[go: up one dir, main page]

CN112341191B - Lead-free ceramic dielectric with high energy storage density and high energy storage efficiency and preparation method thereof - Google Patents

Lead-free ceramic dielectric with high energy storage density and high energy storage efficiency and preparation method thereof Download PDF

Info

Publication number
CN112341191B
CN112341191B CN202011156932.7A CN202011156932A CN112341191B CN 112341191 B CN112341191 B CN 112341191B CN 202011156932 A CN202011156932 A CN 202011156932A CN 112341191 B CN112341191 B CN 112341191B
Authority
CN
China
Prior art keywords
ceramic
energy storage
ceramic powder
high energy
dielectric
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.)
Active
Application number
CN202011156932.7A
Other languages
Chinese (zh)
Other versions
CN112341191A (en
Inventor
翟继卫
闫非
沈波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tongji University
Original Assignee
Tongji University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tongji University filed Critical Tongji University
Priority to CN202011156932.7A priority Critical patent/CN112341191B/en
Publication of CN112341191A publication Critical patent/CN112341191A/en
Application granted granted Critical
Publication of CN112341191B publication Critical patent/CN112341191B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C04B35/475—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 bismuth titanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/29—Producing shaped prefabricated articles from the material by profiling or strickling the material in open moulds or on moulding surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/003—Apparatus or processes for treating or working the shaped or preshaped articles the shaping of preshaped articles, e.g. by bending
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6264—Mixing media, e.g. organic solvents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium 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
    • C04B2235/3205—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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C04B2235/3234—Titanates, not containing zirconia
    • C04B2235/3236—Alkaline earth 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

本发明属于储能陶瓷介质材料技术领域，提供了一种无铅高储能密度和高储能效率的陶瓷电介质及其制备方法，通过固相反应合成内层陶瓷粉体和外层陶瓷粉体，将粉体进一步制成陶瓷浆料，通过流延成型工艺获得相应的陶瓷膜，将得到的陶瓷膜在不同温度和压力条件下进行加压，最后经1050‑1200℃高温烧结得到具有层状三明治结构的无铅高储能密度和高储能效率的陶瓷电介质，其第一、第三电介质层具有高击穿场强，第二电介质层具有高极化强度；或第一、第三电介质层具有高极化强度，第二电介质层具有高击穿场强。本发明不含铅，制备过程简单、制备工艺稳定、适合工业化批量生产，且耐压特性优异、储能密度和效率高，同时兼具多种材料优异性能于一体。

Figure 202011156932

The invention belongs to the technical field of energy storage ceramic dielectric materials, and provides a lead-free ceramic dielectric with high energy storage density and high energy storage efficiency and a preparation method thereof. , the powder is further made into a ceramic slurry, the corresponding ceramic film is obtained through the tape casting process, the obtained ceramic film is pressurized under different temperature and pressure conditions, and finally sintered at a high temperature of 1050-1200 ℃ to obtain a layered film. Sandwich structure lead-free ceramic dielectric with high energy storage density and high energy storage efficiency, the first and third dielectric layers have high breakdown field strength, and the second dielectric layer has high polarization strength; or the first and third dielectric layers The layer has a high polarization and the second dielectric layer has a high breakdown field. The invention does not contain lead, has simple preparation process, stable preparation process, is suitable for industrial mass production, and has excellent pressure resistance properties, high energy storage density and efficiency, and simultaneously has the excellent properties of various materials in one.

