its making technique Download PDFInfo
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- CN1688004A CN1688004A CN 200510041966 CN200510041966A CN1688004A CN 1688004 A CN1688004 A CN 1688004A CN 200510041966 CN200510041966 CN 200510041966 CN 200510041966 A CN200510041966 A CN 200510041966A CN 1688004 A CN1688004 A CN 1688004A
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Abstract
This invention discloses an anti-ferroelectric ceramic capacitor material and its preparation technology, which applies Sn of positive four valency to replace Zr of positive 4 valency, applies the positive 3 valency La to replace 2 valency Pb in the compound of Pb(Zr, Ti) O3 to form a multi-component solid solution with Pb vacancy. The balanced formula of the charge and the valency is: (Pb1-3 2/2Laz)[(Zri-ysny)1-Tix]O3, in which, x varies between 0.06`0.20, y: 0.2010.40, z varies between 0.02-0.08, or positive 2 valency Sr or Ba is added to replace 2 valency Pb in Pb(zr, Ti) O3, the formula is [(Pb1-wBw)1-3z/2Laz][Zr1-ySny]1-xTix ]O3, B expresses Sr or Ba of 2 valency, w varies between 0.02-0.12. A conventional electronic ceramic preparation method is applied in the method.
Description
Technical field
The invention belongs to the material and the components and parts technical field that are used for the electric flux storage and discharge.Be particularly related to the ceramic material and the manufacture craft thereof that are used to make dielectric nonlinear capacitor.
Background technology
Capacitor is a kind of components and parts that are used for the electric flux storage and discharge, and is widely used in electronics and the power instrument.Energy storage density (electric energy stored in the unit volume) is an important performance indexes of capacitor, and the energy storage density of capacitor is high more, and the ability of storage and release electric flux is just big more.Along with electronics and power equipment to development efficient, miniaturization, industrial quarters has active demand to the capacitor with high energy storage density and high electromotive power output.The material that is used to make capacitor at present mainly adopts organic and inorganic dielectric material, utilizes the electric polarization characteristic of dielectric substance to reach the storage and the release of electric flux.For dielectric capacitor, the dielectric coefficient of the dielectric substance energy storage density of high capacitance more is just high more.Being used to make the problem that the conventional dielectric material of capacitor exists has: (1) is for linear dielectric substance, its dielectric coefficient is all smaller usually, need improve its energy storage density by applying very high electric field strength, this anti-electric breakdown strength and electric insulation protection to material proposes very high requirement; (2) for the ferroelectric material with high-dielectric coefficient, though its dielectric coefficient can significantly descend at its dielectric coefficient of high field intensity situation than higher under the low field intensity condition, and the common anti-electric breakdown strength of the ferroelectric ceramic of high-dielectric coefficient is lower.Because the problems referred to above have limited the raising of capacitor energy storage density, common capacitor energy storage density is in 0.2-0.4 joule/cubic centimetre scope.Research novel capacitor modulator material has important scientific and technical meaning to improve its energy storage density and power output.
Antiferroelectric materials can be transformed into ferroelectric phase from antiferroelectric phase under sufficiently high electric field strength effect, absorbed electric flux in this process; Metastable ferroelectric phase can spontaneously revert to antiferroelectric phase when extra electric field is removed, and in this process stored electric flux is discharged.This electric field-induced phase transition characteristic of antiferroelectric materials can be used for the storage and the release of electric flux.The research that is applied to capacitor about antiferroelectric materials all has some bibliographical informations at home and abroad.Nineteen ninety for latter stage, the inferior National Laboratory in the U.S. Holy Land has carried out the assessment Journal of Sex Research of antiferroelectric ceramic as the electric detonator initiation capacitor, University of Pennsylvania's Materials Research Laboratories has been carried out anti-ferroelectric thin film used flash-over characteristic research.The feasibility of antiferroelectric materials in high energy storage and high power capacitor application explored in these work, and the antiferroelectric materials performance that is used for capacitor proposed the suggestion of some directiveness.Lead zirconate titanate compound Pb (the Zr of low titanium component
1-xTi
x) O
3(x＜0.05) is a kind of antiferroelectric ceramic material commonly used, and has been used to the development of quick-fried electric transducing power supply.That but the lead zirconate titanate antiferroelectric ceramic exists is antiferroelectric-problem such as the ferroelectric transition temperature scope is narrow, electric hysteresis is wide, dependent variable is big, be difficult to reach the requirement of capacitor material.
