CN108409319A - The lead-free ceramics material and preparation method thereof of high energy storage density and charge-discharge performance - Google Patents
The lead-free ceramics material and preparation method thereof of high energy storage density and charge-discharge performance Download PDFInfo
- Publication number
- CN108409319A CN108409319A CN201810184288.0A CN201810184288A CN108409319A CN 108409319 A CN108409319 A CN 108409319A CN 201810184288 A CN201810184288 A CN 201810184288A CN 108409319 A CN108409319 A CN 108409319A
- Authority
- CN
- China
- Prior art keywords
- lead
- energy storage
- charge
- temperature
- discharge performance
- 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.)
- Granted
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
- C04B35/4682—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 based on BaTiO3 perovskite phase
-
- 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
-
- 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
- C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
-
- 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
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
Abstract
The present invention relates to high energy storage density and the lead-free ceramics material and preparation method thereof of charge-discharge performance, ceramics group becomes (1 x) BaTiO3‑x(Bi0.9Na0.1)(In1‑yZry)O3(0≤x≤0.2,0.1≤y≤0.3), and the ceramics are obtained by ordinary sinter method.Compare lead base antiferroelectric materials, and material disclosed by the invention is free of lead, is a kind of environmentally friendly material.Compared with antiferroelectric materials, system disclosed by the invention has prodigious energy storage density, current density and power density, and the charge and discharge time with submicrosecond grade.This characteristic largely facilitates the application of pulsed capacitor.The material manufacture craft is simple, and has superior charge-discharge performance, the application being suitble on the high-voltage pulse capacitor for requiring energy storage, charge-discharge characteristic.
Description
Technical field
The invention belongs to ceramic material technical field, more particularly, to a kind of high energy storage density and charge-discharge performance
Lead-free ceramics material and preparation method thereof.
Background technology
Impulse capacitor can store a small-power power to the rechargeable energy of capacitor in long period interval
Get up, needs certain in a flash, stored energy is discharged rapidly out in extremely short time interval, is formed powerful
Electric current and power are mainly used for the necks such as high-voltage test techniques, high-energy physics, laser technology, oscillation circuit, geological exploration
Domain.As accelerator, laser, electron beam etc. constantly develop, people to the demand of high-voltage pulse strong current generator
It is continuously increased.Although battery has higher energy density, since carrier moving therein is slow, power density is past
It is past relatively low.Although dielectric capacitor energy density is not very high, its power density is very big, can release in a short period of time
Electric discharge lotus, so being used to generate pulse voltage and electric current.
It is largely divided into three classes currently used as the material of impulse capacitor：Linear dielectric substance, ferroelectric material and lead base are anti-
Ferroelectric material.When the electric field applied is more than the electric field of antiferroelectric-ferroelectricity transformation, antiferroelectric materials forms double ferroelectric hysteresis loops,
The dielectric displacement of material and dielectric constant sharply increase, and material is in charged state at this time.When cancelling electric field, the iron of electric field induction
Electricity mutually returns to original antiferroelectric phase, and material is in discharge condition.Due to the dipole reversed arrangement in antiferroelectric materials, institute
The charge of storage can be released completely, so its energy storage density and energy storage efficiency are usually higher, the antiferroelectric pottery of lead base
Porcelain is the hot topic studied in current energy storage material.Xu Chenhong, Liu Zhen of Shanghai silicate research institute, Xi'an Communications University Xu
Many work have all been done in terms of this by tall and erect teacher seminar.But there are following problems for lead base antiferroelectric materials：1, lead
Contain virose Pb in based antiferroelectric material, is polluted the environment during making and production.2, lead base is antiferroelectric
Ceramic Curie temperature is generally relatively low, and when temperature is more than Curie temperature, energy storage density, current density and power density can be substantially
Decline, temperature dependency is stronger.3, antiferroelectric-ferroelectricity transformation electric field of antiferroelectric materials is generally large, can cause to reduce electricity
The cycle life of container.
Relaxation ceramic material has dielectric dispersion characteristic, i.e., its dielectric constant will not obviously become within the scope of very wide temperature
Change, the dependence of energy storage density and temperature can decrease.The intelligent seminars of Tsinghua University Wang Xiao have studied BaTiO3Material
Energy storage characteristic, by the way that BiYO is added3Second constituent element adjusts its Relaxivity, and then optimizes its energy storage characteristic.
0.91BaTiO3-0.09BiYO3In system, energy storage density reaches~0.71J/cm3.L.X.Xia seminars of University Of Tianjin pass through
In Ba1-xSm2x/3Zr0.15Ti0.85O3In system, the Relaxivity of the system is adjusted to replace A Ba ions with Sm, works as x
When=0.03, the energy storage density of the system reaches maximum value~1.13J/cm3.Shanghai silicate research institute Dong Xian woodss research institute class
Topic group also studies the storage effect of barium titanate based ceramic.In (Ba0.85Ca0.15)(Zr0.10Ti0.90)O3In system, use
Compound ion (Ni1/3Nb2/3)4+Replace the positions the B ion of above-mentioned system, optimizes the storage effect of the system with this.As (Ni1/ 3Nb2/3)4+When the molar fraction of ion is 30%, energy storage density reaches maximum value~0.66J/cm3.In conclusion about metatitanic acid
The storage effect of barium sill is also relatively low.In addition the research work of barium titanate energy storage material mainly still concentrates on improving its storage
In energy density, but also it is rarely reported about the charge-discharge characteristic of barium phthalate base relaxation ferroelectric ceramic at present.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of high energy storage density and
Lead-free ceramics material of charge-discharge performance and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
The lead-free ceramics material of high energy storage density and charge-discharge performance, chemical composition are：(1-x)BaTiO3-x
(Bi0.9Na0.1)(In1-yZry)O3, wherein 0≤x≤0.2,0.1≤y≤0.3.
As preferred embodiment, x 0.1, y 0.2.Under the proportioning, the disruptive field intensity of material is optimal, and
And ferroelectric hysteresis loop becomes very thin and keeps higher maximum polarization and very low remanent polarization at this time, therefore energy storage is close
Degree reaches maximum.
The preparation method of the lead-free ceramics material of high energy storage density and charge-discharge performance, using following steps：
(1) BaCO that purity is more than 99% is chosen3,TiO2, Bi2O3, Na2CO3, In2O3, ZrO2Original as lead-free ceramics
Material；
(2) it presses chemical composition and carries out weighing, ball-milling medium is added and carries out ball milling, discharges, drying；
(3) powder of drying is calcined to 850~1000 DEG C of 1~5h of heat preservation in Muffle furnace, with grinding after being taken out after calcining
Alms bowl is regrind, after carry out secondary clacining, soaking time and temperature are the same as the first time；
(4) powder after calcining is subjected to secondary ball milling, discharged, drying adds PVA and is granulated, and in 4~8MPa
Pressure under be pressed into ceramic disks；
(5) obtained ceramic body in Muffle furnace is subjected to dumping, 5~10h is kept the temperature at 500~600 DEG C；
(6) ceramic body after dumping is sintered at 1200~1300 DEG C, controls 2~5 DEG C/min of heating rate, and
And 2~5h is kept the temperature in the highest temperature, after naturally cooling to room temperature, sintered potsherd is beaten with varigrained sand paper
Mill, obtains the smooth thin potsherd of surface-brightening.
Ball milling carries out in planetary ball mill twice, and zirconia beads and absolute ethyl alcohol is added as ball-milling medium.
Ball-milling Time is 6~8 hours in step (2), and Ball-milling Time is 8~12 hours in step (4), and powder is dry in air blast
It is dried in dry case, temperature is controlled at 100~120 DEG C.The PVA of 5wt% is added when being granulated for step (4).
Further include that potsherd after polishing also coats high temperature silver paste in tow sides, silver ink firing is carried out in Muffle furnace,
500~600 DEG C of temperatures 0.5~1 hour.
Compared with prior art, the present invention is free of Pb, is producing, will not cause to endanger to environment during using and discarding
Evil is a kind of environmentally friendly energy storage and capacitor material.Simultaneously as selected component has dielectric dispersion characteristic, energy storage
Density has preferable temperature stability, particularly, still there is superior charge-discharge performance, energy storage density to reach at room temperature
To 1.33J/cm3, and current density and power density are up to 659A/cm respectively2And 33MW/cm3(room temperature).Importantly,
Since the energy stored by the intrinsic structure of material and nanometer domain structure 90% can release within the submicrosecond grade time,
Performance is higher by reported lead base antiferroelectric ceramics and other relaxation property ceramic materials.
Description of the drawings
Fig. 1 is lead-free ceramics material 0.9BaTiO made from embodiment 13-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3XRD
Collection of illustrative plates (SEM of the included composition schemes)；
Fig. 2 is lead-free ceramics material 0.9BaTiO made from embodiment 23-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Jie
Warm collection of illustrative plates；
Fig. 3 is lead-free ceramics material 0.9BaTiO made from embodiment 33-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Electricity
Hysteresis curves；
Fig. 4 is lead-free ceramics material 0.9BaTiO made from embodiment 43-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Owe
When m- curent change curve under damping state different temperatures.
Fig. 5 is lead-free ceramics material 0.9BaTiO made from embodiment 53-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Mistake
When m- curent change curve under damping state different temperatures；
Fig. 6 is lead-free ceramics material 0.9BaTiO made from embodiment 53-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Energy
Measure change schematic diagram of the storage density with discharge time.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
The preparation method of the lead-free ceramics material of high energy storage density and charge-discharge performance, using following steps：
(1) it is the traditional Chinese medicines reagent BaCO more than 99% to choose purity3,TiO2, Bi2O3, Na2CO3, In2O3, ZrO2As nothing
The raw material of lead ceramic material.By chemical formula 0.9BaTiO3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Weighing is carried out, in nylon tank
Middle addition absolute ethyl alcohol and zirconia balls carry out ball milling, discharge, drying.Ball-milling Time is 8 hours, and drying temperature is 120 DEG C.
Powder after drying is fitted into corundum crucible, crucible cover is covered after compacting, is put into Muffle furnace and is calcined, 5 DEG C/min liters
To 950 DEG C, 3 hours are kept the temperature, taking-up mortar grinder after room temperature is cooled to, is calcined in method corundum crucible again, heating rate
And soaking time is the same as the first time.
(2) powder for the synthesis for obtaining step (1) carries out secondary ball milling, discharges, drying.Drying temperature and step (1)
Identical, Ball-milling Time is 12 hours.Suitable 5%PVA is added in the powder of drying to be granulated, and is pushed in the pressure of 4MPa
Type is made, obtains a diameter of 10mm, thickness is the ceramic disks of 1mm.
(3) ceramic body that step (2) obtains is put into Muffle furnace and carries out dumping, 2 DEG C/min is raised to be protected after 550 DEG C
Temperature 10 hours.
(4) ceramic body after dumping that step (3) obtains is sintered at a temperature of 1260 DEG C, 3 DEG C of heating rate/
Min, and keep the temperature 3 hours in the highest temperature.Room temperature then is naturally cooled to, obtains barium titanate-based lead-free ceramic material.
(5) it will burn after the potsherd come wears into powdery with mortar and carry out XRD tests, 5 degree/min of sweep speed.
Metal spraying after the potsherd absolute ethyl alcohol wiped clean burnt is carried out to the test of SEM.
Lead-free ceramics material 0.9BaTiO obtained by the embodiment 1 that Fig. 1 is3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3
XRD diffracting spectrums, the results are shown in Figure 1, and phase structure is shown to be single ABO3Structure.The SEM charts of the included component
Bright ceramic chip structure obtained is close, and pore-free, particle size is at 0.8 μm or so.
Embodiment 2
The preparation method of the lead-free ceramics material of high energy storage density and charge-discharge performance, using following steps：
(1) it is the traditional Chinese medicines reagent BaCO more than 99% to choose purity3,TiO2, Bi2O3, Na2CO3, In2O3, ZrO2As nothing
The raw material of lead ceramic material.By chemical formula 0.9BaTiO3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Weighing is carried out, in nylon tank
Middle addition absolute ethyl alcohol and zirconia balls carry out ball milling, discharge, drying.Ball-milling Time is 8 hours, and drying temperature is 120 DEG C.
Powder after drying is fitted into corundum crucible, crucible cover is covered after compacting, is put into Muffle furnace and is calcined, 5 DEG C/min liters
To 950 DEG C, 2 hours are kept the temperature, taking-up mortar grinder after room temperature is cooled to, is calcined in method corundum crucible again, heating rate
And soaking time is the same as the first time.
(2) the powder secondary ball milling for the synthesis for obtaining step (1) discharges, drying.Drying temperature is identical as step (1),
Ball-milling Time is 12 hours.Suitable 5%PVA is added in the powder of drying to be granulated, and is pressed under the pressure of 4MPa
Type, obtains a diameter of 10mm, and thickness is the ceramic disks of 1mm.
(3) ceramic body that step (2) obtains is put into Muffle furnace and carries out dumping, 2 DEG C/min is raised to be protected after 550 DEG C
Temperature 10 hours.
(4) ceramic body after dumping that step (3) obtains is sintered at a temperature of 1260 DEG C, 3 DEG C of heating rate/
Min, and keep the temperature 3 hours in the highest temperature.Room temperature then is naturally cooled to, obtains barium titanate-based lead-free relaxation ferroelectric ceramic.
(5) the sintered potsherd that step (4) obtains is polished with varigrained sand paper, obtains surface-brightening
Smooth ceramic sheet.It equably puts on high temperature silver paste on the two sides of ceramics, is subsequently placed into Muffle furnace and carries out dumping, 5 DEG C/
Min keeps the temperature half an hour after being raised to 600 DEG C.
Polarization finishes, by potsherd with washes of absolute alcohol it is clean after be put into dielectric temperature spectrum test.
Lead-free ceramics material 0.9BaTiO after the obtained polarization of embodiment 2 that Fig. 2 is3-0.1(Bi0.9Na0.1)
(In0.8Zr0.2)O3Dielectric temperature spectrum.As can be seen from the figure the Curie temperature of the system is modulated onto near room temperature, is conducive to
Improve the polarization intensity of the system.
Embodiment 3
The preparation method of the lead-free ceramics material of high energy storage density and charge-discharge performance, using following steps：
(1) it is the traditional Chinese medicines reagent BaCO more than 99% to choose purity3,TiO2, Bi2O3, Na2CO3, In2O3, ZrO2As nothing
The raw material of lead ceramic material.By chemical formula 0.9BaTiO3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Weighing is carried out, in nylon tank
Middle addition absolute ethyl alcohol and zirconia balls carry out ball milling, discharge, drying.Ball-milling Time is 8 hours, and drying temperature is 120 DEG C.
Powder after drying is fitted into corundum crucible, crucible cover is covered after compacting, is put into Muffle furnace and is calcined, 5 DEG C/min liters
To 950 DEG C, 3 hours are kept the temperature, taking-up mortar grinder after room temperature is cooled to, is calcined in method corundum crucible again, heating rate
And soaking time is the same as the first time.
(2) the powder secondary ball milling for the synthesis for obtaining step (1) discharges, drying.Drying temperature is identical as step (1),
Ball-milling Time is 12 hours.Suitable 5%PVA is added in the powder of drying to be granulated, and is pressed under the pressure of 4MPa
Type, obtains a diameter of 10mm, and thickness is the ceramic disks of 1mm.
(3) ceramic body that step (2) obtains is put into Muffle furnace and carries out dumping, 2 DEG C/min is raised to be protected after 550 DEG C
Temperature 10 hours.
(4) ceramic body after dumping that step (3) obtains is sintered at a temperature of 1260 DEG C, 3 DEG C of heating rate/
Min, and keep the temperature 3 hours in the highest temperature.Room temperature then is naturally cooled to, obtains barium titanate-based lead-free relaxation ferroelectric ceramic.
(5) the sintered potsherd that step (4) obtains is polished with varigrained sand paper, obtains surface-brightening
Smooth ceramic sheet.It equably puts on high temperature silver paste on the two sides of ceramics, is subsequently placed into Muffle furnace and carries out dumping, 5 DEG C/
Min keeps the temperature half an hour after being raised to 600 DEG C, and sample is taken out after being cooled to room temperature and carries out ferroelectric properties test.
Lead-free ceramics material 0.9BaTiO obtained by the embodiment 3 that Fig. 3 is3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3
Ferroelectric hysteresis loop, we have observed that, ferroelectric hysteresis loop P-E becomes very very thin from figure, maximum polarization keep higher value and
Remanent polarization is conducive to the energy storage characteristic for improving material close to zero.
Embodiment 4
The preparation method of the lead-free ceramics material of high energy storage density and charge-discharge performance, using following steps：
(1) it is the traditional Chinese medicines reagent BaCO more than 99% to choose purity3,TiO2, Bi2O3, Na2CO3, In2O3, ZrO2As nothing
The raw material of lead ceramic material.By chemical formula 0.9BaTiO3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Weighing is carried out, in nylon tank
Middle addition absolute ethyl alcohol and zirconia balls carry out ball milling, discharge, drying.Ball-milling Time is 8 hours, and drying temperature is 120 DEG C.
Powder after drying is fitted into corundum crucible, crucible cover is covered after compacting, is put into Muffle furnace and is calcined, 5 DEG C/min liters
To 950 DEG C, 3 hours are kept the temperature, taking-up mortar grinder after room temperature is cooled to, is calcined in method corundum crucible again, heating rate
And soaking time is the same as the first time.
(2) the powder secondary ball milling for the synthesis for obtaining step (1) discharges, drying.Drying temperature is identical as step (1),
Ball-milling Time is 12 hours.Suitable 5%PVA is added in the powder of drying to be granulated, and is pressed under the pressure of 4MPa
Type, obtains a diameter of 10mm, and thickness is the ceramic disks of 1mm.
(3) ceramic body that step (2) obtains is put into Muffle furnace and carries out dumping, 2 DEG C/min is raised to be protected after 550 DEG C
Temperature 10 hours.
(4) ceramic body after dumping that step (3) obtains is sintered at a temperature of 1260 DEG C, 3 DEG C of heating rate/
Min, and keep the temperature 3 hours in the highest temperature.Room temperature then is naturally cooled to, obtains barium titanate-based lead-free relaxation ferroelectric ceramic.
(5) the sintered potsherd that step (4) obtains is polished with varigrained sand paper, obtains surface-brightening
Smooth ceramic sheet.Potsherd diameter and thickness after wherein polishing is respectively 4mm and 0.4mm.It is uniform on the two sides of ceramics
Ground is put on high temperature silver paste, is subsequently placed into Muffle furnace and is carried out dumping, 5 DEG C/min keeps the temperature half an hour after being raised to 600 DEG C, is cooled to
Sample is taken out after room temperature carries out charge-discharge performance test.
Obtained by the embodiment 4 that Fig. 4 is under the action of 10kV/mm electric fields, lead-free ceramics material 0.9BaTiO3-0.1
(Bi0.9Na0.1)(In0.8Zr0.2)O3Electric current~time (current~time) figure when underdamping state.From the oscillating curve
Above it will be seen that most of energy has all discharged finish in a relatively short period of time, to be conducive to improve filling for the material
Discharge performance.
Embodiment 5
The preparation method of the lead-free ceramics material of high energy storage density and charge-discharge performance, using following steps：
(1) it is the traditional Chinese medicines reagent BaCO more than 99% to choose purity3,TiO2, Bi2O3, Na2CO3, In2O3, ZrO2As nothing
The raw material of lead ceramic material.By chemical formula 0.9BaTiO3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Weighing is carried out, in nylon tank
Middle addition absolute ethyl alcohol and zirconia balls carry out ball milling, discharge, drying.Ball-milling Time is 8 hours, and drying temperature is 120 DEG C.
Powder after drying is fitted into corundum crucible, crucible cover is covered after compacting, is put into Muffle furnace and is calcined, 5 DEG C/min liters
To 950 DEG C, 3 hours are kept the temperature, taking-up mortar grinder after room temperature is cooled to, is calcined in method corundum crucible again, heating rate
And soaking time is the same as the first time.
(2) the powder secondary ball milling for the synthesis for obtaining step (1) discharges, drying.Drying temperature is identical as step (1),
Ball-milling Time is 12 hours.Suitable 5%PVA is added in the powder of drying to be granulated, and is pressed under the pressure of 4MPa
Type, obtains a diameter of 10mm, and thickness is the ceramic disks of 1mm.
(3) ceramic body that step (2) obtains is put into Muffle furnace and carries out dumping, 2 DEG C/min is raised to be protected after 550 DEG C
Temperature 10 hours.
(4) ceramic body after dumping that step (3) obtains is sintered at a temperature of 1260 DEG C, 3 DEG C of heating rate/
Min, and keep the temperature 3 hours in the highest temperature.Room temperature then is naturally cooled to, obtains barium titanate-based lead-free relaxation ferroelectric ceramic.
(5) the sintered potsherd that step (4) obtains is polished with varigrained sand paper, obtains surface-brightening
Smooth ceramic sheet.Potsherd diameter and thickness after wherein polishing is respectively 4mm and 0.4mm.It is uniform on the two sides of ceramics
Ground is put on high temperature silver paste, is subsequently placed into Muffle furnace and is carried out dumping, 5 DEG C/min keeps the temperature half an hour after being raised to 600 DEG C, is cooled to
Sample is taken out after room temperature carries out charge-discharge performance test.In rlc circuit, chooses resistance value and come for the clovershrub resistance of 275 Ω
Test the charging and discharging state under overdamp.
Fig. 5,6 are the lead-free ceramics material 0.9BaTiO obtained by embodiment 5 under the action of 10kV/mm electric fields3-0.1
(Bi0.9Na0.1)(In0.8Zr0.2)O3Electric current~time (current~time) figure and energy stores when overdamping state is close
Spend the change schematic diagram with discharge time.Pass through formula wd=R∫1(t)2Dt/V can obtain energy storage density WdWith time change
Schematic diagram.Therefrom we have observed that 90% charge all releases (such as dotted line in 0.185 μ s or so times in a short period of time
Indicate), this greatly will be conducive to generate transient high-current, be conducive to the application of high-voltage pulse capacitor.
Table 1
Table 1 is the comparison of the system and antiferroelectric system energy storage and charge-discharge performance of the present invention, it can be seen that this hair
Bright barium phthalate base system system more antiferroelectric than lead base has higher energy storage current density and power density, is conducive to pulsed
The application of capacitor.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (8)
1. the lead-free ceramics material of high energy storage density and charge-discharge performance, which is characterized in that the chemical composition of the material is：(1-
x)BaTiO3-x(Bi0.9Na0.1)(In1-yZry)O3, wherein 0≤x≤0.2,0.1≤y≤0.3.
2. the lead-free ceramics material of high energy storage density according to claim 1 and charge-discharge performance, which is characterized in that wherein
X is preferably that 0.1, y is preferably 0.2.
3. the preparation method of the lead-free ceramics material of high energy storage density as described in claim 1 and charge-discharge performance, feature
It is, this method uses following steps：
(1) BaCO that purity is more than 99% is chosen3,TiO2, Bi2O3, Na2CO3, In2O3, ZrO2Raw material as lead-free ceramics；
(2) it presses chemical composition and carries out weighing, ball-milling medium is added and carries out ball milling, discharges, drying；
(3) powder of drying is calcined to 850~1000 DEG C of 1~5h of heat preservation in Muffle furnace, after being taken out after calcining again with mortar
Secondary grinding, after carry out secondary clacining, soaking time and temperature are the same as the first time；
(4) powder after calcining is subjected to secondary ball milling, discharged, drying adds PVA and is granulated, and in the pressure of 4~8MPa
It is pressed into ceramic disks under power；
(5) obtained ceramic body in Muffle furnace is subjected to dumping, 5~10h is kept the temperature at 500~600 DEG C；
(6) ceramic body after dumping is sintered at 1200~1300 DEG C, control 2~5 DEG C/min of heating rate, and
The highest temperature keeps the temperature 2~5h, after naturally cooling to room temperature, sintered potsherd is polished with varigrained sand paper, is obtained
The thin potsherd smooth to surface-brightening.
4. the preparation method of the lead-free ceramics material of high energy storage density according to claim 3 and charge-discharge performance, special
Sign is that ball milling carries out in planetary ball mill twice, and zirconia beads and absolute ethyl alcohol is added as ball-milling medium.
5. the preparation method of the lead-free ceramics material of high energy storage density according to claim 3 and charge-discharge performance, special
Sign is that Ball-milling Time is 6~8 hours in step (2), and Ball-milling Time is 8~12 hours in step (4).
6. the preparation method of the lead-free ceramics material of high energy storage density according to claim 3 and charge-discharge performance, special
Sign is that step (2) is dried with the powder in step (4) in air dry oven, and temperature is controlled at 100~120 DEG C.
7. the preparation method of the lead-free ceramics material of high energy storage density according to claim 3 and charge-discharge performance, special
Sign is that the PVA of 5wt% is added when being granulated for step (4).
8. the preparation method of the lead-free ceramics material of high energy storage density according to claim 3 and charge-discharge performance, special
Sign is, further includes that potsherd after polishing also coats high temperature silver paste in tow sides, silver ink firing is carried out in Muffle furnace,
500~600 DEG C of temperatures 0.5~1 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810184288.0A CN108409319B (en) | 2018-03-06 | 2018-03-06 | Lead-free ceramic material with high energy storage density and charge-discharge performance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810184288.0A CN108409319B (en) | 2018-03-06 | 2018-03-06 | Lead-free ceramic material with high energy storage density and charge-discharge performance and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108409319A true CN108409319A (en) | 2018-08-17 |
| CN108409319B CN108409319B (en) | 2021-03-26 |
Family
ID=63130019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810184288.0A Active CN108409319B (en) | 2018-03-06 | 2018-03-06 | Lead-free ceramic material with high energy storage density and charge-discharge performance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108409319B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111398709A (en) * | 2020-03-20 | 2020-07-10 | 中国科学院上海硅酸盐研究所 | Method for testing energy storage density of energy storage capacitor |
| CN114394829A (en) * | 2022-01-07 | 2022-04-26 | 武汉理工大学 | High-energy-storage-density barium titanium lithium acid ceramic and preparation method thereof |
| CN114671681A (en) * | 2022-04-11 | 2022-06-28 | 北京科技大学 | Barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4599677A (en) * | 1984-06-01 | 1986-07-08 | Lawless William N | Capacitive energy storage device for use at cryogenic temperatures |
| CN1303959A (en) * | 1999-11-24 | 2001-07-18 | 中国科学院物理研究所 | Indium-doped barium-titanate material and its preparation method |
| JP2001240465A (en) * | 2000-02-25 | 2001-09-04 | Kyocera Corp | Porcelain of dielectrics |
| CN101971381A (en) * | 2008-03-19 | 2011-02-09 | 国立大学法人山梨大学 | Piezoelectric material |
| CN102381875A (en) * | 2010-09-02 | 2012-03-21 | 纵坚平 | Preparation method of double-perovskite ferroelectrics (FET)-antiferromagnetism (AFM) compound molecule with oxygen bridge |
| CN103130502A (en) * | 2011-11-23 | 2013-06-05 | 三菱综合材料株式会社 | Ferroelectric film and film capacitor using same |
| CN104671777A (en) * | 2015-03-10 | 2015-06-03 | 桂林电子科技大学 | Multi-functional lead-free ceramic having high electrostrictive strain, high energy density, highly stable dielectric property and the like and preparation method thereof |
| CN105374931A (en) * | 2014-08-26 | 2016-03-02 | 中国科学院上海硅酸盐研究所 | Bi(Mg1/2Ti1/2)O3-PbTiO3(BMT-PT)-based high-temperature piezoelectric material and preparation method thereof |
| CN106032318A (en) * | 2015-03-12 | 2016-10-19 | 中国科学院上海硅酸盐研究所 | A low-temperature co-fired ceramic material and a preparing method thereof |
| CN106587986A (en) * | 2016-12-22 | 2017-04-26 | 桂林电子科技大学 | Multifunctional lead-free ceramic with energy storage, strain and wide dielectric temperature region functions and preparation method |
| CN107746273A (en) * | 2017-11-14 | 2018-03-02 | 周开珍 | The lead-free ceramicses material and preparation method of a kind of high energy storage density |
-
2018
- 2018-03-06 CN CN201810184288.0A patent/CN108409319B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4599677A (en) * | 1984-06-01 | 1986-07-08 | Lawless William N | Capacitive energy storage device for use at cryogenic temperatures |
| CN1303959A (en) * | 1999-11-24 | 2001-07-18 | 中国科学院物理研究所 | Indium-doped barium-titanate material and its preparation method |
| JP2001240465A (en) * | 2000-02-25 | 2001-09-04 | Kyocera Corp | Porcelain of dielectrics |
| CN101971381A (en) * | 2008-03-19 | 2011-02-09 | 国立大学法人山梨大学 | Piezoelectric material |
| CN102381875A (en) * | 2010-09-02 | 2012-03-21 | 纵坚平 | Preparation method of double-perovskite ferroelectrics (FET)-antiferromagnetism (AFM) compound molecule with oxygen bridge |
| CN103130502A (en) * | 2011-11-23 | 2013-06-05 | 三菱综合材料株式会社 | Ferroelectric film and film capacitor using same |
| CN105374931A (en) * | 2014-08-26 | 2016-03-02 | 中国科学院上海硅酸盐研究所 | Bi(Mg1/2Ti1/2)O3-PbTiO3(BMT-PT)-based high-temperature piezoelectric material and preparation method thereof |
| CN104671777A (en) * | 2015-03-10 | 2015-06-03 | 桂林电子科技大学 | Multi-functional lead-free ceramic having high electrostrictive strain, high energy density, highly stable dielectric property and the like and preparation method thereof |
| CN106032318A (en) * | 2015-03-12 | 2016-10-19 | 中国科学院上海硅酸盐研究所 | A low-temperature co-fired ceramic material and a preparing method thereof |
| CN106587986A (en) * | 2016-12-22 | 2017-04-26 | 桂林电子科技大学 | Multifunctional lead-free ceramic with energy storage, strain and wide dielectric temperature region functions and preparation method |
| CN107746273A (en) * | 2017-11-14 | 2018-03-02 | 周开珍 | The lead-free ceramicses material and preparation method of a kind of high energy storage density |
Non-Patent Citations (1)
| Title |
|---|
| 周飞: "BaTiO3-Bi0.5Na0.5TiO3系无铅压电陶瓷的结构与电性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111398709A (en) * | 2020-03-20 | 2020-07-10 | 中国科学院上海硅酸盐研究所 | Method for testing energy storage density of energy storage capacitor |
| CN111398709B (en) * | 2020-03-20 | 2021-11-02 | 中国科学院上海硅酸盐研究所 | Method for testing energy storage density of energy storage capacitor |
| CN114394829A (en) * | 2022-01-07 | 2022-04-26 | 武汉理工大学 | High-energy-storage-density barium titanium lithium acid ceramic and preparation method thereof |
| CN114671681A (en) * | 2022-04-11 | 2022-06-28 | 北京科技大学 | Barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency and preparation method thereof |
| CN114671681B (en) * | 2022-04-11 | 2023-04-11 | 北京科技大学 | Barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108409319B (en) | 2021-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Glass–ceramic dielectric materials with high energy density and ultra-fast discharge speed for high power energy storage applications | |
| CN105198416B (en) | A kind of low sintering high energy storage density anti-ferroelectric ceramic material and preparation method thereof | |
| CN109133915B (en) | Barium titanate-based dielectric material with high energy storage capacity and preparation method thereof | |
| CN109574656A (en) | A kind of high energy storage bismuth-sodium titanate-strontium titanate base dielectric material and preparation method thereof | |
| CN110204335B (en) | Ceramic material with high energy storage density and efficiency and preparation method thereof | |
| CN108409319A (en) | The lead-free ceramics material and preparation method thereof of high energy storage density and charge-discharge performance | |
| CN111233470B (en) | Antiferroelectric ceramic material with excellent charge and discharge performance and preparation method thereof | |
| CN110526707A (en) | A kind of zirconium titanium stannic acid lanthanum lead thick film ceramic of high tin content and its preparation method and application | |
| CN108623300A (en) | Unleaded relaxation ferroelectric energy storage ceramic of barium titanate-niobic zincic acid bismuth base and preparation method thereof | |
| CN110451955A (en) | Unleaded relaxation ferroelectric energy storage ceramic of bismuth sodium titanate-barium titanate base and preparation method thereof | |
| CN113213929A (en) | Potassium sodium niobate based ferroelectric ceramic material with high energy storage efficiency and density and preparation method thereof | |
| CN115504784B (en) | Leadless relaxation ferroelectric high energy storage density ceramic material and preparation method thereof | |
| CN105753471B (en) | A kind of preparation method of high electric card effect strontium barium niobate ceramics | |
| CN106631021A (en) | Ceramic material high in energy storage density and energy storage efficiency and preparation method of ceramic material | |
| CN110668816A (en) | Lead-free energy storage dielectric ceramic material with tungsten bronze structure and preparation method thereof | |
| CN104725041A (en) | La-doped lead zirconate stannate titanate anti-ferroelectric ceramics with high energy storage efficiency and preparation method thereof | |
| CN107840655A (en) | The preparation method of the unleaded relaxation ferroelectric ceramic of bismuth potassium titanate base of quasi- homotype phase boundary | |
| CN111018516A (en) | Barium titanate-based high-energy-density electronic ceramic and preparation method thereof | |
| CN111253151B (en) | Bismuth ferrite barium titanate-based ceramic with high energy storage density and high power density and preparation method thereof | |
| CN109320236B (en) | Composite material with high energy storage density and charge-discharge performance and preparation method thereof | |
| CN105198409B (en) | A kind of preparation method of the barium-strontium titanate-based glass complex phase ceramic of high energy storage density | |
| CN112142466B (en) | Lead niobate ytterbium acid based antiferroelectric ceramic material and preparation method thereof | |
| Jin et al. | Microstructure, dielectric properties and energy storage performance of Ba0. 4Sr0. 6TiO3 ceramics prepared by hydrothermal method and microwave sintering | |
| CN106957174A (en) | BNT-BA-KNN non-plumbum ferroelectric Phase transformation ceramics and preparation method thereof | |
| CN108069713A (en) | A kind of high energy storage density ST-NBT-BT ceramic materials and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |