CN103077828B - Charging-discharging module based on giant permittivity ceramic capacitor and preparation method of charging-discharging module - Google Patents
Charging-discharging module based on giant permittivity ceramic capacitor and preparation method of charging-discharging module Download PDFInfo
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Abstract
The invention relates to a charging-discharging module based on a giant permittivity ceramic capacitor and a preparation method of the charging-discharging module. The module is provided with at least two giant permittivity ceramic capacitor bodies, wherein the two giant permittivity ceramic capacitor bodies are connected in serial or/and in parallel, and each giant permittivity ceramic capacitor body is sequentially provided with 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. The preparation method comprises the following steps of preparing the intermediate dielectric layer of the giant permittivity ceramic capacitor body; covering the lower electric-breakdown-resistant layer on the lower surface of the intermediate dielectric layer; covering the upper electric-breakdown-resistant layer on the upper surface of the intermediate dielectric layer; coating conductive silver paste on the lower surface of the lower electric-breakdown-resistant, and thermally treating the silver paste to obtain the lower silver electrode layer; coating conductive silver paste on the upper surface of the upper electric-breakdown-resistant layer, thermally treating the silver paste to obtain the upper silver electrode layer, and obtaining the giant permittivity ceramic capacitor body; and assembling the produced giant permittivity ceramic capacitor bodies in serial or/and in parallel to obtain the charging-discharging module based on the giant permittivity ceramic capacitor.
Description
Technical field
The present invention relates to capacitor, particularly relate to a kind of charge-discharge modules based on huge permittivity ceramic capacitor and preparation method thereof.
Background technology
The mobile appliance equipment such as mobile phone, notebook computer becomes indispensable instrument in modern day work and life, and function gets more and more, and power demand is increasing.These mobile appliance equipments adopt lithium ion chemical cell etc. as store electrical energy element mostly, chemical cell itself exist charge/discharge rates slowly, energy storage amount is less, cycle life is limited and the shortcoming such as potential safety hazard, have influence on the long-term normal of mobile appliance equipment and use.
Along with world energy sources crisis is on the rise, the extensive use of the emerging energy such as solar energy, wind energy becomes the effective way solving energy scarcity in the world, has developed wind power generation and solar energy power generating rapidly thus.But solar energy and wind power generation have strong depend-ence to natural weather, when wind-force and sunlight enrich, generated output may be greater than loading demand amount and cause power wastage; When wind-force and sunlight lack, energy output is difficult to again meet load needs.So it is significant to the efficiency utilization realizing the energy to develop fast energy stocking system in the system such as photovoltaic generation, wind power generation.And conventional storage and the large electric energy of release generally adopt lead acid accumulator; its advantage is that manufacturing process is ripe and cost performance is high; but containing the harmful substance such as heavy metal lead and sulfuric acid; Health Status For Workers Exposed and environmental protection are all constituted a serious threat; and the liquid such as sulfuric acid in use progressively can volatilize and make battery failure, accident of also may blasting when serviceability temperature is higher.
And general ultracapacitor volume is portable more greatly and not, most of ultracapacitor contains liquid or emulsion, easily dries up and inefficacy is scrapped.（Jayalakshmi M,Balasubramanian K.，Simple Capacitors toSupercapacitors-An Overview[J].International Journal of Electrochemical Science,2008,3(11)1196-1217;Burke A,Ultracapacitors:why,how,and where is thetechnology[J].Journal of Power Sources,2000,91(1):37-50）。
Exploitation high-performance Large Copacity fast energy storage capacitor is one of important process of exploring of new forms of energy, and the physics energy storage mechnism of ceramic capacitor has the unexistent advantage of many chemical cells: can big current fast charging and discharging, compact, containing poisonous metal, can not to environment, charge and discharge cycles often etc.CaCu 3 Ti 4 O is a kind of novel huge permittivity oxide functional material had a extensive future.This material reaches 10 at 100 ~ 600K temperature range low frequency permittivity
5, and there is good temperature stability; CaCu 3 Ti 4 O is centrosymmetric crystal structure, it not the ferroelectric with electric dipole moment, there will not be situation [the Subramanian M A of ferroelectric material dielectric property marked change near ferroelectric-paraelectric phase temperature, Li D, Duan N, et al.High dielectric constant in ACu
3ti
4o
12and ACu
3ti
4o
12phases.Journalof Solid State Chemistry, 200,151 (2): 323-325].
Summary of the invention
The object of the invention is to the above-mentioned shortcoming existed for existing ultracapacitor, there is provided there is fast charging and discharging speed, the feature such as high capacitance, small size, high-temperature stability, pollution-free, long-life, miniaturization are convenient for carrying, can when the mobile device such as mobile phone, notebook computer electric energy is not enough to its fast supply electric energy, a kind of charge-discharge modules based on huge permittivity ceramic capacitor effectively extending the operating time of electric equipment (comprising mobile phone, notebook computer etc.) and preparation method thereof.