Under the support of the Department of Science and Technology great basic research project 973 material fields " the some underlying issue researchs of informational function pottery " and General Armament Department's weaponry beforehand research fund project " microstructure design of antiferroelectric phase transformation pottery ", the field that modification lead zirconate titanate antiferroelectric materials has systematically been studied by Xi'an Communications University's electronic material and device research institute causes (electric field, temperature and pressure etc.) dielectric, nonlinear characteristic and the manufacture craft thereof under induced transformation and the strong electric field condition, it is wide that optimization possesses operating temperature range, dielectric loss is little, long service life, in antiferroelectric ceramic material and the manufacture craft thereof that the operating voltage range dielectric coefficient increases substantially, be used to make high energy storage density and high-output power capacitor.
Summary of the invention
The purpose of this invention is to provide a kind of antiferroelectric ceramic material and manufacture craft thereof, capacitor can be used in voltage and temperature range than broad, have the long number of times that recycles with high energy storage density and high-output power capacitor.
Design of the present invention is the antiferroelectric-ferroelectric phase transition characteristic of utilizing the electric field of antiferroelectric materials to induce, make the antiferroelectric phase of initial state be transformed into the consistent ferroelectric phase reservoir electrode energy of polarization intensity orientation by charging voltage, the antiferroelectric phase that makes metastable ferroelectric phase spontaneously revert to no macroscopic polarization intensity when discharge discharges the electric polarization energy, reaches the purpose that stores and discharge electric flux.Utilize near antiferroelectric materials dielectric coefficient antiferroelectric-ferroelectric conversion field to improve energy storage density and power output with the dielectric, nonlinear characteristic that electric field strength sharply changes.
Antiferroelectric capacitor ceramic material of the present invention is characterised in that: partly replace lead zirconate titanate compound Pb (Zr, Ti) O with trace chemical elements
3In chemical element, by regulating the density that field that chemical composition and proportioning optimize material causes (electric field, temperature, pressure) induced transformation performance and improves pottery.
1. be that the tin element of positive tetravalence partly replaces lead zirconate titanate compound Pb (Zr, Ti) O with chemical valence
3In the zr element of positive tetravalence, partly replace Pb (Zr, Ti) O with the lanthanum element of positive trivalent
3In positive divalence lead element, form the antiferroelectric solid solution of multicomponent with plumbous room.According to electric charge and the requirement of chemical valence balance, the chemical constitution formula of solid solution is (Pb
1-3z/2La
z) [(Zr
1-ySn
y)
1-xTi
x] O
3, wherein the variable quantity of x is between 0.06-0.20, and the variable quantity of y is between 0.20-0.40, and the variable quantity of z is between 0.02-0.08;
2. be positive divalence chemical element such as strontium or barium element replacement (Pb with chemical valence
1-3z/2La
z) [(Zr
1-ySn
y)
1-xTi
x] O
3In positive divalence lead element, the chemical constitution formula of its electric charge and chemical valence balance is [(Pb
1-wB
w)
1-3z/2La
z] [(Zr
1-ySn
y)
1-xTi
x] O
3
(1) when B gets the Sr element, chemical formula writing [(Pb
1-wSr
w)
1-3z/2La
z] [(Zr
1-ySn
y)
1-xTi
x] O
3, wherein the variable quantity of x is between 0.04-0.18, and the variable quantity of y is between 0.20-0.40, and the variable quantity of z is between 0.02-0.10, and the variable quantity of w is between 0.02-0.06;
(2) when B gets the Ba element, chemical formula writing [(Pb
1-wBa
w)
1-3z/2La
z] [(Zr
1-ySn
y)
1-xTi
x] O
3, wherein the variable quantity of x is between 0.04-0.18, and the variable quantity of y is between 0.20-0.40, and the variable quantity of z is between 0.02-0.10, and the variable quantity of w is between 0.02-0.12;
3. can also add the trace chemical elements that helps burning in the material, the chemical constitution formula writing (Pb of its solid solution
1-3z/2La
z) [(Zr
1-ySn
y)
1-xTi
x] O
3+ C, wherein C represents bismuth, nickel or copper, and the mole atom variable quantity of C element is at 1%-2%.