Figure 202011156932

Description

Lead-free ceramic dielectric with high energy storage density and high energy storage efficiency and preparation method thereof
Technical Field
The invention belongs to the technical field of energy storage ceramic dielectric materials, and particularly relates to a lead-free ceramic dielectric medium with high energy storage density and high energy storage efficiency and a preparation method thereof.
Background
In recent years, with the rapid development of information technology, the demand for material properties has been increasing. Ceramic electric applianceThe dielectric capacitor has the characteristics of high charging and discharging speed, high power density, long cycle life, wide working temperature range, good stability and the like, and has wide application prospects in various fields of new energy electric automobiles, laser weapons, smart grids, electromagnetic guns and the like. With the limitation of lead-containing materials in electronic components in various countries around the world, the search and development of lead-free ceramic dielectric capacitors which can replace lead-based materials are the current research hotspots. However, the breakdown electric field strength and the maximum polarization strength of the lead-free ceramic dielectric are often difficult to be simultaneously improved, so that the energy storage density of most lead-free ceramic capacitors is small (< 3J/cm)3) And the energy storage efficiency is low (less than 80 percent), thereby limiting the development requirements of lead-free electronic components for miniaturization, integration and high performance.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a lead-free ceramic dielectric having high energy storage density and high energy storage efficiency, and a method for preparing the same.
The invention provides a preparation method of a lead-free ceramic dielectric medium with high energy storage density and high energy storage efficiency, which comprises the following steps: step 1, selecting Bi2O3、BaCO3、Na2CO3、TiO2、SrCO3、Al2O3And Nb2O5As a raw material, Bi of chemical formula 0.800.5Na0.5TiO3-0.20SrNb0.5Al0.5O3Weighing, and preparing BNTSNA ceramic powder; step 2, selecting Bi2O3、BaCO3、Na2CO3And TiO2As a raw material, Bi of chemical formula 0.940.55Na0.45TiO3-0.06BaTiO3Weighing, and preparing BNBT ceramic powder; or Bi is selected2O3、Na2CO3、TiO2And SrCO3As a raw material, 0.75Bi according to the chemical formula0.52Na0.48TiO3-0.25SrTiO3Weighing, and preparing BNST ceramic powder; step 3, selecting BNTSNA ceramic powder as outer layer ceramic powder, and selecting BNBT ceramic powder orBNST ceramic powder is used as inner layer ceramic powder; or BNTSNA ceramic powder is selected as inner layer ceramic powder, and BNBT ceramic powder or BNST ceramic powder is selected as outer layer ceramic powder; step 4, adding absolute ethyl alcohol, butanone 90-100%, dispersing agent 3-3.5%, adhesive 9-9.5%, dibutyl phthalate 3-3.5% and polyethylene glycol 3-3.5% of the outer layer ceramic powder according to 50-55% of the outer layer ceramic powder by mass to prepare outer layer ceramic slurry; step 5, adding absolute ethyl alcohol, butanone 90-100%, dispersing agent 3-3.5%, adhesive 9-9.5%, dibutyl phthalate 3-3.5% and polyethylene glycol 3-3.5% into the inner ceramic powder according to 50-55% of the inner ceramic powder by mass to prepare inner ceramic slurry; step 6, preparing the outer ceramic slurry and the inner ceramic slurry into an outer ceramic membrane and an inner ceramic membrane respectively through a tape casting process; step 7, covering two outer ceramic films on the upper surface and the lower surface of the inner ceramic film respectively, and performing compression molding to obtain a ceramic green body with a sandwich structure; and 8, removing the ceramic green body for 8-10 h, and sintering for 3-4 h to prepare the lead-free ceramic dielectric medium with a sandwich structure and high energy storage density and energy storage efficiency.
The preparation method of the lead-free ceramic dielectric with high energy storage density and high energy storage efficiency provided by the invention can also have the following characteristics: the preparation method of the BNTSNA ceramic powder in the step 1 comprises the following steps: step 1-1, weighing Bi according to stoichiometric ratio2O3、Na2CO3、TiO2、SrCO3、Al2O3And Nb2O5Adding the BNTSNA ceramic powder serving as a raw material into a ball milling tank; step 1-2, weighing a certain mass of ball milling medium, adding the ball milling medium into a ball milling tank, and placing the ball milling tank into a ball mill for ball milling for 10h-15 h; step 1-3, drying the mixed raw materials of the BNTSNA ceramic powder for 8-10 h at the temperature of 100 ℃; step 1-4, calcining the dried raw material of the BNTSNA ceramic powder for 3-4 h at the temperature of 800-850 ℃ under the sealed condition to obtain pre-synthesized BNTSNA powder; step 1-5, pre-synthesized BNTSNA powder and ball millingAdding the medium into the ball milling tank again, placing the ball milling tank in a ball mill, carrying out ball milling for 10-15 h to obtain crude BNTSNA ceramic powder, drying and sieving the crude BNTSNA ceramic powder to obtain BNTSNA ceramic powder, wherein the preparation method of the BNBT ceramic powder or the BNST ceramic powder in the step 2 comprises the following steps: step 2-1, weighing Bi according to stoichiometric ratio2O3、BaCO3、Na2CO3、TiO2And SrCO3Adding the raw materials of BNBT ceramic powder or BNST ceramic powder into a ball milling tank; step 2-2, weighing a certain mass of ball milling medium, adding the ball milling medium into a ball milling tank, and placing the ball milling tank into a ball mill for ball milling for 10-15 hours; 2-3, drying the mixed BNBT ceramic powder raw material or the mixed BNST ceramic powder raw material for 8-10 h at the temperature of 100 ℃; step 2-4, calcining the dried BNBT ceramic powder raw material or the dried BNST ceramic powder raw material for 3h-4h at the temperature of 800 ℃ to 850 ℃ under the sealing condition to obtain pre-synthesized BNBT powder or pre-synthesized BNST powder; and 2-5, adding the pre-synthesized BNBT powder or the pre-synthesized BNST powder into a ball milling tank, adding a ball milling medium into the ball milling tank, placing the ball milling tank into a ball mill, carrying out ball milling for 10-15 h to obtain rough BNBT ceramic powder or rough BNST ceramic powder, drying and sieving the rough BNBT ceramic powder or rough BNST ceramic powder, and preparing to obtain the BNBT ceramic powder or the BNST ceramic powder.
The preparation method of the lead-free ceramic dielectric with high energy storage density and high energy storage efficiency provided by the invention can also have the following characteristics: wherein the rotation speed of the ball mill is 350r/min-450r/min, and the ball milling medium is absolute ethyl alcohol and ZrO2The mass ratio of the ball and the absolute ethyl alcohol to the inner layer raw material or the outer layer raw material is 1.2-1.5:1, and ZrO2The mass ratio of the ball to the inner layer raw material or the outer layer raw material is 1.5-2.0: 1.
The preparation method of the lead-free ceramic dielectric with high energy storage density and high energy storage efficiency provided by the invention can also have the following characteristics: the method comprises the following steps of pressing and forming a ceramic green body at the temperature of 40-45 ℃ and the pressure of 50-250 MPa, discharging gel from the ceramic green body at the temperature of 550-600 ℃, sintering the ceramic green body after gel discharge in a closed crucible, and in the sintering process in the step 8, increasing the sintering temperature from room temperature to 1180-1200 ℃ at the heating rate of 3-4 ℃/min, and then reducing the temperature to 1050-1060 ℃ at the cooling rate of 10-20 ℃/min for sintering.
The preparation method of the lead-free ceramic dielectric with high energy storage density and high energy storage efficiency provided by the invention can also have the following characteristics: wherein, Bi2O3、BaCO3、Na2CO3、TiO2、SrCO3、Al2O3And Nb2O5The purities of (A) are all more than 98%.
The preparation method of the lead-free ceramic dielectric with high energy storage density and high energy storage efficiency provided by the invention can also have the following characteristics: wherein the dispersant is triolein glyceride, and the adhesive is polyvinyl butyral.
The present invention also provides a lead-free ceramic dielectric with high energy storage density and high energy storage efficiency, having the characteristics comprising: the dielectric layer comprises a first dielectric layer, a second dielectric layer and a third dielectric layer which are attached in sequence, wherein the first dielectric layer, the second dielectric layer and the third dielectric layer form a sandwich structure, and the first dielectric layer and the third dielectric layer are made of the same material.
The lead-free ceramic dielectric with high energy storage density and high energy storage efficiency provided by the invention can also have the following characteristics: wherein the first dielectric layer is BNTSNA, and the second dielectric layer is BNBT or BNST.
The preparation method of the lead-free ceramic dielectric with high energy storage density and high energy storage efficiency provided by the invention can also have the following characteristics: wherein the first dielectric layer is BNBT or BNST, and the second dielectric layer is BNTSNA.
The lead-free ceramic dielectric with high energy storage density and high energy storage efficiency provided by the invention can also have the following characteristics: wherein, the breakdown field strength of BNTSNA is above 300kV/cm, and the polarization strength of BNBT is 30 μ C/cm2Above, the polarization intensity of BNST is 40 μ C/cm2The above.
Action and Effect of the invention
