CN103077828A - Charging-discharging module based on giant permittivity ceramic capacitor and preparation method of charging-discharging module - Google Patents

Abstract

A charging and discharging module based on a giant permittivity ceramic capacitor and a preparation method thereof relate to a capacitor. The module is provided with at least 2 giant permittivity ceramic capacitor monomers, all of which are connected in series or/and in parallel, and the monomers are sequentially provided with a lower silver electrode layer, a lower electrical breakdown resistance layer, and an intermediate dielectric layer from bottom to top , the upper electric breakdown resistance layer and the upper silver electrode layer. Prepare the intermediate dielectric layer of the giant permittivity ceramic capacitor monomer; cover the lower surface of the intermediate dielectric layer with a lower electrical breakdown resistance layer; cover the upper surface of the intermediate dielectric layer with an electrical breakdown resistance layer; coat the lower surface of the lower electrical breakdown resistance layer Coating conductive silver paste, and then heat treatment, the lower silver electrode layer is obtained; coating conductive silver paste on the upper surface of the upper electric breakdown resistance layer, and then heat treatment, that is, the upper silver electrode layer, so far a large permittivity ceramic capacitor monomer is obtained; The obtained giant permittivity ceramic capacitor monomers are assembled into a charging and discharging module based on giant permittivity ceramic capacitors in series or/and in parallel.

Description

A charging and discharging module based on a giant permittivity ceramic capacitor and its preparation method

technical field

The invention relates to capacitors, in particular to a charging and discharging module based on a giant permittivity ceramic capacitor and a preparation method thereof.

Background technique

Mobile electrical equipment such as mobile phones and laptops have become indispensable tools in modern daily work and life, with more and more functions and more and more power requirements. Most of these mobile electrical devices use lithium-ion chemical batteries as energy storage components. The chemical batteries themselves have disadvantages such as slow charging and discharging, small energy storage, limited cycle life, and potential safety hazards, which affect the long-term normal use of mobile electrical devices.

As the world's energy crisis is becoming more and more serious, the wide application of new energy sources such as solar energy and wind energy has become an effective way to solve the energy shortage in the world, and thus wind power and solar photovoltaic power generation have developed rapidly. However, solar and wind power generation are strongly dependent on natural weather. When the wind and sunlight are abundant, the power generated may be greater than the load demand, resulting in power waste; when the wind and sunlight are lacking, the power generation is difficult to meet the load demand. Therefore, it is of great significance to develop fast energy storage systems in photovoltaic power generation, wind power generation and other systems to achieve efficient use of energy. Traditionally, lead-acid batteries are used to store and release large amounts of electrical energy, which has the advantages of mature manufacturing technology and high cost performance, but contains harmful substances such as heavy metal lead and sulfuric acid, which pose a serious threat to the health of workers and environmental protection, and liquid substances such as sulfuric acid During use, it will gradually volatilize and make the battery invalid, and explosion accidents may occur when the temperature is high.

However, ordinary supercapacitors are bulky and difficult to carry. Most supercapacitors contain liquid or emulsion, which is easy to dry out and become invalid and scrapped. (Jayalakshmi M, Balasubramanian K., Simple Capacitors to Supercapacitors-An Overview [J]. International Journal of Electrochemical Science, 2008, 3(11) 1196-1217; Burke A, Ultracapacitors: why, how, and where is the technology [J] .Journal of Power Sources, 2000, 91(1):37-50).

The development of high-performance and large-capacity fast energy storage capacitors is one of the important tasks in the exploration of new energy. The physical energy storage mechanism of ceramic capacitors has many advantages that chemical batteries do not have: fast charging and discharging with large currents, small size, no harmful metals, It will not cause pollution to the environment, and the number of charging and discharging cycles will be large. Calcium copper titanate is a new type of oxide functional material with large permittivity and broad application prospects. The material has a low-frequency permittivity of 10 ⁵ in the temperature range of 100-600K, and has good temperature stability; copper calcium titanate is a centrosymmetric crystal structure, not a ferroelectric with electric dipole moment, and does not appear iron Significant changes in the dielectric properties of electric materials near the ferroelectric-paraelectric phase transition temperature [Subramanian M A, Li D, Duan N, et al. High dielectric constant in ACu ₃ Ti ₄ O ₁₂ and ACu ₃ Ti ₄ O ₁₂ phases. Journal of Solid State Chemistry, 200, 151(2):323-325].

Contents of the invention

The purpose of the present invention is to aim at the above-mentioned shortcomings existing in the existing supercapacitors, and provide the characteristics of fast charge and discharge rate, large capacitance, small volume, high temperature stability, no pollution, long life, miniaturization and convenient portability, etc., which can be used in A charge-discharge module based on a large permittivity ceramic capacitor and a preparation method thereof for quickly supplying electric energy to mobile devices such as mobile phones and notebook computers when the electric energy is insufficient, effectively prolonging the working time of electrical equipment (including mobile phones, notebook computers, etc.).