Realize the technology of above-mentioned three class antiferroelectric ceramic material preparations, it is characterized in that: adopt conventional electronic ceramic preparation method, comprise the operation that ball milling, pre-burning, sintering, making metal electrode, process conditions such as seasoned are optimized:
1. after the oxide raw material that includes above-mentioned element or other raw materials of compound being done oven dry and handled, accurately weigh according to the above-mentioned material prescription;
2. in the ball milling operation, make that raw material mixes, granularity is about 400 nanometers;
3. in the pre-burning operation, become pressed by powder block to be placed in the alumina crucible heated sealed, make the raw material generation chemosynthesis reaction of mechanical mixture form the perovskite crystal phase to 750-860 ℃ of insulation 1-2 hour;
4. in sintering circuit, base substrate is placed in the alumina crucible heated sealed to 1100-1300 ℃ of insulation 2-3 hour, and pottery is sintering in the atmosphere of rich plumbous and oxygen enrichment, and cooling rate is slow;
5. in seasoned operation, the antiferroelectric ceramic that obtains is cut, polishes, cleans the back make the good metal electrode of electric conductivity, do seasoned processing then.The method of seasoned processing is: in room temperature environment, the alternating voltage that applies an electric field strength and be 1.5 times of antiferroelectric ceramic forward conversion electric field strength between ceramic positive and negative electrode face circulates 5-10 time repeatedly.
During use, connect plain conductor, be made into the antiferroelectric ceramic capacitor after the encapsulation at the upper and lower electrode surface of pottery.The method that adopts the stack of multi-disc pottery, each interlayer electrode surface to do the circuit serial or parallel connection is made multi-layer capacitor and is used.The operating voltage of capacitor and temperature range and dielectric coefficient change by the chemical composition of regulating material.
Description of drawings
Fig. 1 is that the electrode area quantity of electric charge σ of antiferroelectric materials unit of the present invention is with extra electric field intensity E variation relation schematic diagram.
Fig. 2 is the schematic diagram that antiferroelectric ceramic material of the present invention stored and discharged electric flux.
Fig. 3 is that the differential permittivity of the antiferroelectric capacitor ceramic material for preparing of the present invention is with the electric field strength change curve.
Fig. 4 is that the antiferroelectric capacitor ceramic material polarization intensity for preparing of the present invention is with the electric field strength change curve.
Fig. 5 is the discharge curve of antiferroelectric ceramic capacitor in electric capacity, inductance, resistance series circuit that the present invention makes.
Fig. 6 is that the antiferroelectric ceramic capacitor that the present invention prepares is eliminated upper punch peak, electric pulse forward position as pressurizer.
Wherein:
Among Fig. 1, abscissa is extra electric field intensity E, and ordinate is the quantity of electric charge σ on the ceramic unit electrode area.This figure explanation antiferroelectric phase under enough big extra electric field effect is transformed into metastable ferroelectric phase, and the quantity of electric charge increases rapidly; Ferroelectric phase reverts to antiferroelectric phase when extra electric field is removed, and the quantity of electric charge is reduced to zero rapidly.The E here
FBe to make antiferroelectric phase be transformed into the needed electric field strength threshold value of ferroelectric phase, E
BBe to stop ferroelectric phase to revert to the electric field strength threshold value of antiferroelectric phase.
Among Fig. 2, abscissa is extra electric field intensity E, and ordinate is the quantity of electric charge σ on the ceramic unit electrode area.Energy content computing formula according to unit volume
The electric flux that antiferroelectric ceramic stores is the I+II+III zone, the electric flux II+III zone that discharges, and linear dielectric electric flux stored and that discharge is the III zone.This figure explanation antiferroelectric ceramic when applying same electric field strength store and the electric flux that discharges much larger than the dielectric energy of linearity.
Among Fig. 3, abscissa is extra electric field intensity E, and ordinate is the relative dielectric coefficient of differential of pottery
ε wherein
oBe the vacuum dielectric coefficient, P is a polarization intensity.This figure illustrates that the antiferroelectric condenser ceramics of the present invention dielectric coefficient when voltage raises increases, and forms maximum at the conversion field intensity place that induces antiferroelectric-ferroelectric phase transition.
Among Fig. 4, abscissa is extra electric field intensity E, and ordinate is the polarization intensity P of pottery.This figure illustrates that the antiferroelectric condenser ceramics of the present invention sharply increases greater than forward conversion electric field after-polarization intensity in electric field strength, and energy storage capacity increases accordingly.When electric field strength reduces rapidly less than reverse conversion electric field strength after-polarization intensity, discharge electric flux accordingly.