According to the preparation method of the lead-free ceramic dielectric with high energy storage density and high energy storage efficiency, which is provided by the invention, Bi is used2O3、BaCO3、Na2CO3、TiO2、SrCO3、Al2O3And Nb2O5Preparing outer-layer ceramic powder and inner-layer ceramic powder as raw materials, adding an organic solvent, a dispersing agent, an adhesive and a plasticizer to prepare outer-layer ceramic slurry and inner-layer ceramic slurry, and taking absolute ethyl alcohol and butanone as the organic solvent, so that the volatility is high and the removal is easy; the dispersing agent can separate powder particles and form a suspension, so that the powder particles can keep uniform suspension property; the adhesive can bond the powder particles, and the dibutyl phthalate and the polyethylene glycol which are used as the plasticizer can enable the prepared ceramic green body to have certain plasticity, so that the ceramic green body is convenient for later-stage processing. The outer ceramic slurry and the inner ceramic slurry can be prepared into the outer ceramic membrane and the inner ceramic membrane respectively through a tape casting process, and the tape casting process is mature, simple and easy to realize industrial mass production. The ceramic dielectric medium obtained by pressing, binder removal and sintering of the outer ceramic membrane and the inner ceramic membrane does not contain lead elements which are harmful to human health and pollute the environment, and meets the requirements of sustainable development. Therefore, the preparation method of the lead-free ceramic dielectric medium with high energy storage density and high energy storage efficiency is easy to industrialize, simple and convenient, and the prepared lead-free ceramic dielectric medium with high energy storage density and high energy storage efficiency has excellent performance and is expected to replace a lead-based energy storage ceramic medium.
The lead-free ceramic dielectric with high energy storage density and high energy storage efficiency is a sandwich structure consisting of a first dielectric layer, a second dielectric layer and a third dielectric layer which are sequentially attached together, wherein the first dielectric layer and the third dielectric layer provide higher maximum polarization intensity, the second dielectric layer provides high breakdown field intensity and smaller residual polarization intensity, or the first dielectric layer and the third dielectric layer provide a high breakdown field strength and a small remnant polarization, the second dielectric layer provides a high maximum polarization, therefore, the invention integrates various excellent performances of various materials by a composite method, greatly improves the energy storage density and the energy storage efficiency of the lead-free ceramic dielectric medium with high energy storage density and high energy storage efficiency, and can be widely applied to pulse power systems such as high-power microwave weapons, laser weapons, electromagnetic transmitters, hybrid electric vehicles and the like.
Drawings
FIG. 1 is a hysteresis loop of a lead-free ceramic dielectric of high energy storage density and high energy storage efficiency in example 1 of the present invention;
FIG. 2 is a graph showing the total energy storage density W of the lead-free ceramic dielectric with high energy storage density and high energy storage efficiency at different electric field strengths in example 1 of the present inventiontotAvailable energy storage density WrecEnergy loss density WlossAnd energy storage efficiency η;
FIG. 3 is a hysteresis loop of a lead-free ceramic dielectric of high energy storage density and high energy storage efficiency in example 2 of the present invention;
FIG. 4 is a graph showing the total energy storage density W of the lead-free ceramic dielectric with high energy storage density and high energy storage efficiency in example 2 of the present invention at different electric field strengthstotAvailable energy storage density WrecEnergy loss density WlossAnd energy storage efficiency η;
FIG. 5 is a hysteresis loop of a lead-free ceramic dielectric of high energy storage density and high energy storage efficiency in example 3 of the present invention;
FIG. 6 is a graph showing the total energy storage density W of lead-free ceramic dielectrics with high energy storage density and high energy storage efficiency at different electric field strengths in example 3 of the present inventiontotAvailable energy storage density WrecEnergy loss density WlossAnd energy storage efficiency η;
FIG. 7 is a hysteresis loop of a lead-free ceramic dielectric with high energy storage density and high energy storage efficiency in example 4 of the present invention;
FIG. 8 is a graph showing the total energy storage density W of lead-free high energy storage density and high energy storage efficiency ceramic dielectrics under different electric field strengths in example 4 of the present inventiontotAvailable energy storage density WrecEnergy loss density WlossAnd energy storage efficiency η。
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the following will specifically describe the lead-free ceramic dielectric with high energy storage density and high energy storage efficiency and the preparation method thereof with reference to the embodiment and the accompanying drawings.
The raw materials used in the examples of the present invention were purchased from general commercial sources, and the CAS numbers were as follows:
absolute ethyl alcohol, CAS number 64-17-5;
butanone, CAS number 78-93-3;
triolein having a CAS number of 122-32-7;
dibutyl phthalate having CAS number 84-74-2;
polyvinyl butyral having a CAS number of 63148-65-2;
polyethylene glycol, CAS number 25322-68-3.
The preparation method of the lead-free ceramic dielectric medium with high energy storage density and high energy storage efficiency comprises the following steps:
step 1, selecting Bi2O3、BaCO3、Na2CO3、TiO2、SrCO3、Al2O3And Nb2O5As a raw material, Bi of chemical formula 0.800.5Na0.5TiO3-0.20SrNb0.5Al0.5O3Weighing, and preparing BNTSNA ceramic powder;
step 2, selecting Bi2O3、BaCO3、Na2CO3And TiO2As a raw material, Bi of chemical formula 0.940.55Na0.45TiO3-0.06BaTiO3Weighing, and preparing BNBT ceramic powder;
or Bi is selected2O3、Na2CO3、TiO2And SrCO3As a raw material, 0.75Bi according to the chemical formula0.52Na0.48TiO3-0.25SrTiO3Weighing, and preparing BNST ceramic powder;
step 3, BNTSNA ceramic powder is selected as outer layer ceramic powder, and BNBT ceramic powder or BNST ceramic powder is selected as inner layer ceramic powder;
or BNTSNA ceramic powder is used as inner layer ceramic powder, and BNBT ceramic powder or BNST ceramic powder is used as outer layer ceramic powder;
step 4, adding absolute ethyl alcohol, butanone 90-100%, dispersing agent 3-3.5%, adhesive 9-9.5%, dibutyl phthalate 3-3.5% and polyethylene glycol 3-3.5% of the outer layer ceramic powder according to 50-55% of the outer layer ceramic powder by mass to prepare outer layer ceramic slurry;
step 5, adding absolute ethyl alcohol, butanone 90-100%, dispersing agent 3-3.5%, adhesive 9-9.5%, dibutyl phthalate 3-3.5% and polyethylene glycol 3-3.5% into the inner ceramic powder according to 50-55% of the inner ceramic powder by mass to prepare inner ceramic slurry;
step 6, preparing the outer ceramic slurry and the inner ceramic slurry into an outer ceramic membrane and an inner ceramic membrane respectively through a tape casting process;
step 7, covering two outer ceramic films on the upper surface and the lower surface of the inner ceramic film respectively, and performing compression molding to obtain a ceramic green body with a three-layer structure, namely the ceramic green body with a sandwich structure;
and 8, removing the glue of the ceramic green body for 8-10 h, and sintering for 3-4 h to prepare the lead-free ceramic dielectric medium with high energy storage density and energy storage efficiency and a three-layer structure, namely the lead-free ceramic dielectric medium with high energy storage density and energy storage efficiency and a sandwich structure.
The preparation method of the BNTSNA ceramic powder in the step 1 comprises the following steps:
step 1-1, weighing Bi according to stoichiometric ratio2O3、Na2CO3、TiO2、SrCO3、Al2O3And Nb2O5Adding the BNTSNA ceramic powder serving as a raw material into a ball milling tank;
step 1-2, weighing a certain mass of ball milling medium, adding the ball milling medium into a ball milling tank, and placing the ball milling tank into a ball mill for ball milling for 10h-15 h;
step 1-3, drying the mixed raw materials of the BNTSNA ceramic powder for 8-10 h at the temperature of 100 ℃;
step 1-4, calcining the dried raw material of the BNTSNA ceramic powder for 3-4 h at the temperature of 800-850 ℃ under the sealed condition to obtain pre-synthesized BNTSNA powder;
step 1-5, adding the pre-synthesized BNTSNA powder and the ball milling medium into the ball milling tank again, placing the ball milling tank in a ball mill, performing ball milling for 10h-15h to obtain rough BNTSNA ceramic powder, drying and sieving the rough BNTSNA ceramic powder to obtain BNTSNA ceramic powder,
the preparation method of the BNBT ceramic powder or the BNST ceramic powder in the step 2 comprises the following steps:
step 2-1, weighing Bi according to stoichiometric ratio2O3、BaCO3、Na2CO3、TiO2And SrCO3Adding the raw materials of BNBT ceramic powder or BNST ceramic powder into a ball milling tank;
step 2-2, weighing a certain mass of ball milling medium, adding the ball milling medium into a ball milling tank, and placing the ball milling tank into a ball mill for ball milling for 10-15 h;
2-3, drying the mixed BNBT ceramic powder raw material or the mixed BNST ceramic powder raw material for 8-10 h at the temperature of 100 ℃;
step 2-4, calcining the dried BNBT ceramic powder raw material or the dried BNST ceramic powder raw material for 3h-4h at the temperature of 800 ℃ to 850 ℃ under the sealing condition to obtain pre-synthesized BNBT powder or pre-synthesized BNST powder;