The described charge-discharge modules based on huge permittivity ceramic capacitor is 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, lower electrical breakdown withstand layer, interlayer dielectric, upper electrical breakdown withstand layer and upper silver electrode layer from bottom to up successively.
Described lower silver electrode layer is coated in lower electrical breakdown withstand layer lower surface, and upper silver electrode layer is coated in electrical breakdown withstand layer upper surface, and 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.
Described interlayer dielectric is using huge permittivity calcium copper titanate ceramics or CaCu 3 Ti 4 O base pottery as dielectric, and interlayer dielectric be laminar, and thickness can be 1 ~ 5000 μm.
Described lower electrical breakdown withstand layer can be the one in nano oxidized aluminium lamination, nano oxidized titanium layer or nano oxidized silicon layer etc., and the thickness of described lower electrical breakdown withstand layer can be 5 ~ 500nm.
Described upper electrical breakdown withstand layer can be the one in nano oxidized aluminium lamination, nano oxidized titanium layer or nano oxidized silicon layer etc., and the thickness of described lower electrical breakdown withstand layer can be 5 ~ 500nm.
The preparation method of described a kind of charge-discharge modules based on huge permittivity ceramic capacitor is as follows:
1) interlayer dielectric of huge permittivity ceramic capacitor monomer is prepared;
In step 1), described interlayer dielectric using huge permittivity calcium copper titanate ceramics or CaCu 3 Ti 4 O base pottery as dielectric, described calcium copper titanate ceramics is with containing calcium, copper and titanyl compound, carbonate compound, chloride, the compounds such as metallo-organic compound are as raw material, by calcium: copper: the ratio of the molal quantity of titanium is 1: 3: 4 mixing, the powder mixed is generated CaCu 3 Ti 4 O powder at 850 ~ 950 DEG C of pre-burning 2 ~ 5h, by CaCu 3 Ti 4 O powder, 6wt% polyvinyl alcohol water solution, glycerol and defoamer mix in mass ratio at 40 ~ 50: 30 ~ 45: 5: 0.2, casting technique is adopted to prepare the blank that thickness is 1 ~ 5000 μm, blank 1060 ~ 1100 DEG C of insulation 2 ~ 10h sintering in electric furnace obtain calcium copper titanate ceramics,
Described CaCu 3 Ti 4 O base pottery is with calcium, copper and titanyl compound, carbonate compound, the compounds such as chloride are as based on the obtained CaCu 3 Ti 4 O powder of raw material, add in CaCu 3 Ti 4 O powder containing vanadium, the compound of strontium or niobium etc. forms CaCu 3 Ti 4 O base mixed powder, by CaCu 3 Ti 4 O base mixed powder, 6wt% polyvinyl alcohol water solution, glycerol and defoamer mix in mass ratio at 40 ~ 50: 30 ~ 45: 5: 0.2, casting technique is adopted to prepare the blank that thickness is 1 ~ 5000 μm, blank 1060 ~ 1100 DEG C of insulation 2 ~ 10h sintering in electric furnace obtain CaCu 3 Ti 4 O base pottery.
2) sol-gel coating process, vacuum vapor deposition method or vacuum sputtering electrical breakdown withstand layer under interlayer dielectric lower surface covers is adopted;
3) sol-gel coating process, vacuum vapor deposition method or vacuum sputtering electrical breakdown withstand layer on interlayer dielectric upper surface covers is adopted;
4) at lower electrical breakdown withstand layer lower surface coated with conductive silver slurry, then heat treatment, obtain lower silver electrode layer;
In step 4), described heat treated temperature can be 600 DEG C, and the heat treated time can be 30min.
5) at upper electrical breakdown withstand layer upper surface coated with conductive silver slurry, then heat treatment, obtain silver electrode layer, so far obtain huge permittivity ceramic capacitor monomer;
In step 5), described heat treated temperature can be 600 DEG C, and the heat treated time can be 30min.
6) adopt series connection or/and parallel way is assembled into the charge-discharge modules based on huge permittivity ceramic capacitor the huge permittivity ceramic capacitor monomer obtained.
In step 6), the described charge-discharge modules be assembled into based on huge permittivity ceramic capacitor, huge permittivity ceramic capacitor monomer can be unified into multiple-layer sheet ceramic capacitor, specifically by huge permittivity ceramic capacitor monomer, external electrode and interior electrode composition, 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, lower electrical breakdown withstand layer is had between two adjacent interior electrodes, interlayer dielectric and upper electrical breakdown withstand layer separate, external electrode is drawn in two opposite flanks of interior electrode, then by multiple-layer sheet ceramic capacitor series connection or/and parallel connection obtain can the super ceramic condenser module of fast charging and discharging.
