CN108623301B - A kind of unleaded low-dielectric loss and high energy storage density ceramics and preparation method thereof with sandwich structure - Google Patents
A kind of unleaded low-dielectric loss and high energy storage density ceramics and preparation method thereof with sandwich structure Download PDFInfo
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Abstract
A kind of unleaded low-dielectric loss and high energy storage density ceramics and preparation method thereof with sandwich structure, organic solvent and emulsifier are uniformly mixed, SrTiO is then added3Powder, binder, dispersing agent and plasticizer, and be uniformly mixed, obtain SrTiO3Casting slurry；(1-x) SrTiO is similarly obtained using the tape casting3‑xBaFe0.5Nb0.5O3Casting slurry；The mode that tape casting is respectively adopted in two kinds of casting slurries is subjected to tape casting, obtains two kinds of casting films；Then superposition, pressurization, dumping, sintering.Ceramic material preparation process of the invention is simple, technology maturation, is suitble to industrialized production, and energy storage characteristic is excellent, and the discharge energy density calculated based on ferroelectric hysteresis loop is in 1.67~1.90J/cm3Between, energy storage efficiency can achieve 86%, and electric field strength can show lower dielectric loss value in 300kV/cm or more.
Description
Technical field
The invention belongs to energy storage ceramic field, specifically a kind of unleaded low-dielectric loss with sandwich structure and high storage
Energy density ceramic and preparation method thereof.
Background technique
High energy storage density dielectric has high-energy density and high power density, can be used for developing high capacity capacitor,
There is huge application potential in the directions such as Pulse Power Techniques, power electronic circuit, electric car, grid power adjusting.With battery
It is compared with other energy storage devices, ceramic capacitor has the advantages that fast charging and discharging and high temperature stability.But mesh
Preceding existing most of unleaded energy storage ceramic dielectric materials are not high enough there is breakdown strength or polarization intensity is smaller, cause to store up
Energy density is not high, it is difficult to meet the needs of new technology continuous development.
Under normal conditions, the energy storage density of material refers to the electric energy that unit volume material can accommodate, universal in the world at present
The unit used is J/cm3, energy storage density can calculate with formula (1):
In formula: J --- energy storage density (J/cm3)；E --- electric field strength (kV/cm)；ε0--- permittivity of vacuum；
εr--- relative dielectric constant.From the above equation, we can see that obtain higher energy storage density, the electric field strength of ceramic medium material is improved
It is effective approach with relative dielectric constant.
BaFe0.5Nb0.5O3Cause the extensive concern of people due to giant dielectric Chang Xiaoying.However BaFe0.5Nb0.5O3Pottery
The dielectric loss of ceramic material is about 4.29 under the test frequency of 1kHz, higher dielectric loss value and poor breakdown performance
So that the needs of component prepared is difficult to meet energy storage ceramic capacitor in practical applications.SrTiO3It is vertical at room temperature
Square structure shows paraelectric phase, has lesser dielectric loss and higher compressive resistance, and frequency stability is good, is mesh
One of most extensive, most attractive unleaded energy-storing dielectric ceramic system of preceding research.But SrTiO3The dielectric constant of ceramics
It is smaller, at room temperature about 300.Therefore, Yao Tuokuan SrTiO3And BaFe0.5Nb0.5O3Ceramic dielectric energy storage field application,
It needs to be modified it research.
Currently, the electric field strength of unleaded energy storage ceramic dielectric material, energy storage density and energy storage efficiency are to be improved.
Summary of the invention
It is an object of the invention to overcome defect existing in the prior art, provide a kind of with the unleaded of sandwich structure
Low-dielectric loss and high energy storage density ceramics and preparation method thereof, electric field strength, energy storage density and the energy storage of this ceramic material
Efficiency is excellent, and discharge energy density can achieve 1.90J/cm3, energy storage efficiency can achieve 86%, and electric field strength exists
300kV/cm or more, and the tape casting technology maturation used during the preparation process, what is used is cheap, has ring
The characteristics such as border is friendly, practicability is good.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of preparation method of unleaded low-dielectric loss and high energy storage density ceramics with sandwich structure, including it is following
Step:
(1) preparation of casting slurry: organic solvent and emulsifier are uniformly mixed, SrTiO is then added3Powder, bonding
Agent, dispersing agent and plasticizer, and be uniformly mixed, obtain SrTiO3Casting slurry；
Organic solvent and emulsifier are uniformly mixed, (1-x) SrTiO is then added3-xBaFe0.5Nb0.5O3Powder, bonding
Agent, dispersing agent and plasticizer, and be uniformly mixed, obtain (1-x) SrTiO3-xBaFe0.5Nb0.5O3Casting slurry；Wherein, x is indicated
BaFe0.5Nb0.5O3Molar fraction, and 0.05≤x≤0.15；
(2) preparation of green compact: the SrTiO that will be obtained in step (2)3Casting slurry and (1-x) SrTiO3-
xBaFe0.5Nb0.5O3The mode that tape casting is respectively adopted in casting slurry carries out tape casting, obtains SrTiO3Casting films and (1-
x)SrTiO3-xBaFe0.5Nb0.5O3Casting films；Then it is cut and is superimposed, and added under the pressure of 150~200MPa
Pressure, obtains the SrTiO with sandwich structure3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3Ceramic green；
(3) the ceramic green sample by step (2) preparation carries out dumping processing, then sinters porcelain into, obtains with Sanming City
Control the SrTiO of structure3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3Ceramics.
A further improvement of the present invention lies in that SrTiO3Powder is prepared by following procedure: pressing chemical formula SrTiO3It will analysis
Pure SrCO3And TiO2Carry out ingredient simultaneously be uniformly mixed, then sieving, briquetting, then through 1150~1200 DEG C pre-burning 3~5 hours,
Blocks of solid is obtained, blocks of solid is then smashed it through into 120 meshes, obtains SrTiO3Powder.
A further improvement of the present invention lies in that (1-x) SrTiO3-xBaFe0.5Nb0.5O3Powder is prepared by following procedure:
Chemical formula BaFe is pressed first0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out ingredient and is uniformly mixed, then mistake
Sieve, briquetting, then through 1200~1250 DEG C pre-burning 3~4 hours, obtain blocks of solid, blocks of solid then smashed it through into 120 mesh
Sieve, obtains BaFe0.5Nb0.5O3Powder；Finally according to chemical formula (1-x) SrTiO3-xBaFe0.5Nb0.5O3The SrTiO that will be obtained3
Powder and BaFe0.5Nb0.5O3Powder carries out ingredient and is uniformly mixed, and 120 meshes are crossed after drying, obtain (1-x) SrTiO3-
xBaFe0.5Nb0.5O3Powder.
A further improvement of the present invention lies in that uniformly mixed detailed process is: using dehydrated alcohol as medium, passing through ball milling
It carries out, wherein Ball-milling Time is 12~16 hours, and is dried at 100 DEG C after ball milling.
A further improvement of the present invention lies in that organic solvent is the mixture of dehydrated alcohol and butanone；Emulsifier is three oil
Acid glyceride；Binder is polyvinyl butyral；Dispersing agent is polyethylene glycol；Plasticizer is dibutyl phthalate.
A further improvement of the present invention lies in that the additional amount of dehydrated alcohol is SrTiO3Powder or (1-x) SrTiO3-
xBaFe0.5Nb0.5O3The 50~55% of powder quality；The additional amount and SrTiO of butanone3Powder or (1-x) SrTiO3-
xBaFe0.5Nb0.5O3Powder quality is identical；The additional amount of olein is SrTiO3Powder or (1-x) SrTiO3-
xBaFe0.5Nb0.5O3The 3~4% of powder quality；The additional amount of polyvinyl butyral is SrTiO3Powder or (1-x) SrTiO3-
xBaFe0.5Nb0.5O3The 9.5~10.5% of powder quality；The additional amount of polyethylene glycol is SrTiO3Powder or (1-x) SrTiO3-
xBaFe0.5Nb0.5O3The 3~4% of powder quality；The additional amount of dibutyl phthalate is the 3~4% of powder quality.
A further improvement of the present invention lies in that dumping processing detailed process is: keeping the temperature 10~15 hours at 500~600 DEG C.
A further improvement of the present invention lies in that the temperature of sintering is 1350~1380 DEG C, the time is 2~3 hours.
A kind of unleaded low-dielectric loss and high energy storage density ceramics with sandwich structure, chemical formula are as follows: SrTiO3/
((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3, wherein x is BaFe0.5Nb0.5O3Molar fraction, and 0.05≤x≤
0.15。
A further improvement of the present invention lies in that the electric field strength of the ceramic material is in 300kV/cm or more, discharge energy
Density can reach 1.90J/cm3, energy storage efficiency can reach 86%.
Compared with prior art, the invention has the benefit that the present invention is respectively by SrTiO3Powder and (1-x)
SrTiO3-xBaFe0.5Nb0.5O3Powder carries out tape casting, is then designed by structure, prepares the pottery with sandwich structure
Then ceramic material carries out dumping processing to the ceramic green material prepared and is sintered, can be obtained with sandwich structure
Unleaded low-dielectric loss and high energy storage density ceramics.The unleaded low-dielectric loss with sandwich structure of the invention and high energy storage
The preparation process of density ceramic is simple, have excellent performance, stability is good, can meet the needs of different application, unleaded pollution-free, involved
And it is cheap, technical matters is mature, is suitble to industrialized production.
Further, the organic solvent in casting slurry of the invention is made of dehydrated alcohol and butanone, dehydrated alcohol and
The mass ratio of butanone is 0.5~0.55, since the evaporation rate of dehydrated alcohol and butanone is variant, selects the anhydrous of special ratios
Ethyl alcohol and butanone can guarantee also there is residual while solvent volatilization, and the surface as caused by volatilization is too fast is effectively avoided to open
It splits.Meanwhile the casting slurry that obtains of the present invention has stability and rheological characteristic good, solid content is high, can drying rapidly and efficiently,
Shorten drying time, is conducive to industrialized mass production.
The breakdown electric field of unleaded low-dielectric loss and high energy storage density ceramics with sandwich structure of the invention is high, is situated between
Electrical loss is low, can effectively improve energy storage characteristic, and discharge energy density can achieve 1.90J/cm3, energy storage efficiency can be with
Reach 86%, electric field strength is in 300kV/cm or more.
Detailed description of the invention
Fig. 1 is that the unleaded low-dielectric loss and high energy storage density ceramics prepared by embodiment 1 with sandwich structure exist
Ferroelectric hysteresis loop figure under 10Hz test frequency；
Fig. 2 is that the unleaded low-dielectric loss and high energy storage density ceramics prepared by embodiment 2 with sandwich structure exist
Ferroelectric hysteresis loop figure under 10Hz test frequency；
Fig. 3 is that the unleaded low-dielectric loss and high energy storage density ceramics prepared by embodiment 3 with sandwich structure exist
Ferroelectric hysteresis loop figure under 10Hz test frequency；
Fig. 4 is that the unleaded low-dielectric loss and high energy storage density ceramics prepared by embodiment 1 with sandwich structure exist
Jie's frequency map under different test frequencies；
Fig. 5 is that the unleaded low-dielectric loss and high energy storage density ceramics prepared by embodiment 2 with sandwich structure exist
Jie's frequency map under different test frequencies；
Fig. 6 is that the unleaded low-dielectric loss and high energy storage density ceramics prepared by embodiment 3 with sandwich structure exist
Jie's frequency map under different test frequencies；
Fig. 7 is that the unleaded low-dielectric loss and high energy storage density ceramics prepared by embodiment 1 with sandwich structure exist
Jie's temperature map under different test frequencies；
Fig. 8 is that the unleaded low-dielectric loss and high energy storage density ceramics prepared by embodiment 2 with sandwich structure exist
Jie's temperature map under different test frequencies；
Fig. 9 is that the unleaded low-dielectric loss and high energy storage density ceramics prepared by embodiment 3 with sandwich structure exist
Jie's temperature map under different test frequencies.
Specific embodiment
The present invention is described in further details with reference to the accompanying drawings and detailed description.
A kind of unleaded low-dielectric loss and high energy storage density ceramics with sandwich structure, chemical formula are as follows: SrTiO3/
((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3, wherein x indicates BaFe0.5Nb0.5O3Molar fraction, and 0.05≤x≤
0.15。
The preparation method of unleaded low-dielectric loss and high energy storage density ceramics with sandwich structure of the invention, including
Following steps:
(1) chemical formula SrTiO is pressed3By analytically pure SrCO3And TiO2After ingredient, using dehydrated alcohol as medium, pass through ball milling
It is uniformly mixed within 12~16 hours, is then dried at 100 DEG C, crosses 120 meshes, briquetting, again through 1150~1200 DEG C of pre-burnings 3~5
Hour, blocks of solid is obtained, blocks of solid is then smashed it through into 120 meshes, obtains SrTiO3Powder；
(2) chemical formula (1-x) SrTiO is pressed3-xBaFe0.5Nb0.5O3Powder is prepared by following procedure: pressing chemical formula first
BaFe0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out ingredient and is uniformly mixed, then sieving, briquetting, then pass through
1200~1250 DEG C pre-burning 3~4 hours, obtain blocks of solid, blocks of solid then smashed it through into 120 meshes, is obtained
BaFe0.5Nb0.5O3Powder.Finally according to chemical formula (1-x) SrTiO3-xBaFe0.5Nb0.5O3The SrTiO that will be obtained3Powder and
BaFe0.5Nb0.5O3Powder carries out ingredient and is uniformly mixed, and 120 meshes are crossed after drying, obtain (1-x) SrTiO3-
xBaFe0.5Nb0.5O3Powder；
(3) preparation of casting slurry: organic solvent (dehydrated alcohol and butanone) and emulsifier (three oleic acid are 1. weighed according to the ratio
Glyceride), and ball milling 4~6 hours are uniformly mixed；2. step (1) acquisition is added into the slurry of step 1. after mixing
Powder, binder (polyvinyl butyral) dispersing agent (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 4
It is uniformly mixed within~6 hours, obtains SrTiO3Casting slurry；Wherein, the additional amount of dehydrated alcohol is the 50~55% of powder quality；
The additional amount of butanone is identical as powder quality；The additional amount of olein is the 3~4% of powder quality；Polyvinyl alcohol contracting
The additional amount of butyraldehyde is the 9.5~10.5% of powder quality；The additional amount of polyethylene glycol is the 3~4% of powder quality；Adjacent benzene two
The additional amount of formic acid dibutyl ester is the 3~4% of powder quality；
Organic solvent and emulsifier are uniformly mixed, (1-x) SrTiO is then added3-xBaFe0.5Nb0.5O3Powder, bonding
Agent, dispersing agent and plasticizer, and be uniformly mixed, obtain (1-x) SrTiO3-xBaFe0.5Nb0.5O3Casting slurry；Wherein, x is indicated
BaFe0.5Nb0.5O3Molar fraction, and 0.05≤x≤0.15；Wherein, the additional amount of dehydrated alcohol be powder quality 50~
55%；The additional amount of butanone is identical as powder quality；The additional amount of olein is the 3~4% of powder quality；Polyethylene
The additional amount of butyral is the 9.5~10.5% of powder quality；The additional amount of polyethylene glycol is the 3~4% of powder quality；It is adjacent
The additional amount of dibatyl phithalate is the 3~4% of powder quality；
(4) SrTiO that will be obtained in step (3)3Casting slurry and (1-x) SrTiO3-xBaFe0.5Nb0.5O3Casting slurry
The mode that tape casting is respectively adopted carries out tape casting, obtains SrTiO3Casting films and (1-x) SrTiO3-xBaFe0.5Nb0.5O3
Casting films.Then it is cut and is superimposed as required, and pressurizeed under the pressure of 150~200MPa, obtain SrTiO3/
((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3Ceramic green；Wherein, cut can size according to actual needs carry out,
Superposition refers to SrTiO3Casting films and (1-x) SrTiO3-xBaFe0.5Nb0.5O3Casting films superposition, specifically, by (1-x)
SrTiO3-xBaFe0.5Nb0.5O3Casting films are placed in SrTiO3Among casting films, sandwich structure is obtained.
(5) SrTiO for obtaining step (4)3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3Ceramic green exists
500~600 DEG C of heat preservations progress dumping processing in 10~15 hours, then keeps the temperature 2~3 hours at 1350~1380 DEG C and sinters into
Porcelain obtains the unleaded low-dielectric loss with sandwich structure and high energy storage density ceramics；
(6) SrTiO that will be sintered3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3Two tables of ceramics sample
The clean simultaneously gold-plated electrode of face polishing, then tests its ferroelectric properties, and carry out energy storage characteristic meter under room temperature and the frequency of 10Hz
It calculates, rechargeable energy density (WC), discharge energy density (WD) and energy storage efficiency (η) calculation formula are as follows:
Wherein PmaxIndicate maximum polarization, PrIndicate remanent polarization, E indicates electric field strength, and P indicates that polarization is strong
Degree.
Ball-milling Time is 12~16 hours in step (1) and step (3).
The embodiment being given by the following can further be apparent from the contents of the present invention, but it is not to this hair
Bright restriction.
Embodiment 1
The chemical formula of the present embodiment ceramic material are as follows: SrTiO3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3,
Wherein x indicates BaFe0.5Nb0.5O3Molar fraction, and x=0.05.
The preparation method of above-mentioned unleaded high energy storage density ceramic material, comprising the following steps:
(1) chemical formula SrTiO is pressed3By analytically pure SrCO3And TiO2After ingredient, using dehydrated alcohol as medium, pass through ball milling
12 hours be uniformly mixed, then at 100 DEG C dry, cross 120 meshes, briquetting, again through 1150 DEG C pre-burning 5 hours, obtain bulk
Then blocks of solid is smashed it through 120 meshes, obtains SrTiO by solid3Powder；
(2) chemical formula 0.95SrTiO is pressed3-0.05BaFe0.5Nb0.5O3Powder is prepared by following procedure: first by chemistry
Formula BaFe0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out ingredient and is uniformly mixed, then sieving, briquetting, then pass through
1200 DEG C pre-burning 4 hours, obtain blocks of solid, blocks of solid then smashed it through into 120 meshes, obtains BaFe0.5Nb0.5O3Powder
Body.Finally according to chemical formula 0.95SrTiO3-0.05BaFe0.5Nb0.5O3The SrTiO that will be obtained3Powder and BaFe0.5Nb0.5O3Powder
Body carries out ingredient and is uniformly mixed, and 120 meshes are crossed after drying, obtain 0.95SrTiO3-0.05BaFe0.5Nb0.5O3Powder；
(3) preparation of casting slurry: organic solvent (dehydrated alcohol and butanone) and emulsifier (three oleic acid are 1. weighed according to the ratio
Glyceride), and ball milling 4 hours are uniformly mixed；2. the powder that step (1) obtains is added into the slurry of step 1. after mixing
Body, binder (polyvinyl butyral) dispersing agent (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 4 is small
When be uniformly mixed, obtain SrTiO3Casting slurry.Wherein, the additional amount of dehydrated alcohol is the 50% of powder quality；Butanone adds
It is identical as powder quality to enter amount；The additional amount of olein is the 3% of powder quality；The additional amount of polyvinyl butyral
It is the 9.5% of powder quality；The additional amount of polyethylene glycol is the 3% of powder quality；The additional amount of dibutyl phthalate is
The 3% of powder quality；
1. weighing organic solvent (dehydrated alcohol and butanone) and emulsifier (olein) according to the ratio, and ball milling 4 is small
When be uniformly mixed；2. powder, the binder (polyvinyl alcohol that step (2) obtain are added into the slurry of step 1. after mixing
Butyral) dispersing agent (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 4 hours are uniformly mixed, and obtain
0.95SrTiO3-0.05BaFe0.5Nb0.5O3Casting slurry.Wherein, the additional amount of dehydrated alcohol is the 50% of powder quality；Butanone
Additional amount it is identical as powder quality；The additional amount of olein is the 3% of powder quality；Polyvinyl butyral adds
Enter 9.5% that amount is powder quality；The additional amount of polyethylene glycol is the 3% of powder quality；The addition of dibutyl phthalate
Amount is the 3% of powder quality；
(4) SrTiO that will be obtained in step (3)3Casting slurry and 0.95SrTiO3-0.05BaFe0.5Nb0.5O3Curtain coating slurry
Material carries out tape casting by the way of tape casting, obtains SrTiO3Casting films and 0.95SrTiO3-0.05BaFe0.5Nb0.5O3
Casting films.Then it is cut and is superimposed as required, and pressurizeed under the pressure of 150MPa, obtain SrTiO3/
(0.95SrTiO3-0.05BaFe0.5Nb0.5O3)/SrTiO3Ceramic green；
(5) SrTiO for obtaining step (4)3/(0.95SrTiO3-0.05BaFe0.5Nb0.5O3)/SrTiO3Ceramic green
In 500 DEG C of heat preservations progress dumping processing in 15 hours, 3 hours then are kept the temperature at 1350 DEG C and sinters porcelain into, is obtained with sandwich
Unleaded low-dielectric loss and the high energy storage density ceramics of structure；
(6) SrTiO that will be sintered3/(0.95SrTiO3-0.05BaFe0.5Nb0.5O3)/SrTiO3Two of ceramics sample
The clean simultaneously gold-plated electrode of surface polishing, then tests its ferroelectric properties under room temperature and the frequency of 10Hz, is as shown in Figure 1 this reality
Apply the ferroelectric hysteresis loop of a ceramic material.As seen from the figure, the ferroelectric hysteresis loop of the ceramics sample is more elongated, and breakdown strength is
334kV/cm. can be calculated by carrying out energy storage characteristic, and the rechargeable energy density of the unleaded energy-storing dielectric ceramic of the present embodiment is
2.21J/cm3, discharge energy density 1.90J/cm3, energy storage efficiency 86%.Fig. 4 is that energy storage ceramic manufactured in the present embodiment exists
Jie's frequency map measured at room temperature.As seen from the figure, SrTiO3/(0.95SrTiO3-0.05BaFe0.5Nb0.5O3)/SrTiO3Ceramics
Dielectric constant at 1 khz is 317, and corresponding dielectric loss value is 0.005.Fig. 7 is that energy storage ceramic manufactured in the present embodiment exists
Jie's temperature map measured under different frequency.It can be found that SrTiO from figure3/(0.95SrTiO3-0.05BaFe0.5Nb0.5O3)/
SrTiO3The dielectric loss of ceramics keeps smaller within the temperature range of -180-150 DEG C.Table 1 is the unleaded energy storage of the present embodiment
Dielectric, ferroelectricity and the energy storage characteristic of medium ceramic material.
Embodiment 2
The chemical formula of the present embodiment ceramic material are as follows: SrTiO3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3,
Wherein x indicates BaFe0.5Nb0.5O3Molar fraction, and x=0.10.
The preparation method of above-mentioned unleaded high energy storage density ceramic material, comprising the following steps:
(1) chemical formula SrTiO is pressed3By analytically pure SrCO3And TiO2After ingredient, using dehydrated alcohol as medium, pass through ball milling
12 hours be uniformly mixed, then at 100 DEG C dry, cross 120 meshes, briquetting, again through 1200 DEG C pre-burning 3 hours, obtain bulk
Then blocks of solid is smashed it through 120 meshes, obtains SrTiO by solid3Powder；
(2) chemical formula 0.90SrTiO is pressed3-0.10BaFe0.5Nb0.5O3Powder is prepared by following procedure: first by chemistry
Formula BaFe0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out ingredient and is uniformly mixed, then sieving, briquetting, then pass through
1250 DEG C pre-burning 3 hours, obtain blocks of solid, blocks of solid then smashed it through into 120 meshes, obtains BaFe0.5Nb0.5O3Powder
Body.Finally according to chemical formula 0.90SrTiO3-0.10BaFe0.5Nb0.5O3The SrTiO that will be obtained3Powder and BaFe0.5Nb0.5O3Powder
Body carries out ingredient and is uniformly mixed, and 120 meshes are crossed after drying, obtain 0.90SrTiO3-0.10BaFe0.5Nb0.5O3Powder；
(3) preparation of casting slurry: organic solvent (dehydrated alcohol and butanone) and emulsifier (three oleic acid are 1. weighed according to the ratio
Glyceride), and ball milling 6 hours are uniformly mixed；2. the powder that step (1) obtains is added into the slurry of step 1. after mixing
Body, binder (polyvinyl butyral) dispersing agent (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 6 is small
When be uniformly mixed, obtain SrTiO3Casting slurry.Wherein, the additional amount of dehydrated alcohol is the 56% of powder quality；Butanone adds
It is identical as powder quality to enter amount；The additional amount of olein is the 4% of powder quality；The additional amount of polyvinyl butyral
It is the 10.5% of powder quality；The additional amount of polyethylene glycol is the 4% of powder quality；The additional amount of dibutyl phthalate is
The 4% of powder quality；
1. weighing organic solvent (dehydrated alcohol and butanone) and emulsifier (olein) according to the ratio, and ball milling 4 is small
When be uniformly mixed；2. powder, the binder (polyvinyl alcohol that step (2) obtain are added into the slurry of step 1. after mixing
Butyral) dispersing agent (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 4 hours are uniformly mixed, and obtain
0.90SrTiO3-0.10BaFe0.5Nb0.5O3Casting slurry.Wherein, the additional amount of dehydrated alcohol is the 56% of powder quality；Butanone
Additional amount it is identical as powder quality；The additional amount of olein is the 4% of powder quality；Polyvinyl butyral adds
Enter 10.5% that amount is powder quality；The additional amount of polyethylene glycol is the 4% of powder quality；The addition of dibutyl phthalate
Amount is the 4% of powder quality；
(4) SrTiO that will be obtained in step (3)3Casting slurry and 0.90SrTiO3-0.10BaFe0.5Nb0.5O3Curtain coating slurry
Material carries out tape casting by the way of tape casting, obtains SrTiO3Casting films and 0.90SrTiO3-0.10BaFe0.5Nb0.5O3
Casting films.Then it is cut and is superimposed as required, and pressurizeed under the pressure of 200MPa, obtain SrTiO3/
(0.90SrTiO3-0.10BaFe0.5Nb0.5O3)/SrTiO3Ceramic green；
(5) SrTiO for obtaining step (4)3/(0.90SrTiO3-0.10BaFe0.5Nb0.5O3)/SrTiO3Ceramic green
In 600 DEG C of heat preservations progress dumping processing in 10 hours, 2 hours then are kept the temperature at 1380 DEG C and sinters porcelain into, is obtained with sandwich
Unleaded low-dielectric loss and the high energy storage density ceramics of structure；
(6) SrTiO that will be sintered3/(0.90SrTiO3-0.10BaFe0.5Nb0.5O3)/SrTiO3Two of ceramics sample
The clean simultaneously gold-plated electrode of surface polishing, then tests its ferroelectric properties under room temperature and the frequency of 10Hz, is illustrated in figure 2 this reality
Apply the ferroelectric hysteresis loop of a ceramic material.As seen from the figure, the ferroelectric hysteresis loop of the ceramics sample is more elongated, and breakdown strength is
329kV/cm. can be calculated by carrying out energy storage characteristic, and the rechargeable energy density of the unleaded energy-storing dielectric ceramic of the present embodiment is
2.35J/cm3, discharge energy density 1.90J/cm3, energy storage efficiency 81%.Fig. 5 is that energy storage ceramic manufactured in the present embodiment exists
Jie's frequency map measured at room temperature.As seen from the figure, SrTiO3/(0.90SrTiO3-0.10BaFe0.5Nb0.5O3)/SrTiO3Ceramics
Dielectric constant at 1 khz is 377, and corresponding dielectric loss value is 0.021.Fig. 8 is that energy storage ceramic manufactured in the present embodiment exists
Jie's temperature map measured under different frequency.It can be found that SrTiO from figure3/(0.90SrTiO3-0.10BaFe0.5Nb0.5O3)/
SrTiO3The dielectric loss of ceramics keeps smaller within the temperature range of -180-150 DEG C.Table 1 is the unleaded energy storage of the present embodiment
Dielectric, ferroelectricity and the energy storage characteristic of medium ceramic material.
Embodiment 3
The chemical formula of the present embodiment ceramic material are as follows: SrTiO3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3,
Wherein x indicates BaFe0.5Nb0.5O3Molar fraction, and x=0.15.
The preparation method of above-mentioned unleaded high energy storage density ceramic material, comprising the following steps:
(1) chemical formula SrTiO is pressed3By analytically pure SrCO3And TiO2After ingredient, using dehydrated alcohol as medium, pass through ball milling
12 hours be uniformly mixed, then at 100 DEG C dry, cross 120 meshes, briquetting, again through 1175 DEG C pre-burning 4 hours, obtain bulk
Then blocks of solid is smashed it through 120 meshes, obtains SrTiO by solid3Powder；
(2) chemical formula 0.85SrTiO is pressed3-0.15BaFe0.5Nb0.5O3Powder is prepared by following procedure: first by chemistry
Formula BaFe0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out ingredient and is uniformly mixed, then sieving, briquetting, then
Through 1225 DEG C pre-burning 3.5 hours, obtain blocks of solid, blocks of solid then smashed it through into 120 meshes, is obtained
BaFe0.5Nb0.5O3Powder.Finally according to chemical formula 0.85SrTiO3-0.15BaFe0.5Nb0.5O3The SrTiO that will be obtained3Powder and
BaFe0.5Nb0.5O3Powder carries out ingredient and is uniformly mixed, and 120 meshes are crossed after drying, obtain 0.85SrTiO3-
0.15BaFe0.5Nb0.5O3Powder；
(3) preparation of casting slurry: organic solvent (dehydrated alcohol and butanone) and emulsifier (three oleic acid are 1. weighed according to the ratio
Glyceride), and ball milling 5 hours are uniformly mixed；2. the powder that step (1) obtains is added into the slurry of step 1. after mixing
Body, binder (polyvinyl butyral) dispersing agent (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 5 is small
When be uniformly mixed, obtain SrTiO3Casting slurry.Wherein, the additional amount of dehydrated alcohol is the 53% of powder quality；Butanone adds
It is identical as powder quality to enter amount；The additional amount of olein is the 3.5% of powder quality；The addition of polyvinyl butyral
Amount is the 10% of powder quality；The additional amount of polyethylene glycol is the 3.5% of powder quality；The additional amount of dibutyl phthalate
It is the 3.5% of powder quality；
1. weighing organic solvent (dehydrated alcohol and butanone) and emulsifier (olein) according to the ratio, and ball milling 4 is small
When be uniformly mixed；2. powder, the binder (polyvinyl alcohol that step (2) obtain are added into the slurry of step 1. after mixing
Butyral) dispersing agent (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 4 hours are uniformly mixed, and obtain
0.85SrTiO3-0.15BaFe0.5Nb0.5O3Casting slurry.Wherein, the additional amount of dehydrated alcohol is the 53% of powder quality；Butanone
Additional amount it is identical as powder quality；The additional amount of olein is the 3.5% of powder quality；Polyvinyl butyral
Additional amount is the 10% of powder quality；The additional amount of polyethylene glycol is the 3.5% of powder quality；Dibutyl phthalate adds
Enter 3.5% that amount is powder quality；
(4) SrTiO that will be obtained in step (3)3Casting slurry and 0.85SrTiO3-0.15BaFe0.5Nb0.5O3Curtain coating slurry
Material carries out tape casting by the way of tape casting, obtains SrTiO3Casting films and 0.85SrTiO3-0.15BaFe0.5Nb0.5O3
Casting films.Then it is cut and is superimposed as required, and pressurizeed under the pressure of 150MPa, obtain SrTiO3/
(0.85SrTiO3-0.15BaFe0.5Nb0.5O3)/SrTiO3Ceramic green；
(5) SrTiO for obtaining step (4)3/(0.85SrTiO3-0.15BaFe0.5Nb0.5O3)/SrTiO3Ceramic green
In 500 DEG C of heat preservations progress dumping processing in 15 hours, 2.5 hours then are kept the temperature at 1360 DEG C and sinters porcelain into, is obtained with Sanming City
Control the unleaded low-dielectric loss and high energy storage density ceramics of structure；
(6) SrTiO that will be sintered3/(0.85SrTiO3-0.15BaFe0.5Nb0.5O3)/SrTiO3Two of ceramics sample
The clean simultaneously gold-plated electrode of surface polishing, then tests its ferroelectric properties under room temperature and the frequency of 10Hz, is illustrated in figure 3 this reality
Apply the ferroelectric hysteresis loop of a ceramic material.As seen from the figure, the ferroelectric hysteresis loop of the ceramics sample is more elongated, and breakdown strength is
302kV/cm. can be calculated by carrying out energy storage characteristic, and the rechargeable energy density of the unleaded energy-storing dielectric ceramic of the present embodiment is
2.44J/cm3, discharge energy density 1.67J/cm3, energy storage efficiency 68%.Fig. 6 is that energy storage ceramic manufactured in the present embodiment exists
Jie's frequency map measured at room temperature.As seen from the figure, SrTiO3/(0.85SrTiO3-0.15BaFe0.5Nb0.5O3)/SrTiO3Ceramics
Dielectric constant at 1 khz is 394, and corresponding dielectric loss value is 0.013.Fig. 9 is that energy storage ceramic manufactured in the present embodiment exists
Jie's temperature map measured under different frequency.It can be found that SrTiO from figure3/(0.85SrTiO3-0.15BaFe0.5Nb0.5O3)/
SrTiO3The dielectric loss of ceramics keeps smaller within the temperature range of -180-150 DEG C.Table 1 is the unleaded energy storage of the present embodiment
Dielectric, ferroelectricity and the energy storage characteristic of medium ceramic material.
Dielectric, ferroelectricity and the energy storage characteristic of the unleaded energy storage ceramic material of each embodiment of table 1
As shown in Table 1, for SrTiO of the invention3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3Energy storage pottery
Ceramic material, with BaFe0.5Nb0.5O3Content is continuously increased, and the breakdown field strength of sample is gradually reducing, residual polarization
Intensity constantly increases, but maximum polarization is continuously increased, and high energy storage density and storage can be obtained under certain proportion
It can efficiency.By above embodiments it can be found that the discharge energy density calculated the present invention is based on ferroelectric hysteresis loop 1.67~
1.90J/cm3Between, energy storage efficiency can achieve 86%.Meanwhile the breakdown potential field strength of energy storage ceramic dielectric material of the invention
Degree is in 300kV/cm or more.In addition, SrTiO of the invention3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3Energy storage
The dielectric constant of ceramic material at 1 khz is with BaFe0.5Nb0.5O3The increase of content and show the trend being gradually increased, but
It is corresponding dielectric loss then between 0.005~0.021, shows lower dielectric loss value.
Embodiment 4
The chemical formula of the present embodiment ceramic material are as follows: SrTiO3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3,
Wherein x indicates BaFe0.5Nb0.5O3Molar fraction, and x=0.07.
The preparation method of above-mentioned unleaded high energy storage density ceramic material, comprising the following steps:
(1) chemical formula SrTiO is pressed3By analytically pure SrCO3And TiO2After ingredient, using dehydrated alcohol as medium, pass through ball milling
12 hours be uniformly mixed, then at 100 DEG C dry, cross 120 meshes, briquetting, again through 1150 DEG C pre-burning 5 hours, obtain bulk
Then blocks of solid is smashed it through 120 meshes, obtains SrTiO by solid3Powder；
(2) chemical formula 0.93SrTiO is pressed3-0.07BaFe0.5Nb0.5O3Powder is prepared by following procedure: first by chemistry
Formula BaFe0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out ingredient and is uniformly mixed, then sieving, briquetting, then pass through
1200 DEG C pre-burning 4 hours, obtain blocks of solid, blocks of solid then smashed it through into 120 meshes, obtains BaFe0.5Nb0.5O3Powder
Body.Finally according to chemical formula 0.93SrTiO3-0.07BaFe0.5Nb0.5O3The SrTiO that will be obtained3Powder and BaFe0.5Nb0.5O3Powder
Body carries out ingredient and is uniformly mixed, and 120 meshes are crossed after drying, obtain 0.93SrTiO3-0.07BaFe0.5Nb0.5O3Powder；
(3) preparation of casting slurry:
1. weighing organic solvent (dehydrated alcohol and butanone) and emulsifier (olein) according to the ratio, and ball milling 4 is small
When be uniformly mixed；2. powder, the binder (polyvinyl alcohol that step (1) obtains are added into the slurry of step 1. after mixing
Butyral) dispersing agent (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 4 hours are uniformly mixed, and obtain
SrTiO3Casting slurry.Wherein, the additional amount of dehydrated alcohol is the 50% of powder quality；The additional amount of butanone and powder quality phase
Together；The additional amount of olein is the 3% of powder quality；The additional amount of polyvinyl butyral is powder quality
9.5%；The additional amount of polyethylene glycol is the 3% of powder quality；The additional amount of dibutyl phthalate is powder quality
3%；
1. weighing organic solvent (dehydrated alcohol and butanone) and emulsifier (olein) according to the ratio, and ball milling 4 is small
When be uniformly mixed；2. powder, the binder (polyvinyl alcohol that step (2) obtain are added into the slurry of step 1. after mixing
Butyral) dispersing agent (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 4 hours are uniformly mixed, and obtain (1-
x)SrTiO3-xBaFe0.5Nb0.5O3Casting slurry.Wherein, the additional amount of dehydrated alcohol is the 50% of powder quality；Butanone adds
It is identical as powder quality to enter amount；The additional amount of olein is the 3% of powder quality；The additional amount of polyvinyl butyral
It is the 9.5% of powder quality；The additional amount of polyethylene glycol is the 3% of powder quality；The additional amount of dibutyl phthalate is
The 3% of powder quality；
(4) SrTiO that will be obtained in step (3)3Casting slurry and 0.93SrTiO3-0.07BaFe0.5Nb0.5O3Curtain coating slurry
Material carries out tape casting by the way of tape casting, obtains SrTiO3Casting films and 0.93SrTiO3-0.07BaFe0.5Nb0.5O3
Casting films.Then it is cut and is superimposed as required, and pressurizeed under the pressure of 150MPa, obtain SrTiO3/
(0.93SrTiO3-0.07BaFe0.5Nb0.5O3)/SrTiO3Ceramic green；
(5) SrTiO for obtaining step (4)3/(0.93SrTiO3-0.07BaFe0.5Nb0.5O3)/SrTiO3Ceramic green
In 500 DEG C of heat preservations progress dumping processing in 15 hours, 3 hours then are kept the temperature at 1350 DEG C and sinters porcelain into, is obtained with sandwich
Unleaded low-dielectric loss and the high energy storage density ceramics of structure；
By example given above, the contents of the present invention can be further apparent from, but it is not to this hair
Bright restriction.
Claims (10)
1. a kind of preparation method of unleaded low-dielectric loss and high energy storage density ceramics with sandwich structure, feature exist
In, comprising the following steps:
(1) preparation of casting slurry: organic solvent and emulsifier are uniformly mixed, SrTiO is then added3Powder, divides binder
Powder and plasticizer, and be uniformly mixed, obtain SrTiO3Casting slurry；
Organic solvent and emulsifier are uniformly mixed, (1-x) SrTiO is then added3-xBaFe0.5Nb0.5O3Powder, divides binder
Powder and plasticizer, and be uniformly mixed, obtain (1-x) SrTiO3-xBaFe0.5Nb0.5O3Casting slurry；Wherein, x is indicated
BaFe0.5Nb0.5O3Molar fraction, and 0.05≤x≤0.15；
(2) preparation of green compact: the SrTiO that will be obtained in step (2)3Casting slurry and (1-x) SrTiO3-xBaFe0.5Nb0.5O3Stream
Prolong slurry the mode of tape casting is respectively adopted and carry out tape casting, obtains SrTiO3Casting films and (1-x) SrTiO3-
xBaFe0.5Nb0.5O3Casting films；Then it is cut and is superimposed, and pressurizeed under the pressure of 150~200MPa, had
There is the SrTiO of sandwich structure3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3Ceramic green；
(3) the ceramic green sample by step (2) preparation carries out dumping processing, then sinters porcelain into, obtains with sandwich knot
The SrTiO of structure3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3Ceramics.
2. the preparation of the unleaded low-dielectric loss and high energy storage density ceramics according to claim 1 with sandwich structure
Method, which is characterized in that SrTiO3Powder is prepared by following procedure: pressing chemical formula SrTiO3By analytically pure SrCO3And TiO2
Carry out ingredient simultaneously be uniformly mixed, then sieving, briquetting, then through 1150~1200 DEG C pre-burning 3~5 hours, obtain blocks of solid, so
Blocks of solid is smashed it through into 120 meshes afterwards, obtains SrTiO3Powder.
3. the preparation of the unleaded low-dielectric loss and high energy storage density ceramics according to claim 1 with sandwich structure
Method, which is characterized in that (1-x) SrTiO3-xBaFe0.5Nb0.5O3Powder is prepared by following procedure: pressing chemical formula first
BaFe0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out ingredient and is uniformly mixed, then sieving, briquetting, then pass through
1200~1250 DEG C pre-burning 3~4 hours, obtain blocks of solid, blocks of solid then smashed it through into 120 meshes, is obtained
BaFe0.5Nb0.5O3Powder；Finally according to chemical formula (1-x) SrTiO3-xBaFe0.5Nb0.5O3The SrTiO that will be obtained3Powder and
BaFe0.5Nb0.5O3Powder carries out ingredient and is uniformly mixed, and 120 meshes are crossed after drying, obtain (1-x) SrTiO3-
xBaFe0.5Nb0.5O3Powder.
4. the unleaded low-dielectric loss and high energy storage density ceramics according to claim 2 or 3 with sandwich structure
Preparation method, which is characterized in that uniformly mixed detailed process is: using dehydrated alcohol as medium, being carried out by ball milling,
In, Ball-milling Time is 12~16 hours, and is dried at 100 DEG C after ball milling.
5. the preparation of the unleaded low-dielectric loss and high energy storage density ceramics according to claim 1 with sandwich structure
Method, which is characterized in that organic solvent is the mixture of dehydrated alcohol and butanone；Emulsifier is olein；Binder
For polyvinyl butyral；Dispersing agent is polyethylene glycol；Plasticizer is dibutyl phthalate.
6. the preparation of the unleaded low-dielectric loss and high energy storage density ceramics according to claim 5 with sandwich structure
Method, which is characterized in that the additional amount of dehydrated alcohol is SrTiO3Powder or (1-x) SrTiO3-xBaFe0.5Nb0.5O3Powder matter
The 50~55% of amount；The additional amount and SrTiO of butanone3Powder or (1-x) SrTiO3-xBaFe0.5Nb0.5O3Powder quality is identical；
The additional amount of olein is SrTiO3Powder or (1-x) SrTiO3-xBaFe0.5Nb0.5O3The 3~4% of powder quality；It is poly-
The additional amount of vinyl butyral is SrTiO3Powder or (1-x) SrTiO3-xBaFe0.5Nb0.5O3The 9.5 of powder quality~
10.5%；The additional amount of polyethylene glycol is SrTiO3Powder or (1-x) SrTiO3-xBaFe0.5Nb0.5O3The 3 of powder quality~
4%；The additional amount of dibutyl phthalate is the 3~4% of powder quality.
7. the preparation of the unleaded low-dielectric loss and high energy storage density ceramics according to claim 1 with sandwich structure
Method, which is characterized in that dumping processing detailed process is: 10~15 hours are kept the temperature at 500~600 DEG C.
8. the preparation of the unleaded low-dielectric loss and high energy storage density ceramics according to claim 1 with sandwich structure
Method, which is characterized in that the temperature of sintering is 1350~1380 DEG C, and the time is 2~3 hours.
9. a kind of unleaded low dielectric damage with sandwich structure based on the preparation of any one of claim 1-8 the method
Consumption and high energy storage density ceramics, which is characterized in that its chemical formula are as follows: SrTiO3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/
SrTiO3, wherein x is BaFe0.5Nb0.5O3Molar fraction, and 0.05≤x≤0.15.
10. a kind of unleaded low-dielectric loss with sandwich structure as claimed in claim 9 and high energy storage density ceramics,
It is characterized in that, for the electric field strength of the ceramic material in 300kV/cm or more, discharge energy density can reach 1.90J/cm3,
Energy storage efficiency can reach 86%.
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