CN106938928A - A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material - Google Patents

A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material Download PDF

Info

Publication number
CN106938928A
CN106938928A CN201710206586.0A CN201710206586A CN106938928A CN 106938928 A CN106938928 A CN 106938928A CN 201710206586 A CN201710206586 A CN 201710206586A CN 106938928 A CN106938928 A CN 106938928A
Authority
CN
China
Prior art keywords
hours
nbo
tio
ceramic capacitor
nio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710206586.0A
Other languages
Chinese (zh)
Inventor
李玲霞
蔡朝阳
李江腾
张宁
王瑞杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University
Original Assignee
Tianjin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin University filed Critical Tianjin University
Priority to CN201710206586.0A priority Critical patent/CN106938928A/en
Publication of CN106938928A publication Critical patent/CN106938928A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C04B2235/3248—Zirconates or hafnates, e.g. zircon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C04B2235/3255—Niobates or tantalates, e.g. silver niobate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6582—Hydrogen containing atmosphere
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Capacitors (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses the anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material of one kind, with BaTiO3Powder is base-material, on this basis, and additional mass percent is 0.3~0.8% Na0.5Bi0.5TiO3；0.6~1.5% (NiO)1‑x(NbO2.5)x, wherein x=0.6~0.8；0.1~0.5% (MnO)1‑y(NbO2.5)y, wherein y=0.4~0.6；1.0~3.0% CaZrO3.First with BaTiO3As base-material, adulterate Na0.5Bi0.5TiO3, BT NBT mixtures are made；Again (NiO) is added in BT NBT1‑x(NbO2.5)x、(MnO)1‑y(NbO2.5)yAnd CaZrO3, compressing is green compact.1290~1315 DEG C of sintering in reducing atmosphere, ceramic capacitor dielectric material needed for being made.The present invention can prevent barium titanate semiconducting process, while lifting dielectric constant, ensureing that operation temperature area is wider, with relatively low dielectric loss and high insulation resistivity.In 55 DEG C~150 DEG C warm areas, rate of change of capacitance is within ± 10%, and with high room temperature dielectric constant (15000@1kHz) and low room temperature dielectric constant dielectric loss (tan=2.2%), the insulation resistivity of material is more than 2.0 × 1011Ω·cm。