The huge permittivity ceramic capacitor that the present invention adopts has compared with chemical capacitor that charge/discharge rates is fast, proof voltage is high, without chemical contamination, little, that fail safe is high feature of generating heat, and overcome the little shortcoming of existing conventional ceramic condenser capacity.
The feature such as the present invention has fast charging and discharging speed, Large Copacity, high-temperature stability, pollution-free, long-life, miniaturization are convenient for carrying, when the mobile device such as mobile phone, notebook computer electric energy is not enough to its quick function of supplying power, can effectively extend the operating time of electric equipment (comprising mobile phone, notebook computer etc.).
Accompanying drawing explanation
Fig. 1 is the structural representation of the huge permittivity ceramic capacitor monomer of the embodiment of the present invention.
Fig. 2 is the multiple-layer sheet ceramic capacitor structural representation of the embodiment of the present invention.
Fig. 3 is the charge-discharge modules structural representation of the huge permittivity ceramic capacitor of the embodiment of the present invention.
Fig. 4 is the application system schematic diagram of the embodiment of the present invention.
Embodiment
Following examples will the invention will be further described by reference to the accompanying drawings.It should be emphasized that following explanation is only exemplary, instead of in order to limit the scope of the invention and apply.
See Fig. 1, the described charge-discharge modules based on huge permittivity ceramic capacitor is 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 1, lower electrical breakdown withstand layer 2, interlayer dielectric 3, upper electrical breakdown withstand layer 4 and upper silver electrode layer 5 from bottom to up successively.
Described lower silver electrode layer 1 is coated in lower electrical breakdown withstand layer 2 lower surface, and upper silver electrode layer 5 is coated in electrical breakdown withstand layer 4 upper surface, and the thickness of described lower silver electrode layer 1 can be 5 ~ 500nm, and the thickness of described upper silver electrode layer 5 can be 5 ~ 500nm.
Described interlayer dielectric 3 is using huge permittivity calcium copper titanate ceramics or CaCu 3 Ti 4 O base pottery as dielectric, and interlayer dielectric 3 be laminar, and thickness can be 1 ~ 5000 μm.
Described lower electrical breakdown withstand layer 2 can be the one in nano oxidized aluminium lamination, nano oxidized titanium layer or nano oxidized silicon layer etc., and the thickness of described lower electrical breakdown withstand layer 2 can be 5 ~ 500nm.
Described upper electrical breakdown withstand layer 4 can be the one in nano oxidized aluminium lamination, nano oxidized titanium layer or nano oxidized silicon layer etc., and the thickness of described lower electrical breakdown withstand layer 4 can be 5 ~ 500nm.
See Fig. 2, described multiple-layer sheet ceramic capacitor is specifically made up of huge permittivity ceramic capacitor monomer 6, external electrode 7 and interior electrode 8.The metal electrode layer of huge permittivity ceramic capacitor monomer is as interior electrode 8, multiple-layer sheet ceramic capacitor comprises the interior electrode of at least two interaction cascadings, engaged by interlayer dielectric and electrical breakdown withstand layer between two adjacent interior electrodes, external electrode 7 is drawn in two opposite flanks of interior electrode.
See Fig. 3, multiple-layer sheet ceramic capacitor 9 is connected or/and parallel connection obtain can the super ceramic condenser module of fast charging and discharging, module has total electrode 10 in order to being connected with external circuit.
Embodiment 1:
It is interlayer dielectric 3 that the present embodiment makes with calcium copper titanate ceramics, aluminium oxide nano insulating barrier is the huge permittivity ceramic capacitor monomer of lower electrical breakdown withstand layer 2 and upper electrical breakdown withstand layer 4, monomer forms the charge-discharge modules of huge permittivity ceramic capacitor thus, and concrete steps are:
1) solid reaction process prepares calcium copper titanate ceramics.Calcium carbonate, cupric oxide and titanium oxide are mixed in molar ratio at 1: 3: 4, the powder mixed is generated CaCu 3 Ti 4 O powder at 850 DEG C of pre-burning 5h, CaCu 3 Ti 4 O powder, 6wt% polyvinyl alcohol water solution, glycerol and defoamer are mixed in mass ratio at 40: 30: 5: 0.2, adopt casting technique to prepare the blank that thickness is 1 μm, blank 1060 DEG C of insulation 10h sintering in electric furnace obtain calcium copper titanate ceramics.
2) sol-gal process is at the aluminium oxide nano insulating barrier of ceramic sheet surface-coated even compact.10g aluminium isopropoxide is dissolved in 140g deionized water, at 85 DEG C of stirring in water bath 10min, adds HNO
3adjust ph, to about 3, continues 85 DEG C of stirring in water bath 5h, obtains vitreosol.Solids content about 5% in alumina sol.Be immersed in by ceramic sheet in alumina sol, reduce liquid level with the speed of 10cm/min, alumina sol uniform wet is surperficial at calcium copper titanate ceramics, then dry 30min in 90 DEG C of baking ovens, and then repetitive coatings once.At room temperature rise to 100 DEG C of insulation 30min with 3 DEG C/min, the water in xerogel is thoroughly discharged, then rises to 600 DEG C with 1 DEG C/min, and then rise to 1000 DEG C of insulation 2h with 3 DEG C/min, obtain 100nm compact aluminum oxide nanometer insulating barrier.
3) the potsherd upper and lower surface coating 5nm silver slurry of aluminium oxide nano insulating barrier is coated with, at room temperature rise to 600 DEG C of insulation 30min with 3 DEG C/min, obtain with sour copper calcium pottery for interlayer dielectric 3, aluminium oxide nano insulating barrier is the huge permittivity ceramic capacitor monomer of lower electrical breakdown withstand layer 2 and upper electrical breakdown withstand layer 4.
4) 100 huge permittivity ceramic capacitor monomers are unified into multiple-layer sheet ceramic capacitor, then 10 multiple-layer sheet ceramic capacitors series connection are obtained huge permittivity ceramic capacitor module, the capacitance of module is 100F.
5) the present embodiment application system schematic diagram as shown in Figure 4.This system is made up of power module 11, huge permittivity ceramic capacitor charging/discharging module 12, intelligent control circuit plate 13 and load appliance 14.Power module is wind generator system in the present embodiment, and load is the electricity-saving lamp of 10 power 20W.The unnecessary electrical power storage of the present embodiment is in huge permittivity ceramic capacitor charging/discharging module, and the electric energy stored when both end voltage is 100V is 500kJ.When being in calm and gentle breeze weather, the generated output of wind generator system is less than bearing power, intelligent control circuit plate is by the fault offset in huge permittivity ceramic capacitor charging/discharging module, and for powering to the load, stored energy normally can to work about 1h for the electricity-saving lamp of 10 power 20W.
Embodiment 2:
It is interlayer dielectric 3 that the present embodiment makes with calcium copper titanate ceramics, TiOx nano insulating barrier is the huge permittivity ceramic capacitor monomer of lower electrical breakdown withstand layer 2 and upper electrical breakdown withstand layer 4, monomer forms the charge-discharge modules of huge permittivity ceramic capacitor thus, and concrete steps are:
1) solid reaction process prepares calcium copper titanate ceramics.Calcium carbonate, copper chloride and titanium oxide are mixed in molar ratio at 1: 3: 4, the powder mixed is generated CaCu 3 Ti 4 O powder at 950 DEG C of pre-burning 2h, CaCu 3 Ti 4 O powder, 6wt% polyvinyl alcohol water solution, glycerol and defoamer are mixed in mass ratio at 50: 45: 5: 0.2, adopt casting technique to prepare the blank that thickness is 100 μm, blank 1080 DEG C of insulation 5h sintering in electric furnace obtain calcium copper titanate ceramics.
2) sol-gal process is at the TiOx nano insulating barrier of calcium copper titanate ceramics surface-coated even compact.5g butyl titanate is dissolved in 20g absolute ethyl alcohol, adds HNO
3adjust ph, to about 3, obtains yellow transparent titanium oxide sol.Be immersed in by ceramic sheet in titanium oxide sol, reduce liquid level with the speed of 10cm/min, titanium oxide sol uniform wet is surperficial at calcium copper titanate ceramics, then dry 30min in 90 DEG C of baking ovens, then repetitive coatings once.Adopt the method for heat stepwise, at room temperature rise to 100 DEG C of insulation 30min with 3 DEG C/min, the water in xerogel is thoroughly discharged, then rise to 600 DEG C of insulation 2h with 1 DEG C/min, obtain 50nm dense oxide titanium nanometer insulating barrier.
3) the potsherd upper and lower surface coating 200nm silver slurry of TiOx nano insulating barrier is coated with, at room temperature rise to 600 DEG C of insulation 30min with 3 DEG C/min, obtaining calcium copper titanate ceramics is interlayer dielectric 3, and TiOx nano insulating barrier is the huge permittivity ceramic capacitor monomer of lower electrical breakdown withstand layer 2 and upper electrical breakdown withstand layer 4.
4) 100 huge permittivity ceramic capacitor monomers are unified into multiple-layer sheet ceramic capacitor, then the multiple-layer sheet ceramic capacitor series connection after 10 parallel connections is obtained huge permittivity ceramic capacitor module, the capacitance of module is 500F.
5) the application system schematic diagram of the present embodiment as shown in Figure 4.This system is made up of power module 11, huge permittivity ceramic capacitor charging/discharging module 12, intelligent control circuit plate 13 and load appliance 14.Power module is wind generator system in the present embodiment, and load is the computer of two power 50W.The present embodiment by electrical power storage unnecessary in power module in huge permittivity ceramic capacitor charging/discharging module.The electric energy that both end voltage stores when being 100V is 2500kJ.When being in calm and gentle breeze weather, the generated output of wind generator system is less than bearing power, intelligent control circuit plate is by the fault offset in huge permittivity ceramic capacitor charging/discharging module, and for powering to the load, stored energy normally can to work about 7h for the computer of two 50W.
Embodiment 3:
It is interlayer dielectric 3 that the present embodiment makes with calcium copper titanate ceramics, monox nanometer insulating barrier is the huge permittivity ceramic capacitor monomer of lower electrical breakdown withstand layer 2 and upper electrical breakdown withstand layer 4, monomer forms the charge-discharge modules of huge permittivity ceramic capacitor thus, and concrete steps are:
1) solid reaction process prepares calcium copper titanate ceramics.Calcium nitrate, cupric oxide and titanium oxide are mixed in molar ratio at 1: 3: 4, the powder mixed is generated CaCu 3 Ti 4 O powder at 900 DEG C of pre-burning 3h, CaCu 3 Ti 4 O powder, 6wt% polyvinyl alcohol water solution, glycerol and defoamer are mixed in mass ratio at 45: 40: 5: 0.2, adopt casting technique to prepare the blank that thickness is 2000 μm, blank 1100 DEG C of insulation 2h sintering in electric furnace obtain calcium copper titanate ceramics.
2) sol-gal process is at the monox nanometer insulating barrier of ceramic sheet surface-coated even compact.According to tetraethoxysilane: ethanol: H
2o: H
+the molar ratio of=1: 6.5: 3.7: 0.08, tetraethoxysilane is fully mixed with absolute ethyl alcohol, the mixture of deionized water and acidic catalyst is dripped under magnetic agitation strong agitation, by reactant mixture stirring and refluxing certain hour at a certain temperature after dropwising, a certain amount of N is added after colloidal sol cooling, dinethylformamide, as drying control chemical additive, continues to stir 15min and obtains silica sol.Be immersed in by ceramic sheet in silica sol, reduce liquid level with the speed of 10cm/min, silica sol uniform wet is surperficial at calcium copper titanate ceramics, then dry 30min in 90 DEG C of baking ovens, and then repetitive coatings once.In order to obtain the fissureless monox nanometer layer of complete densification, adopt the method for heat stepwise, at room temperature rise to 100 DEG C of insulation 30min with 3 DEG C/min, water in xerogel is thoroughly discharged, then 600 DEG C are risen to 1 DEG C/min, and then rise to 800 DEG C of insulation 2h with 3 DEG C/min, obtain dense oxide silicon nanometer insulating barrier.
3) the potsherd upper and lower surface coating 500nm silver slurry of monox nanometer insulating barrier is coated with, at room temperature rise to 600 DEG C of insulation 30min with 3 DEG C/min, obtaining calcium copper titanate ceramics is interlayer dielectric 3, and monox nanometer insulating barrier is the huge permittivity ceramic capacitor monomer of lower electrical breakdown withstand layer 2 and upper electrical breakdown withstand layer 4.
4) 50 huge permittivity ceramic capacitor monomers are unified into multiple-layer sheet ceramic capacitor, then the multiple-layer sheet ceramic capacitor series connection after 20 parallel connections is obtained huge permittivity ceramic capacitor module, the capacitance of module is 200F.
5) the application system schematic diagram of the present embodiment as shown in Figure 4.This system is made up of power module, huge permittivity ceramic capacitor charging/discharging module, intelligent control circuit plate and load appliance.Power module is photovoltaic generating system in the present embodiment, and load is the electricity-saving lamp of 5 power 20W.When sunlight is sufficient, generating efficiency is high, power consumption is few by electrical power storage unnecessary in power module in huge permittivity ceramic capacitor module.The electric energy that both end voltage stores when being 200V is 4000kJ.When being in evening or the insufficient weather of sunlight, the generated output of photovoltaic generating system is less than bearing power, intelligent control circuit plate is by the fault offset in huge permittivity ceramic capacitor module, for powering to the load, stored energy normally can to work about 6h for the electricity-saving lamp of 5 power 20W.
Embodiment 4:
The present embodiment makes with CaCu 3 Ti 4 O base pottery for interlayer dielectric, and aluminium oxide nano insulating barrier is the huge permittivity ceramic capacitor monomer of electrical breakdown withstand layer, and monomer forms the charge-discharge modules of huge permittivity ceramic capacitor thus, and concrete steps are:
1) solid reaction process prepares CaCu 3 Ti 4 O base pottery.Calcium carbonate, cupric oxide and titanium oxide are mixed in molar ratio at 1: 3: 4, the powder mixed is generated CaCu 3 Ti 4 O powder at 900 DEG C of pre-burning 3h, CaCu 3 Ti 4 O powder and strontium carbonate are mixed into CaCu 3 Ti 4 O original washing powder body in mass ratio at 99.5: 0.5, CaCu 3 Ti 4 O original washing powder body, 6wt% polyvinyl alcohol water solution, glycerol and defoamer are mixed in mass ratio at 50: 45: 5: 0.2, adopt casting technique to prepare the blank that thickness is 2000 μm, blank 1100 DEG C of insulation 2h sintering in electric furnace obtain CaCu 3 Ti 4 O base pottery.