and 2-5, adding the pre-synthesized BNBT powder or the pre-synthesized BNST powder into a ball milling tank, adding a ball milling medium into the ball milling tank, placing the ball milling tank into a ball mill, carrying out ball milling for 10-15 h to obtain rough BNBT ceramic powder or rough BNST ceramic powder, drying and sieving the rough BNBT ceramic powder or rough BNST ceramic powder, and preparing to obtain the BNBT ceramic powder or the BNST ceramic powder.
The rotation speed of the ball mill is 350r/min-450r/min, and the ball milling media are absolute ethyl alcohol and ZrO2The mass ratio of the ball and the absolute ethyl alcohol to the inner layer raw material or the outer layer raw material is 1.2-1.5:1, and ZrO2The mass ratio of the ball to the inner layer raw material or the outer layer raw material is 1.5-2.0: 1.
The ceramic green body is pressed and formed under the temperature condition of 40-45 ℃ and the pressure condition of 50-250 MPa, the ceramic green body is subjected to rubber discharge under the temperature condition of 550-600 ℃, the rubber discharge aims at removing organic additives, and the organic additives used in the invention comprise: anhydrous alcohol, butanone, triolein, dibutyl phthalate, polyvinyl butyral and polyethylene glycol.
And (3) sintering the ceramic green body after the glue is removed in a closed crucible, in the sintering process in the step (8), heating the sintering temperature to 1180-1200 ℃ from room temperature at the heating rate of 3-4 ℃/min, and then cooling to 1050-1060 ℃ at the cooling rate of 10-20 ℃/min for sintering.
Bi2O3、BaCO3、Na2CO3、TiO2、SrCO3、Al2O3And Nb2O5The purities of (A) are all more than 98%.
The dispersing agent is triolein glyceride, and the adhesive is polyvinyl butyral.
The energy storage density of the lead-free ceramic dielectric with high energy storage density and high energy storage efficiency obtained in the examples (total energy storage density W)totAnd available energy storage density Wrec) And the energy storage efficiency (η) may be calculated based on the measured hysteresis loop (P-E loop) in combination with the following equation:
Figure BDA0002743077570000111
Figure BDA0002743077570000112
η＝Wrec/Wtot×100％＝Wrec/(Wrec+Wloss)×100％ (3)
in the formula PmaxAt maximum polarization, PrFor residual polarization, E is the applied field strength, P is the polarization, WlossIs the energy loss density. From the above formula, it can be seen that to obtain higher energy storage density, it is necessary to have large P simultaneouslymaxSmall PrAnd a high E.
< example 1>
A method for preparing a lead-free ceramic dielectric medium (hereinafter referred to as ceramic dielectric medium) with high energy storage density and high energy storage efficiency comprises the following steps:
step S1, according to chemical formula 0.80Bi0.5Na0.5TiO3-0.20SrNb0.5Al0.5O3(hereinafter referred to as BNTSNA) 14.3964g of Bi were weighed2O3、3.2484g Na2CO、4.5612g SrCO3、9.9714g TiO2、0.7797g Al2O3And 2.0428g Nb2O5Preparing an outer dielectric material as a raw material, and preparing the dielectric material according to a chemical formula of 0.94Bi0.55Na0.45TiO3-0.06BaTiO3(hereinafter referred to as BNBT) 40.9673g of Bi were weighed2O3、7.5632g Na2CO3、4.0271g BaCO3、27.4423g TiO2Preparing an inner dielectric material as a raw material;
step S2, the raw material of the dielectric material of the outer layer and the raw material of the dielectric material of the inner layer are respectively put into two ball milling tanks, and then the absolute ethyl alcohol and ZrO are respectively added into the two ball milling tanks2The balls being as a ball-milling medium, ZrO2The mass ratio of the ball to the two raw materials is 1.5:1, the mass ratio of the absolute ethyl alcohol to the two raw materials is 1.2: 1, setting the rotation speed of a ball mill to be 350r/min, and carrying out primary ball milling on the two raw materials for 15 hours to respectively obtain two uniformly mixed raw materials;
step S3, drying the two raw materials uniformly mixed in the step S2, and calcining the dried raw materials for 4 hours at 800 ℃ respectively to obtain pre-synthesized outer-layer ceramic powder and pre-synthesized inner-layer ceramic powder;
step S4, putting the two pre-synthesized powders obtained in the step S3 into two ball milling tanks respectively, and adding absolute ethyl alcohol into the two ball milling tanks respectivelyAnd ZrO2The balls being as a ball-milling medium, ZrO2The mass ratio of the ball to the two pre-synthesized powders is 2.0:1, the mass ratio of the absolute ethyl alcohol to the two pre-synthesized powders is 1.5: setting the rotating speed of a ball mill to be 450r/min, carrying out secondary ball milling on two pre-synthesized powders for 10 hours, drying the two pre-synthesized powders at the temperature of 100 ℃, and sieving the two pre-synthesized powders with a 120-mesh sieve to obtain outer-layer ceramic powder and inner-layer ceramic powder;
step S5, weighing 10g of the outer layer ceramic powder obtained in the step S4, uniformly mixing the outer layer ceramic powder with 5g of absolute ethyl alcohol, 10g of butanone, 0.3g of triolein, 0.3g of dibutyl phthalate, 0.9g of polyvinyl butyral and 0.3g of polyethylene glycol to obtain outer layer ceramic slurry, and weighing 10g of the inner layer ceramic powder obtained in the step S4, uniformly mixing the inner layer ceramic powder with 5g of absolute ethyl alcohol, 10g of butanone, 0.3g of triolein, 0.3g of dibutyl phthalate, 0.9g of polyvinyl butyral and 0.3g of polyethylene glycol to obtain inner layer ceramic slurry;
step S6, preparing outer layer ceramic slurry into an outer layer ceramic film through a tape casting process, cutting the outer layer ceramic film into two square sheets of 12mmX12mm, preparing an inner layer ceramic film through a tape casting process, cutting the inner layer ceramic slurry into square sheets of 12mmX12mm, respectively attaching the two cut outer layer ceramic films to the upper surface and the lower surface of the inner layer ceramic film to form a sandwich structure, and finally, sequentially applying pressures of 50MPa, 100MPa, 150MPa, 200MPa and 250MPa to the product of the sandwich structure for compression molding at 40 ℃ to obtain a lead-free ceramic dielectric green body with high energy storage density and energy storage efficiency;
and S7, removing the binder from the green body obtained in the step S6 at 550 ℃ for 10 hours, putting the green body after binder removal into a crucible, sintering under a sealed condition, heating the green body to 1180 ℃ at the speed of 4 ℃/min in a sintering furnace, then cooling to 1060 ℃ at the speed of 10 ℃/min, stopping heating after sintering for 3 hours, and cooling to room temperature along with the furnace temperature to obtain the ceramic dielectric with the sandwich structure.
The ceramic dielectric obtained in this example includes a first dielectric layer, a second dielectric layer, and a third dielectric layer, which are sequentially laminated, where the first dielectric layer and the third dielectric layer are 0.80Bi0.5Na0.5TiO3-0.20SrNb0.5Al0.5O3(abbreviated as BNTSNA) and a second dielectric layer of 0.94Bi0.55Na0.45TiO3-0.06BaTiO3(abbreviated as BNBT).
The two sides of the ceramic dielectric obtained in this example were plated with gold electrodes by ion sputtering, and the performance was characterized to obtain fig. 1, and fig. 2 was obtained by calculation.
FIG. 1 is a ferroelectric hysteresis loop of a ceramic dielectric in the present embodiment; FIG. 2 shows the total energy storage density W of the ceramic dielectric in this embodiment at different electric field strengthstotAvailable energy storage density WrecEnergy loss density WlossAnd energy storage efficiency η.
As can be seen from FIG. 1, the ceramic dielectric prepared in this example has a long hysteresis loop, and the applied electric field strength is high, and the electric field strength can reach 557 kV/cm. Total energy storage density (W) calculated based on hysteresis looptot) Can reach 6.99J/cm3The energy storage density (W) can be utilizedrec) Is 6.54J/cm3Energy loss density (W)loss) Only 0.45J/cm3The corresponding energy storage efficiency (eta) is as high as 94%. As can be seen from FIG. 2, the total energy storage density (W) of the ceramic dielectric obtained in this example is increased with the increase of the electric field strengthtot) And available energy storage density (W)rec) Obtain rapid increase of energy loss density (W)loss) The value is always kept small, and the energy storage efficiency (η) is maintained above 90%.
< example 2>
A preparation method of a lead-free ceramic dielectric with high energy storage density and energy storage efficiency comprises the following steps:
step S1, according to chemical formula 0.94Bi0.55Na0.45TiO3-0.06BaTiO3(hereinafter referred to as BNBT) 40.9673g of Bi were weighed2O3、7.5632g Na2CO3、4.0271g BaCO3、27.4423g TiO2Preparing an outer dielectric material as a raw material, and preparing the dielectric material according to a chemical formula of 0.80Bi0.5Na0.5TiO3-0.20SrNb0.5Al0.5O3(hereinafter referred to as BNTSNA) 14.3964g of Bi were weighed2O3、3.2484g Na2CO、4.5612g SrCO3、9.9714g TiO2、0.7797g Al2O3And 2.0428g Nb2O5Preparing an inner dielectric material as a raw material;
step S2, the raw material of the dielectric material of the outer layer and the raw material of the dielectric material of the inner layer are respectively put into two ball milling tanks, and then the absolute ethyl alcohol and ZrO are respectively added into the two ball milling tanks2The balls being as a ball-milling medium, ZrO2The mass ratio of the ball to the two raw materials is 2: 1, the mass ratio of the absolute ethyl alcohol to the two raw materials is 1.5:1, setting the rotation speed of a ball mill to be 450r/min, and performing primary ball milling on the two raw materials for 10 hours to respectively obtain two uniformly mixed raw materials;
step S3, drying the two raw materials uniformly mixed in the step S2, and calcining the dried raw materials for 3 hours at 850 ℃ respectively to obtain pre-synthesized outer-layer ceramic powder and pre-synthesized inner-layer ceramic powder;
step S4, putting the two pre-synthesized powders obtained in the step S3 into two ball milling tanks respectively, and adding absolute ethyl alcohol and ZrO into the two ball milling tanks respectively2The balls being as a ball-milling medium, ZrO2The mass ratio of the ball to the two pre-synthesized powders is 1.7: 1, the mass ratio of the absolute ethyl alcohol to the two pre-synthesized powders is 1.3: setting the rotation speed of a ball mill to 400r/min, carrying out secondary ball milling on two pre-synthesized powders for 12h, drying the two pre-synthesized powders at 100 ℃, and sieving the two pre-synthesized powders with a 120-mesh sieve to obtain outer-layer ceramic powder and inner-layer ceramic powder;
step S5, weighing 10g of the outer layer ceramic powder obtained in the step S4, uniformly mixing the outer layer ceramic powder with 5g of absolute ethyl alcohol, 10g of butanone, 0.3g of triolein, 0.3g of dibutyl phthalate, 0.9g of polyvinyl butyral and 0.3g of polyethylene glycol to obtain outer layer ceramic slurry, weighing 10g of the inner layer ceramic powder obtained in the step S4, and uniformly mixing the inner layer ceramic powder with 5g of absolute ethyl alcohol, 10g of butanone, 0.3g of triolein, 0.3g of dibutyl phthalate, 0.9g of polyvinyl butyral and 0.3g of polyethylene glycol to obtain inner layer ceramic slurry;
step S6, preparing outer layer ceramic slurry into an outer layer ceramic film through a tape casting process, cutting the outer layer ceramic film into two square sheets of 12mmX12mm, preparing an inner layer ceramic film through a tape casting process, cutting the inner layer ceramic slurry into square sheets of 12mmX12mm, respectively attaching the two cut outer layer ceramic films to the upper surface and the lower surface of the inner layer ceramic film to form a sandwich structure, and finally, sequentially applying pressures of 50MPa, 100MPa, 150MPa, 200MPa and 250MPa to the product of the sandwich structure for compression molding at the temperature of 45 ℃ to obtain a lead-free ceramic dielectric green body with high energy storage density and energy storage efficiency;
and S7, removing the binder from the green body obtained in the step S6 at 550 ℃ for 10 hours, putting the green body after binder removal into a crucible, sintering under a sealed condition, heating the green body to 1180 ℃ at the speed of 3 ℃/min in a sintering furnace, then cooling to 1050 ℃ at the speed of 20 ℃/min, stopping heating after sintering for 4 hours, and cooling to room temperature along with the furnace temperature to obtain the ceramic dielectric with the sandwich structure.
The ceramic dielectric obtained in this example includes a first dielectric layer, a second dielectric layer, and a third dielectric layer laminated in this order, in which the first dielectric layer and the third dielectric layer are 0.94Bi0.55Na0.45TiO3-0.06BaTiO3(abbreviated as BNBT), and the second dielectric layer is 0.80Bi0.5Na0.5TiO3-0.20SrNb0.5Al0.5O3(abbreviated as BNTSNA).
The two sides of the ceramic dielectric obtained in this example were plated with gold electrodes by ion sputtering, and the performance was characterized to obtain fig. 3, and fig. 4 was obtained by calculation.
FIG. 3 is a ferroelectric hysteresis loop of the ceramic dielectric in the present embodiment; FIG. 4 shows the total energy storage density W of the ceramic dielectric in this embodiment at different electric field strengthstotAvailable energy storage density WrecEnergy loss density WlossAnd energy storage efficiency η.
As can be seen from FIG. 3, the ceramic dielectric prepared in this example has a long hysteresis loop, and the applied electric field strength is high, and the electric field strength can reach 374 kV/cm. Calculated and obtained based on hysteresis loopTotal energy storage Density (W)tot) Can reach 4.92J/cm3The energy storage density (W) can be utilizedrec) Is 4.46J/cm3Energy loss density (W)loss) Only 0.46J/cm3The corresponding energy storage efficiency (eta) is up to 91%. As can be seen from FIG. 4, the ceramic dielectric obtained in this example has a total energy storage density (W) with increasing electric field strengthtot) And available energy storage density (W)rec) Obtain rapid increase of energy loss density (W)loss) The value is always kept small, and the energy storage efficiency (η) is maintained above 88%.
< example 3>
A preparation method of a lead-free ceramic dielectric with high energy storage density and energy storage efficiency comprises the following steps:
step S1, according to chemical formula 0.80Bi0.5Na0.5TiO3-0.20SrNb0.5Al0.5O3(hereinafter referred to as BNTSNA) 14.3964g of Bi were weighed2O3、3.2484g Na2CO、4.5612g SrCO3、9.9714g TiO2、0.7797g Al2O3And 2.0428g Nb2O5Preparing an outer dielectric material as a raw material, and preparing the dielectric material according to a chemical formula of 0.75Bi0.52Na0.48TiO3-0.25SrTiO3(hereinafter referred to as BNST) 15.9842g of Bi were weighed2O3、3.3293g Na2CO3、6.4927g SrCO3、14.1939g TiO2Preparing an inner dielectric material as a raw material;
step S2, the raw material of the dielectric material of the outer layer and the raw material of the dielectric material of the inner layer are respectively put into two ball milling tanks, and then the absolute ethyl alcohol and ZrO are respectively added into the two ball milling tanks2The balls being as a ball-milling medium, ZrO2The mass ratio of the ball to the two raw materials is 1.5:1, the mass ratio of the absolute ethyl alcohol to the two raw materials is 1.2: 1, setting the rotation speed of a ball mill to be 350r/min, and carrying out primary ball milling on the two raw materials for 15 hours to respectively obtain two uniformly mixed raw materials;
step S3, drying the two raw materials uniformly mixed in the step S2, and calcining the dried raw materials for 4 hours at 800 ℃ respectively to obtain pre-synthesized outer-layer ceramic powder and pre-synthesized inner-layer ceramic powder;
step S4, putting the two pre-synthesized powders obtained in the step S3 into two ball milling tanks respectively, and adding absolute ethyl alcohol and ZrO into the two ball milling tanks respectively2The balls being as a ball-milling medium, ZrO2The mass ratio of the ball to the two pre-synthesized powders is 2.0:1, the mass ratio of the absolute ethyl alcohol to the two pre-synthesized powders is 1.5: setting the rotating speed of a ball mill to be 450r/min, carrying out secondary ball milling on two pre-synthesized powders for 10 hours, drying the two pre-synthesized powders at the temperature of 100 ℃, and sieving the two pre-synthesized powders with a 120-mesh sieve to obtain outer-layer ceramic powder and inner-layer ceramic powder;
step S5, weighing 10g of the outer layer ceramic powder obtained in the step S4, uniformly mixing the outer layer ceramic powder with 5.5g of absolute ethyl alcohol, 9g of butanone, 0.35g of glycerol trioleate, 0.35g of dibutyl phthalate, 0.95 g of polyvinyl butyral and 0.35g of polyethylene glycol to obtain outer layer ceramic slurry, and weighing 10g of the inner layer ceramic powder obtained in the step S4, uniformly mixing the inner layer ceramic powder with 5.4g of absolute ethyl alcohol, 9.6g of butanone, 0.32g of glycerol trioleate, 0.33g of dibutyl phthalate, 0.93g of polyvinyl butyral and 0.34 g of polyethylene glycol to obtain inner layer ceramic slurry;
step S6, preparing outer layer ceramic slurry into an outer layer ceramic film through a tape casting process, cutting the outer layer ceramic film into two square sheets of 12mmX12mm, preparing an inner layer ceramic film through a tape casting process, cutting the inner layer ceramic slurry into square sheets of 12mmX12mm, respectively attaching the two cut outer layer ceramic films to the upper surface and the lower surface of the inner layer ceramic film to form a sandwich structure, and finally, sequentially applying pressures of 50MPa, 100MPa, 150MPa, 200MPa and 250MPa to the product of the sandwich structure for compression molding at the temperature of 45 ℃ to obtain a lead-free ceramic dielectric green body with high energy storage density and energy storage efficiency;
and S7, removing the binder from the green body obtained in the step S6 at 600 ℃ for 8 hours, putting the green body after binder removal into a crucible, sintering under a sealed condition, heating the green body to 1200 ℃ at a speed of 4 ℃/min in a sintering furnace, then cooling to 1060 ℃ at a speed of 15 ℃/min, stopping heating after sintering for 4 hours, and cooling to room temperature along with the furnace temperature to obtain the ceramic dielectric with the sandwich structure.
The ceramic dielectric obtained in this example includes a first dielectric layer, a second dielectric layer, and a third dielectric layer laminated in this order, in which the first dielectric layer and the third dielectric layer are 0.80Bi0.5Na0.5TiO3-0.20SrNb0.5Al0.5O3(abbreviated as BNTSNA) and a second dielectric layer of 0.75Bi0.52Na0.48TiO3-0.25SrTiO3(abbreviated as BNST).
The two sides of the ceramic dielectric obtained in this example were plated with gold electrodes by ion sputtering, and the performance was characterized to obtain fig. 5, and fig. 6 was obtained by calculation.
FIG. 5 is a ferroelectric hysteresis loop of the ceramic dielectric in the present embodiment; FIG. 6 shows the total energy storage density W of the ceramic dielectric in this embodiment at different electric field strengthstotAvailable energy storage density WrecEnergy loss density WlossAnd energy storage efficiency η.
As shown in FIG. 5, the ceramic dielectric prepared in this example has a long hysteresis loop, and the applied electric field strength is high, and the electric field strength can reach 506 kV/cm. Total energy storage density (W) calculated based on hysteresis looptot) Can reach 6.30J/cm3The energy storage density (W) can be utilizedrec) Is 5.97J/cm3Energy loss density (W)loss) Only 0.33J/cm3The corresponding energy storage efficiency (eta) is as high as 95%. As shown in FIG. 6, the total energy storage density (W) of the ceramic dielectric prepared in this example is increased with the increase of the electric field strengthtot) And available energy storage density (W)rec) Obtain rapid increase of energy loss density (W)loss) The value is always kept small and the energy storage efficiency (η) is maintained at 94-95%.
< example 4>
A preparation method of a lead-free ceramic dielectric with high energy storage density and energy storage efficiency comprises the following steps:
step S1, according to chemical formula 0.75Bi0.52Na0.48TiO3-0.25SrTiO3(hereinafter referred to as BNST) 15.9842g of Bi were weighed2O3、3.3293g Na2CO3、6.4927g SrCO3、14.1939g TiO2Preparing an outer dielectric material as a raw material, and preparing the dielectric material according to a chemical formula of 0.80Bi0.5Na0.5TiO3-0.20SrNb0.5Al0.5O3(hereinafter referred to as BNTSNA) 14.3964g of Bi were weighed2O3、3.2484g Na2CO、4.5612g SrCO3、9.9714g TiO2、0.7797g Al2O3And 2.0428g Nb2O5Preparing an inner dielectric material as a raw material;
step S2, the raw material of the dielectric material of the outer layer and the raw material of the dielectric material of the inner layer are respectively put into two ball milling tanks, and then the absolute ethyl alcohol and ZrO are respectively added into the two ball milling tanks2The balls being as a ball-milling medium, ZrO2The mass ratio of the ball to the two raw materials is 1.5:1, the mass ratio of the absolute ethyl alcohol to the two raw materials is 1.2: 1, setting the rotating speed of a ball mill to be 380r/min, and carrying out primary ball milling on the two raw materials for 12 hours to respectively obtain two uniformly mixed raw materials;
step S3, drying the two raw materials uniformly mixed in the step S2, and calcining the dried raw materials for 4 hours at 800 ℃ respectively to obtain pre-synthesized outer-layer ceramic powder and pre-synthesized inner-layer ceramic powder;
step S4, putting the two pre-synthesized powders obtained in the step S3 into two ball milling tanks respectively, and adding absolute ethyl alcohol and ZrO into the two ball milling tanks respectively2The balls being as a ball-milling medium, ZrO2The mass ratio of the ball to the two pre-synthesized powders is 2.0:1, the mass ratio of the absolute ethyl alcohol to the two pre-synthesized powders is 1.5: setting the rotating speed of a ball mill to be 450r/min, carrying out secondary ball milling on two pre-synthesized powders for 10 hours, drying the two pre-synthesized powders at the temperature of 100 ℃, and sieving the two pre-synthesized powders with a 120-mesh sieve to obtain outer-layer ceramic powder and inner-layer ceramic powder;
step S5, weighing 10g of the outer layer ceramic powder obtained in the step S4, uniformly mixing the outer layer ceramic powder with 5g of absolute ethyl alcohol, 10g of butanone, 0.3g of triolein, 0.3g of dibutyl phthalate, 0.9g of polyvinyl butyral and 0.3g of polyethylene glycol to obtain outer layer ceramic slurry, and weighing 10g of the inner layer ceramic powder obtained in the step S4, uniformly mixing the inner layer ceramic powder with 5g of absolute ethyl alcohol, 10g of butanone, 0.3g of triolein, 0.3g of dibutyl phthalate, 0.9g of polyvinyl butyral and 0.3g of polyethylene glycol to obtain inner layer ceramic slurry;
step S6, preparing outer layer ceramic slurry into an outer layer ceramic film through a tape casting process, cutting the outer layer ceramic film into two square sheets of 12mmX12mm, preparing an inner layer ceramic film through a tape casting process, cutting the inner layer ceramic slurry into square sheets of 12mmX12mm, respectively attaching the two cut outer layer ceramic films to the upper surface and the lower surface of the inner layer ceramic film to form a three-layer structure, and finally, sequentially applying pressures of 50MPa, 100MPa, 150MPa, 200MPa and 250MPa to the sandwich-structure product for compression molding at 45 ℃ to obtain a lead-free ceramic dielectric green body with high energy storage density and energy storage efficiency;
and S7, removing the binder from the green body obtained in the step S6 at 600 ℃ for 10 hours, putting the green body after binder removal into a crucible, sintering under a sealed condition, heating the green body to 1180 ℃ at the speed of 4 ℃/min in a sintering furnace, then cooling to 1060 ℃ at the speed of 10 ℃/min, stopping heating after sintering for 3 hours, and cooling to room temperature along with the furnace temperature to obtain the ceramic dielectric with the sandwich structure.
The ceramic dielectric obtained in this example includes a first dielectric layer, a second dielectric layer, and a third dielectric layer laminated in this order, in which the first dielectric layer and the third dielectric layer are 0.75Bi0.52Na0.48TiO3-0.25SrTiO3(abbreviated as BNST), the second dielectric layer is 0.80Bi0.5Na0.5TiO3-0.20SrNb0.5Al0.5O3(abbreviated as BNTSNA).
The ceramic dielectric obtained in this example was plated with gold electrodes on both sides by ion sputtering, and the performance was characterized to obtain fig. 7 and fig. 8 by calculation.
FIG. 7 is a ferroelectric hysteresis loop of the ceramic dielectric in the present embodiment; FIG. 8 shows the total energy storage density W of the ceramic dielectric in this embodiment at different electric field strengthstotAvailable energy storage density WrecEnergy loss density WlossAnd energy storage efficiencyThe ratio eta.
As shown in FIG. 7, the ceramic dielectric prepared in this example has a long hysteresis loop, and the applied electric field strength is high, and the electric field strength can reach 475 kV/cm. Total energy storage density (W) calculated based on hysteresis looptot) Can reach 6.53J/cm3The energy storage density (W) can be utilizedrec) Is 6.25J/cm3Energy loss density (W)loss) Only 0.28J/cm3The corresponding energy storage efficiency (eta) is up to 96%. As shown in FIG. 8, the total energy storage density (W) of the ceramic dielectric prepared in this example is increased with the increase of the electric field strengthtot) And available energy storage density (W)rec) Obtain rapid increase of energy loss density (W)loss) The value is always kept small, and the energy storage efficiency (η) is maintained above 95%.
Effects and effects of the embodiments
According to the preparation method of the lead-free ceramic dielectric with high energy storage density and high energy storage efficiency provided by the embodiment, Bi is used2O3、BaCO3、Na2CO3、TiO2、SrCO3、Al2O3And Nb2O5Preparing outer-layer ceramic powder and inner-layer ceramic powder as raw materials, adding an organic solvent, a dispersing agent, an adhesive and a plasticizer to prepare outer-layer ceramic slurry and inner-layer ceramic slurry, and taking absolute ethyl alcohol and butanone as the organic solvent, so that the volatility is high and the removal is easy; the dispersing agent can separate powder particles and form a suspension, so that the powder particles can keep uniform suspension property; the adhesive can bond the powder particles, and the dibutyl phthalate and the polyethylene glycol which are used as the plasticizer can enable the prepared ceramic green body to have certain plasticity, so that the ceramic green body is convenient for later-stage processing. The outer ceramic slurry and the inner ceramic slurry can be prepared into the outer ceramic membrane and the inner ceramic membrane respectively through a tape casting process, and the tape casting process is mature, simple and easy to realize industrial mass production. The ceramic dielectric medium obtained by pressing, binder removal and sintering of the outer ceramic membrane and the inner ceramic membrane does not contain lead elements which are harmful to human health and pollute the environment, and meets the requirements of sustainable development.
In addition, the mass ratio of the absolute ethyl alcohol as a ball milling medium to the inner layer raw material or the outer layer raw material is 1.2-1.5:1, so that the ball milling of the inner layer raw material or the outer layer raw material in the mixing process is more sufficient; ZrO (ZrO)2The mass ratio of the ball to the inner layer raw material or the outer layer raw material is 1.5-2.0:1, which is beneficial to ZrO2The balls and the inner layer raw material or the outer layer raw material are fully collided in the ball milling process, and the optimal effect is achieved.
Therefore, the preparation method of the lead-free ceramic dielectric medium with high energy storage density and energy storage efficiency provided by the embodiment is easy to industrialize, the preparation method is simple and convenient, and the prepared lead-free ceramic dielectric medium with high energy storage density and energy storage efficiency is excellent in performance and is expected to replace a lead-based energy storage ceramic medium.
The lead-free ceramic dielectric with high energy storage density and high energy storage efficiency is a sandwich structure formed by a first dielectric layer, a second dielectric layer and a third dielectric layer which are sequentially attached together, wherein the first dielectric layer and the third dielectric layer provide high maximum polarization intensity, the second dielectric layer provides high breakdown field strength and smaller remanent polarization intensity, or the first dielectric layer and the third dielectric layer provide a high breakdown field strength and a small remnant polarization, the second dielectric layer provides a high maximum polarization, therefore, the embodiment integrates various excellent performances of various materials by a composite method, greatly improves the energy storage density and the energy storage efficiency of the lead-free ceramic dielectric with high energy storage density and energy storage efficiency, and can be widely applied to pulse power systems such as high-power microwave weapons, laser weapons, electromagnetic transmitters, hybrid electric vehicles and the like.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.

Claims (9)

1.一种无铅高储能密度和高储能效率的陶瓷电介质的制备方法，其特征在于，包括如下步骤：1. a preparation method of the ceramic dielectric of lead-free high energy storage density and high energy storage efficiency, is characterized in that, comprises the steps: 步骤1，选用Bi2O3、BaCO3、Na2CO3、TiO2、SrCO3、Al2O3和Nb2O5作为原料，按照化学式0.80Bi0.5Na0.5TiO3-0.20SrNb0.5Al0.5O3称取，制备得到BNTSNA陶瓷粉体；Step 1, select Bi 2 O 3 , BaCO 3 , Na 2 CO 3 , TiO 2 , SrCO 3 , Al 2 O 3 and Nb 2 O 5 as raw materials, according to the chemical formula 0.80Bi 0.5 Na 0.5 TiO 3 -0.20SrNb 0.5 Al 0.5 O 3 is weighed to prepare BNTSNA ceramic powder; 步骤2，选用所述Bi2O3、所述BaCO3、所述Na2CO3和所述TiO2作为原料，按照化学式0.94Bi0.55Na0.45TiO3-0.06BaTiO3称取，制备得到BNBT陶瓷粉体；In step 2, the Bi 2 O 3 , the BaCO 3 , the Na 2 CO 3 and the TiO 2 are selected as raw materials, and weighed according to the chemical formula 0.94Bi 0.55 Na 0.45 TiO 3 -0.06BaTiO 3 to prepare BNBT ceramics powder; 或选用所述Bi2O3、所述Na2CO3、所述TiO2和所述SrCO3作为原料，按照化学式0.75Bi0.52Na0.48TiO3-0.25SrTiO3称取，制备得到BNST陶瓷粉体；Or select the Bi 2 O 3 , the Na 2 CO 3 , the TiO 2 and the SrCO 3 as raw materials, and weigh according to the chemical formula 0.75Bi 0.52 Na 0.48 TiO 3 -0.25SrTiO 3 to prepare the BNST ceramic powder ; 步骤3，选用所述BNTSNA陶瓷粉体作为外层陶瓷粉体，选用所述BNBT陶瓷粉体或所述BNST陶瓷粉体作为内层陶瓷粉体；Step 3, selecting the BNTSNA ceramic powder as the outer layer ceramic powder, and selecting the BNBT ceramic powder or the BNST ceramic powder as the inner layer ceramic powder; 或选用所述BNTSNA陶瓷粉体作为内层陶瓷粉体，选用所述BNBT陶瓷粉体或所述BNST陶瓷粉体作为外层陶瓷粉体；Or select the BNTSNA ceramic powder as the inner layer ceramic powder, and select the BNBT ceramic powder or the BNST ceramic powder as the outer layer ceramic powder; 步骤4，向所述外层陶瓷粉体中按照所述外层陶瓷粉体质量的50%-55%添加无水乙醇、90%-100%添加丁酮、3%-3.5%添加分散剂、9%-9.5%添加黏结剂、3%-3.5%添加邻苯二甲酸二丁酯、3%-3.5%添加聚乙二醇，制备外层陶瓷浆料；Step 4, adding absolute ethanol, 90%-100% butanone, 3%-3.5% dispersant, 50%-55% of the mass of the outer layer ceramic powder to the outer layer ceramic powder, 9%-9.5% adding binder, 3%-3.5% adding dibutyl phthalate, 3%-3.5% adding polyethylene glycol to prepare outer layer ceramic slurry; 步骤5，向所述内层陶瓷粉体中按照所述内层陶瓷粉体质量的50%-55%添加无水乙醇、90%-100%添加丁酮、3%-3.5%添加分散剂、9%-9.5%添加黏结剂、3%-3.5%添加邻苯二甲酸二丁酯、3%-3.5%添加聚乙二醇，制备内层陶瓷浆料；Step 5, adding absolute ethanol, 90%-100% of butanone, 3%-3.5% of dispersant, 90%-100% of the mass of the inner-layer ceramic powder into the inner-layer ceramic powder 9%-9.5% adding binder, 3%-3.5% adding dibutyl phthalate, 3%-3.5% adding polyethylene glycol to prepare inner layer ceramic slurry; 步骤6，所述外层陶瓷浆料和所述内层陶瓷浆料分别通过流延成型工艺，制备成为外层陶瓷膜和内层陶瓷膜；Step 6, the outer layer ceramic slurry and the inner layer ceramic slurry are respectively prepared into an outer layer ceramic film and an inner layer ceramic film through a tape casting process; 步骤7，将两片所述外层陶瓷膜分别覆盖在所述内层陶瓷膜的上表面和下表面上，通过压制成型得到具有三明治结构的陶瓷生坯；Step 7: Cover the upper surface and the lower surface of the inner ceramic film with two pieces of the outer ceramic film respectively, and obtain a green ceramic body with a sandwich structure by pressing and molding; 步骤8，将所述陶瓷生坯排胶8 h-10 h后，进行3 h-4 h的烧结，制备得到具有三明治结构的无铅高储能密度和储能效率陶瓷电介质，Step 8: After debinding the ceramic green body for 8 h-10 h, sintering for 3 h-4 h is performed to prepare a lead-free high energy storage density and energy storage efficiency ceramic dielectric with a sandwich structure, 其中，步骤1中所述BNTSNA陶瓷粉体的制备方法如下：Wherein, the preparation method of BNTSNA ceramic powder described in step 1 is as follows: 步骤1-1，按化学计量比称取所述Bi2O3、所述BaCO3、所述Na2CO3、所述TiO2、所述SrCO3、所述Al2O3以及所述Nb2O5作为所述BNTSNA陶瓷粉体的原料，加入球磨罐；Step 1-1, weigh the Bi 2 O 3 , the BaCO 3 , the Na 2 CO 3 , the TiO 2 , the SrCO 3 , the Al 2 O 3 and the Nb according to the stoichiometric ratio 2 O 5 is used as the raw material of the BNTSNA ceramic powder, added to the ball mill tank; 步骤1-2，称取球磨介质加入所述球磨罐中，将所述球磨罐置于球磨机中球磨10 h-15h；Step 1-2, weigh the ball milling medium and add it to the ball mill tank, and place the ball mill tank in the ball mill for ball milling for 10h-15h; 步骤1-3，将混合后的所述BNTSNA陶瓷粉体的原料在100℃的条件下，干燥8 h-10 h；Steps 1-3, drying the mixed raw materials of the BNTSNA ceramic powder at 100° C. for 8 h-10 h; 步骤1-4，将干燥后的所述BNTSNA陶瓷粉体的原料在密封条件下，在800℃-850℃的温度下煅烧3 h-4 h，得到预合成BNTSNA粉体；Steps 1-4, calcining the dried raw materials of the BNTSNA ceramic powder at a temperature of 800°C-850°C for 3 h-4 h under sealing conditions to obtain pre-synthesized BNTSNA powder; 步骤1-5，将所述预合成BNTSNA粉体和所述球磨介质再次加入球磨罐，置于球磨机后，球磨10 h-15 h得到粗制BNTSNA陶瓷粉体，对所述粗制BNTSNA陶瓷粉体进行烘干、过筛后，制备得到所述BNTSNA陶瓷粉体，In steps 1-5, the pre-synthesized BNTSNA powder and the ball milling medium are added to the ball milling tank again, placed in the ball mill, and ball-milled for 10 h-15 h to obtain crude BNTSNA ceramic powder. After the body is dried and sieved, the BNTSNA ceramic powder is prepared, 步骤2中所述BNBT陶瓷粉体或所述BNST陶瓷粉体的制备方法如下：The preparation method of the BNBT ceramic powder or the BNST ceramic powder described in step 2 is as follows: 步骤2-1，按化学计量比称取所述Bi2O3、所述BaCO3、所述Na2CO3、所述TiO2和所述SrCO3作为所述BNBT陶瓷粉体或所述BNST陶瓷粉体的原料，加入所述球磨罐；Step 2-1, weighing the Bi 2 O 3 , the BaCO 3 , the Na 2 CO 3 , the TiO 2 and the SrCO 3 according to the stoichiometric ratio as the BNBT ceramic powder or the BNST The raw material of ceramic powder is added into the ball mill tank; 步骤2-2，称取球磨介质加入所述球磨罐，将所述球磨罐置于所述球磨机中球磨10 h—15 h；Step 2-2, weigh the ball milling medium and add it to the ball mill tank, and place the ball mill tank in the ball mill for ball milling for 10 h to 15 h; 步骤2-3，将混合后的所述BNBT陶瓷粉体的原料或混合后的所述BNST陶瓷粉体的原料在100℃的条件下，干燥8 h-10 h；Step 2-3, drying the mixed raw material of the BNBT ceramic powder or the mixed raw material of the BNST ceramic powder under the condition of 100° C. for 8 h-10 h; 步骤2-4，将干燥后的所述BNBT陶瓷粉体的原料或干燥后的所述BNST陶瓷粉体的原料在密封条件下，在800℃-850℃的温度下煅烧3 h-4 h，得到预合成BNBT粉体或预合成BNST粉体；Step 2-4, calcining the dried raw material of the BNBT ceramic powder or the dried raw material of the BNST ceramic powder at a temperature of 800°C-850°C for 3 h-4 h under a sealed condition, Obtain pre-synthesized BNBT powder or pre-synthesized BNST powder; 步骤2-5，将所述预合成BNBT粉体或所述预合成BNST粉体加入所述球磨罐，将所述球磨介质也加入所述球磨罐，再将所述球磨罐置入所述球磨机，然后球磨10 h-15 h得到粗制BNBT陶瓷粉体或粗制BNST陶瓷粉体，对所述粗制BNBT陶瓷粉体或所述粗制BNST陶瓷粉体进行烘干、过筛后，制备得到所述BNBT陶瓷粉体或所述BNST陶瓷粉体。Step 2-5, adding the pre-synthesized BNBT powder or the pre-synthesized BNST powder to the ball mill tank, adding the ball milling medium to the ball mill tank, and then placing the ball mill tank into the ball mill , and then ball-milled for 10 h-15 h to obtain crude BNBT ceramic powder or crude BNST ceramic powder, and dried and sieved the crude BNBT ceramic powder or the crude BNST ceramic powder to prepare The BNBT ceramic powder or the BNST ceramic powder is obtained. 2.根据权利要求1所述的无铅高储能密度和高储能效率的陶瓷电介质的制备方法，其特征在于：2. the preparation method of the ceramic dielectric of lead-free high energy storage density and high energy storage efficiency according to claim 1, is characterized in that: 其中，所述球磨机的转速为350r/min-450 r/min，Wherein, the rotating speed of the ball mill is 350r/min-450r/min, 所述球磨介质为无水乙醇和ZrO2球， The ball milling medium is absolute ethanol and ZrO balls, 所述无水乙醇与所述内层陶瓷粉体或所述外层陶瓷粉体的质量比为1.2-1.5:1，The mass ratio of the absolute ethanol to the inner layer ceramic powder or the outer layer ceramic powder is 1.2-1.5:1, 所述ZrO2球与所述内层陶瓷粉体或所述外层陶瓷粉体的质量比为1.5-2.0:1。The mass ratio of the ZrO 2 balls to the inner layer ceramic powder or the outer layer ceramic powder is 1.5-2.0:1. 3.根据权利要求1所述的无铅高储能密度和高储能效率的陶瓷电介质的制备方法，其特征在于：3. the preparation method of the ceramic dielectric of lead-free high energy storage density and high energy storage efficiency according to claim 1, is characterized in that: 其中，所述陶瓷生坯在40℃-45℃的温度条件以及50MPa-250 MPa的压力条件下压制成型，Wherein, the ceramic green body is press-molded under the temperature condition of 40℃-45℃ and the pressure condition of 50MPa-250MPa, 所述陶瓷生坯在550℃-600℃的温度条件下排胶，The ceramic green body is debonded at a temperature of 550°C-600°C, 排胶后的所述陶瓷生坯在密闭的坩埚内进行烧结，The ceramic green body after debinding is sintered in a closed crucible, 在步骤8中的烧结工艺中，烧结温度以3℃/min-4℃/min的升温速率由室温升至1180℃-1200℃，再以10℃/min-20℃/min的降温速率降至1050℃-1060℃进行烧结。In the sintering process in step 8, the sintering temperature is raised from room temperature to 1180°C-1200°C at a heating rate of 3°C/min-4°C/min, and then lowered at a cooling rate of 10°C/min-20°C/min Sinter at 1050℃-1060℃. 4.根据权利要求1所述的无铅高储能密度和高储能效率陶瓷电介质的制备方法，其特征在于：4. the preparation method of lead-free high energy storage density and high energy storage efficiency ceramic dielectric according to claim 1, is characterized in that: 其中，所述Bi2O3、所述BaCO3、所述Na2CO3、所述TiO2、所述SrCO3、所述Al2O3以及所述Nb2O5的纯度均大于98%。Wherein, the purity of the Bi 2 O 3 , the BaCO 3 , the Na 2 CO 3 , the TiO 2 , the SrCO 3 , the Al 2 O 3 and the Nb 2 O 5 are all greater than 98% . 5.根据权利要求1所述的无铅高储能密度和高储能效率的陶瓷电介质的制备方法，其特征在于：5. the preparation method of the ceramic dielectric of lead-free high energy storage density and high energy storage efficiency according to claim 1, is characterized in that: 其中，所述分散剂为三油酸甘油脂，Wherein, the dispersing agent is triolein, 所述黏结剂为聚乙烯醇缩丁醛。The binder is polyvinyl butyral. 6.一种无铅高储能密度和高储能效率的陶瓷电介质，其特征在于，包括：6. A lead-free ceramic dielectric with high energy storage density and high energy storage efficiency, characterized in that, comprising: 依次贴合的第一电介质层、第二电介质层以及第三电介质层，The first dielectric layer, the second dielectric layer and the third dielectric layer, which are laminated in sequence, 其中，所述第一电介质层、所述第二电介质层和所述第三电介质层形成三明治结构，Wherein, the first dielectric layer, the second dielectric layer and the third dielectric layer form a sandwich structure, 所述第一电介质层和所述第三电介质层材料相同，The first dielectric layer and the third dielectric layer are of the same material, 所述无铅高储能密度和高储能效率的陶瓷电介质为权利要求1-5中任意一项所述的制备方法制备得到的无铅高储能密度和高储能效率的陶瓷电介质。The lead-free high energy storage density and high energy storage efficiency ceramic dielectric is the lead-free high energy storage density and high energy storage efficiency ceramic dielectric prepared by the preparation method described in any one of claims 1-5. 7.根据权利要求6所述的无铅高储能密度和高储能效率的陶瓷电介质，其特征在于：7. The lead-free ceramic dielectric with high energy storage density and high energy storage efficiency according to claim 6, characterized in that: 其中，所述第一电介质层为BNTSNA，所述第二电介质层为BNBT或BNST。Wherein, the first dielectric layer is BNTSNA, and the second dielectric layer is BNBT or BNST. 8.根据权利要求6中所述的无铅高储能密度和高储能效率的陶瓷电介质，其特征在于：8. The lead-free high-energy-storage density and high-energy-storage efficiency ceramic dielectric according to claim 6, characterized in that: 其中，所述第一电介质层为BNBT或BNST，所述第二电介质层为BNTSNA。Wherein, the first dielectric layer is BNBT or BNST, and the second dielectric layer is BNTSNA. 9.根据权利要求7或8中所述的无铅高储能密度和高储能效率的陶瓷电介质，其特征在于：9. The ceramic dielectric of lead-free high energy storage density and high energy storage efficiency according to claim 7 or 8, characterized in that: 其中，所述BNTSNA的击穿场强为在300 kV/cm以上，Wherein, the breakdown field strength of the BNTSNA is above 300 kV/cm, 所述BNBT的极化强度为在30 μC/cm2以上，The polarization strength of the BNBT is above 30 μC/cm 2 , 所述BNST的极化强度为在40 μC/cm2以上。The polarization intensity of the BNST is above 40 μC/cm 2 .
CN202011156932.7A 2020-10-26 2020-10-26 Lead-free ceramic dielectric with high energy storage density and high energy storage efficiency and preparation method thereof Active CN112341191B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011156932.7A CN112341191B (en) 2020-10-26 2020-10-26 Lead-free ceramic dielectric with high energy storage density and high energy storage efficiency and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011156932.7A CN112341191B (en) 2020-10-26 2020-10-26 Lead-free ceramic dielectric with high energy storage density and high energy storage efficiency and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112341191A CN112341191A (en) 2021-02-09
CN112341191B true CN112341191B (en) 2022-02-22