The charging and discharging module based on the giant permittivity ceramic capacitor is provided with at least 2 giant permittivity ceramic capacitor monomers, all the giant permittivity ceramic capacitor monomers are connected in series or/and in parallel, and the giant permittivity ceramic capacitor monomers are connected from the bottom A lower silver electrode layer, a lower electric breakdown-resistant layer, an intermediate dielectric layer, an upper electric breakdown-resistant layer and an upper silver electrode layer are sequentially provided on top.

The lower silver electrode layer is coated on the lower surface of the lower electrical breakdown-resistant layer, and the upper silver electrode layer is coated on the upper surface of the upper electrical breakdown-resistant layer. The thickness of the lower silver electrode layer can be 5-500 nm. The thickness of the silver electrode layer may be 5-500nm.

The intermediate dielectric layer uses copper calcium titanate ceramics or copper calcium titanate-based ceramics with a large permittivity as the dielectric, and the intermediate dielectric layer is in the shape of a sheet with a thickness of 1-5000 μm.

The lower electrical breakdown resistance layer may be one of nano-alumina layer, nano-titanium oxide layer or nano-silicon oxide layer, etc., and the thickness of the lower electrical breakdown resistance layer may be 5-500 nm.

The upper electrical breakdown resistance layer may be one of nano-alumina layer, nano-titanium oxide layer or nano-silicon oxide layer, etc., and the thickness of the lower electrical breakdown resistance layer may be 5-500 nm.

The preparation method of the charging and discharging module based on the giant permittivity ceramic capacitor is as follows:

1) Prepare the intermediate dielectric layer of the giant permittivity ceramic capacitor monomer;

In step 1), the intermediate dielectric layer uses giant permittivity copper calcium titanate ceramics or copper calcium titanate based ceramics as the dielectric; the copper calcium titanate ceramics is made of oxides containing calcium, copper and titanium, Compounds, chlorides, metal-organic compounds and other compounds are used as raw materials, and the molar ratio of calcium: copper: titanium is mixed at 1:3:4, and the uniformly mixed powder is pre-fired at 850-950°C for 2-5 hours to form titanium. Copper-calcium titanate powder, mix copper-calcium titanate powder, 6wt% polyvinyl alcohol aqueous solution, glycerin and defoaming agent in a mass ratio of 40-50:30-45:5:0.2, and prepare the thickness by casting process It is a green sheet of 1-5000 μm, and the green sheet is sintered in an electric furnace at 1060-1100 °C for 2-10 hours to obtain copper calcium titanate ceramics;

The copper calcium titanate-based ceramics are based on copper calcium titanate powder prepared from calcium, copper and titanium oxides, carbonates, chlorides and other compounds as raw materials, and the copper calcium titanate powder is added with vanadium, Compounds such as strontium or niobium form copper calcium titanate-based mixed powder, and the copper calcium titanate-based mixed powder, 6wt% polyvinyl alcohol aqueous solution, glycerol and defoaming agent are in a mass ratio of 40-50:30-45:5: 0.2 Mix evenly, prepare a green sheet with a thickness of 1-5000 μm by tape casting process, and sinter the green sheet in an electric furnace at 1060-1100 °C for 2-10 hours to obtain copper calcium titanate-based ceramics.

2) Using sol-gel coating method, vacuum evaporation method or vacuum sputtering method to cover the lower surface of the intermediate dielectric layer with an electrical breakdown resistance layer;

3) Using sol-gel coating method, vacuum evaporation method or vacuum sputtering method to cover the upper surface of the intermediate dielectric layer with an electric breakdown resistance layer;

4) Coating conductive silver paste on the lower surface of the lower electric breakdown resistant layer, and then heat-treating to obtain the lower silver electrode layer;

In step 4), the heat treatment temperature may be 600° C., and the heat treatment time may be 30 minutes.

5) Coating conductive silver paste on the upper surface of the upper electric breakdown resistance layer, and then heat treatment, that is, the upper silver electrode layer is obtained, so far a large permittivity ceramic capacitor monomer is obtained;

In step 5), the heat treatment temperature may be 600° C., and the heat treatment time may be 30 minutes.

6) The obtained giant permittivity ceramic capacitor monomers are assembled into a charging and discharging module based on giant permittivity ceramic capacitors in series or/and in parallel.

In step 6), the charging and discharging module based on the giant permittivity ceramic capacitor can be assembled into a multilayer chip ceramic capacitor by connecting the giant permittivity ceramic capacitor monomers in parallel. Specifically, the giant permittivity ceramic capacitor monomer, the outer Composed of electrode and internal electrode, the silver electrode layer of the giant permittivity ceramic capacitor is used as the internal electrode, and the multilayer chip ceramic capacitor includes alternately stacked internal electrodes, and there is a lower electric breakdown resistance layer between two adjacent internal electrodes , the middle dielectric layer and the upper electric breakdown resistance layer are separated, and the external electrodes are drawn from the two opposite sides of the internal electrodes, and then the multilayer chip ceramic capacitors are connected in series or/and in parallel to obtain a fast charge and discharge super ceramic capacitor module.

Compared with chemical capacitors, the huge permittivity ceramic capacitors adopted in the present invention have the characteristics of fast charging and discharging speed, high withstand voltage, no chemical pollution, low heat generation, and high safety, and overcome the shortcomings of the existing ordinary ceramic capacitors with small capacitance .

The invention has the characteristics of fast charge and discharge rate, large capacity, high temperature stability, no pollution, long life, miniaturization and easy portability, etc. It can quickly supply power to mobile devices such as mobile phones and notebook computers when the power is insufficient, and effectively extend the life of electrical appliances. Working hours of devices (including mobile phones, laptops, etc.).

Description of drawings

FIG. 1 is a schematic structural view of a monolithic ceramic capacitor with a large permittivity according to an embodiment of the present invention.

FIG. 2 is a schematic structural diagram of a multilayer chip ceramic capacitor according to an embodiment of the present invention.

FIG. 3 is a schematic structural diagram of a charging and discharging module of a giant permittivity ceramic capacitor according to an embodiment of the present invention.

Fig. 4 is a schematic diagram of the application system of the embodiment of the present invention.

Detailed ways

The following embodiments will further illustrate the present invention in conjunction with the accompanying drawings. It should be emphasized that the following description is only exemplary and not intended to limit the scope of the invention and its application.

Referring to Fig. 1, the charging and discharging module based on the giant permittivity ceramic capacitor is provided with at least 2 giant permittivity ceramic capacitor monomers, and all giant permittivity ceramic capacitor monomers are connected in series or/and in parallel, and the giant permittivity ceramic capacitor The monomer is sequentially provided with a lower silver electrode layer 1 , a lower breakdown-resistant layer 2 , an intermediate dielectric layer 3 , an upper breakdown-resistant layer 4 and an upper silver electrode layer 5 from bottom to top.

The lower silver electrode layer 1 is coated on the lower surface of the lower electrical breakdown-resistant layer 2, and the upper silver electrode layer 5 is coated on the upper surface of the upper electrical breakdown-resistant layer 4. The thickness of the lower silver electrode layer 1 can be 5-5. 500 nm, the thickness of the upper silver electrode layer 5 may be 5-500 nm.

The intermediate dielectric layer 3 uses copper calcium titanate ceramics or copper calcium titanate-based ceramics with a large permittivity as the dielectric, and the intermediate dielectric layer 3 is in the shape of a sheet with a thickness of 1-5000 μm.

The lower electrical breakdown resistant layer 2 can be one of nano-alumina layer, nano-titanium oxide layer or nano-silicon oxide layer, etc., and the thickness of the lower electrical breakdown resistant layer 2 can be 5-500 nm.

The upper electrical breakdown resistance layer 4 can be one of nano-alumina layer, nano-titanium oxide layer or nano-silicon oxide layer, etc., and the thickness of the lower electrical breakdown resistance layer 4 can be 5-500 nm.

Referring to FIG. 2 , the multilayer chip ceramic capacitor is specifically composed of a large permittivity ceramic capacitor cell 6 , an external electrode 7 and an internal electrode 8 . The metal electrode layer of the giant permittivity ceramic capacitor is used as the internal electrode 8. The multilayer chip ceramic capacitor includes at least two alternately stacked internal electrodes. The layers are bonded, and the external electrodes 7 are led out on two opposite sides of the internal electrodes.

Referring to FIG. 3 , the multilayer chip ceramic capacitors 9 are connected in series or/and in parallel to obtain a fast charge and discharge super ceramic capacitor module, and the module has a total electrode 10 for connection with an external circuit.

Example 1:

In this embodiment, a large permittivity ceramic capacitor monomer is made with copper calcium titanate ceramics as the intermediate dielectric layer 3, and the aluminum oxide nano-insulation layer is the lower breakdown-resistant layer 2 and the upper breakdown-resistant layer 4. To form a charging and discharging module of a giant permittivity ceramic capacitor, the specific steps are:

1) Preparation of copper calcium titanate ceramics by solid state reaction method. Mix calcium carbonate, copper oxide and titanium oxide in a molar ratio of 1:3:4, and pre-fire the mixed powder at 850°C for 5 hours to form copper calcium titanate powder. Copper calcium titanate powder, 6wt% Polyvinyl alcohol aqueous solution, glycerin and defoaming agent are mixed evenly at a mass ratio of 40:30:5:0.2, and a green sheet with a thickness of 1 μm is prepared by casting technology, and the green sheet is sintered in an electric furnace at 1060 ° C for 10 hours to obtain copper titanate calcium ceramics.

2) The sol-gel method coats a uniform and dense aluminum oxide nano-insulation layer on the surface of the ceramic sheet. Dissolve 10g of aluminum isopropoxide in 140g of deionized water, stir in a water bath at 85°C for 10 minutes, add HNO ₃ to adjust the pH value to about 3, and continue stirring in a water bath at 85°C for 5 hours to obtain a transparent sol. The solid content in alumina sol is about 5%. Dip the ceramic flakes in alumina sol, lower the liquid level at a speed of 10cm/min, the alumina sol evenly wets the surface of copper calcium titanate ceramics, and then dry it in an oven at 90°C for 30min, and then repeat the coating once. Rise to 100°C at room temperature for 30 minutes at a rate of 3°C/min to completely drain the water in the dry gel, then rise to 600°C at 1°C/min, then raise to 1000°C at 3°C/min and keep for 2 hours. A 100nm dense aluminum oxide nano insulating layer was obtained.

3) The upper and lower surfaces of the ceramic sheet coated with an alumina nano-insulation layer are coated with 5nm silver paste, and the temperature is raised to 600°C at room temperature for 30 minutes at a temperature of 3°C/min to obtain the intermediate dielectric layer 3 with acid copper calcium ceramics, alumina The nano insulating layer is a single ceramic capacitor with a large permittivity of the lower electric breakdown resistance layer 2 and the upper electric breakdown resistance layer 4 .

4) Connect 100 large permittivity ceramic capacitors in parallel to form a multilayer chip ceramic capacitor, and then connect 10 multilayer chip ceramic capacitors in series to obtain a giant permittivity ceramic capacitor module. The capacitance of the module is 100F.

5) The schematic diagram of the application system of this embodiment is shown in Figure 4. The system is composed of a power supply module 11 , a charging and discharging module 12 of a ceramic capacitor with a large permittivity, an intelligent control circuit board 13 and a load electrical appliance 14 . In this embodiment, the power module is a wind power generation system, and the load is 10 energy-saving lamps with a power of 20W. In this embodiment, the excess electric energy is stored in the charge-discharge module of the ceramic capacitor with a large permittivity, and the electric energy stored when the voltage at both ends is 100V is 500kJ. When there is no wind or light wind, the power generated by the wind power generation system is less than the load power, and the intelligent control circuit board releases the energy in the charging and discharging module of the giant permittivity ceramic capacitor to supply power to the load. The stored energy can supply 10 Only energy-saving lamps with a power of 20W work normally for about 1 hour.

Example 2:

In this embodiment, a large permittivity ceramic capacitor monomer is made with copper calcium titanate ceramics as the intermediate dielectric layer 3, and the titanium oxide nano-insulation layer as the lower breakdown-resistant layer 2 and the upper breakdown-resistant layer 4. To form a charging and discharging module of a giant permittivity ceramic capacitor, the specific steps are:

1) Preparation of copper calcium titanate ceramics by solid state reaction method. Mix calcium carbonate, copper chloride and titanium oxide in a molar ratio of 1:3:4, and pre-fire the mixed powder at 950°C for 2 hours to form copper calcium titanate powder. Copper calcium titanate powder, 6wt % polyvinyl alcohol aqueous solution, glycerol and antifoaming agent were mixed evenly at a mass ratio of 50:45:5:0.2, and a green sheet with a thickness of 100 μm was prepared by tape casting technology, and the green sheet was sintered in an electric furnace at 1080 ° C for 5 hours to obtain titanic acid copper calcium ceramics.

2) Coating a uniform and dense titanium oxide nano-insulation layer on the surface of copper calcium titanate ceramics by sol-gel method. Dissolve 5 g of butyl titanate in 20 g of absolute ethanol, add HNO ₃ to adjust the pH value to about 3, and obtain a yellow transparent titanium oxide sol. Soak the ceramic flakes in the titanium oxide sol, lower the liquid level at a speed of 10cm/min, the titanium oxide sol evenly wets the surface of copper calcium titanate ceramics, and then dry it in an oven at 90°C for 30 minutes, and then repeat the coating once. Using segmented heating method, heat at room temperature at 3°C/min to 100°C for 30 minutes to completely drain the water in the xerogel, and then at 1°C/min to 600°C for 2 hours to obtain 50nm dense titanium oxide Nano insulating layer.

3) The upper and lower surfaces of the ceramic sheet coated with the titanium oxide nano-insulation layer are coated with 200nm silver paste, and the temperature is raised to 600°C at room temperature for 30 minutes at a temperature of 3°C/min to obtain copper calcium titanate ceramics as the intermediate dielectric layer 3, titanium oxide The nano insulating layer is a single ceramic capacitor with a large permittivity of the lower electric breakdown resistance layer 2 and the upper electric breakdown resistance layer 4 .

4) Connect 100 large permittivity ceramic capacitors in parallel to form a multilayer chip ceramic capacitor, and then connect 10 parallel multilayer chip ceramic capacitors in series to obtain a giant permittivity ceramic capacitor module. The capacitance of the module is 500F.

5) The schematic diagram of the application system of this embodiment is shown in FIG. 4 . The system is composed of a power supply module 11 , a charging and discharging module 12 of a ceramic capacitor with a large permittivity, an intelligent control circuit board 13 and a load electrical appliance 14 . In this embodiment, the power module is a wind power generation system, and the loads are two computers with a power of 50W. In this embodiment, the excess electric energy in the power supply module is stored in the charging and discharging module of the ceramic capacitor with a large permittivity. When the voltage across the two ends is 100V, the stored electric energy is 2500kJ. When there is no wind and light wind, the power generated by the wind power generation system is less than the load power, and the intelligent control circuit board releases the energy in the charging and discharging module of the giant permittivity ceramic capacitor to supply power to the load. The stored energy can be used for two A 50W computer works normally for about 7 hours.

Example 3:

In this embodiment, a large permittivity ceramic capacitor monomer is made with copper calcium titanate ceramics as the intermediate dielectric layer 3, and the silicon oxide nano-insulation layer as the lower breakdown-resistant layer 2 and the upper breakdown-resistant layer 4. To form a charging and discharging module of a giant permittivity ceramic capacitor, the specific steps are:

1) Preparation of copper calcium titanate ceramics by solid state reaction method. Mix calcium nitrate, copper oxide and titanium oxide in a molar ratio of 1:3:4, and pre-fire the mixed powder at 900°C for 3 hours to form copper calcium titanate powder. Copper calcium titanate powder, 6wt% Polyvinyl alcohol aqueous solution, glycerin and defoaming agent are mixed evenly at a mass ratio of 45:40:5:0.2, and a green sheet with a thickness of 2000 μm is prepared by casting technology, and the green sheet is sintered in an electric furnace at 1100 ° C for 2 hours to obtain copper titanate calcium ceramics.

2) The sol-gel method coats a uniform and dense silicon oxide nano-insulation layer on the surface of the ceramic sheet. According to the molar ratio of ethyl orthosilicate: ethanol: H ₂ O: H ⁺ =1:6.5:3.7:0.08, fully mix ethyl orthosilicate and absolute ethanol, and add deionized The mixture of water and acidic catalyst, after the dropwise addition, the reaction mixture is stirred and refluxed at a certain temperature for a certain period of time, after the sol is cooled, a certain amount of N, N-dimethylformamide is added as a dryness control chemical additive, and the stirring is continued for 15 minutes to obtain Silica sol. Soak the ceramic flakes in the silica sol, lower the liquid level at a speed of 10cm/min, the silica sol evenly wets the surface of copper calcium titanate ceramics, then dry it in an oven at 90°C for 30min, and then repeat the coating once. In order to obtain a complete and dense silicon oxide nano-layer without cracks, adopt the method of segmental heating at room temperature at 3°C/min to 100°C for 30 minutes to completely drain the water in the dry gel, and then heat at 1°C/min Raise to 600°C, then rise to 800°C at 3°C/min for 2 hours to obtain a dense silicon oxide nano-insulation layer.

3) The upper and lower surfaces of the ceramic sheet coated with a silicon oxide nano-insulation layer are coated with 500nm silver paste, and the temperature is raised to 600°C at room temperature for 30 minutes to obtain copper calcium titanate ceramics as the intermediate dielectric layer 3, silicon oxide The nano insulating layer is a single ceramic capacitor with a large permittivity of the lower electric breakdown resistance layer 2 and the upper electric breakdown resistance layer 4 .

4) Connect 50 large permittivity ceramic capacitors in parallel to form a multilayer chip ceramic capacitor, and then connect 20 parallel multilayer chip ceramic capacitors in series to obtain a giant permittivity ceramic capacitor module. The capacitance of the module is 200F.

5) The schematic diagram of the application system of this embodiment is shown in FIG. 4 . The system consists of a power supply module, a charging and discharging module for ceramic capacitors with a large permittivity, an intelligent control circuit board, and load appliances. In this embodiment, the power module is a photovoltaic power generation system, and the loads are five energy-saving lamps with a power of 20W. When the sunlight is sufficient, the power generation efficiency is high, and the electricity consumption is low, the excess electric energy in the power supply module is stored in the large permittivity ceramic capacitor module. When the voltage across the two ends is 200V, the stored electric energy is 4000kJ. At night or when the sun is insufficient, the power generated by the photovoltaic power generation system is lower than the load power, and the intelligent control circuit board releases the energy in the ceramic capacitor module with a large permittivity to supply power to the load. The stored energy can be used for Five energy-saving lamps with a power of 20W work normally for about 6 hours.