2) adopt vacuum sputtering at CaCu 3 Ti 4 O base ceramic sheet surface sputtering aluminium oxide nano insulating barrier.Magnetron sputtering process by vacuum degree control 10
-3~ 10
-2pa, power controls at 8 ~ 10W, and substrate rotary speed is fixed as 36r/min, sputtering time 30s, and the thickness obtaining aluminium oxide nano insulating barrier is 30nm.
3) sputtering has the potsherd upper and lower surface coating silver slurry of aluminium oxide nano insulating barrier, at room temperature rise to 600 DEG C of insulation 30min with 3 DEG C/min, obtain CaCu 3 Ti 4 O base pottery for interlayer dielectric, aluminium oxide nano insulating barrier is the huge permittivity ceramic capacitor monomer of electrical breakdown withstand layer.
4) 50 huge permittivity ceramic capacitor monomers are unified into multiple-layer sheet ceramic capacitor, then the multiple-layer sheet ceramic capacitor series connection after 20 parallel connections is obtained huge permittivity ceramic capacitor module, the capacitance of module is 600F.
5) the application system schematic diagram of the present embodiment as shown in Figure 4.This system is made up of power module, huge permittivity ceramic capacitor charging/discharging module, intelligent control circuit plate and load appliance.Power module is photovoltaic generating system in the present embodiment, and load is the computer of 10 power 50W.The electrical power storage unnecessary in power module when sunlight is sufficient, generating efficiency is high, power consumption is few is in huge permittivity ceramic capacitor module.The electric energy that both end voltage stores when being 150V is 6750kJ.When being in evening or the insufficient weather of sunlight, the generated output of photovoltaic generating system is less than bearing power, intelligent control circuit plate is by the fault offset in huge permittivity ceramic capacitor module, for powering to the load, stored electric energy normally can to work about 3h for the computer of 10 50W.
Embodiment 5:
The present embodiment makes with CaCu 3 Ti 4 O base pottery for interlayer dielectric, and monox nanometer insulating barrier is the huge permittivity ceramic capacitor monomer of electrical breakdown withstand layer, and monomer forms the charge-discharge modules of huge permittivity ceramic capacitor thus, and concrete steps are:
1) solid reaction process prepares CaCu 3 Ti 4 O base pottery.Calcium carbonate, cupric oxide and titanium oxide are mixed in molar ratio at 1: 3: 4, the powder mixed is generated CaCu 3 Ti 4 O powder at 950 DEG C of pre-burning 2h, CaCu 3 Ti 4 O powder and vanadic oxide are mixed into CaCu 3 Ti 4 O original washing powder body in mass ratio at 99: 1, CaCu 3 Ti 4 O original washing powder body, 6wt% polyvinyl alcohol water solution, glycerol and defoamer are mixed in mass ratio at 40: 30: 5: 0.2, adopt casting technique to prepare the blank that thickness is 400 μm, blank 1060 DEG C of insulation 10h sintering in electric furnace obtain CaCu 3 Ti 4 O base pottery.
2) adopt vacuum sputtering at CaCu 3 Ti 4 O base ceramic surface sputtering monox nanometer insulating barrier.Magnetron sputtering process by vacuum degree control 10
-3~ 10
-2pa, power controls at 6 ~ 8W, and substrate rotary speed is fixed as 36r/min, sputtering time 30s, and the thickness obtaining monox nanometer insulating barrier is 20nm.
3) the potsherd upper and lower surface coating silver slurry of silica nanometer insulating barrier is sputtered, at room temperature rise to 600 DEG C of insulation 30min with 3 DEG C/min, obtain CaCu 3 Ti 4 O base pottery for interlayer dielectric, monox nanometer insulating barrier is the huge permittivity ceramic capacitor monomer of electrical breakdown withstand layer.
4) 50 huge permittivity ceramic capacitor monomers are unified into multiple-layer sheet ceramic capacitor, then the multiple-layer sheet ceramic capacitor series connection after 2 parallel connections is obtained huge permittivity ceramic capacitor module, the capacitance of module is 200F.