Fig. 5 and Fig. 6 be antiferroelectric ceramic of the present invention as high energy storage capacitor in resistance, electric capacity and inductive load discharge curve and as the application example of pulse voltage adjuster.
The present invention is described in further detail below in conjunction with embodiment that accompanying drawing and inventor provide, need to prove that given below is the more excellent example of the present invention, the present invention is not limited to these embodiment, mainly, all can reach purpose of the present invention at formula range of the present invention.
Embodiment
Embodiment 1: the non-linear relation that antiferroelectric ceramic polarization intensity of the present invention changes with applied voltage
With chemical valence is that the lanthanum of positive trivalent partly replaces the positive divalence lead element in the lead zirconate titanate compound, partly replace the zirconium tin titanate lead solid solution that positive tetravalence zr element in the lead zirconate titanate compound becomes the lanthanum modification with the tin element of positive tetravalence, the chemical composition expression formula that obtains antiferroelectric ceramic capacitor of the present invention is (Pb
0.925La
0.05) [(Zr
0.70Sn
0.30)
0.85Ti
0.15] O
3Employing contains oxide PbO, the ZrO of above-mentioned element
2, SnO
2, TiO
2, La
2O
3After pressing element molar ratio weighing mixing, make the bulk antiferroelectric ceramic through ball milling, pre-burning, secondary ball milling, granulation, pressed compact, plastic removal, sintering, annealing operation.Wherein: in the ball milling operation levigate about 400 nanometers of average particle size that reach of raw material; In the pre-burning operation, be that 15mm, diameter are that the base substrate of 50mm is put into alumina crucible and heated pre-burning at electric furnace be pressed into thickness through the powder after grinding.The pre-burning program is, heating rate is to be heated to 850 ℃ in 60 minutes/hour, naturally cools to room temperature with stove 850 ℃ of insulations after 2 hours.Add in pre-burning and to pine for alumina crucible and will seal the PbO that prevents in the base substrate and distribute, the base substrate after the pre-burning will form the perovskite crystal phase by chemosynthesis reaction; In the ceramic post sintering operation, the sintering program is that heating rate is to be heated to 1280 ℃ in 120 minutes/hour, naturally cools to room temperature with stove 1280 ℃ of insulations after 3 hours.In ceramic post sintering, adopt double-deck alumina crucible back-off sealing means to prevent that the PbO in the base substrate from distributing, and will in alumina crucible, place the PbZrO3 sheet and keep PbO atmosphere.Ceramic length shrinkage after burning till is 12%, and average grain size is 4 microns, is the perovskite crystal phase.
It is that 1.00mm, width are square side's sheet of 30.00mm that antiferroelectric ceramic cuts into thickness, prepares the metal electrode face through silver ink firing after the polished and cleaned.Be placed on then be heated in the transformer insulation oil 220 ℃ of insulations after 0.5 hour natural cooling carry out hot clean, in hot clean process with sheet metal pottery pole-face and the bottom electrode face connection that powers on.After overheated clean pottery being applied electric field strength is that the sinusoidal alternating voltage cycle of 5kV/mm is done electric seasoned processing for 10 times.Will be through the ceramic welding lead after the above-mentioned processing, just can be used as the antiferroelectric ceramic capacitor after sealing and use.
Embodiment 2: antiferroelectric ceramic of the present invention is as the embodiment of discharging capacitor
With chemical valence is the lead element that the strontium of the lanthanum of positive trivalent and positive divalence partly replaces positive divalence in the lead zirconate titanate compound, partly replace the zirconium tin titanate lead solid solution that positive tetravalence zr element in the lead zirconate titanate compound becomes lanthanum and the common doping vario-property of strontium with the tin element of positive tetravalence, the chemical composition expression formula that obtains antiferroelectric ceramic capacitor of the present invention is (Pb
0.91La
0.02Sr
0.06) (Zr
0.54Sn
0.30Ti
0.16) O
3The condition that pottery is close with capacitor fabrication technology among employing and the embodiment 1 obtains antiferroelectric ceramic and capacitor, and antiferroelectric ceramic is that thickness 0.060cm, area are the disk of 7.80cm.After applying amplitude and be the direct voltage charging of 3kV, do the short circuit condition discharge then.Discharging current is damped oscillation, and maximum current peak reaches 1500 amperes.
