CN108623301A - 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
- Publication number
- CN108623301A CN108623301A CN201810609045.7A CN201810609045A CN108623301A CN 108623301 A CN108623301 A CN 108623301A CN 201810609045 A CN201810609045 A CN 201810609045A CN 108623301 A CN108623301 A CN 108623301A
- Authority
- CN
- China
- Prior art keywords
- srtio
- powder
- energy storage
- xbafe
- dielectric loss
- 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
- C04B35/47—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 strontium titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- 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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3215—Barium 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
- C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6025—Tape casting, e.g. with a doctor blade
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, dispersant 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 two kinds of casting slurries are respectively adopted to tape casting carries out tape casting, obtains two kinds of casting films；Then superposition, pressurization, dumping, sintering.The ceramic material preparation process of the present 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 reach 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 technology
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 vehicle, 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 or polarization intensity is smaller there is breakdown strength, 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 smaller 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, SrTiO is widened3And 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.
Invention content
It is an object of the invention to overcome defect existing in the prior art, provide a kind of unleaded with 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 reach 1.90J/cm3, energy storage efficiency can reach 86%, and electric field strength exists
300kV/cm or more, and the tape casting technology maturation used in 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, dispersant 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, dispersant 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 for preparing step (2) carries out dumping processing, then sinters porcelain into, obtains with Sanming City
Control the SrTiO of structure3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3Ceramics.
The present invention, which further improves, to be, SrTiO3Powder is prepared by following procedure：By chemical formula SrTiO3It will analysis
Pure SrCO3And TiO2It carries out dispensing to be simultaneously uniformly mixed, then sieving, briquetting, then through 1150~1200 DEG C of pre-burnings 3~5 hours,
Blocks of solid is obtained, blocks of solid is then smashed it through into 120 mesh sieve, obtains SrTiO3Powder.
The present invention, which further improves, to be, (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 dispensing and is uniformly mixed, then mistake
Sieve, briquetting, then through 1200~1250 DEG C of pre-burnings 3~4 hours, obtain blocks of solid, blocks of solid is 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 dispensing and is uniformly mixed, and 120 mesh sieve is crossed after drying, obtains (1-x) SrTiO3-
xBaFe0.5Nb0.5O3Powder.
The present invention, which further improves, to be, uniformly mixed detailed process is：Using absolute ethyl alcohol as medium, pass through ball milling
It carries out, wherein Ball-milling Time is 12~16 hours, and is dried at 100 DEG C after ball milling.
The present invention, which further improves, to be, organic solvent is the mixture of absolute ethyl alcohol and butanone；Emulsifier is three oil
Acid glyceride；Binder is polyvinyl butyral；Dispersant is polyethylene glycol；Plasticizer is dibutyl phthalate.
The present invention, which further improves, to be, the addition of absolute ethyl alcohol is SrTiO3Powder or (1-x) SrTiO3-
xBaFe0.5Nb0.5O3The 50~55% of powder quality；The addition and SrTiO of butanone3Powder or (1-x) SrTiO3-
xBaFe0.5Nb0.5O3Powder quality is identical；The addition of olein is SrTiO3Powder or (1-x) SrTiO3-
xBaFe0.5Nb0.5O3The 3~4% of powder quality；The addition of polyvinyl butyral is SrTiO3Powder or (1-x) SrTiO3-
xBaFe0.5Nb0.5O3The 9.5~10.5% of powder quality；The addition of polyethylene glycol is SrTiO3Powder or (1-x) SrTiO3-
xBaFe0.5Nb0.5O3The 3~4% of powder quality；The addition of dibutyl phthalate is the 3~4% of powder quality.
The present invention, which further improves, to be, dumping processing detailed process is：10~15 hours are kept the temperature at 500~600 DEG C.