5) the application system schematic diagram of the present embodiment as shown in Figure 4.This system is made up of power module, huge permittivity ceramic capacitor charging/discharging module, intelligent control circuit plate and load appliance.Power module is domestic power supply in the present embodiment, and load is 1 smart mobile phone.The present embodiment is charged in huge permittivity ceramic capacitor module lower than the electric energy connecting and control power supply during set point when the store electrical energy of intelligent control circuit plate detects huge permittivity ceramic capacitor module, and can cut off the electricity supply when intelligent control circuit plate detects that the store electrical energy of huge permittivity ceramic capacitor module reaches set point and no longer continue huge permittivity ceramic capacitor module charging; Electric energy can be exported by huge permittivity ceramic capacitor module when it detects and connects smart mobile phone to use to smart mobile phone normal power supply.The electric energy that huge permittivity ceramic capacitor module both end voltage stores when being 20V is 4kJ.Stored energy normally can to work about 6h for 1 smart mobile phone.
Embodiment 6:
The present embodiment makes with CaCu 3 Ti 4 O base pottery for interlayer dielectric, and TiOx nano insulating barrier is the huge permittivity ceramic capacitor monomer of electrical breakdown withstand layer, and monomer forms the charge-discharge modules of huge permittivity ceramic capacitor thus, and concrete steps are:
1) solid reaction process prepares CaCu 3 Ti 4 O base pottery.Calcium carbonate, cupric oxide and titanium oxide are mixed in molar ratio at 1: 3: 4, the powder mixed is generated CaCu 3 Ti 4 O powder at 900 DEG C of pre-burning 3h, CaCu 3 Ti 4 O powder and niobium pentaoxide are mixed into CaCu 3 Ti 4 O original washing powder body in mass ratio at 98: 2, CaCu 3 Ti 4 O original washing powder body, 6wt% polyvinyl alcohol water solution, glycerol and defoamer are mixed in mass ratio at 45: 35: 5: 0.2, adopt casting technique to prepare the blank that thickness is 1500 μm, blank 1080 DEG C of insulation 5h sintering in electric furnace obtain CaCu 3 Ti 4 O base pottery.
2) adopt vacuum vapor deposition method at CaCu 3 Ti 4 O base ceramic sheet surface-coated TiOx nano insulating barrier.Vacuum evaporation is matrix coated with CaCu 3 Ti 4 O base ceramic sheet, and the vacuum degree control of vaporization chamber is 10
-3~ 10
-2pa, evaporation current controls at 60mA, and CaCu 3 Ti 4 O base ceramic sheet temperature controls at 200 ~ 250 DEG C, rotates to ensure that film forming is even, obtain the TiOx nano insulating barrier that thickness is 28nm with the speed of 5r/min.
3) the potsherd upper and lower surface coating silver slurry of TiOx nano insulating barrier is coated with, at room temperature rise to 600 DEG C of insulation 30min with 3 DEG C/min, obtain CaCu 3 Ti 4 O base pottery for interlayer dielectric, TiOx nano insulating barrier is the huge permittivity ceramic capacitor monomer of electrical breakdown withstand layer.
4) 50 huge permittivity ceramic capacitor monomers are unified into multiple-layer sheet ceramic capacitor, then the multiple-layer sheet ceramic capacitor series connection after 5 parallel connections is obtained huge permittivity ceramic capacitor module, the capacitance of module is 150F.
5) the application system schematic diagram of the present embodiment as shown in Figure 4.This system is made up of power module, huge permittivity ceramic capacitor charging/discharging module, intelligent control circuit plate and load appliance.Power module is domestic power supply in the present embodiment, and load is 1 notebook computer.The present embodiment is charged in huge permittivity ceramic capacitor charging/discharging module lower than the electric energy connecting and control power supply during set point when the store electrical energy of intelligent control circuit plate detects huge permittivity ceramic capacitor charging/discharging module, and can cut off the electricity supply when intelligent control circuit plate detects that the store electrical energy of huge permittivity ceramic capacitor charging/discharging module reaches set point and no longer continue huge permittivity ceramic capacitor charging/discharging module charging; Electric energy can be exported by huge permittivity ceramic capacitor charging/discharging module when it detects and connects notebook computer to use to notebook computer normal power supply.The electric energy that huge permittivity ceramic capacitor charging/discharging module both end voltage stores when being 100V is 750kJ.Stored electric energy normally can to work about 30h for 1 notebook computer.
Claims (7)
1. the 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, in parallel or the series connection of all huge permittivity ceramic capacitor monomers and in parallel, described huge permittivity ceramic capacitor monomer is provided with lower silver electrode layer, lower electrical breakdown withstand layer, interlayer dielectric, upper electrical breakdown withstand layer and upper silver electrode layer from bottom to up successively;
Described lower silver electrode layer is coated in lower electrical breakdown withstand layer lower surface, and upper silver electrode layer is coated in electrical breakdown withstand layer upper surface, and the thickness of described lower silver electrode layer is 5 ~ 500nm, and the thickness of described upper silver electrode layer is 5 ~ 500nm;
Described interlayer dielectric is using huge permittivity calcium copper titanate ceramics or CaCu 3 Ti 4 O base pottery as dielectric, and interlayer dielectric be laminar, and thickness is 1 ~ 5000 μm;
Described lower electrical breakdown withstand layer is the one in nano oxidized aluminium lamination, nano oxidized titanium layer or nano oxidized silicon layer, and the thickness of described lower electrical breakdown withstand layer is 5 ~ 500nm; Described upper electrical breakdown withstand layer is the one in nano oxidized aluminium lamination, nano oxidized titanium layer or nano oxidized silicon layer.
2. the preparation method of a kind of charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 1, is characterized in that comprising the following steps:
1) interlayer dielectric of huge permittivity ceramic capacitor monomer is prepared;
2) sol-gel coating process, vacuum vapor deposition method or vacuum sputtering electrical breakdown withstand layer under interlayer dielectric lower surface covers is adopted;
3) sol-gel coating process, vacuum vapor deposition method or vacuum sputtering electrical breakdown withstand layer on interlayer dielectric upper surface covers is adopted;
4) at lower electrical breakdown withstand layer lower surface coated with conductive silver slurry, then heat treatment, obtain lower silver electrode layer;
5) at upper electrical breakdown withstand layer upper surface coated with conductive silver slurry, then heat treatment, obtain silver electrode layer, so far obtain huge permittivity ceramic capacitor monomer;
6) the huge permittivity ceramic capacitor monomer obtained is adopted in parallel or series connection and parallel way is assembled into charge-discharge modules based on huge permittivity ceramic capacitor.
3. the preparation method of a kind of charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 2, is characterized in that in step 1) in, described interlayer dielectric is using huge permittivity calcium copper titanate ceramics or CaCu 3 Ti 4 O base pottery as dielectric, described calcium copper titanate ceramics is with containing 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 1: 3: 4 mixing, the powder mixed is generated CaCu 3 Ti 4 O powder at 850 ~ 950 DEG C of pre-burning 2 ~ 5h, by CaCu 3 Ti 4 O powder, 6wt% polyvinyl alcohol water solution, glycerol and defoamer mix in mass ratio at 40 ~ 50: 30 ~ 45: 5: 0.2, casting technique is adopted to prepare the blank that thickness is 1 ~ 5000 μm, blank 1060 ~ 1100 DEG C of insulation 2 ~ 10h sintering in electric furnace obtain calcium copper titanate ceramics.
4. the preparation method of a kind of charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 3, it is characterized in that described CaCu 3 Ti 4 O base pottery is with calcium, copper and titanyl compound, carbonate compound, chloride is as based on the obtained CaCu 3 Ti 4 O powder of raw material, add in CaCu 3 Ti 4 O powder containing vanadium, the compound of strontium or niobium forms CaCu 3 Ti 4 O base mixed powder, by CaCu 3 Ti 4 O base mixed powder, 6wt% polyvinyl alcohol water solution, glycerol and defoamer mix in mass ratio at 40 ~ 50: 30 ~ 45: 5: 0.2, casting technique is adopted to prepare the blank that thickness is 1 ~ 5000 μm, blank 1060 ~ 1100 DEG C of insulation 2 ~ 10h sintering in electric furnace obtain CaCu 3 Ti 4 O base pottery.
5. the preparation method of a kind of charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 2, is characterized in that in step 4) in, described heat treated temperature is 600 DEG C, and the heat treated time is 30min.
6. the preparation method of a kind of charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 2, is characterized in that in step 5) in, described heat treated temperature is 600 DEG C, and the heat treated time is 30min.
7. the preparation method of a kind of charge-discharge modules based on huge permittivity ceramic capacitor as claimed in claim 2, it is characterized in that in step 6) in, the described charge-discharge modules be assembled into based on huge permittivity ceramic capacitor, be by huge permittivity ceramic capacitor monomer and be unified into multiple-layer sheet ceramic capacitor, specifically by huge permittivity ceramic capacitor monomer, external electrode and interior electrode composition, 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, lower electrical breakdown withstand layer is had between two adjacent interior electrodes, interlayer dielectric and upper electrical breakdown withstand layer separate, external electrode is drawn in two opposite flanks of interior electrode, then multiple-layer sheet ceramic capacitor parallel connection or connection in series-parallel being obtained can the super ceramic condenser module of fast charging and discharging.
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| CN201994182U (en) * | 2010-11-18 | 2011-09-28 | 韩星爱肯特（任丘）电子有限公司 | Element structure for capacitor |
| CN102651278A (en) * | 2012-05-24 | 2012-08-29 | 北京科技大学 | Embedded capacitor and preparation method thereof |
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| US7428137B2 (en) * | 2004-12-03 | 2008-09-23 | Dowgiallo Jr Edward J | High performance capacitor with high dielectric constant material |
| CN201994182U (en) * | 2010-11-18 | 2011-09-28 | 韩星爱肯特（任丘）电子有限公司 | Element structure for capacitor |
| CN102651278A (en) * | 2012-05-24 | 2012-08-29 | 北京科技大学 | Embedded capacitor and preparation method thereof |
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