Embodiment 3: antiferroelectric ceramic of the present invention is as the embodiment of discharging capacitor
Present embodiment as different from Example 2, with chemical valence is the lead element that the barium of positive divalence partly replaces positive divalence in the lead zirconate titanate compound, become the zirconium tin titanate lead solid solution of lanthanum and the common doping vario-property of barium, the chemical composition expression formula that obtains antiferroelectric ceramic capacitor of the present invention is (Pb
0.92La
0.04Ba
0.02) (Zr
0.56Sn
0.40Ti
0.12) O
3, all the other are with embodiment 2.
Embodiment 4: antiferroelectric ceramic of the present invention is as the embodiment of discharging capacitor
Present embodiment as different from Example 2, with chemical valence is zirconium, tin and the titanium elements that the niobium of positive pentavalent partly replaces positive tetravalence in the lead zirconate titanate compound, become the zirconium tin titanate lead solid solution of niobium doping vario-property, the chemical composition expression formula that obtains antiferroelectric ceramic capacitor of the present invention is (Pb
0.99Nb
0.02) [(Zr
0.60Sn
0.40)
0.95Ti
0.05]
0.98O
3, all the other are with embodiment 2.
Embodiment 5: antiferroelectric ceramic of the present invention is as the embodiment of discharging capacitor
Present embodiment adds the trace chemical elements bismuth that helps burning as different from Example 2 in material, the chemical constitution formula writing (Pb of its solid solution
0.97La
0.02) [(Zr
0.60Sn
0.40)
0.90Ti
0.10] O
3+ 2%wBi wherein helps and burns element Bi CO
3Weight be 2% of PbO weight, sintering temperature is 1160 ℃, all the other are with embodiment 2.
Embodiment 6: antiferroelectric ceramic of the present invention is as the embodiment of pulse voltage adjuster
Adopt with embodiment 2 in the ceramic condition identical with capacitor fabrication technology obtain antiferroelectric ceramic and capacitor.The pulse power is output as the rectangle electric pulse that has upper punch peak, forward position.A slice in parallel is that thickness 0.10cm, area are that the disk antiferroelectric ceramic of 0.50cm can be eliminated the overshoot spike and can not reduce rectangle electric pulse voltage in circuit.
The present invention adopts tin element partly to replace zr element in the lead zirconate titanate compound, partly replace dependent variable and the electric hysteresis width that lead element in the lead zirconate titanate compound can make the conversion field intensity and the phase transition temperature of inducing antiferroelectric-ferroelectric phase transition regulate, produce in the time of can reducing phase transformation with lanthanum, strontium and barium element in wideer scope, thereby the antiferroelectric ceramic capacitor can be used in the different operating voltage range, reduce the dielectric loss of antiferroelectric ceramic, improve anti-electric breakdown strength and access times.Antiferroelectric capacitor ceramic material of the present invention, solved the ferroelectric ceramic defective that dielectric coefficient descends with electric field strength when high pressure, solved the defective of the low and temperature stability difference of liquid and organic dielectric dielectric coefficient, a kind of dielectric nonlinear capacitor material with high energy storage density, high-output power is provided.The antiferroelectric capacitor ceramic material preparation technology of the present invention makes the heterogeneous microstructure densification of antiferroelectric ceramic, and ceramic performance is stable, the height of anti-the electric breakdown strength.This manufacture method is consistent with the conditional electronic ceramic preparation, can be used as the industrial process that a kind of operation is simple, cost is low.
The energy storage density of antiferroelectric ceramic capacitor material of the present invention can reach erg-ten/cubic centimetre, discharge pulse power 1 megawatt/more than the cubic centimetre, can use in temperature range more than-40 ℃.The antiferroelectric ceramic capacitor can be made into monolithic ceramic capacitor, also can be made into the MULTILAYER COMPOSITE ceramic capacitor by the stack of multi-disc pottery.The charging voltage of antiferroelectric ceramic capacitor and discharge voltage can be set by the chemical composition of adjusting material, also can regulate by the circuit series-parallel system that changes potsherd thickness or a plurality of capacitor assemblies.