The present invention, which further improves, to be, the temperature of sintering is 1350~1380 DEG C, and 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：SrTiO3/
((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3, wherein x is BaFe0.5Nb0.5O3Molar fraction, and 0.05≤x≤
0.15。
The present invention, which further improves, to be, 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 device have the advantages that：The present invention is respectively by SrTiO3Powder and (1-x)
SrTiO3-xBaFe0.5Nb0.5O3Powder carries out tape casting and prepares the pottery with sandwich structure then by structure design
Then ceramic material carries out dumping processing to the ceramic green material prepared and is sintered, you can obtains having sandwich structure
Unleaded low-dielectric loss and high energy storage density ceramics.The unleaded low-dielectric loss with sandwich structure of the present 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 ripe, is suitble to industrialized production.
Further, the organic solvent in casting slurry of the invention is made of absolute ethyl alcohol and butanone, absolute ethyl alcohol and
The mass ratio of butanone is 0.5~0.55, since the evaporation rate of absolute ethyl alcohol and butanone is variant, selects the anhydrous of special ratios
Ethyl alcohol and butanone can ensure also there is residual while solvent volatilization, and surface caused by since 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, drying that can be rapidly and efficiently,
Shorten drying time, is conducive to industrialized mass production.
The breakdown electric field of the unleaded low-dielectric loss and high energy storage density ceramics with sandwich structure of the present invention is high, is situated between
Electrical loss is low, can effectively improve energy storage characteristic, and discharge energy density can reach 1.90J/cm3, energy storage efficiency can be with
Reach 86%, electric field strength is in 300kV/cm or more.
Description of the drawings
Fig. 1 is that unleaded low-dielectric loss with sandwich structure prepared by embodiment 1 and high energy storage density ceramics exist
Ferroelectric hysteresis loop figure under 10Hz test frequencies；
Fig. 2 is that unleaded low-dielectric loss with sandwich structure prepared by embodiment 2 and high energy storage density ceramics exist
Ferroelectric hysteresis loop figure under 10Hz test frequencies；
Fig. 3 is that unleaded low-dielectric loss with sandwich structure prepared by embodiment 3 and high energy storage density ceramics exist
Ferroelectric hysteresis loop figure under 10Hz test frequencies；
Fig. 4 is that unleaded low-dielectric loss with sandwich structure prepared by embodiment 1 and high energy storage density ceramics exist
Jie's frequency collection of illustrative plates under different test frequencies；
Fig. 5 is that unleaded low-dielectric loss with sandwich structure prepared by embodiment 2 and high energy storage density ceramics exist
Frequency collection of illustrative plates under different test frequencies；
Fig. 6 is that unleaded low-dielectric loss with sandwich structure prepared by embodiment 3 and high energy storage density ceramics exist
Frequency collection of illustrative plates under different test frequencies；
Fig. 7 is that unleaded low-dielectric loss with sandwich structure prepared by embodiment 1 and high energy storage density ceramics exist
Jie's temperature collection of illustrative plates under different test frequencies；
Fig. 8 is that unleaded low-dielectric loss with sandwich structure prepared by embodiment 2 and high energy storage density ceramics exist
Jie's temperature collection of illustrative plates under different test frequencies；
Fig. 9 is that unleaded low-dielectric loss with sandwich structure prepared by embodiment 3 and high energy storage density ceramics exist
Jie's temperature collection of illustrative plates under different test frequencies.
Specific implementation mode
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：SrTiO3/
((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3, wherein x expressions BaFe0.5Nb0.5O3Molar fraction, and 0.05≤x≤
0.15。
The preparation method of the unleaded low-dielectric loss and high energy storage density ceramics with sandwich structure of the present invention, including
Following steps：
(1) chemical formula SrTiO is pressed3By analytically pure SrCO3And TiO2After dispensing, using absolute ethyl alcohol as medium, pass through ball milling
It is uniformly mixed within 12~16 hours, is then dried at 100 DEG C, crosses 120 mesh sieves, 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 mesh sieve, obtains SrTiO3Powder；
(2) chemical formula (1-x) SrTiO is pressed3-xBaFe0.5Nb0.5O3Powder is prepared by following procedure：Chemical formula is pressed first
BaFe0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out dispensing and is uniformly mixed, then sieving, briquetting, then pass through
1200~1250 DEG C of pre-burnings 3~4 hours, obtain blocks of solid, and blocks of solid is then smashed it through 120 mesh sieve, 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 dispensing and is uniformly mixed, and 120 mesh sieve is crossed after drying, obtains (1-x) SrTiO3-
xBaFe0.5Nb0.5O3Powder；
(3) preparation of casting slurry：1. weighing organic solvent (absolute ethyl alcohol and butanone) and emulsifier (three oleic acid according to the ratio
Glyceride), and ball milling is uniformly mixed for 4~6 hours；2. being added what step (1) obtained into the slurry of step 1. after mixing
Powder, binder (polyvinyl butyral) dispersant (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 4
It is uniformly mixed within~6 hours, obtains SrTiO3Casting slurry；Wherein, the addition of absolute ethyl alcohol is the 50~55% of powder quality；
The addition of butanone is identical as powder quality；The addition of olein is the 3~4% of powder quality；Polyvinyl alcohol contracts
The addition of butyraldehyde is the 9.5~10.5% of powder quality；The addition of polyethylene glycol is the 3~4% of powder quality；Adjacent benzene two
The addition 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, dispersant 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 addition of absolute ethyl alcohol be powder quality 50~
55%；The addition of butanone is identical as powder quality；The addition of olein is the 3~4% of powder quality；Polyethylene
The addition of butyral is the 9.5~10.5% of powder quality；The addition of polyethylene glycol is the 3~4% of powder quality；It is adjacent
The addition 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, size progress that can be according to actual needs is cut,
Superposition refers to by SrTiO3Casting films and (1-x) SrTiO3-xBaFe0.5Nb0.5O3Casting films are superimposed, 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 carry out dumping processing in 10~15 hours, then keep the temperature 2~3 hours at 1350~1380 DEG C and sinter 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 the calculation formula of energy storage efficiency (η) be：
Wherein PmaxIndicate maximum polarization, PrIndicate that remanent polarization, E indicate that electric field strength, P indicate that polarization is strong
Degree.
Step (1) is 12~16 hours with Ball-milling Time in step (3).
The embodiment being given by the following can further be apparent from present disclosure, but it is not to this hair
Bright restriction.
Embodiment 1
The chemical formula of the present embodiment ceramic material is：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, includes the following steps：
(1) chemical formula SrTiO is pressed3By analytically pure SrCO3And TiO2After dispensing, using absolute ethyl alcohol as medium, pass through ball milling
It is uniformly mixed within 12 hours, is then dried at 100 DEG C, crosses 120 mesh sieves, briquetting, again through 1150 DEG C of pre-burnings 5 hours, obtain bulk
Then blocks of solid is smashed it through 120 mesh sieve, obtains SrTiO by solid3Powder；
(2) chemical formula 0.95SrTiO is pressed3-0.05BaFe0.5Nb0.5O3Powder is prepared by following procedure：Chemistry is pressed first
Formula BaFe0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out dispensing and is uniformly mixed, then sieving, briquetting, then pass through
1200 DEG C of pre-burnings 4 hours, obtain blocks of solid, and blocks of solid is then smashed it through 120 mesh sieve, 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 dispensing and is uniformly mixed, and 120 mesh sieve is crossed after drying, obtains 0.95SrTiO3-0.05BaFe0.5Nb0.5O3Powder；
(3) preparation of casting slurry：1. weighing organic solvent (absolute ethyl alcohol and butanone) and emulsifier (three oleic acid according to the ratio
Glyceride), and ball milling is uniformly mixed for 4 hours；2. the powder that step (1) obtains is added into the slurry of step 1. after mixing
Body, binder (polyvinyl butyral) dispersant (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 4 is small
When be uniformly mixed, obtain SrTiO3Casting slurry.Wherein, the addition of absolute ethyl alcohol is the 50% of powder quality；Butanone adds
It is identical as powder quality to enter amount；The addition of olein is the 3% of powder quality；The addition of polyvinyl butyral
It is the 9.5% of powder quality；The addition of polyethylene glycol is the 3% of powder quality；The addition of dibutyl phthalate is
The 3% of powder quality；
1. weighing organic solvent (absolute ethyl 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) obtains are added into the slurry of step 1. after mixing
Butyral) dispersant (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling is uniformly mixed for 4 hours, is obtained
0.95SrTiO3-0.05BaFe0.5Nb0.5O3Casting slurry.Wherein, the addition of absolute ethyl alcohol is the 50% of powder quality；Butanone
Addition it is identical as powder quality；The addition of olein is the 3% of powder quality；Polyvinyl butyral adds
Enter 9.5% that amount is powder quality；The addition 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
15 hours are kept the temperature at 500 DEG C and carries out dumping processing, are then kept the temperature 3 hours at 1350 DEG C and are sintered porcelain into, obtain 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 collection of illustrative plates 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 collection of illustrative plates 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 is：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, includes the following steps：
(1) chemical formula SrTiO is pressed3By analytically pure SrCO3And TiO2After dispensing, using absolute ethyl alcohol as medium, pass through ball milling
It is uniformly mixed within 12 hours, is then dried at 100 DEG C, crosses 120 mesh sieves, briquetting, again through 1200 DEG C of pre-burnings 3 hours, obtain bulk
Then blocks of solid is smashed it through 120 mesh sieve, obtains SrTiO by solid3Powder；
(2) chemical formula 0.90SrTiO is pressed3-0.10BaFe0.5Nb0.5O3Powder is prepared by following procedure：Chemistry is pressed first
Formula BaFe0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out dispensing and is uniformly mixed, then sieving, briquetting, then pass through
1250 DEG C of pre-burnings 3 hours, obtain blocks of solid, and blocks of solid is then smashed it through 120 mesh sieve, 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 dispensing and is uniformly mixed, and 120 mesh sieve is crossed after drying, obtains 0.90SrTiO3-0.10BaFe0.5Nb0.5O3Powder；
(3) preparation of casting slurry：1. weighing organic solvent (absolute ethyl alcohol and butanone) and emulsifier (three oleic acid according to the ratio
Glyceride), and ball milling is uniformly mixed for 6 hours；2. the powder that step (1) obtains is added into the slurry of step 1. after mixing
Body, binder (polyvinyl butyral) dispersant (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 6 is small
When be uniformly mixed, obtain SrTiO3Casting slurry.Wherein, the addition of absolute ethyl alcohol is the 56% of powder quality；Butanone adds
It is identical as powder quality to enter amount；The addition of olein is the 4% of powder quality；The addition of polyvinyl butyral
It is the 10.5% of powder quality；The addition of polyethylene glycol is the 4% of powder quality；The addition of dibutyl phthalate is
The 4% of powder quality；
1. weighing organic solvent (absolute ethyl 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) obtains are added into the slurry of step 1. after mixing
Butyral) dispersant (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling is uniformly mixed for 4 hours, is obtained
0.90SrTiO3-0.10BaFe0.5Nb0.5O3Casting slurry.Wherein, the addition of absolute ethyl alcohol is the 56% of powder quality；Butanone
Addition it is identical as powder quality；The addition of olein is the 4% of powder quality；Polyvinyl butyral adds
Enter 10.5% that amount is powder quality；The addition 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
10 hours are kept the temperature at 600 DEG C and carries out dumping processing, are then kept the temperature 2 hours at 1380 DEG C and are sintered porcelain into, obtain 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 collection of illustrative plates 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 collection of illustrative plates 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 is：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, includes the following steps：
(1) chemical formula SrTiO is pressed3By analytically pure SrCO3And TiO2After dispensing, using absolute ethyl alcohol as medium, pass through ball milling
It is uniformly mixed within 12 hours, is then dried at 100 DEG C, crosses 120 mesh sieves, briquetting, again through 1175 DEG C of pre-burnings 4 hours, obtain bulk
Then blocks of solid is smashed it through 120 mesh sieve, obtains SrTiO by solid3Powder；
(2) chemical formula 0.85SrTiO is pressed3-0.15BaFe0.5Nb0.5O3Powder is prepared by following procedure：Chemistry is pressed first
Formula BaFe0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out dispensing and is uniformly mixed, then sieving, briquetting, then
Through 1225 DEG C of pre-burnings 3.5 hours, blocks of solid is obtained, blocks of solid is then smashed it through into 120 mesh sieve, 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 dispensing and is uniformly mixed, and 120 mesh sieve is crossed after drying, obtains 0.85SrTiO3-
0.15BaFe0.5Nb0.5O3Powder；
(3) preparation of casting slurry：1. weighing organic solvent (absolute ethyl alcohol and butanone) and emulsifier (three oleic acid according to the ratio
Glyceride), and ball milling is uniformly mixed for 5 hours；2. the powder that step (1) obtains is added into the slurry of step 1. after mixing
Body, binder (polyvinyl butyral) dispersant (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling 5 is small
When be uniformly mixed, obtain SrTiO3Casting slurry.Wherein, the addition of absolute ethyl alcohol is the 53% of powder quality；Butanone adds
It is identical as powder quality to enter amount；The addition of olein is the 3.5% of powder quality；The addition of polyvinyl butyral
Amount is the 10% of powder quality；The addition of polyethylene glycol is the 3.5% of powder quality；The addition of dibutyl phthalate
It is the 3.5% of powder quality；
1. weighing organic solvent (absolute ethyl 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) obtains are added into the slurry of step 1. after mixing
Butyral) dispersant (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling is uniformly mixed for 4 hours, is obtained
0.85SrTiO3-0.15BaFe0.5Nb0.5O3Casting slurry.Wherein, the addition of absolute ethyl alcohol is the 53% of powder quality；Butanone
Addition it is identical as powder quality；The addition of olein is the 3.5% of powder quality；Polyvinyl butyral
Addition is the 10% of powder quality；The addition 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
15 hours are kept the temperature at 500 DEG C and carries out dumping processing, are then kept the temperature 2.5 hours at 1360 DEG C and are sintered porcelain into, obtain 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 collection of illustrative plates 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 collection of illustrative plates 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 1 each embodiment of table
As shown in Table 1, for the SrTiO of the present invention3/((1-x)SrTiO3-xBaFe0.5Nb0.5O3)/SrTiO3Energy storage is made 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 proportioning
It can efficiency.By above example 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 reach 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, the SrTiO of the present 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 gradual increased trend, 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 is：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, includes the following steps：
(1) chemical formula SrTiO is pressed3By analytically pure SrCO3And TiO2After dispensing, using absolute ethyl alcohol as medium, pass through ball milling
It is uniformly mixed within 12 hours, is then dried at 100 DEG C, crosses 120 mesh sieves, briquetting, again through 1150 DEG C of pre-burnings 5 hours, obtain bulk
Then blocks of solid is smashed it through 120 mesh sieve, obtains SrTiO by solid3Powder；
(2) chemical formula 0.93SrTiO is pressed3-0.07BaFe0.5Nb0.5O3Powder is prepared by following procedure：Chemistry is pressed first
Formula BaFe0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out dispensing and is uniformly mixed, then sieving, briquetting, then pass through
1200 DEG C of pre-burnings 4 hours, obtain blocks of solid, and blocks of solid is then smashed it through 120 mesh sieve, 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 dispensing and is uniformly mixed, and 120 mesh sieve is crossed after drying, obtains 0.93SrTiO3-0.07BaFe0.5Nb0.5O3Powder；
(3) preparation of casting slurry：
1. weighing organic solvent (absolute ethyl 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) dispersant (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling is uniformly mixed for 4 hours, is obtained
SrTiO3Casting slurry.Wherein, the addition of absolute ethyl alcohol is the 50% of powder quality；The addition of butanone and powder quality phase
Together；The addition of olein is the 3% of powder quality；The addition of polyvinyl butyral is powder quality
9.5%；The addition of polyethylene glycol is the 3% of powder quality；The addition of dibutyl phthalate is powder quality
3%；
1. weighing organic solvent (absolute ethyl 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) obtains are added into the slurry of step 1. after mixing
Butyral) dispersant (polyethylene glycol) and plasticizer (dibutyl phthalate), and ball milling is uniformly mixed for 4 hours, obtains (1-
x)SrTiO3-xBaFe0.5Nb0.5O3Casting slurry.Wherein, the addition of absolute ethyl alcohol is the 50% of powder quality；Butanone adds
It is identical as powder quality to enter amount；The addition of olein is the 3% of powder quality；The addition of polyvinyl butyral
It is the 9.5% of powder quality；The addition of polyethylene glycol is the 3% of powder quality；The addition 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
15 hours are kept the temperature at 500 DEG C and carries out dumping processing, are then kept the temperature 3 hours at 1350 DEG C and are sintered porcelain into, obtain with sandwich
Unleaded low-dielectric loss and the high energy storage density ceramics of structure；
By example given above, it can be further apparent from present disclosure, 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 including 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 for preparing step (2) 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 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：By chemical formula SrTiO3By analytically pure SrCO3And TiO2
It carries out dispensing to be simultaneously uniformly mixed, then sieving, briquetting, then through 1150~1200 DEG C of pre-burnings 3~5 hours, obtains blocks of solid, so
Blocks of solid is smashed it through into 120 mesh sieve afterwards, obtains SrTiO3Powder.
3. the preparation of 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：Chemical formula is pressed first
BaFe0.5Nb0.5O3By analytically pure BaCO3, Fe2O3And Nb2O5It carries out dispensing and is uniformly mixed, then sieving, briquetting, then pass through
1200~1250 DEG C of pre-burnings 3~4 hours, obtain blocks of solid, and blocks of solid is then smashed it through 120 mesh sieve, 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 dispensing and is uniformly mixed, and 120 mesh sieve is crossed after drying, obtains (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 absolute ethyl alcohol as medium, 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 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 absolute ethyl alcohol and butanone；Emulsifier is olein；Binder
For polyvinyl butyral；Dispersant is polyethylene glycol；Plasticizer is dibutyl phthalate.
6. the preparation of unleaded low-dielectric loss and high energy storage density ceramics according to claim 5 with sandwich structure
Method, which is characterized in that the addition of absolute ethyl alcohol is SrTiO3Powder or (1-x) SrTiO3-xBaFe0.5Nb0.5O3Powder matter
The 50~55% of amount；The addition and SrTiO of butanone3Powder or (1-x) SrTiO3-xBaFe0.5Nb0.5O3Powder quality is identical；
The addition of olein is SrTiO3Powder or (1-x) SrTiO3-xBaFe0.5Nb0.5O3The 3~4% of powder quality；It is poly-
The addition of vinyl butyral is SrTiO3Powder or (1-x) SrTiO3-xBaFe0.5Nb0.5O3The 9.5 of powder quality~
10.5%；The addition of polyethylene glycol is SrTiO3Powder or (1-x) SrTiO3-xBaFe0.5Nb0.5O3The 3 of powder quality~
4%；The addition of dibutyl phthalate is the 3~4% of powder quality.
7. the preparation of unleaded low-dielectric loss and high energy storage density ceramics according to claim 1 with sandwich structure
Method, which is characterized in that dumping, which handles detailed process, is：10~15 hours are kept the temperature at 500~600 DEG C.
8. the preparation of 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 prepared based on any one of claim 1-8 the methods
Consumption and high energy storage density ceramics, which is characterized in that its chemical formula is：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 and high energy storage density ceramics as claimed in claim 9 with sandwich structure,
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%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810609045.7A CN108623301B (en) | 2018-06-13 | 2018-06-13 | A kind of unleaded low-dielectric loss and high energy storage density ceramics and preparation method thereof with sandwich structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810609045.7A CN108623301B (en) | 2018-06-13 | 2018-06-13 | A kind of unleaded low-dielectric loss and high energy storage density ceramics and preparation method thereof with sandwich structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108623301A true CN108623301A (en) | 2018-10-09 |
| CN108623301B CN108623301B (en) | 2019-10-11 |
Family
ID=63691395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810609045.7A Active CN108623301B (en) | 2018-06-13 | 2018-06-13 | A kind of unleaded low-dielectric loss and high energy storage density ceramics and preparation method thereof with sandwich structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108623301B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734440A (en) * | 2019-03-11 | 2019-05-10 | 西南科技大学 | SrTiO with heterogeneous layer structure3Base energy storage medium ceramic and preparation method thereof |
| CN111205087A (en) * | 2020-01-14 | 2020-05-29 | 同济大学 | Bismuth-based sandwich-structured high-energy-density ceramic and preparation method thereof |
| CN111302789A (en) * | 2020-03-17 | 2020-06-19 | 华南理工大学 | Pulse energy storage dielectric material with sandwich structure and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100008019A1 (en) * | 2008-07-08 | 2010-01-14 | Ian Burn Consulting Inc. | Sintered Dielectric Ceramic, Composition for Making, and Use Thereof In Multilayer Capacitor And Energy Storage Device |
| CN104044318A (en) * | 2013-03-11 | 2014-09-17 | 清华大学 | Laminated-structure polymer-based dielectric energy-storage composite material and preparation method thereof |
| CN104557030A (en) * | 2015-01-14 | 2015-04-29 | 陕西科技大学 | SrTiO3-based high-frequency layered magnetoelectric composite material and preparation method thereof |
| CN105645954A (en) * | 2015-12-29 | 2016-06-08 | 陕西科技大学 | Ba3Co0.8Zn1.2Fe24O4l/SrTiO3 lamellar magneto-electric composite material and preparation method of Ba3Co0.8Zn1.2Fe24O4l/SrTiO3 lamellar magneto-electric composite material |
| CN105924153A (en) * | 2016-04-15 | 2016-09-07 | 电子科技大学 | Multilayer film with sandwich structure and preparation method thereof |
| CN106854453A (en) * | 2016-12-15 | 2017-06-16 | 陕西科技大学 | A kind of preparation method of lamellar composite absorbing material |
| CN107473732A (en) * | 2017-08-31 | 2017-12-15 | 陕西科技大学 | A kind of strontium titanate base high energy storage density and low-dielectric-loss ceramic material and preparation method thereof |
-
2018
- 2018-06-13 CN CN201810609045.7A patent/CN108623301B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100008019A1 (en) * | 2008-07-08 | 2010-01-14 | Ian Burn Consulting Inc. | Sintered Dielectric Ceramic, Composition for Making, and Use Thereof In Multilayer Capacitor And Energy Storage Device |
| CN104044318A (en) * | 2013-03-11 | 2014-09-17 | 清华大学 | Laminated-structure polymer-based dielectric energy-storage composite material and preparation method thereof |
| CN104557030A (en) * | 2015-01-14 | 2015-04-29 | 陕西科技大学 | SrTiO3-based high-frequency layered magnetoelectric composite material and preparation method thereof |
| CN105645954A (en) * | 2015-12-29 | 2016-06-08 | 陕西科技大学 | Ba3Co0.8Zn1.2Fe24O4l/SrTiO3 lamellar magneto-electric composite material and preparation method of Ba3Co0.8Zn1.2Fe24O4l/SrTiO3 lamellar magneto-electric composite material |
| CN105924153A (en) * | 2016-04-15 | 2016-09-07 | 电子科技大学 | Multilayer film with sandwich structure and preparation method thereof |
| CN106854453A (en) * | 2016-12-15 | 2017-06-16 | 陕西科技大学 | A kind of preparation method of lamellar composite absorbing material |
| CN107473732A (en) * | 2017-08-31 | 2017-12-15 | 陕西科技大学 | A kind of strontium titanate base high energy storage density and low-dielectric-loss ceramic material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734440A (en) * | 2019-03-11 | 2019-05-10 | 西南科技大学 | SrTiO with heterogeneous layer structure3Base energy storage medium ceramic and preparation method thereof |
| CN109734440B (en) * | 2019-03-11 | 2021-08-24 | 西南科技大学 | SrTiO with heterogeneous layered structure3Base energy storage medium ceramic and preparation method thereof |
| CN111205087A (en) * | 2020-01-14 | 2020-05-29 | 同济大学 | Bismuth-based sandwich-structured high-energy-density ceramic and preparation method thereof |
| CN111302789A (en) * | 2020-03-17 | 2020-06-19 | 华南理工大学 | Pulse energy storage dielectric material with sandwich structure and preparation method and application thereof |
| CN111302789B (en) * | 2020-03-17 | 2021-01-19 | 华南理工大学 | Pulse energy storage dielectric material with sandwich structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108623301B (en) | 2019-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108623301B (en) | A kind of unleaded low-dielectric loss and high energy storage density ceramics and preparation method thereof with sandwich structure | |
| CN109574656A (en) | A kind of high energy storage bismuth-sodium titanate-strontium titanate base dielectric material and preparation method thereof | |
| CN104446468B (en) | A kind of X9R type ceramic capacitor dielectric material and preparation method thereof | |
| CN107602115B (en) | Lead-free high-energy-storage-density wide-temperature-range stable ceramic material and preparation method thereof | |
| CN106699170A (en) | Strontium titanate-based lead-free high-energy storage density and high-energy storage efficiency ceramic material and preparation method thereof | |
| CN109133915A (en) | A kind of high energy storage barium phthalate base dielectric material and preparation method thereof | |
| CN106915960A (en) | A kind of unleaded high energy storage density and energy storage efficiency ceramic material and preparation method thereof | |
| CN107140974A (en) | A kind of unleaded high energy storage density ST NBT ceramic materials of microwave sintering and preparation method thereof | |
| CN108751982A (en) | A kind of unleaded high energy storage density ceramic material and preparation method thereof | |
| CN107253857A (en) | A kind of unleaded high energy storage density ceramic material and preparation method thereof | |
| CN104692799A (en) | High-energy-density zirconium titanium and lead stannate antiferroelectric ceramic and preparation method thereof | |
| CN104183342A (en) | New application and preparation method of copper calcium titanate (CaCu3Ti4O12) (CCTO) | |
| CN107473732B (en) | Strontium titanate-based ceramic material with high energy storage density and low dielectric loss and preparation method thereof | |
| CN106747410A (en) | The bias titania-based composite dielectric ceramic material of stable type giant dielectric low-loss | |
| CN106587997A (en) | SrTiO<3>-based lead-free high-energy-density ceramic material and preparation method thereof | |
| CN113213929A (en) | Potassium sodium niobate based ferroelectric ceramic material with high energy storage efficiency and density and preparation method thereof | |
| CN109650875B (en) | Giant dielectric calcium copper titanate composite ceramic material and preparation method and application thereof | |
| CN107445616A (en) | A kind of unleaded high pressure resistant energy storage ceramic material of strontium titanate base and preparation method thereof | |
| CN108774060A (en) | A kind of bismuth-sodium titanate based high energy storage density ceramic material and preparation method thereof | |
| CN107445611A (en) | A kind of unleaded low-loss high energy storage density ceramic material and preparation method thereof | |
| CN104098330B (en) | Post growth annealing is adopted to prepare the method for high-performance barium strontium titanate pyroelectric ceramics | |
| CN106915964A (en) | A kind of unleaded high energy storage density ceramic material 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 | |
| CN107857585A (en) | (Na0.5Bi0.5)(1‑x)BaxTi(1‑x)SnxO3Ceramics and preparation method thereof | |
| CN107244912A (en) | A kind of novel B CZT bases energy storage ceramic material and its preparation method and application |
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 |