Description

A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material
Technical field
The invention belongs to a kind of ceramic composition being characterized with composition, and in particular to one kind meets reducing atmosphere sintering will Ask and with huge dielectric constant, higher insulation resistivity, more low-loss temperature-stable X8R type ceramic capacitor dielectric materials And preparation method thereof.
Background technology
Electronics based on chip multilayer ceramic capacitor (Multilayer Ceramic Capacitor, abbreviation MLCC) Component, application field is extensive.Barium titanate (BaTiO3) base temperature-stable MLCC dielectric materials are because of its environmental sound, one It is directly the focus of research,
Traditional MLCC uses intermediate sintering temperature technique, and matching interior electrode is used is used as interior electricity with noble metals such as Pt, Pd Pole material, this occupies MLCC manufacturing costs 60%~70%.Develop with MLCC towards high capacity, its interior media number of plies increases Plus, inner electrode layer number is consequently increased, and MLCC manufacturing costs are improved constantly.Use nickel metal as interior electrode cost for silver-colored palladium electricity / 20th of pole, considerably reduces cost.Nickel metal inner electrode multilayer ceramic capacitor (Ni-MLCC) has resistivity It is low, reduce internal and external electrode equivalent resistance the advantages of, but need to sinter under reducing atmosphere with prevent nickel electrode be oxidized, BaTiO3 Semiconductor transformation occurs in sintering under reducing atmosphere, and insulation resistivity declines, and as semiconductor, loses dielectric behavior.Therefore make Ni-MLCC keys are to develop nickel electrode co-fire match anti-reduction material.
Huge dielectric constant (ε>103) dielectric material be make high-performance energy storage device ideal material, can be applicable to Gao Jie MLCC, the field such as solid-state super capacitor.Nowadays, the loss of most huge dielectric constant dielectric materials it is universal it is higher (> 0.1), insulation resistivity is not high, and regulation dielectric loss often brings the deterioration of temperature stability, it is difficult to apply.Therefore, prepare A kind of huge dielectric material of the high insulation resistivity of low-loss seems particularly significant.
The content of the invention
The purpose of the present invention, is to overcome existing barium phthalate base ceramic capacity to use nickel metal inner electrode and reducing atmosphere The semiconducting problem that lower sintering barium titanate occurs, and solve dielectric loss present in huge dielectric constant dielectric material and stability Between mismatch problem；Simultaneously, it is to avoid leaded, environmentally hazardous problem in production or synthesis component.There is provided one kind has Excellent dielectric properties and the huge dielectric constant X8R types medium material for multilayer ceramic capacitors of higher insulaion resistance and its preparation side Method.
The present invention is achieved by following technical solution.
A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material, with BaTiO3Powder is base Material, on this basis, additional mass percent are 0.3~0.8% Na0.5Bi0.5TiO3；0.6~1.5% (NiO)1-x (NbO2.5)x, wherein x=0.6~0.8；0.1~0.5% (MnO)1-y(NbO2.5)y, wherein y=0.4~0.6；1.0~ 3.0% CaZrO3；
Described Na0.5Bi0.5TiO3, it is by Na2CO3、Bi2O3And TiO2It is 1 by mole ratio:1:4 synthesis；
(NiO)1-x(NbO2.5)xCompound, is by NiO and Nb2O51-x in molar ratio：X/2, wherein x=0.6~ 0.8 synthesis；
(MnO)1-y(NbO2.5)yCompound, is by MnCO3、Nb2O51-y in molar ratio：Y/2, wherein y=0.4~ 0.6 synthesis
The CaZrO3By CaCO3And ZrO21: 1 synthesis in molar ratio；
The preparation method of the ceramic capacitor dielectric material, with following steps：
(1) Na is synthesized0.5Bi0.5TiO3
By Na2CO3、Bi2O3And TiO2It is 1 by mole ratio:1:4 carry out dispensing, and mixing and ball milling dries after 4 hours, crosses 40 Mesh sub-sieve, is calcined 4 hours in 950 DEG C, and Na is made0.5Bi0.5TiO3；
(2) (NiO) is synthesized1-x(NbO2.5)xCompound, wherein x=0.6~0.8
By NiO, Nb2O51-x in molar ratio：The dispensing of x/2, wherein x=0.6~0.8, raw material mixed with deionized water after ball Mill 4 hours, in 120 DEG C of drying, crosses 40 mesh sub-sieves, is calcined 2 hours in 1000 DEG C, then secondary ball milling 6 hours, drying, crosses 80 Mesh sub-sieve, is made (NiO)1-x(NbO2.5)x, wherein x=0.6~0.8；
(3) (MnO) is synthesized1-y(NbO2.5)yCompound, wherein y=0.4~0.6
By MnCO3、Nb2O51-y in molar ratio：The dispensing of y/2, wherein y=0.4~0.6, after raw material is mixed with deionized water Ball milling 4 hours, in 120 DEG C of drying, crosses 40 mesh sub-sieves, in 800~1000 DEG C of calcinings, then secondary ball milling 6 hours, drying, mistake 80 mesh sub-sieves, are made (MnO)1-y(NbO2.5)y, wherein y=0.4~0.6；
(4) CaZrO is synthesized3
By CaCO3、ZrO2In molar ratio 1:1 dispensing, raw material mixed with deionized water after ball milling 4 hours, dried in 120 DEG C, 40 mesh sub-sieves are crossed, are calcined 2 hours in 1000 DEG C, CaZrO is made3；