Claims (4)
1. antiferroelectric ceramic capacitor material is characterized in that: it is that the tin element of positive tetravalence partly replaces lead zirconate titanate compound Pb (Zr, Ti) O that this material adopts chemical valence
3In the zr element of positive tetravalence, partly replace Pb (Zr, Ti) O with the lanthanum element of positive trivalent
3In positive divalence lead element, form multicomponent solid solution with plumbous room; Chemical constitution formula writing (the Pb of its electric charge and chemical valence balance
1-3z/2La
z) [(Zr
1-ySn
y)
1-xTi
x] O
3, wherein the variable quantity of x is between 0.06-0.20, and the variable quantity of y is between 0.20-0.40, and the variable quantity of z is between 0.02-0.08.
2. antiferroelectric ceramic capacitor material is characterized in that: it is that positive diad strontium or barium element replace Pb (Zr, Ti) O that this material adopts chemical valence
3In positive divalence lead element, the chemical constitution formula of its electric charge and chemical valence balance writing [(Pb
1-wB
w)
1-3z/2La
z] [(Zr
1-ySn
y)
1-xTi
x] O
3, in the formula, B represents the chemical element of the Pb of replacement element of equal value;
1) when B gets the Sr element, chemical formula writing [(Pb
1-wSr
w)
1-3z/2La
z] [(Zr
1-ySn
y)
1-xTi
x] O
3, wherein the variable quantity of x is between 0.04-0.18, and the variable quantity of y is between 0.20-0.40, and the variable quantity of z is between 0.02-0.10, and the variable quantity of w is between 0.02-0.06;
2) when B gets the Ba element, chemical formula writing [(Pb
1-wBa
w)
1-3z/2La
z] [(Zr
1-ySn
y)
1-xTi
x] O
3, wherein the variable quantity of x is between 0.04-0.18, and the variable quantity of y is between 0.20-0.40, and the variable quantity of z is between 0.02-0.10, and the variable quantity of w is between 0.02-0.12.
3. antiferroelectric ceramic capacitor material according to claim 1 and 2 is characterized in that: add the trace chemical elements that helps burning in the material, the chemical constitution formula writing (Pb of its solid solution
1-3z/2La
z) [(Zr
1-ySn
y)
1-xTi
x] O
3+ C, wherein C represents bismuth, nickel or copper, and the mole atom variable quantity of C is 1%-2%.
4. the manufacture craft of antiferroelectric capacitor ceramic material, it is characterized in that, adopt conventional electronic ceramic technology, antiferroelectric ceramic capacitor material prescription to claim 1 or 2 or 3 is weighed, the process conditions of ball milling, pre-burning, sintering and seasoned operation are optimized, and it is characterized in that comprising the following steps:
1) in the ball milling operation, makes that raw material mixes, granularity is about 400 nanometers;
2) in the pre-burning operation, become pressed by powder block to be placed in the alumina crucible heated sealed, make the raw material generation chemosynthesis reaction of mechanical mixture form the perovskite crystal phase to 750-860 ℃ of insulation 1-2 hour;
3) in sintering circuit, base substrate is placed in the alumina crucible heated sealed to 1100-1300 ℃ of insulation 2-3 hour, and pottery is sintering in the atmosphere of rich plumbous and oxygen enrichment, and cooling rate is slow;
4) in seasoned operation, the antiferroelectric ceramic that obtains is cut, polishes, cleans the back make the good metal electrode of electric conductivity, do seasoned processing then; The method of seasoned processing is: in room temperature environment, the alternating voltage that applies an electric field strength and be 1.5 times of antiferroelectric ceramic forward conversion electric field strength between ceramic positive and negative electrode face circulates 5-10 time repeatedly.
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| CN102515755A (en) * | 2011-11-11 | 2012-06-27 | 内蒙古科技大学 | Lead-zirconate-based antiferroelectric thick film with high energy storage density, and preparation method thereof |
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| CN112960981B (en) * | 2021-05-07 | 2022-07-01 | 重庆文理学院 | Preparation method of lanthanum-tin doped lead zirconate titanate ceramic material |
| CN115947598A (en) * | 2022-10-21 | 2023-04-11 | 西安交通大学 | Antiferroelectric material capable of being co-fired with base metal inner electrode and preparation method thereof |
| CN115947598B (en) * | 2022-10-21 | 2024-03-22 | 西安交通大学 | Antiferroelectric material capable of being co-fired with base metal inner electrode and preparation method thereof |
| CN116514547A (en) * | 2023-04-27 | 2023-08-01 | 同济大学 | Lead ytterbium niobate-based antiferroelectric ceramic material and preparation method and application thereof |
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