CN106892659A - 一种抗还原巨介电常数多层陶瓷电容器介质材料 - Google Patents
一种抗还原巨介电常数多层陶瓷电容器介质材料 Download PDFInfo
- Publication number
- CN106892659A CN106892659A CN201710206567.8A CN201710206567A CN106892659A CN 106892659 A CN106892659 A CN 106892659A CN 201710206567 A CN201710206567 A CN 201710206567A CN 106892659 A CN106892659 A CN 106892659A
- Authority
- CN
- China
- Prior art keywords
- tio
- dielectric constant
- multilayer ceramic
- hours
- ceramic capacitors
- 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
Links
- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 11
- 229910003237 Na0.5Bi0.5TiO3 Inorganic materials 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 238000005469 granulation Methods 0.000 claims abstract description 7
- 230000003179 granulation Effects 0.000 claims abstract description 7
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 238000000498 ball milling Methods 0.000 claims description 9
- 229910010252 TiO3 Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000003989 dielectric material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- MTZOKGSUOABQEO-UHFFFAOYSA-L barium(2+);phthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O MTZOKGSUOABQEO-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
-
- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/638—Removal 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1254—Ceramic dielectrics characterised by the ceramic dielectric material based on niobium or tungsteen, tantalum oxides or niobates, tantalates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- 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
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- 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
-
- 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
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
-
- 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
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- 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
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- 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
-
- 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
- C04B2235/94—Products characterised by their shape
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Capacitors (AREA)
Abstract
本发明公开了一种抗还原巨介电常数多层陶瓷电容器介质材料，以BaTiO3粉体为基料，在此基础上，外加质量百分比为0.3～1.3％的Na0.5Bi0.5TiO3及0.6～3.5％的Nb2O5；所述的Na0.5Bi0.5TiO3，是将Na2CO3、Bi2O3和TiO2按摩尔量比为1:1:4合成。造粒后压制成生型，于氢气百分比为0％～5％的氮氢混合还原气氛中1290℃～1315℃烧结而成。本发明在还原气氛下烧结，可阻止钛酸钡半导化进程加剧，显著提升了介电常数，具有宽的工作温区和较低的介电损耗。在‑55℃～150℃温区内，电容量变化率在±15％以内，室温介电常数达13700，介电损耗低至0.06，电阻率大于1010Ω·cm。
Description
技术领域
本发明属于一种以成分为特征的陶瓷组合物，具体涉及一种满足抗还原特性的具有巨介电常数以及优异温度稳定性的X8R型多层陶瓷电容器介质材料及其制备方法
背景技术
片式多层陶瓷电容器(Multilayer Ceramic Capacitor，简称MLCC)作为基础电子元器件，除在智能手机、平板电脑、广播电视、移动通信、家用计算机、家用电器、测量仪器、医疗设备等民用产品及消费电子中普遍使用外，在航空航天、坦克电子、军用移动通讯、武器弹头控制和军事信号监控等军用电子设备以及石油勘探等行业都具有相当广泛的应用。钛酸钡(BaTiO3)基温度稳定型MLCC用介质材料因其对环境无害，一直是研究的热点，
传统MLCC采用中温烧结工艺，与之匹配的内电极采用用Pt、Pd等贵金属作为内电极材料，这占据MLCC制造成本60％～70％。随着MLCC需求量的增加，MLCC向着大容量化发展，其内部介质层数增加，相应地，内电极层数也随之增加，MLCC制造成本不断提高。采用镍金属作为内电极成本为银钯电极的二十分之一，极大地减少了成本，
镍金属内电极多层陶瓷电容器(Ni-MLCC)具有电阻率低、减少内外电极等效电阻等优点，但需在还原气氛下烧结以防止镍电极被氧化，BaTiO3在还原气氛下烧结会出现半导体化，绝缘电阻率下降，成为半导体，失去介质性能。因此制作Ni-MLCC关键在于研制出镍电极共烧匹配抗还原介质材料。巨介电常数(ε>103)的高温度稳定低损耗介质材料是制作高性能储能器件的理想材料，可应用在髙介MLCC，固态超级电容器等领域。
发明内容
本发明的目的，在于克服现有技术的陶瓷电容器介质的容量变化率虽能达到X8R的要求，但是不能避免在还原气氛下钛酸钡基介质材料出现半导化的问题。解决巨介电常数介质材料中存在的介电损耗与稳定性之间的不匹配问题。同时，避免生产或者合成组分中含铅，危害环境。提供一种巨介电常数且具有优异的温度稳定性的无铅X8R型多层陶瓷电容器介质材料及其制备方法。
本发明通过如下技术方案予以实现。
一种抗还原巨介电常数多层陶瓷电容器介质材料，以BaTiO3粉体为基料，在此基础上，外加质量百分比为0.3～1.3％的Na0.5Bi0.5TiO3及0.6～3.5％的Nb2O5；
所述的Na0.5Bi0.5TiO3，是将Na2CO3、Bi2O3和TiO2按摩尔量比为1:1:4合成；
该抗还原巨介电常数多层陶瓷电容器介质材料的制备方法，具有如下步骤：
(1)合成Na0.5Bi0.5TiO3
将Na2CO3、Bi2O3和TiO2按摩尔量比为1:1:4进行配料，混合球磨4小时后烘干、过40目分样筛，于950℃煅烧4小时，制得Na0.5Bi0.5TiO3；
(2)以BaTiO3作为基料，掺杂质量百分比0.3～1.3％的Na0.5Bi0.5TiO3，混合球磨4小时，烘干后于1050℃空气气氛煅烧8小时，制得BT-NBT混合物；
(3)在BT-NBT中添加质量百分比的0.6～3.5％的Nb2O5，所配原料与去离子水混合后球磨4～8小时，烘干后外加质量百分比为7％的粘结剂，过80目分样筛造粒；
(4)将步骤(3)的造粒粉料压制成生坯，经排胶后，于氢气百分比为0％～5％的氮氢混合还原气氛中1290℃～1315℃烧结，气体流速40～120mL/min，保温3小时，制得抗还原巨介电常数多层陶瓷电容器介质材料。
所述Na0.5Bi0.5TiO3的外加质量百分比为0.5wt％。
所述步骤(4)的生坯为Ф15×1～1.3mm的圆片生坯。
所述步骤(4)的生坯经3.5小时升温至550℃排胶，再经3.5小时升至1300℃烧结，保温3小时，升温速率控制在3～4℃/min。
所述步骤(4)中通入的氮氢混合气体气流流速为80mL/min。
本发明的有益效果如下：
(1)本发明公开的多层陶瓷电容器介质材料通过钛酸铋钠及五氧化二铌的添加，在还原气氛下烧结，可阻止钛酸钡半导化进程加剧，显著提升了介电常数，具有宽的工作温区和较低的介电损耗。
(2)本发明公开的多层陶瓷电容器介质材料具有优良的介电性能：在-55℃～150℃温区内，电容量变化率在±15％以内，且具有很高的室温介电常数(～13700)和较低介电损耗(～0.06)，电阻率大于1010Ω·cm。
具体实施方式
下面结合具体实施例对本发明作进一步的详细描述。
实施例1
首先，用电子天平称量分析纯级(≥99％)的将2.6497g Na2CO3、11.6490g Bi2O3和7.9898gTiO2混合，以去离子水作为球磨介质，球磨4小时后烘干、过筛，于950℃煅烧制得Na0.5Bi0.5TiO3；
将20g BaTiO3和0.10g Na0.5Bi0.5TiO3混合球磨4小时，烘干，在1050℃煅烧8小时；在煅烧后的BT-NBT中添加0.5gNb2O5与去离子水混合后球磨4小时，烘干后外加质量百分比为7％的石蜡，过80目分样筛造粒。
成型与烧结：
将造粒后的粉料在3MPa下压制成Ф15×1.2mm的圆片生坯，在流速为80ml/min氮气气流中，经3.5小时升温至550℃排胶，再经3.5小时升至1300℃烧结，保温3小时，制得巨介温度稳定型多层陶瓷电容器介质材料。
在所得制品上下表面均匀涂覆银浆，经850℃烧渗制备电极，制得待测样品，测试介电性能及TC特性。
实施例2-4
实施例2-4的不同组分以及烧结条件详见表1，其他制作工艺与实施例1相同。
实施例1-4的具体原料配比详见表1。
表1
本发明的测试方法如下：
(1)介电性能测试(交流测试信号：频率为1kHz，电压为1V)
使用HEWLETT PACKARD 4278A型电容量测试仪测试样品的电容量C和损耗tanδ，并计算出样品的介电常数，计算公式为：
(2)TC特性测试
利用GZ-ESPEC MPC-710P型高低温循环温箱、HM27002型电容器C-T/V特性专用测试仪和HEWLETT PACKARD 4278A进行测试。测量样品在温区-55℃～150℃内的电容量，采用下述公式计算电容量变化率：
本发明具体实施例的介电性能及TC特性的检测结果详见表2。
表2
本发明并不局限于上述实施例，很多细节的变化是可能的，但这并不因此违背本发明的范围和精神。
Claims (5)
1.一种抗还原巨介电常数多层陶瓷电容器介质材料，以BaTiO3粉体为基料，在此基础上，外加质量百分比为0.3～1.3％的Na0.5Bi0.5TiO3及0.6～3.5％的Nb2O5。
所述的Na0.5Bi0.5TiO3，是将Na2CO3、Bi2O3和TiO2按摩尔量比为1:1:4合成；
该抗还原巨介电常数多层陶瓷电容器介质材料的制备方法，具有如下步骤：
(1)合成Na0.5Bi0.5TiO3
将Na2CO3、Bi2O3和TiO2按摩尔量比为1:1:4进行配料，混合球磨4小时后烘干、过40目分样筛，于950℃煅烧4小时，制得Na0.5Bi0.5TiO3；
(2)以BaTiO3作为基料，掺杂质量百分比0.3～1.3％的Na0.5Bi0.5TiO3，混合球磨4小时，烘干后于1050℃空气气氛煅烧8小时，制得BT-NBT混合物；
(3)在BT-NBT中添加质量百分比的0.6～3.5％的Nb2O5，所配原料与去离子水混合后球磨4～8小时，烘干后外加质量百分比为7％的粘结剂，过80目分样筛造粒；
(4)将步骤(3)的造粒粉料压制成生坯，经排胶后，于氢气百分比为0％～5％的氮氢混合还原气氛中1290℃～1315℃烧结，气体流速40～120mL/min，保温3小时，制得抗还原巨介电常数多层陶瓷电容器介质材料。
2.根据权利要求1所述的一种抗还原巨介电常数多层陶瓷电容器介质材料，其特征在于，所述Na0.5Bi0.5TiO3的外加质量百分比为0.5wt％。
3.根据权利要求1所述的一种抗还原巨介电常数多层陶瓷电容器介质材料，其特征在于，所述步骤(4)的生坯为Ф15×1～1.3mm的圆片生坯。
4.根据权利要求1所述的一种抗还原巨介电常数多层陶瓷电容器介质材料，其特征在于，所述步骤(4)的生坯经3.5小时升温至550℃排胶，再经3.5小时升至1300℃烧结，保温3小时，升温速率控制在3～4℃/min。
5.根据权利要求1所述的一种抗还原巨介电常数多层陶瓷电容器介质材料，其特征在于，所述步骤(4)中通入的氮氢混合气体气流流速为80mL/min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710206567.8A CN106892659A (zh) | 2017-03-31 | 2017-03-31 | 一种抗还原巨介电常数多层陶瓷电容器介质材料 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710206567.8A CN106892659A (zh) | 2017-03-31 | 2017-03-31 | 一种抗还原巨介电常数多层陶瓷电容器介质材料 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106892659A true CN106892659A (zh) | 2017-06-27 |
Family
ID=59193438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710206567.8A Pending CN106892659A (zh) | 2017-03-31 | 2017-03-31 | 一种抗还原巨介电常数多层陶瓷电容器介质材料 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106892659A (zh) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107686347A (zh) * | 2017-08-28 | 2018-02-13 | 天津大学 | 一种巨介电常数多层陶瓷电容器介质材料及其制备方法 |
| CN107759215A (zh) * | 2017-11-01 | 2018-03-06 | 苏州大学 | 制备巨介电常数低损耗陶瓷电容器的方法 |
| CN108546115A (zh) * | 2018-04-29 | 2018-09-18 | 天津大学 | 一种钛酸钡基低损耗巨介电常数电介质材料及其制备方法 |
| CN109180177A (zh) * | 2018-09-27 | 2019-01-11 | 中国科学院上海硅酸盐研究所 | 一种x9r型多层陶瓷电容器介质材料及其制备方法和应用 |
| CN110002864A (zh) * | 2019-02-23 | 2019-07-12 | 天津大学 | 一种高绝缘抗还原型电介质材料的制备方法 |
| CN110183224A (zh) * | 2019-06-19 | 2019-08-30 | 天津大学 | 一种施受主共掺高介电常数低损耗电介质材料的制备方法 |
| CN110256067A (zh) * | 2019-06-19 | 2019-09-20 | 天津大学 | 一种铌锰掺杂抗还原型电介质材料的制备方法 |
| CN110304916A (zh) * | 2019-04-25 | 2019-10-08 | 武汉理工大学 | 一种抗还原BaTiO3基介质陶瓷及制备方法 |
| CN110451955A (zh) * | 2019-08-14 | 2019-11-15 | 清华大学 | 钛酸铋钠-钛酸钡基无铅弛豫铁电体储能陶瓷及其制备方法 |
| CN113307622A (zh) * | 2021-07-07 | 2021-08-27 | 天津大学 | 高性能抗还原钛酸钡基介质陶瓷及其制备方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030526A (zh) * | 2010-11-11 | 2011-04-27 | 厦门松元电子有限公司 | 一种抗还原陶瓷介质材料及其制备方法 |
| CN103011805A (zh) * | 2012-12-24 | 2013-04-03 | 陕西科技大学 | 一种BaTiO3 基无铅X8R 型陶瓷电容器介质材料及其制备方法 |
| CN103936410A (zh) * | 2014-04-03 | 2014-07-23 | 天津大学 | 碳酸锰掺杂高温稳定型钛酸钡基介质材料 |
| CN105016727A (zh) * | 2015-08-05 | 2015-11-04 | 天津大学 | 高耐压多层陶瓷电容器介质材料的制备方法 |
-
2017
- 2017-03-31 CN CN201710206567.8A patent/CN106892659A/zh active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030526A (zh) * | 2010-11-11 | 2011-04-27 | 厦门松元电子有限公司 | 一种抗还原陶瓷介质材料及其制备方法 |
| CN103011805A (zh) * | 2012-12-24 | 2013-04-03 | 陕西科技大学 | 一种BaTiO3 基无铅X8R 型陶瓷电容器介质材料及其制备方法 |
| CN103936410A (zh) * | 2014-04-03 | 2014-07-23 | 天津大学 | 碳酸锰掺杂高温稳定型钛酸钡基介质材料 |
| CN105016727A (zh) * | 2015-08-05 | 2015-11-04 | 天津大学 | 高耐压多层陶瓷电容器介质材料的制备方法 |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107686347A (zh) * | 2017-08-28 | 2018-02-13 | 天津大学 | 一种巨介电常数多层陶瓷电容器介质材料及其制备方法 |
| CN107759215A (zh) * | 2017-11-01 | 2018-03-06 | 苏州大学 | 制备巨介电常数低损耗陶瓷电容器的方法 |
| CN108546115A (zh) * | 2018-04-29 | 2018-09-18 | 天津大学 | 一种钛酸钡基低损耗巨介电常数电介质材料及其制备方法 |
| CN109180177A (zh) * | 2018-09-27 | 2019-01-11 | 中国科学院上海硅酸盐研究所 | 一种x9r型多层陶瓷电容器介质材料及其制备方法和应用 |
| CN110002864A (zh) * | 2019-02-23 | 2019-07-12 | 天津大学 | 一种高绝缘抗还原型电介质材料的制备方法 |
| CN110304916A (zh) * | 2019-04-25 | 2019-10-08 | 武汉理工大学 | 一种抗还原BaTiO3基介质陶瓷及制备方法 |
| CN110304916B (zh) * | 2019-04-25 | 2022-01-04 | 武汉理工大学 | 一种抗还原BaTiO3基介质陶瓷及制备方法 |
| CN110256067A (zh) * | 2019-06-19 | 2019-09-20 | 天津大学 | 一种铌锰掺杂抗还原型电介质材料的制备方法 |
| CN110183224A (zh) * | 2019-06-19 | 2019-08-30 | 天津大学 | 一种施受主共掺高介电常数低损耗电介质材料的制备方法 |
| CN110451955A (zh) * | 2019-08-14 | 2019-11-15 | 清华大学 | 钛酸铋钠-钛酸钡基无铅弛豫铁电体储能陶瓷及其制备方法 |
| CN110451955B (zh) * | 2019-08-14 | 2022-02-08 | 清华大学 | 钛酸铋钠-钛酸钡基无铅弛豫铁电体储能陶瓷及其制备方法 |
| CN113307622A (zh) * | 2021-07-07 | 2021-08-27 | 天津大学 | 高性能抗还原钛酸钡基介质陶瓷及其制备方法 |
| CN113307622B (zh) * | 2021-07-07 | 2023-03-10 | 天津大学 | 高性能抗还原钛酸钡基介质陶瓷及其制备方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106892659A (zh) | 一种抗还原巨介电常数多层陶瓷电容器介质材料 | |
| CN106938928A (zh) | 一种抗还原巨介电常数低损耗高阻值陶瓷电容器介质材料 | |
| CN101781115B (zh) | X8r型多层陶瓷电容器介质材料及制备方法 | |
| CN107686347A (zh) | 一种巨介电常数多层陶瓷电容器介质材料及其制备方法 | |
| CN105732020B (zh) | 一种巨介电、低损耗二氧化钛基复合陶瓷的制备方法 | |
| CN108610042A (zh) | 具有巨介电常数高绝缘特性的介质材料及其制备方法 | |
| CN106747410A (zh) | 偏压稳定型巨介电低损耗二氧化钛基复合介电陶瓷材料 | |
| CN107399967A (zh) | 一种超低损耗巨介电常数温度稳定型电容器介质材料 | |
| CN109231985A (zh) | 一种低损耗x8r型电介质材料的制备方法 | |
| CN107512906A (zh) | 一种抗还原x9r型陶瓷电容器介质材料及其制备方法 | |
| CN109265162A (zh) | 一种高性能巨介电常数介质材料 | |
| CN103936411B (zh) | 采用退火法制备超宽温稳定型钛酸钡基介质材料的方法 | |
| CN103936410B (zh) | 碳酸锰掺杂高温稳定型钛酸钡基介质材料 | |
| CN109231981A (zh) | 一种三、五价异质元素共掺的巨介电常数介质材料 | |
| CN104310986B (zh) | 一种高介电常数温度稳定型陶瓷电容器介质材料 | |
| CN107640970A (zh) | 低频低介电损耗的AgNb共掺二氧化钛基介电陶瓷材料及其制备方法 | |
| CN105294098B (zh) | 超宽工作温区的多层陶瓷电容器介质材料及其制备方法 | |
| CN100434394C (zh) | B位先驱体掺杂改性的钛酸钡基金属复合陶瓷及制备方法 | |
| CN101030478B (zh) | 一种高介金属-电介质复合陶瓷电容器介质及其制备方法 | |
| CN104446443B (zh) | 宽工作温度范围多层陶瓷电容器介质材料及其制备方法 | |
| CN105272192B (zh) | 一种低介电常数ag特性多层瓷介电容器瓷料及其制备方法 | |
| CN110002864A (zh) | 一种高绝缘抗还原型电介质材料的制备方法 | |
| CN113307622B (zh) | 高性能抗还原钛酸钡基介质陶瓷及其制备方法 | |
| CN109437896A (zh) | 一种正温度系数x7r陶瓷介质材料及其制备方法 | |
| CN105272220B (zh) | 一种宽温稳定、高介、低损耗的mlcc介质材料及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170627 |
|
| WD01 | Invention patent application deemed withdrawn after publication |