Example 4:

In this embodiment, a large permittivity ceramic capacitor monomer is made with copper calcium titanate-based ceramics as the intermediate dielectric layer, and the alumina nano-insulation layer is the electric breakdown resistance layer, and the charge and discharge module of the giant permittivity ceramic capacitor is composed of this monomer , the specific steps are:

1) Preparation of copper calcium titanate based ceramics by solid state reaction method. Mix calcium carbonate, copper oxide and titanium oxide uniformly in a molar ratio of 1:3:4, pre-fire the mixed powder at 900°C for 3 hours to form copper calcium titanate powder, copper calcium titanate powder and strontium carbonate The mass ratio of 99.5:0.5 is mixed to form copper calcium titanate-based powder, and the copper calcium titanate-based powder, 6wt% polyvinyl alcohol aqueous solution, glycerol and defoamer are mixed evenly in a mass ratio of 50:45:5:0.2, A green sheet with a thickness of 2000 μm was prepared by tape casting, and the green sheet was sintered in an electric furnace at 1100 °C for 2 hours to obtain copper calcium titanate-based ceramics.

2) The vacuum sputtering method is used to sputter the aluminum oxide nano insulating layer on the surface of the copper calcium titanate based ceramic sheet. In the process of magnetron sputtering, the vacuum degree is controlled at 10 ^-3 ~ 10 ^-2 Pa, the power is controlled at 8 ~ 10W, the rotation speed of the substrate is fixed at 36r/min, and the sputtering time is 30s. The thickness of the aluminum oxide nano insulating layer is 30nm.

3) The upper and lower surfaces of the ceramic sheet sputtered with an alumina nano-insulation layer are coated with silver paste, and the temperature is raised to 600 ° C at room temperature for 30 minutes to obtain a copper-calcium titanate-based ceramic as the intermediate dielectric layer, and the aluminum oxide nano The insulating layer is a single ceramic capacitor with a large permittivity of the electric breakdown resistance layer.

4) Connect 50 large permittivity ceramic capacitors in parallel to form a multilayer chip ceramic capacitor, and then connect 20 parallel multilayer chip ceramic capacitors in series to obtain a giant permittivity ceramic capacitor module. The capacitance of the module is 600F.

5) The schematic diagram of the application system of this embodiment is shown in FIG. 4 . The system consists of a power supply module, a charging and discharging module for ceramic capacitors with a large permittivity, an intelligent control circuit board, and load appliances. In this embodiment, the power module is a photovoltaic power generation system, and the loads are 10 computers with a power of 50W. When the sunlight is sufficient, the power generation efficiency is high, and the electricity consumption is low, the excess electric energy in the power supply module is stored in the large permittivity ceramic capacitor module. When the voltage across the two ends is 150V, the stored electric energy is 6750kJ. At night or when the sun is insufficient, the power generated by the photovoltaic power generation system is less than the load power, and the intelligent control circuit board releases the energy in the ceramic capacitor module with a large permittivity to supply power to the load. The stored electric energy can be used for Ten 50W computers work normally for about 3 hours.

Example 5:

In this embodiment, a large permittivity ceramic capacitor monomer is made with copper calcium titanate-based ceramics as the intermediate dielectric layer and a silicon oxide nano-insulation layer as the electric breakdown resistance layer, and the charge and discharge module of the giant permittivity ceramic capacitor is composed of this monomer , the specific steps are:

1) Preparation of copper calcium titanate based ceramics by solid state reaction method. Mix calcium carbonate, copper oxide and titanium oxide uniformly in a molar ratio of 1:3:4, pre-fire the mixed powder at 950°C for 2 hours to form copper calcium titanate powder, copper calcium titanate powder and di Vanadium is mixed into copper calcium titanate-based powder at a mass ratio of 99:1, and the copper calcium titanate-based powder, 6wt% polyvinyl alcohol aqueous solution, glycerin and defoamer are mixed at a mass ratio of 40:30:5:0.2 Uniform, using a casting process to prepare a green sheet with a thickness of 400 μm, the green sheet was sintered in an electric furnace at 1060 ° C for 10 hours to obtain copper calcium titanate-based ceramics.

2) A silicon oxide nano-insulation layer is sputtered on the surface of copper calcium titanate based ceramics by vacuum sputtering method. During the magnetron sputtering process, the vacuum degree is controlled at 10 ^-3 ~ 10 ^-2 Pa, the power is controlled at 6 ~ 8W, the substrate rotation speed is fixed at 36r/min, and the sputtering time is 30s. The thickness of the silicon oxide nano insulating layer is 20nm.

3) The upper and lower surfaces of the ceramic sheet sputtered with a silicon oxide nano-insulation layer are coated with silver paste, and the temperature is raised to 600 ° C at room temperature for 30 minutes to obtain a copper-calcium titanate-based ceramic as the intermediate dielectric layer, and the silicon oxide nano The insulating layer is a single ceramic capacitor with a large permittivity of the electric breakdown resistance layer.

4) Connect 50 large permittivity ceramic capacitors in parallel to form a multilayer chip ceramic capacitor, and then connect two parallel multilayer chip ceramic capacitors in series to obtain a giant permittivity ceramic capacitor module. The capacitance of the module is 200F.

5) The schematic diagram of the application system of this embodiment is shown in FIG. 4 . The system consists of a power supply module, a charging and discharging module for ceramic capacitors with a large permittivity, an intelligent control circuit board, and load appliances. In this embodiment, the power module is a household power supply, and the load is a smart phone. In this embodiment, when the intelligent control circuit board detects that the stored electric energy of the giant permittivity ceramic capacitor module is lower than the set value, it will turn on and control the electric energy of the power supply to charge into the giant permittivity ceramic capacitor module, and when the intelligent control circuit board detects When the stored electric energy of the giant permittivity ceramic capacitor module reaches the set value, it will cut off the power supply and no longer continue to charge the giant permittivity ceramic capacitor module; when it detects that a smart phone is connected, the giant permittivity ceramic capacitor module will output power to the The smart phone is normally powered on. When the voltage across the large permittivity ceramic capacitor module is 20V, the stored electric energy is 4kJ. The stored energy is enough for a smart phone to work normally for about 6 hours.

Embodiment 6:

In this embodiment, a large permittivity ceramic capacitor monomer is produced with copper calcium titanate-based ceramics as the intermediate dielectric layer and titanium oxide nano-insulation layer as the electric breakdown resistance layer, and the charging and discharging module of the giant permittivity ceramic capacitor is composed of this monomer , the specific steps are:

1) Preparation of copper calcium titanate based ceramics by solid state reaction method. Mix calcium carbonate, copper oxide and titanium oxide uniformly in a molar ratio of 1:3:4, pre-fire the mixed powder at 900°C for 3 hours to form copper calcium titanate powder, copper calcium titanate powder and di Niobium is mixed into copper calcium titanate-based powder at a mass ratio of 98:2, and the copper calcium titanate-based powder, 6wt% polyvinyl alcohol aqueous solution, glycerin and defoamer are mixed at a mass ratio of 45:35:5:0.2 Uniform, using a casting process to prepare a green sheet with a thickness of 1500 μm, the green sheet was sintered in an electric furnace at 1080 ° C for 5 hours to obtain copper calcium titanate-based ceramics.

2) Coating a titanium oxide nano-insulation layer on the surface of copper calcium titanate based ceramic sheet by vacuum evaporation method. Vacuum evaporation coating is based on copper calcium titanate based ceramic sheet, the vacuum degree of the evaporation chamber is controlled at 10 ^-3 ~ 10 ^-2 Pa, the evaporation current is controlled at 60mA, and the temperature of copper calcium titanate based ceramic sheet is controlled at 200 ~ 250 °C, rotating at a speed of 5 r/min to ensure uniform film formation, and obtain a titanium oxide nano-insulation layer with a thickness of 28 nm.

3) The upper and lower surfaces of the ceramic sheet coated with titanium oxide nano-insulation layer are coated with silver paste, and the temperature is raised to 600 ° C at room temperature for 30 min at room temperature to obtain copper calcium titanate-based ceramics as the intermediate dielectric layer, and titanium oxide nano The insulating layer is a single ceramic capacitor with a large permittivity of the electric breakdown resistance layer.

4) Connect 50 large permittivity ceramic capacitors in parallel to form a multilayer chip ceramic capacitor, and then connect 5 parallel multilayer chip ceramic capacitors in series to obtain a giant permittivity ceramic capacitor module. The capacitance of the module is 150F.

5) The schematic diagram of the application system of this embodiment is shown in FIG. 4 . The system consists of a power supply module, a charging and discharging module for ceramic capacitors with a large permittivity, an intelligent control circuit board, and load appliances. In this embodiment, the power module is a household power supply, and the load is a laptop computer. In this embodiment, when the intelligent control circuit board detects that the stored electric energy of the giant permittivity ceramic capacitor charging and discharging module is lower than the set value, it will turn on and control the electric energy of the power supply to charge into the giant permittivity ceramic capacitor charging and discharging module, and when the intelligent When the control circuit board detects that the stored electrical energy of the giant permittivity ceramic capacitor charging and discharging module reaches the set value, it will cut off the power supply and no longer continue to charge the giant permittivity ceramic capacitor charging and discharging module; The charge-discharge module of the permittivity ceramic capacitor outputs electric energy for the normal power supply of the notebook computer. When the voltage across the charging and discharging module of the giant permittivity ceramic capacitor is 100V, the stored electric energy is 750kJ. The stored electric energy can be used for a laptop computer to work normally for about 30 hours.

Claims (10)

1. charge-discharge modules based on huge permittivity ceramic capacitor, it is characterized in that being provided with at least 2 huge permittivity ceramic capacitor monomers, all huge permittivity ceramic capacitors are monomer series-connected or/and in parallel, and described huge permittivity ceramic capacitor monomer is provided with lower silver electrode layer, the lower layer of anti-electrical breakdown the, interlayer dielectric, the upper layer of anti-electrical breakdown the and upper silver electrode layer from bottom to up successively.

2. a kind of charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 1, it is characterized in that described lower silver electrode layer is coated in the lower layer of anti-electrical breakdown lower surface, upper silver electrode layer is coated in the layer of anti-electrical breakdown upper surface, the thickness of described lower silver electrode layer can be 5～500nm, and the thickness of described upper silver electrode layer can be 5～500nm.

3. a kind of charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 1, it is characterized in that described interlayer dielectric with huge permittivity calcium copper titanate ceramics or CaCu 3 Ti 4 O base pottery as dielectric, interlayer dielectric is laminar, and thickness can be 1～5000 μ m.

4. a kind of charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 1, it is characterized in that the described lower layer of anti-the electrical breakdown is a kind of in nano oxidized aluminium lamination, nano oxidized titanium layer or the nano oxidized silicon layer, the thickness of the described lower layer of anti-the electrical breakdown can be 5～500nm; The described layer of anti-the electrical breakdown can be a kind of in nano oxidized aluminium lamination, nano oxidized titanium layer or the nano oxidized silicon layer etc., and the thickness of the described lower layer of anti-the electrical breakdown can be 5～500nm.

5. a kind of preparation method of the charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 1 is characterized in that may further comprise the steps:

1) interlayer dielectric of the huge permittivity ceramic capacitor monomer of preparation;

2) adopt collosol and gel cladding process, vacuum vapor deposition method or the vacuum sputtering layer of anti-electrical breakdown the under the interlayer dielectric lower surface covers;

3) adopt collosol and gel cladding process, vacuum vapor deposition method or the vacuum sputtering layer of anti-electrical breakdown the on the interlayer dielectric upper surface covers;

4) at the lower layer of anti-electrical breakdown lower surface coated with conductive silver slurry, again heat treatment namely gets lower silver electrode layer;

5) at the upper layer of anti-electrical breakdown upper surface coated with conductive silver slurry, again heat treatment namely gets the silver electrode layer, so far obtains huge permittivity ceramic capacitor monomer;

The huge permittivity ceramic capacitor monomer that 6) will obtain adopts series connection or/and parallel way is assembled into the charge-discharge modules based on huge permittivity ceramic capacitor.

6. a kind of preparation method of the charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 5 is characterized in that in step 1), described interlayer dielectric with huge permittivity calcium copper titanate ceramics or CaCu 3 Ti 4 O base pottery as dielectric; Described calcium copper titanate ceramics is to contain calcium, copper and titanyl compound, carbonate compound, chloride, metallo-organic compound is as raw material, by calcium: copper: the ratio of the molal quantity of titanium is to mix at 1: 3: 4, the powder that mixes is generated the CaCu 3 Ti 4 O powder at 850～950 ℃ of pre-burning 2～5h, with the CaCu 3 Ti 4 O powder, the 6wt% polyvinyl alcohol water solution, glycerol and defoamer in mass ratio 40～50: 30～45: mix at 5: 0.2, adopt casting technique to prepare the base sheet that thickness is 1～5000 μ m, base sheet 1060～1100 ℃ of insulation 2～10h sintering in electric furnace obtain calcium copper titanate ceramics.

7. a kind of preparation method of the charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 6, it is characterized in that described CaCu 3 Ti 4 O base pottery is with calcium, copper and titanyl compound, carbonate compound, chloride is the basis as the CaCu 3 Ti 4 O powder that raw material makes, in the CaCu 3 Ti 4 O powder, add and contain vanadium, the compound of strontium or niobium forms CaCu 3 Ti 4 O base mixed powder, with CaCu 3 Ti 4 O base mixed powder, the 6wt% polyvinyl alcohol water solution, glycerol and defoamer in mass ratio 40～50: 30～45: mix at 5: 0.2, adopt casting technique to prepare the base sheet that thickness is 1～5000 μ m, base sheet 1060～1100 ℃ of insulation 2～10h sintering in electric furnace obtain CaCu 3 Ti 4 O base pottery.

8. a kind of preparation method of the charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 5 is characterized in that in step 4), and described heat treated temperature is 600 ℃, and the heat treated time is 30min.

9. a kind of preparation method of the charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 5 is characterized in that in step 5), and described heat treated temperature is 600 ℃, and the heat treated time is 30min.

10. a kind of preparation method of the charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 5, it is characterized in that in step 6), the described charge-discharge modules that is assembled into based on huge permittivity ceramic capacitor, can and be unified into multiple-layer sheet ceramic capacitor with huge permittivity ceramic capacitor monomer, specifically by huge permittivity ceramic capacitor monomer, external electrode and interior electrode form, the silver electrode layer of huge permittivity ceramic capacitor monomer is as interior electrode, multiple-layer sheet ceramic capacitor comprises the interior electrode of interaction cascading, between two adjacent interior electrodes the lower layer of anti-the electrical breakdown is arranged, interlayer dielectric and the upper layer of anti-the electrical breakdown separate, draw external electrode on two opposite flanks of interior electrode, but then multiple-layer sheet ceramic capacitor is connected or/and parallel connection obtains the super ceramic condenser module of fast charging and discharging.

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