Family

ID=74360068

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011156932.7A Active CN112341191B (en) 2020-10-26 2020-10-26 Lead-free ceramic dielectric with high energy storage density and high energy storage efficiency and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112341191B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116874295B (en) * 2023-06-07 2025-02-11 西安电子科技大学 A layered high energy storage density and high energy storage efficiency ceramic medium and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7089659B2 (en) * 2001-05-25 2006-08-15 Kyocera Corporation Method of producing ceramic laminates
CN1176044C (en) * 2002-09-11 2004-11-17 山东大学 Bismuth sodium titanate series film material and preparing process thereof
JP3994163B2 (en) * 2003-09-26 2007-10-17 独立行政法人物質・材料研究機構 Manufacturing method of NBT ferroelectric thin film
CN107140974A (en) * 2017-04-11 2017-09-08 陕西科技大学 A kind of unleaded high energy storage density ST NBT ceramic materials of microwave sintering and preparation method thereof
CN109734440B (en) * 2019-03-11 2021-08-24 西南科技大学 SrTiO3-based energy storage medium ceramic with heterogeneous layered structure and preparation method thereof
CN111205087B (en) * 2020-01-14 2021-05-11 同济大学 A kind of high energy storage density ceramic with bismuth-based sandwich structure and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Significantly enhanced energy storage density and efficiency of BNT-based perovskite ceramics via A-site defect engineering;Fei Yan et. al;《Energy Storage Materials》;20200606;第30卷;第392-400页 *
Tailoring antiferroelectricity with high energy-storage properties in Bi0.5Na0.5TiO3–BaTiO3 ceramics by modulating Bi/Na ratio;Qingning Li et. al;《Journal of Materials Science: Materials in Electronics》;20160620;第27卷(第10期);第10810-10815页 *

Also Published As

Publication number Publication date
CN112341191A (en) 2021-02-09

Similar Documents

Publication Publication Date Title
CN109354492B (en) Bismuth-based lead-free high energy storage density ceramic material and preparation method thereof
CN101183610B (en) Chemical coating prepared base metal internal electrode multi-layer ceramic chip capacitor dielectric material
CN108751982B (en) A kind of lead-free high energy storage density ceramic material and preparation method thereof
CN106915960B (en) Lead-free ceramic material with high energy storage density and energy storage efficiency and preparation method thereof
JPS6036369A (en) Ceramic manufacture
CN102260044A (en) Energy storage niobate microcrystalline glass dielectric material and preparation method thereof
CN111205087B (en) A kind of high energy storage density ceramic with bismuth-based sandwich structure and preparation method thereof
CN102795852A (en) Novel LTCC low-frequency dielectric ceramic capacitor material
CN114621004A (en) High-entropy ceramic material with high energy storage density and preparation method thereof
CN108623300A (en) Unleaded relaxation ferroelectric energy storage ceramic of barium titanate-niobic zincic acid bismuth base and preparation method thereof
CN116947483B (en) A high-capacitance multilayer BME ceramic capacitor prepared by precursor pre-sintering method and its manufacturing method
CN107602115A (en) A kind of unleaded high energy storage density and the stable ceramic material of wide temperature and preparation method thereof
CN112341191B (en) Lead-free ceramic dielectric with high energy storage density and high energy storage efficiency and preparation method thereof
US3028656A (en) Ceramic material and method of producing the same
CN113511893B (en) A kind of BNT-based three-layer structure high energy storage density ceramics and preparation method thereof
CN107739204B (en) Ceramic dielectric material with excellent bias characteristic and preparation method thereof
CN106915964B (en) Lead-free high-energy-storage-density ceramic material and preparation method thereof
CN111253151B (en) Bismuth ferrite barium titanate-based ceramics with high energy storage density and high power density and preparation method thereof
CN109320236B (en) Composite material with high energy storage density and charge-discharge performance and preparation method thereof
CN107573060B (en) Ceramic dielectric material for high-voltage-resistant MLCC and preparation method thereof
CN114605148B (en) Sandwich laminated ceramic material and preparation method thereof
CN105198405B (en) A kind of pressure-sensitive double functional ceramics of electric capacity and preparation method thereof
CN116874295B (en) A layered high energy storage density and high energy storage efficiency ceramic medium and preparation method thereof
CN114573338A (en) Preparation method and application of high-energy-storage-density dielectric ceramic
CN114292104A (en) Energy storage ceramic material for pulse capacitor and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant