CN105712715A - SnO2-doped 0.55NBT-0.45BCTZ ceramic material having high energy storage density and preparation method thereof - Google Patents

SnO2-doped 0.55NBT-0.45BCTZ ceramic material having high energy storage density and preparation method thereof Download PDF

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CN105712715A
CN105712715A CN201610060467.4A CN201610060467A CN105712715A CN 105712715 A CN105712715 A CN 105712715A CN 201610060467 A CN201610060467 A CN 201610060467A CN 105712715 A CN105712715 A CN 105712715A
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energy storage
storage density
high energy
ceramic material
preparation
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蒲永平
姚谋腾
高淑雅
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Shaanxi University of Science and Technology
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Abstract

The invention provides a SnO2-doped 0.55NBT-0.45BCTZ ceramic material having high energy storage density and a preparation method thereof. According to the preparation method of the SnO2-doped 0.55NBT-0.45BCTZ ceramic material having the high energy storage density, BCT0.9-xZSx ceramic powder and NBT ceramic powder are blended according to the chemical formula 0.55NBT-0.45BCT0.9-xZSx, even mixing, granulation and molding are performed, then heat preservation is performed at the temperature of 1150-1180 DEG C for 2-6 hours to form ceramics through sintering, namely the ceramic material having the high energy storage density is obtained, wherein the value range of the x 0.02-0.07. The energy storage density of the SnO2-doped ceramic material prepared by adopting a traditional solid-phase method reaches up to 1.73 J/cm<3>. The preparation method is simple in device, simple in operation, low in cost, capable of achieving mass production and provides a basis for the large-scale and low-cost preparation of the ceramic material having the high energy storage density.

Description

A kind of SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material and preparation method thereof
Technical field
The invention belongs to electronic ceramic fields, relate to a kind of SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material And preparation method thereof.
Background technology
Capacitor is a kind of important electronic devices and components, is widely used in energy storage device in circuit, and capacitance energy storage easily keeps, Need not superconductor.Capacitance energy storage also has the very important point that moment can be provided exactly high-power, is very suitable for laser instrument, The application scenarios such as flash lamp.And ceramic dielectric capacitor has the advantages such as high temperature resistant, life-span length, dependable performance and is widely used. Along with the fast development of science and technology, the miniaturization of electronic equipment, miniaturization and multifunction require that electronic devices and components have more excellent Performance.In order to meet the requirement of application, the energy storage density improving ceramic material is imperative.The energy storage of ferroelectric ceramic material is close Degree is by its Minimum Polarization intensity (Pr), maximum polarization (Pm) and breakdown strength (Eb) together decide on.In order to prepare high storage Energy density ceramic, people generally use oxide or glass as additive and to use advanced technology of preparing (SPS) Etc. strengthening its breakdown strength to improve its energy storage density.
Based on NBT, it is added thereto to BCTZ, finds that the introducing of BCTZ can effectively reduce its remanent polarization (Pr), make its maximum polarization (P simultaneouslym) it is maintained at a bigger value.Wherein, 0.55Na0.5Bi0.5TiO3(NBT)-0.45Ba0.85Ca0.15Ti0.9Zr0.1O3(BCTZ) remanent polarization of ceramic material is 9μC/cm2, maximum polarization is up to 31 μ C/cm2.Research finds, NBT base ceramic material at high temperature has the storage of excellence Can characteristic, but owing at high temperature material is the most breakdown, cause its energy storage density the highest, be also difficult to practical simultaneously.
Summary of the invention
It is an object of the invention to provide a kind of SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material and preparation side Method, the ceramic material energy storage density that the method prepares is up to 1.73J/cm3, and preparation method is simple, low cost, can be extensive Produce.