(5) with BaTiO3It is used as base-material, the Na for mass percent 0.3~0.6% of adulterating0.5Bi0.5TiO3, mixing and ball milling 4 is small When, drying is calcined 8 hours after 1050 DEG C, and BT-NBT mixtures are made；
(6) composition of following mass percents is added in BT-NBT：0.6~1.5% (NiO)1-x(NbO2.5)x, its Middle x=0.6~0.8；0.1~0.5% (MnO)1-y(NbO2.5)y, wherein y=0.4~0.6；1.0~3.0% CaZrO3, Matched somebody with somebody raw material mixed with deionized water after ball milling 4~8 hours, additional mass percent is 7% binding agent after drying, crosses 80 mesh Sub-sieve is granulated；
(7) the granulation powder of step (6) is pressed into green compact, after dumping, in the nitrogen that hydrogen percentages are 0%~5% 1290~1315 DEG C of sintering in hydrogen mixing reducing atmosphere, 40~120mL/min of gas flow rate is incubated 3 hours, anti-reduction is made huge Dielectric constant and low loss high value ceramic capacitor dielectric material.
The Na0.5Bi0.5TiO3Addition be 0.5wt%.
The green compact of the step (6) are 15 × 1~1.3mm of Ф disk green compact.
The green compact of the step (6) were warming up to 550 DEG C of dumpings through 3.5 hours, then rose to 1150 DEG C of sintering through 1 hour, protected Temperature 3 hours.
Beneficial effects of the present invention are as follows：
(1) ceramic capacitor dielectric material disclosed by the invention can be prevented in reduction by the doping vario-property to barium titanate The barium titanate semiconducting process sintered under atmosphere, is obviously improved the dielectric constant of dielectric material, it is ensured that dielectric material operation temperature area While wider, with relatively low dielectric loss and and high insulation resistivity.
(2) ceramic capacitor dielectric material disclosed by the invention has excellent dielectric properties：In -55 DEG C~150 DEG C temperature In area, rate of change of capacitance has high room temperature dielectric constant (~15000@1kHz) and low room temperature within ± 10% (tan=2.2%) is lost in K dielectric, and the insulation resistivity of material is more than 2.0 × 1011Ω·cm。
Embodiment
Below with reference to specific embodiment, the present invention is described in further detail：
Embodiment 1
First, the 2.6497g Na of pure level (>=99%) are analyzed with electronic balance weighing2CO3、11.6490g Bi2O3With 7.9898gTiO2Mixing, using deionized water as ball-milling medium, ball milling is dried after 4 hours, sieved, and is made in 950 DEG C of calcinings Na0.5Bi0.5TiO3；
By 2.2410g NiO and 9.3033g Nb2O5, mixing, using deionized water as ball-milling medium, ball milling dries after 4 hours Dry, sieving, is obtained (NiO) in 1000 DEG C of calcinings0.3(NbO2.5)0.7Compound, then secondary ball milling 6 hours, cross 80 mesh sub-sieves standby With；
The 5.7474g MnCO of pure level (>=99%) are analyzed with electronic balance weighing again3With 6.6452g Nb2O5, mixing, with Deionized water is as ball-milling medium, and ball milling is dried after 4 hours, sieved, and is obtained (MnO) in 900 DEG C of calcinings0.5(NbO2.5)0.5Chemical combination Thing, then secondary ball milling 6 hours, cross 80 mesh sub-sieves standby；
Again by 22.3291g CaCO3With 27.5114g ZrO2Mixing, using deionized water as ball-milling medium, ball milling 4 hours Dry, sieve afterwards, CaZrO is obtained in 1000 DEG C of calcinings3；
By 20g BaTiO3、0.18g(NiO)0.3(NbO2.5)0.7、0.04g(MnO)0.5(NbO2.5)0.5With 0.2g CaZrO3 Ball milling 4 hours after being mixed with deionized water, additional mass percent is 7% paraffin after drying, crosses the granulation of 80 mesh sub-sieves.
Shaping and sintering：
(1) powder after granulation is pressed into 15 × 1.2mm of Ф disk green compact under 3MPa, stream of nitrogen gas flow velocity is kept For 40ml/min, 1290 DEG C were warming up to through 6 hours, 3 hours are incubated, huge Jie's low-loss multilayer ceramic capacitor medium material is made Material.
Silver paste is uniformly coated in resulting product upper and lower surface, electrode is prepared through 850 DEG C of burning infiltrations, testing sample, test is made Dielectric properties and TC characteristics.
The raw material of specific embodiment is matched somebody with somebody and sintering condition refers to table 1.
Embodiment 2-6
Embodiment 2-6 and the preparation process condition of embodiment 1 be substantially the same manner as Example 1, and difference is in body in table 1 It is existing.
Table 1
The method of testing and detection device of the present invention is as follows：
(1) dielectric properties test (AC test signals：Frequency is 1kHz, and voltage is 1V)
Using the capacitance C and loss tan δ of HEWLETT PACKARD 4278A type capacitance tester test samples, and The dielectric constant of sample is calculated, computing formula is：
(2) TC characteristic tests
Utilize GZ-ESPEC MPC-710P types high/low temperature circulation incubator, the special survey of HM27002 type capacitor C-T/V characteristics Examination instrument and HEWLETT PACKARD 4278A are tested.Capacitance of the sample in -55 DEG C~150 DEG C of warm area is measured, is used Following formula calculate rate of change of capacitance：
The test result of the specific embodiment of the invention refers to table 2.
Table 2
The invention is not limited in above-described embodiment, the change of many details is possible, but therefore this do not run counter to this The scope and spirit of invention.

Claims (4)

1. a kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material, with BaTiO3Powder is base-material, On the basis of this, additional mass percent is 0.3~0.8% Na0.5Bi0.5TiO3；0.6~1.5% (NiO)1-x(NbO2.5)x, Wherein x=0.6~0.8；0.1~0.5% (MnO)1-y(NbO2.5)y, wherein y=0.4~0.6；1.0~3.0% CaZrO3；
Described Na0.5Bi0.5TiO3, it is by Na2CO3、Bi2O3And TiO2It is 1 by mole ratio:1:4 synthesis；
(NiO)1-x(NbO2.5)xCompound, is by NiO and Nb2O51-x in molar ratio：X/2, wherein x=0.6~0.8 are closed Into；
(MnO)1-y(NbO2.5)yCompound, is by MnCO3、Nb2O51-y in molar ratio：Y/2, wherein y=0.4~0.6 are closed Into
The CaZrO3By CaCO3And ZrO21: 1 synthesis in molar ratio.
The preparation method of the ceramic capacitor dielectric material, with following steps：
(1) Na is synthesized0.5Bi0.5TiO3
By Na2CO3、Bi2O3And TiO2It is 1 by mole ratio:1:4 carry out dispensing, and mixing and ball milling dries after 4 hours, crosses 40 mesh point Sample is sieved, and is calcined 4 hours in 950 DEG C, and Na is made0.5Bi0.5TiO3；
(2) (NiO) is synthesized1-x(NbO2.5)xCompound, wherein x=0.6~0.8
By NiO, Nb2O51-x in molar ratio：The dispensing of x/2, wherein x=0.6~0.8, ball milling 4 is small after raw material is mixed with deionized water When, in 120 DEG C of drying, 40 mesh sub-sieves are crossed, are calcined 2 hours in 1000 DEG C, then secondary ball milling 6 hours, drying, cross 80 mesh point sample Sieve, is made (NiO)1-x(NbO2.5)x, wherein x=0.6~0.8；
(3) (MnO) is synthesized1-y(NbO2.5)yCompound, wherein y=0.4~0.6
By MnCO3、Nb2O51-y in molar ratio：The dispensing of y/2, wherein y=0.4~0.6, raw material mixed with deionized water after ball milling 4 Hour, in 120 DEG C of drying, 40 mesh sub-sieves are crossed, in 800~1000 DEG C of calcinings, then secondary ball milling 6 hours, drying, 80 mesh point are crossed Sample is sieved, and is made (MnO)1-y(NbO2.5)y, wherein y=0.4~0.6；
(4) CaZrO is synthesized3
By CaCO3、ZrO2In molar ratio 1:1 dispensing, raw material mixed with deionized water after ball milling 4 hours, in 120 DEG C of drying, cross 40 Mesh sub-sieve, is calcined 2 hours in 1000 DEG C, and CaZrO is made3；
(5) with BaTiO3It is used as base-material, the Na for mass percent 0.3~0.6% of adulterating0.5Bi0.5TiO3, mixing and ball milling 4 hours, Drying is calcined 8 hours after 1050 DEG C, and BT-NBT mixtures are made；
(6) composition of following mass percents is added in BT-NBT：0.6~1.5% (NiO)1-x(NbO2.5)x, wherein x= 0.6~0.8；0.1~0.5% (MnO)1-y(NbO2.5)y, wherein y=0.4~0.6；1.0~3.0% CaZrO3, match somebody with somebody original Expect ball milling 4~8 hours after being mixed with deionized water, additional mass percent is 7% binding agent after drying, crosses 80 mesh sub-sieves Granulation；
(7) the granulation powder of step (6) is pressed into green compact, after dumping, mixed in hydrogen percentages for 0%~5% nitrogen hydrogen 1290~1315 DEG C of sintering in reducing atmosphere are closed, 40~120mL/min of gas flow rate is incubated 3 hours, anti-reduction giant dielectric is made Constant low loss, high value ceramic capacitor dielectric material.
2. the anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material of one kind according to claim 1, Characterized in that, the Na0.5Bi0.5TiO3Addition be 0.5wt%.
3. the anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material of one kind according to claim 1, Characterized in that, the green compact of the step (6) are 15 × 1~1.3mm of Ф disk green compact.
4. the anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material of one kind according to claim 1, Characterized in that, the green compact of the step (6) were warming up to 550 DEG C of dumpings through 3.5 hours, then rose to 1150 DEG C of sintering through 1 hour, Insulation 3 hours.
CN201710206586.0A 2017-03-31 2017-03-31 A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material Pending CN106938928A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710206586.0A CN106938928A (en) 2017-03-31 2017-03-31 A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710206586.0A CN106938928A (en) 2017-03-31 2017-03-31 A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material

Publications (1)

Publication Number Publication Date
CN106938928A true CN106938928A (en) 2017-07-11

Family

ID=59463544

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710206586.0A Pending CN106938928A (en) 2017-03-31 2017-03-31 A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material

Country Status (1)

Country Link
CN (1) CN106938928A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107382308A (en) * 2017-07-17 2017-11-24 天津大学 A kind of anti-reduced form dielectric material of high-k
CN109003821A (en) * 2018-08-14 2018-12-14 东北大学 A kind of ultra-high dielectric coefficient composite material, preparation method and application
CN110002864A (en) * 2019-02-23 2019-07-12 天津大学 A kind of preparation method of the high anti-reduced form dielectric substance of insulation
CN110304916A (en) * 2019-04-25 2019-10-08 武汉理工大学 A kind of anti-reduction BaTiO3Base media ceramic and preparation method
CN113307622A (en) * 2021-07-07 2021-08-27 天津大学 High-performance reduction-resistant barium titanate-based dielectric ceramic and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103936410A (en) * 2014-04-03 2014-07-23 天津大学 Manganese carbonate-doped high-temperature stable barium titanate-based dielectric material
CN103936414A (en) * 2014-04-04 2014-07-23 福建火炬电子科技股份有限公司 High temperature stable X9R type multilayer ceramic capacitor dielectric material and preparation method thereof
CN104045341A (en) * 2014-06-24 2014-09-17 天津大学 Lead-free high-dielectric-constant multilayer ceramic capacitor dielectric material and preparation method thereof
CN104310999A (en) * 2014-09-26 2015-01-28 天津大学 Preparation method of low-temperature sintered X8R type ceramic capacitor medium

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103936410A (en) * 2014-04-03 2014-07-23 天津大学 Manganese carbonate-doped high-temperature stable barium titanate-based dielectric material
CN103936414A (en) * 2014-04-04 2014-07-23 福建火炬电子科技股份有限公司 High temperature stable X9R type multilayer ceramic capacitor dielectric material and preparation method thereof
CN104045341A (en) * 2014-06-24 2014-09-17 天津大学 Lead-free high-dielectric-constant multilayer ceramic capacitor dielectric material and preparation method thereof
CN104310999A (en) * 2014-09-26 2015-01-28 天津大学 Preparation method of low-temperature sintered X8R type ceramic capacitor medium

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107382308A (en) * 2017-07-17 2017-11-24 天津大学 A kind of anti-reduced form dielectric material of high-k
CN109003821A (en) * 2018-08-14 2018-12-14 东北大学 A kind of ultra-high dielectric coefficient composite material, preparation method and application
CN110002864A (en) * 2019-02-23 2019-07-12 天津大学 A kind of preparation method of the high anti-reduced form dielectric substance of insulation
CN110304916A (en) * 2019-04-25 2019-10-08 武汉理工大学 A kind of anti-reduction BaTiO3Base media ceramic and preparation method
CN110304916B (en) * 2019-04-25 2022-01-04 武汉理工大学 Anti-reduction BaTiO3Base medium ceramic and preparation method thereof
CN113307622A (en) * 2021-07-07 2021-08-27 天津大学 High-performance reduction-resistant barium titanate-based dielectric ceramic and preparation method thereof
CN113307622B (en) * 2021-07-07 2023-03-10 天津大学 High-performance reduction-resistant barium titanate-based dielectric ceramic and preparation method thereof

Similar Documents

Publication Publication Date Title
CN106892659A (en) A kind of anti-reduction huge dielectric constant medium material for multilayer ceramic capacitors
CN106938928A (en) A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material
CN103214238B (en) Preparation method of barium strontium titanate dielectric temperature stable ceramic capacitor material
CN101781115B (en) X8R type multilayer ceramic capacitor dielectric material and preparation method thereof
CN105732020B (en) A kind of preparation method of giant dielectric, low-loss titanium dioxide base composite ceramic
CN107686347A (en) A kind of huge dielectric constant medium material for multilayer ceramic capacitors and preparation method thereof
CN108975907A (en) The method for improving barium titanate dielectric material resistance to reduction is adulterated by transition-metal ions
CN109231985A (en) A kind of preparation method of low-loss X8R type dielectric substance
CN108610042A (en) Dielectric material and preparation method thereof with the high insulation characterisitic of huge dielectric constant
CN109265162A (en) A kind of high-performance huge dielectric constant dielectric material
CN113248253A (en) Giant dielectric constant strontium titanate dielectric ceramic and preparation method thereof
CN107512906A (en) A kind of anti-reduction X9R type ceramic capacitor dielectric materials and preparation method thereof
CN103936410B (en) Manganous carbonate doped high temperature stable form barium phthalate base dielectric material
CN107399967A (en) A kind of ultra-low loss huge dielectric constant temperature-stable capacitor dielectric material
CN109231981A (en) The huge dielectric constant dielectric material that a kind of three, pentavalent heterogeneous element is co-doped with
CN103936411A (en) Method for preparing ultra-wide temperature stable barium titanate dielectric material by adopting annealing method
CN101030478B (en) High-dielectric metal-electric medium composite ceramic capacitance and its production
CN107226696A (en) X7R types BaTiO3Based capacitor ceramic material and preparation method thereof
CN105294098B (en) The medium material for multilayer ceramic capacitors and preparation method thereof of ultra-wide operation temperature area
CN103864416A (en) Method for preparing barium titanate ceramic capacitor medium at low sintering temperature
CN100434394C (en) B-position precursor doped with modified Barium titanate metal composite ceramic and preparation method thereof
CN108129145B (en) X7R ceramic capacitor dielectric material and preparation method thereof
CN107739204B (en) Ceramic dielectric material with excellent bias characteristic and preparation method thereof
CN113307622B (en) High-performance reduction-resistant barium titanate-based dielectric ceramic and preparation method thereof
CN110002864A (en) A kind of preparation method of the high anti-reduced form dielectric substance of insulation

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170711

WD01 Invention patent application deemed withdrawn after publication