For achieving the above object, the present invention adopts the following technical scheme that:
A kind of SnO2The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material, by chemical formula 0.55NBT-0.45BCT0.9-xZSx, by BCT0.9-xZSxCeramic powder and NBT ceramic powder dispensing, after mix homogeneously through pelletize, After molding, at 1150-1180 DEG C, it is incubated 2-6h sinters porcelain into, obtain high energy storage density ceramic material；Wherein, x span For 0.02-0.07.
Described mix homogeneously is realized by ball milling.
Described ball milling is using deionized water as ball-milling medium.
The time of described ball milling is 6-8h.
Dry at 70 DEG C-90 DEG C after mix homogeneously.
Described BCT0.9-xZSxCeramic powder prepares by the following method: according to chemical formula Ba0.85Ca0.15Ti0.9-xZr0.1SnxO3(BCT0.9-xZSx), brium carbonate, calcium carbonate, titanium dioxide, zirconium oxide and stannum oxide are mixed At 1260 DEG C, it is incubated 2h after Jun Yun, prepares BCT0.9-xZSxCeramic powder；Wherein, x span is 0.02-0.07.
Described NBT ceramic powder prepares by the following method: according to chemical formula Na0.5Bi0.5TiO3(NBT), by sodium carbonate, oxygen At 840 DEG C, it is incubated 4h after changing bismuth and titanium dioxide mix homogeneously, prepares NBT ceramic powder.
A kind of SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material, it is characterised in that chemical formula is 0.55NBT-0.45BCT0.9-xZSx；Wherein, x span is 3-7, and the density of this material is 1.73J/cm3。
Compared with prior art, the invention have the benefit that 0.55NBT-0.45BCTZ has higher maximum polarization (Pm～31 μ C/cm3), but the relatively low (0.62J/cm of its room temperature energy storage density3), and energy storage efficiency the lowest (39.86%), because of This present invention passes through SnO2Its phase transition temperature is moved near room temperature by doping, reduces its energy loss, thus it is close to improve its energy storage Degree.The present invention uses 0.55NBT-0.45BCT prepared by conventional solid-state method0.9-xZSxThe energy storage density of ceramic material is up to 1.73 J/cm3.The preparation method equipment of the present invention is simple, simple to operate, low cost, can be mass-produced, for extensive, low cost Prepare high energy storage density ceramic material to provide the foundation.
Further, the present invention with brium carbonate, calcium carbonate, sodium carbonate, bismuth oxide, titanium dioxide, zirconium oxide and stannum oxide is Raw material, uses solid phase method, prepares 0.55Na0.5Bi0.5TiO3(NBT)-0.45Ba0.85Ca0.15Ti0.9-xZr0.1SnxO3(BCT0.9-xZSx, X=0.02-0.07) ceramic material.
Accompanying drawing explanation
Fig. 1 is 0.55NBT-0.45BCT0.88ZS0.02The ferroelectric hysteresis loop figure of ceramic material.
Fig. 2 is 0.55NBT-0.45BCT0.85ZS0.05The ferroelectric hysteresis loop figure of ceramic material.
Fig. 3 is 0.55NBT-0.45BCT0.83ZS0.07The ferroelectric hysteresis loop figure of ceramic material.
Detailed description of the invention
The present invention will be further described with embodiment below in conjunction with the accompanying drawings.
A kind of SnO2The chemical formula of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material is 0.55NBT- 0.45BCT0.9-xZSx；Wherein, x span is 0.02-0.07.
Embodiment 1
A kind of SnO2The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material:
According to chemical formula Ba0.85Ca0.15Ti0.88Zr0.1Sn0.02O3(BCT0.88ZS0.02), by brium carbonate, calcium carbonate, titanium dioxide, At 1260 DEG C, it is incubated 2h after zirconium oxide and stannum oxide mix homogeneously, synthesizes BCT0.88ZS0.02Ceramic powder；
According to chemical formula Na0.5Bi0.5TiO3(NBT), will protect at 840 DEG C after sodium carbonate, bismuth oxide and titanium dioxide mix homogeneously Temperature 4h, synthesizes NBT ceramic powder.
By BCT0.88ZS0.02Ceramic powder and NBT ceramic powder are according to chemical formula 0.55NBT-0.455BCT0.88ZS0.02Dispensing, With deionized water as ball-milling medium ball milling 6h mix homogeneously, then dry at 80 DEG C, after pelletize, molding, at 1180 DEG C Lower insulation 2h sinters porcelain into, obtains SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material.
Embodiment 2
A kind of SnO2The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material:
According to chemical formula Ba0.85Ca0.15Ti0.88Zr0.1Sn0.02O3(BCT0.88ZS0.02), by brium carbonate, calcium carbonate, titanium dioxide, At 1260 DEG C, it is incubated 2h after zirconium oxide and stannum oxide mix homogeneously, synthesizes BCT0.88ZS0.02Ceramic powder；
According to chemical formula Na0.5Bi0.5TiO3(NBT), will protect at 840 DEG C after sodium carbonate, bismuth oxide and titanium dioxide mix homogeneously Temperature 4h, synthesizes NBT ceramic powder.
By BCT0.88ZS0.02Ceramic powder and NBT ceramic powder are according to chemical formula 0.55NBT-0.455BCT0.88ZS0.02Dispensing, With deionized water as ball-milling medium ball milling 6h mix homogeneously, then dry at 80 DEG C, after pelletize, molding, at 1180 DEG C Lower insulation 4h sinters porcelain into, obtains SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material.
Embodiment 3
A kind of SnO2The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material:
According to chemical formula Ba0.85Ca0.15Ti0.88Zr0.1Sn0.02O3(BCT0.88ZS0.02), by brium carbonate, calcium carbonate, titanium dioxide, At 1260 DEG C, it is incubated 2h after zirconium oxide and stannum oxide mix homogeneously, synthesizes BCT0.88ZS0.02Ceramic powder；
According to chemical formula Na0.5Bi0.5TiO3(NBT), will protect at 840 DEG C after sodium carbonate, bismuth oxide and titanium dioxide mix homogeneously Temperature 4h, synthesizes NBT ceramic powder.
By BCT0.88ZS0.02Ceramic powder and NBT ceramic powder are according to chemical formula 0.55NBT-0.455BCT0.88ZS0.02Dispensing, With deionized water as ball-milling medium ball milling 6h mix homogeneously, then dry at 80 DEG C, after pelletize, molding, at 1180 DEG C Lower insulation 6h sinters porcelain into, obtains SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material.
Embodiment 4
A kind of SnO2The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material:
According to chemical formula Ba0.85Ca0.15Ti0.85Zr0.1Sn0.05O3(BCT0.85ZS0.05), by brium carbonate, calcium carbonate, titanium dioxide, At 1260 DEG C, it is incubated 2h after zirconium oxide and stannum oxide mix homogeneously, synthesizes BCT0.85ZS0.05Ceramic powder；
According to chemical formula Na0.5Bi0.5TiO3(NBT), will protect at 840 DEG C after sodium carbonate, bismuth oxide and titanium dioxide mix homogeneously Temperature 4h, synthesizes NBT ceramic powder.
By BCT0.88ZS0.02Ceramic powder and NBT ceramic powder are according to chemical formula 0.55NBT-0.455BCT0.85ZS0.05Dispensing, With deionized water as ball-milling medium ball milling 6h mix homogeneously, then dry at 80 DEG C, after pelletize, molding, at 1180 DEG C Lower insulation 2h sinters porcelain into, obtains SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material.
Embodiment 5
A kind of SnO2The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material:
According to chemical formula Ba0.85Ca0.15Ti0.85Zr0.1Sn0.05O3(BCT0.85ZS0.05), by brium carbonate, calcium carbonate, titanium dioxide, At 1260 DEG C, it is incubated 2h after zirconium oxide and stannum oxide mix homogeneously, synthesizes BCT0.85ZS0.05Ceramic powder；
According to chemical formula Na0.5Bi0.5TiO3(NBT), will protect at 840 DEG C after sodium carbonate, bismuth oxide and titanium dioxide mix homogeneously Temperature 4h synthesizes NBT ceramic powder.
By BCT0.88ZS0.02Ceramic powder and NBT ceramic powder are according to chemical formula 0.55NBT-0.455BCT0.85ZS0.05Dispensing, With deionized water as ball-milling medium ball milling 6h mix homogeneously, then dry at 80 DEG C, after pelletize, molding, at 1180 DEG C Lower insulation 4h sinters porcelain into, obtains SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material.
Embodiment 6
A kind of SnO2The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material:
According to chemical formula Ba0.85Ca0.15Ti0.85Zr0.1Sn0.05O3(BCT0.85ZS0.05), by brium carbonate, calcium carbonate, titanium dioxide, At 1260 DEG C, it is incubated 2h after zirconium oxide and stannum oxide mix homogeneously, synthesizes BCT0.85ZS0.05Ceramic powder；
According to chemical formula Na0.5Bi0.5TiO3(NBT), will protect at 840 DEG C after sodium carbonate, bismuth oxide and titanium dioxide mix homogeneously Temperature 4h, synthesizes NBT ceramic powder.
By BCT0.88ZS0.02Ceramic powder and NBT ceramic powder are according to chemical formula 0.55NBT-0.455BCT0.85ZS0.05Dispensing, With deionized water as ball-milling medium ball milling 7h mix homogeneously, then dry at 70 DEG C, after pelletize, molding, at 1150 DEG C Lower insulation 6h sinters porcelain into, obtains SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material.
Embodiment 7
A kind of SnO2The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material:
According to chemical formula Ba0.85Ca0.15Ti0.83xZr0.1Sn0.07O3(BCT0.83ZS0.07), by brium carbonate, calcium carbonate, titanium dioxide, At 1260 DEG C, it is incubated 2h after zirconium oxide and stannum oxide mix homogeneously, synthesizes BCT0.83ZS0.07Ceramic powder；
According to chemical formula Na0.5Bi0.5TiO3(NBT), will protect at 840 DEG C after sodium carbonate, bismuth oxide and titanium dioxide mix homogeneously Temperature 4h synthesizes NBT ceramic powder.
By BCT0.88ZS0.02Ceramic powder and NBT ceramic powder are according to chemical formula 0.55NBT-0.455BCT0.83ZS0.07Dispensing, With deionized water as ball-milling medium ball milling 6h mix homogeneously, then dry at 80 DEG C, after pelletize, molding, at 1180 DEG C Lower insulation 2h sinters porcelain into, obtains SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material.
Embodiment 8
A kind of SnO2The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material:
According to chemical formula Ba0.85Ca0.15Ti0.83xZr0.1Sn0.07O3(BCT0.87ZS0.03), by brium carbonate, calcium carbonate, titanium dioxide, At 1260 DEG C, it is incubated 2h after zirconium oxide and stannum oxide mix homogeneously, synthesizes BCT0.87ZS0.03Ceramic powder；
According to chemical formula Na0.5Bi0.5TiO3(NBT), will protect at 840 DEG C after sodium carbonate, bismuth oxide and titanium dioxide mix homogeneously Temperature 4h, synthesizes NBT ceramic powder.
By BCT0.88ZS0.02Ceramic powder and NBT ceramic powder are according to chemical formula 0.55NBT-0.455BCT0.87ZS0.03Dispensing, With deionized water as ball-milling medium ball milling 7h mix homogeneously, then dry at 90 DEG C, after pelletize, molding, at 1170 DEG C Lower insulation 4h sinters porcelain into, obtains SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material.
Embodiment 9
A kind of SnO2The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material:
According to chemical formula Ba0.85Ca0.15Ti0.84Zr0.1Sn0.06O3(BCT0.84ZS0.06), by brium carbonate, calcium carbonate, titanium dioxide, At 1260 DEG C, it is incubated 2h after zirconium oxide and stannum oxide mix homogeneously, synthesizes BCT0.84ZS0.06Ceramic powder；
According to chemical formula Na0.5Bi0.5TiO3(NBT), will protect at 840 DEG C after sodium carbonate, bismuth oxide and titanium dioxide mix homogeneously Temperature 4h synthesizes NBT ceramic powder.
By BCT0.88ZS0.02Ceramic powder and NBT ceramic powder are according to chemical formula 0.55NBT-0.455BCT0.84ZS0.06Dispensing, With deionized water as ball-milling medium ball milling 8h mix homogeneously, then dry at 80 DEG C, after pelletize, molding, at 1160 DEG C Lower insulation 6h sinters porcelain into, obtains SnO2Doping 0.55NBT-0.45BCTZ high energy storage density ceramic material.
See Fig. 1, for the ferroelectric hysteresis loop figure of the ceramics sample of preparation, the energy storage of this sample as we can see from the figure in embodiment 1 Density is up to 1.21J/cm3, energy storage efficiency is up to 56.28%.Fig. 2 is the ferroelectric hysteresis loop of the ceramics sample of preparation in embodiment 4 Figure, the energy storage density of this sample is up to 1.73J/cm as we can see from the figure3, energy storage efficiency is up to 75.54%.Fig. 3 is for implementing The ferroelectric hysteresis loop figure of the ceramics sample of preparation in example 7, the energy storage density of this sample is up to 1.52J/cm as we can see from the figure3, storage Energy efficiency is up to 75.62%.

Claims (8)

1. a SnO2The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material, it is characterised in that press Chemical formula 0.55NBT-0.45BCT0.9-xZSx, by BCT0.9-xZSxCeramic powder and NBT ceramic powder dispensing, after mix homogeneously After pelletize, molding, at 1150-1180 DEG C, it is incubated 2-6h sinters porcelain into, obtain high energy storage density ceramic material；Wherein, x Span is 0.02-0.07.
SnO the most according to claim 12The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material, It is characterized in that, described mix homogeneously is realized by ball milling.
SnO the most according to claim 22The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material, It is characterized in that, described ball milling is using deionized water as ball-milling medium.
4. according to the SnO described in Claims 2 or 32The preparation of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material Method, it is characterised in that the time of described ball milling is 6-8h.
SnO the most according to claim 22The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material, It is characterized in that, dry at 70 DEG C-90 DEG C after mix homogeneously.
SnO the most according to claim 12The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material, It is characterized in that, described BCT0.9-xZSxCeramic powder prepares by the following method: according to chemical formula Ba0.85Ca0.15Ti0.9-xZr0.1SnxO3(BCT0.9-xZSx), brium carbonate, calcium carbonate, titanium dioxide, zirconium oxide and stannum oxide are mixed At 1260 DEG C, it is incubated 2h after Jun Yun, prepares BCT0.9-xZSxCeramic powder；Wherein, x span is 0.02-0.07.
SnO the most according to claim 12The preparation method of doping 0.55NBT-0.45BCTZ high energy storage density ceramic material, It is characterized in that, described NBT ceramic powder prepares by the following method: according to chemical formula Na0.5Bi0.5TiO3(NBT), by carbon At 840 DEG C, it is incubated 4h after acid sodium, bismuth oxide and titanium dioxide mix homogeneously, prepares NBT ceramic powder.
8. the SnO that according to claim 1 prepared by method2Doping 0.55NBT-0.45BCTZ high energy storage density pottery material Material, it is characterised in that chemical formula is 0.55NBT-0.45BCT0.9-xZSx；Wherein, x span is 3-7, this material close Degree is 1.73J/cm3。
CN201610060467.4A 2016-01-28 2016-01-28 SnO2-doped 0.55NBT-0.45BCTZ ceramic material having high energy storage density and preparation method thereof Pending CN105712715A (en)

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