CN102136315A - Multilayer-ceramic total-area LNO (lanthanum nickel oxide)/Ag/LNO composite electrode and preparation method thereof - Google Patents
Multilayer-ceramic total-area LNO (lanthanum nickel oxide)/Ag/LNO composite electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a multilayer-ceramic total-area LNO (lanthanum nickel oxide)/Ag/LNO composite electrode comprising at least two overlapped ceramic plates, wherein an 'LNO conducting buffer layer/ Ag electrode layer/ LNO conducting buffer layer' is arranged between two adjacent ceramic plates; the surfaces of the ceramic plates on the top and the bottom are successively covered with the LNO conducting buffer layer and Ag electrode layer; the shape and the area of the end surface of the LNO conducting buffer layer are same with those of the end surface of the ceramic plate; the shape and the area of the Ag electrode layer are same with those of the end surface of the LNO conducting buffer layer; and the ceramic plate and the LNO conducting buffer layer as well as the LNO conducting buffer layer and the Ag electrode layer are sintered into a whole. The preparation method of the composite electrode comprises the following technical steps: (1) processing the surface of the ceramic plate; (2) preparing an LNO precursor solution; (3) preparing a first cell body; (4) preparing a second unit body; and (5) combining and sintering the cell bodies.
Description
Technical field
The invention belongs to the combination electrode material field, particularly a kind of multi-layer ceramics gross area LNO/Ag/LNO combination electrode and preparation method thereof.
Background technology
The electrode of all kinds of ceramic components adopts metals such as Ag, Pt or Au usually in the electrical engineering, by technologies such as sputter, burning infiltration, sprayings, securely be attached to be used on a certain end face of ceramic material the conduction.Directly do electrode layer with metal, its good conductivity has certain ductility.But there are two significant disadvantage in metal electrode: (1) crystal constant and ceramic substrate do not match, and cause boundary defect to be assembled, and cause the electrode layering to come off easily, cause component failure; (2) under the high-frequency electric field, chemical reaction takes place in counterdiffusion mutually easily between metal electrode and the ceramic phase, makes the dielectric property deterioration.
La
0.5Sr
0.5CoO
3, YB
2Cu
3O
7-δ, SrRuO
3The defective that solves metal electrode that appears as Deng conductive oxide provides new approach.In numerous conductive oxides, LaNiO
3(it is abbreviated as " LNO ", in the present patent application, represents LaNiO with LNO
3) because of its lattice constant be 0.384nm, (it is abbreviated as " PZT " with lead zirconate titanate, in the present patent application, represent lead zirconate titanate with PZT), (it is abbreviated as " PLZT " to lead lanthanum zirconate titanate, in the present patent application, represent lead lanthanum zirconate titanate with PLZT) etc. the piezoelectric ceramic lattice constant very approaching, thereby be subjected to paying close attention to widely.Up to the present, people to have utilized pulsed laser deposition (PLD), radio-frequency magnetron sputter method (RF), chemical solution deposition methods such as (CSD) to prepare resistivity be 10
-3The LNO membrane electrode of Ω cm magnitude, but with respect to noble metal good conductors such as Ag, its resistivity remains than higher.
The advantage of comprehensive conductive oxide and metal electrode, people such as Chen Mingsen and Wu Taibor prepared the LNO/Pt combination electrode (referring to Appl Phys Lett, 1996,68:1430-1432).Though this kind combination electrode has overcome when only making electrode with metal, ceramic and interelectrode counterdiffusion mutually and the higher defective of resistivity when only making electrode with conductive oxide, Pt is a kind of metal than the Ag costliness, and the preparation cost of electrode is improved greatly; In addition, this method prepares the sintering temperature higher (about about 1000 ℃) of LNO/Pt combination electrode, and the LNO film easily decomposes under this sintering temperature, and easily impels the volatilization of PbO among piezoelectric ceramic PZT, the PLZT, thereby cause combination electrode and device electric property to descend, and produce environmental pollution; Moreover because this method sintering temperature height, it is more that preparation process expends the energy.Except that the problems referred to above, disclosed LNO/Pt electrode was partial electrode (area that is electrode is less than substrate working face area) during people such as Chen Mingsen published thesis, the kind electrode structure has electrode part and electrodeless part to be easy to generate differently strained under the voltage effect, cause the gathering of stress, thereby cause the electrodes conduct performance of element to descend at electrode edge.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of multi-layer ceramics gross area LNO/Ag/LNO combination electrode and preparation method thereof is provided,, can increase substantially useful life again so that make electrode material both have good conductivity.
Multi-layer ceramics gross area LNO/Ag/LNO combination electrode of the present invention, the potsherd that comprises at least two overlapping placements, between adjacent two potsherds " LNO conductive buffer layer/Ag electrode layer/LNO conductive buffer layer ", the potsherd surface that is positioned at top and bottom covers the LNO conductive buffer layer successively, the Ag electrode layer, the shape of LNO conductive buffer layer end face is identical with the shape and the area of potsherd end face with area, the shape of Ag electrode layer end face is identical with the shape and the area of LNO conductive buffer layer end face with area, between described potsherd and the LNO conductive buffer layer, between LNO conductive buffer layer and the Ag electrode layer by being sintered into integral structure.
Multi-layer ceramics gross area LNO/Ag/LNO combination electrode of the present invention, preferred 200 nanometers of the thickness of its LNO conductive buffer layer～300 nanometers.
Multi-layer ceramics gross area LNO/Ag/LNO combination electrode of the present invention, the THICKNESS CONTROL of its Ag electrode layer is at 20 microns～100 microns.
Multi-layer ceramics gross area LNO/Ag/LNO combination electrode of the present invention, preferred PLZT of its potsherd or PZT make.
The preparation method of multi-layer ceramics gross area LNO/Ag/LNO combination electrode of the present invention, processing step is as follows:
(1) surface treatment of potsherd
At first potsherd is polished, carry out craft then successively and clean and ultrasonic waves for cleaning;
(2) preparation of LNO precursor solution
Be solute, be solvent, be chelating agent preparation LNO precursor solution with the polyvinyl alcohol that with deionized water and glacial acetic acid the mol ratio of nickel acetate and lanthanum nitrate is 1: 1 that with nickel acetate and lanthanum nitrate the volume ratio of deionized water and glacial acetic acid is 1: 3～5; Nickel acetate is put into reaction vessel and added glacial acetic acid, under normal pressure, room temperature, stir and dissolve fully until nickel acetate, add lanthanum nitrate then and under agitation be warming up to 60 ℃～70 ℃ and add deionized water, after lanthanum nitrate dissolves fully, under agitation be warming up to 70 ℃～80 ℃ and add polyvinyl alcohol, the addition of polyvinyl alcohol is a benchmark with the solution that nickel acetate, lanthanum nitrate, deionized water, glacial acetic acid form, and every liter of described solution adds polyvinyl alcohol 10g～45g; After polyvinyl alcohol dissolved fully, by the concentration that the mode of evaporating solvent or interpolation solvent is regulated described solution, making the content of LNO in the described solution was 0.1mol/L～0.3mol/L, continues after filtering and impurity removing promptly obtains LNO precursor solution;
The preparation of (3) first kinds of cell cubes
First kind of cell cube is by potsherd, cover the LNO conductive buffer layer on the potsherd both ends of the surface and cover an Ag electrode layer on the LNO conductive buffer layer and form respectively;
1. adopt the rotation lacquering technique LNO precursor solution that step (2) is prepared to be coated in and on the both ends of the surface of the potsherd after step (1) processing, form the LNO wet film and heat-treat formation LNO conductive buffer layer, the method of successively handling is adopted in heat treatment, be that every coating one deck LNO wet film carries out a heat treatment, the heat treatment operation of every layer of LNO wet film is identical, rotation whirl coating and heat treated number of times reach 200 nanometers～300 nanometers with the thickness of LNO film and exceed, after last heat treatment is finished, at 600 ℃～850 ℃ insulation 20min～60min, cool to room temperature then with the furnace;
2. the silver slurry is adopted 300 orders～350 order silk screen gross areas to print to a LNO conductive buffer layer, every printing once, wet sheet is obtained at 80 ℃～100 ℃ dry 5min～15min down in this time printshop, the number of times of printing and the dry number of times of wet sheet is reached 20 microns～100 microns with the thickness of Ag electrode layer exceed;
The preparation of (4) second kinds of cell cubes
Second kind of cell cube by potsherd, cover the LNO conductive buffer layer on the potsherd both ends of the surface respectively and the Ag electrode layer that covers respectively on the two LNO conductive buffer layers is formed;
1. adopt rotation whirl coating (Spin-Coating) the method LNO precursor solution that step (2) is prepared to be coated in and on the both ends of the surface of the potsherd after step (1) processing, form the LNO wet film and heat-treat formation LNO conductive buffer layer, the method of successively handling is adopted in heat treatment, be that every coating one deck LNO wet film carries out a heat treatment, the heat treatment operation of every layer of LNO wet film is identical, rotation whirl coating and heat treated number of times reach 200 nanometers～300 nanometers with the thickness of LNO film and exceed, after last heat treatment is finished, at 600 ℃～850 ℃ insulation 20min～60min, cool to room temperature then with the furnace;
2. the silver slurry is adopted 300 orders～350 order silk screen gross areas to print to two LNO conductive buffer layers, every printing once, wet sheet is obtained at 80 ℃～100 ℃ dry 5min～15min down in this time printshop, the number of times of printing and the dry number of times of wet sheet is reached 20 microns～100 microns with the thickness of Ag electrode layer exceed;
(5) combination of cell cube and sintering
With second kind of cell cube is egative film, one or more first kind of cell cube overlayed the base substrate that forms multi-layer ceramics gross area LNO/Ag/LNO combination electrode on second kind of cell cube, then described base substrate is put into the sintering furnace of band pressure apparatus, under the condition that axially applies 1MPa～3MPa pressure to base substrate, be warming up to 750 ℃～850 ℃ sintering 20min～60min, continue after cool to room temperature with the furnace, promptly obtain multi-layer ceramics gross area LNO/Ag/LNO combination electrode.
In first kind of cell cube of the method for the invention and the second kind of cell cube preparation process, the heat treatment operation of LNO wet film is preferred: successively at 150 ℃～200 ℃ following dry 10min～20min, 300 ℃～400 ℃ following decomposing organic matter 10min～20min, 500 ℃～600 ℃ following pre-crystallization treatment 1min～5min.
In the method for the invention, silver slurry slurry can directly be bought from market, also can prepare by following prescription and operation: the mass parts of silver powder is 100 parts, the mass parts of solvent is 4 parts～6 parts, the mass parts of bonding agent is 10 parts～60 parts, to grind by silver powder, solvent and the bonding agent of above-mentioned mass parts metering, the time of grinding is with the fineness≤6 μ m of silver slurry slurry, reach 8 * 10 25 ℃ viscosity
4MPas～12 * 10
4MPas exceeds; Described solvent is a bismuth oxide, described bonding agent is made up of terpinol, turpentine oil, nitrocotton, cyclohexanone and dibutyl phthalate, the mass parts of terpinol is 3.8 parts～4.5 parts, terebinthine mass parts is 1.7 parts～2.6 parts, the mass parts of nitrocotton is 1.3 parts～1.6 parts, the mass parts of cyclohexanone is 14.3 parts～16.2 parts, and the mass parts of dibutyl phthalate is 3.1 parts～4.2 parts.
In the method for the invention, preferred PLZT of potsherd or PZT make.
The present invention has following beneficial effect:
1, multi-layer ceramics gross area LNO/Ag/LNO combination electrode of the present invention has good anti-fatigue performance and anti-breakdown field strength, and its technical indicator is as follows:
(1) electrode resistance rate＜1m Ω cm;
(2) operating voltage-300～+ 300V;
(3) frequency＞10
4Hz, continuous impulse counter-rotating number of times＞10
8(not damaged).
2, multi-layer ceramics gross area LNO/Ag/LNO combination electrode of the present invention has solved " electrode in staggered " structure and has brought the uneven problem of stress distribution, thereby has overcome pottery and the lead rupture phenomenon that causes because of tensile stress, has prolonged the useful life of device.
3, the method for the invention, make the solid solution of the faying face formation structural similarity of Ag electrode layer and LNO conductive buffer layer, LNO conductive buffer layer and potsherd, thereby the Ag electrode layer do not combine with potsherd closely with LNO conductive buffer layer, LNO conductive buffer layer, and is extremely easy to crack and peel off.
4, the method for the invention is because every coating one deck LNO wet film carries out a heat treatment, and last procedure of heat treatment operation is 500 ℃～600 ℃ pre-crystallization treatment 1～5min down, under these process conditions, can continue to remove residual organic matter on the one hand, the more important thing is to make current membrane structure be in noncrystalline state, help closely bonding between the multilayer coated film; After reaching general thickness, can make the plural layers cocrystallization at 600 ℃～850 ℃ insulation 20min～60min, thereby LNO conductive buffer layer crystal grain is evenly distributed, eliminated the interlayer crystal boundary, promoted electric field evenly to distribute, reduce the resistance of carrier moving, improved the sull electric conductivity, and then improved the overall performance of combination electrode.
5, the equipment that uses of the method for the invention is conventional equipment, and the device for exerting of sintering both can be a mechanical press device, also can be other pressure apparatus, and the sintering atmosphere require lowly, thereby cost is low, is easy to suitability for industrialized production.
Description of drawings
Fig. 1 is a kind of structural representation of multi-layer ceramics gross area LNO/Ag/LNO combination electrode of the present invention;
Fig. 2 is the vertical view of Fig. 1;
Fig. 3 is the structural representation of first kind of cell cube;
Fig. 4 is the vertical view of Fig. 3;
Fig. 5 is the structural representation of second kind of cell cube;
Fig. 6 is the vertical view of Fig. 5;
Fig. 7 is the stereoscan photograph with the Ag electrode layer behind the multi-layer ceramics gross area LNO/Ag/LNO combination electrode employing external force stripped ceramic sheet of the present invention, wherein, (a) and (b), (c), (d) are respectively to base substrate and axially apply the Ag electrode layer stereoscan photograph that 0MPa, 1MPa, 2MPa, 3MPa pressure carry out combination electrode that sintering obtains;
The graph of a relation of the mechanical pressure that axially applies to base substrate when Fig. 8 is sintering and the multi-layer ceramics gross area LNO/Ag/LNO combination electrode resistivity that obtains;
When being sintering, Fig. 9 axially applies the fatigue property test figure that different mechanical pressure obtains multi-layer ceramics gross area LNO/Ag/LNO combination electrode to base substrate;
Figure 10 is the electric hysteresis loop figure of multi-layer ceramic capacitance, wherein, (a) being the electric hysteresis loop with the capacitor (applying 2MPa mechanical pressure sintering) of 4 layers of ceramic gross area LNO/Ag/LNO combination electrode preparation of the present invention, (b) is the electric hysteresis loop of the capacitor for preparing with silver electrode.
Among the figure, 1-potsherd, 2-LNO conductive buffer layer, 3-Ag electrode layer.
Embodiment
Below in conjunction with accompanying drawing multi-layer ceramics gross area LNO/Ag/LNO combination electrode of the present invention and preparation method are described further.
Present embodiment prepares Fig. 1, four layers of ceramic gross area LNO/Ag/LNO combination electrode shown in Figure 2, and processing step is as follows:
(1) surface treatment of potsherd
Potsherd is 0.5 millimeter a PLZT sheet, and its surface treatment is followed successively by surface finish and cleaning; Precise grinding polisher is adopted in surface finish, and potsherd is fixed on the polishing machine by paraffin, and its obverse and reverse is all polished by following operation: use 1500
#Emery paper polishes 2h under rotating speed 45rpm, use polishing fabric then instead, polishes 16h under rotating speed 45rpm; Cleaning comprises manual the cleaning and ultrasonic waves for cleaning, at first by the manual paraffin that removes the potsherd surface that cleans, adopt ultrasonic waves for cleaning then: 1. potsherd is put into the container that fills acetone, described container is put into ultrasonic cleaner regenerate cleaning 5min, take out potsherd then, use washed with de-ionized water 3 times; 2. the potsherd after the washed with de-ionized water is put into the container that fills absolute ethyl alcohol, ultrasonic cleaning 5min takes out potsherd then, uses washed with de-ionized water 3 times; 3. the potsherd after the washed with de-ionized water is put into the container ultrasonic cleaning 5min that fills deionized water, taken out potsherd then and put it in the drying box at 60 ℃ of following dry 15min;
(2) preparation of LNO precursor solution
Be solute, be solvent, be chelating agent preparation LNO precursor solution with the polyvinyl alcohol that with deionized water and glacial acetic acid the mol ratio of nickel acetate and nitric hydrate lanthanum is 1: 1 that with nickel acetate and nitric hydrate lanthanum the volume ratio of deionized water and glacial acetic acid is 1: 3; Nickel acetate is put into reaction vessel and added glacial acetic acid, under normal pressure, room temperature (25 ℃), stir and dissolve fully until nickel acetate, add the nitric hydrate lanthanum then and under agitation be warming up to 60 ℃ and add deionized water, after the nitric hydrate lanthanum dissolves fully, under agitation be warming up to 70 ℃ and add polyvinyl alcohol, the addition of polyvinyl alcohol is a benchmark with the solution that nickel acetate, nitric hydrate lanthanum, deionized water, glacial acetic acid form, and every liter of described solution adds polyvinyl alcohol 30g; After polyvinyl alcohol dissolved fully, by the concentration that the mode of evaporating solvent or interpolation solvent is regulated described solution, making the content of LNO in the described solution was 0.2mol/L, continues after 0.2 micron filter filters out impurities, and promptly obtains the LNO precursor solution of green transparent; It is pure that above-mentioned raw materials is analysis.
The preparation of (3) first kinds of cell cubes
The shape of first kind of cell cube and structure as shown in Figure 3, Figure 4, by potsherd 1, cover the LNO conductive buffer layer 2 on the potsherd both ends of the surface and cover an Ag electrode layer 3 on the LNO conductive buffer layer and form respectively;
1. adopt the rotation lacquering technique LNO precursor solution that step (2) is prepared to be coated in and on the both ends of the surface of the potsherd after step (1) processing, form the LNO wet film and heat-treat formation LNO conductive buffer layer, even glue speed 3500rpm, even glue time 20s, the method of successively handling is adopted in heat treatment, be that every coating one deck LNO wet film carries out a heat treatment, the heat treatment operation of every layer of LNO wet film is identical, be: successively at 180 ℃ of following dry 15min, 350 ℃ of following decomposing organic matter 10min, 550 ℃ of following preliminary treatment 2min; Rotation whirl coating and heat treated number of times reach 300 nanometers with the thickness of LNO film and exceed, and after last heat treatment is finished, are incubated 30min at 750 ℃, cool to room temperature then with the furnace;
2. by silver powder, solvent and bonding agent preparation silver slurry slurry, the mass parts of silver powder is 100 parts, the mass parts of solvent is 5 parts, and the mass parts of bonding agent is 30 parts, and described solvent is a bismuth oxide, described bonding agent is made up of terpinol, turpentine oil, nitrocotton, cyclohexanone and dibutyl phthalate, the mass parts of terpinol is 4.0, and terebinthine mass parts is 2.0 parts, and the mass parts of nitrocotton is 1.5 parts, the mass parts of cyclohexanone is 15.0 parts, and the mass parts of dibutyl phthalate is 3.5 parts; To be ground to the fineness≤6 μ m of slurry, be 10 * 10 with three-roll grinder by silver powder, solvent and the bonding agent of the metering of above-mentioned mass parts 25 ℃ viscosity viscosity
4MPas; Adopt the printing of 350 order silk screen gross areas to a LNO conductive buffer layer in the silver slurry slurry of being prepared, every printing once, wet sheet is obtained at 80 ℃ of dry 10min down in this time printshop, the number of times of printing and the dry number of times of wet sheet is reached 80 microns with the thickness of Ag electrode layer exceed; The unnecessary Ag/LNO material that the potsherd periphery overflows is handled by sanding and polishing; It is pure that above-mentioned raw materials is analysis.
The preparation of (4) second kinds of cell cubes
The shape of second kind of cell cube and structure be as Fig. 5, shown in Figure 6, by potsherd 1, cover the LNO conductive buffer layer 2 on the potsherd both ends of the surface respectively and the Ag electrode layer 3 that covers respectively on the two LNO conductive buffer layers is formed;
1. the method at the both ends of the surface covering LNO of potsherd 1 conductive buffer layer 2 is identical with first kind of cell cube of above-mentioned steps (3) preparation;
2. the used silver powder of preparation silver slurry slurry, solvent and bonding agent and first kind of cell cube of operation and above-mentioned steps (3) preparation thereof are identical; Adopt the printing of 350 order silk screen gross areas to two LNO conductive buffer layers in the silver slurry slurry of being prepared, every printing once, wet sheet is obtained at 80 ℃ of dry 10min down in this time printshop, the number of times of printing and the dry number of times of wet sheet is reached 80 microns with the thickness of Ag electrode layer exceed; The unnecessary Ag/LNO material that the potsherd periphery overflows is handled by sanding and polishing;
(5) combination of cell cube and sintering
With Fig. 5, second kind of cell cube shown in Figure 6 is egative film, three Fig. 3, first kind of cell cube shown in Figure 4 is overlayed the base substrate that forms four layers of ceramic gross area LNO/Ag/LNO combination electrode on described second kind of cell cube; Make up the base substrate of 12 described four layers of ceramic gross area LNO/Ag/LNO combination electrodes.
12 described base substrates are put into the sintering furnace of band mechanical press device (its mechanical press device is the disclosed mechanical press device of ZL200810044344.7 patent), per three base substrates are one group, to four assembly axons to applying 0Mpa, 1Mpa, 2Mpa, 3MPa mechanical pressure respectively, under exerting pressure, be warming up to 850 ℃ then by 3.5 ℃/min, under this temperature, be incubated 20min, continue after cool to room temperature with the furnace, promptly obtain 12 four layers ceramic gross area LNO/Ag/LNO combination electrode.
The Ag electrode layer 3 usefulness ESEMs that axial pressure is respectively four layers of ceramic gross area LNO/Ag/LNO combination electrode of 0Mpa, 1Mpa, 2Mpa, 3Mpa during with four sintering scan, the image that obtains is seen Fig. 7, as can be seen from Figure 7: under different pressure sintering conditions, the interface that the big more combination electrode of pressure contacts with pottery is in conjunction with tight more, and the interfacial structure under the 3MPa pressure is best.
Axial pressure is respectively the ceramic gross area LNO/Ag/LNO combination electrode of 0Mpa, 1Mpa, 2Mpa, 3Mpa four layers and adopts four probe methods to test during with four sintering, their resistivity is seen Fig. 8, as can be seen from Figure 8: along with sintering pressure increases, the resistivity of combination electrode reduces.
Three four layers ceramic gross area LNO/Ag/LNO combination electrode that adopt axial pressure 0Mpa, 2Mpa, 3Mpa sintering are carried out the remanent polarization test, normalizing remanent polarization Pr sees Fig. 9 with the variation of electric field cycle-index logarithm logN after their polarization, as can be seen from Figure 9: sintering pressure is big more, normalizing remanent polarization Pr is big more, adopts the prepared piezoelectric ceramic anti-fatigue performance of combination electrode material of the present invention good more.
Four of axial pressure 3Mpa layers of ceramic gross area LNO/Ag/LNO combination electrode prepare capacitor during with sintering, its electric hysteresis loop is seen (a) curve among Figure 10, described (a) curve is compared with (b) curve (electric hysteresis loop of the capacitor of silver electrode Ag/PLZT/Ag preparation) among Figure 10, as can be seen: adopt four layers of ceramic capacitor electric hysteresis loop shape of combination electrode material preparation of the present invention better, polarization intensity is better than adopting the ceramic capacitor of silver electrode.
More than the four point probe instrument has been adopted in test: K2400 voltage table (U.S. Keithley company), polarization parameter tester: Precision LC (U.S. Radient company), pulse generator: Precision High Voltage Interface ± 4000V (U.S. Radient company), and high-voltage amplifier: Model 609E-6 (U.S. Terk company).Test job voltage is-300～+ 300V, the field inversion frequency is 1.8 * 10
4Hz, 6 hours rear electrode not damageds of follow-on test.
Three layers of ceramic gross area LNO/Ag/LNO combination electrode of present embodiment preparation, processing step is as follows:
(1) surface treatment of potsherd
The PZT sheet that potsherd is 1 millimeter, its surface treatment is followed successively by surface finish and cleaning; Surface finish is identical with embodiment 1 with the operation of cleaning.
(2) preparation of LNO precursor solution
Be solute, be solvent, be chelating agent preparation LNO precursor solution with the polyvinyl alcohol that with deionized water and glacial acetic acid the mol ratio of nickel acetate and lanthanum nitrate is 1: 1 that with nickel acetate and lanthanum nitrate the volume ratio of deionized water and glacial acetic acid is 1: 5; Nickel acetate is put into reaction vessel and added glacial acetic acid, under normal pressure, room temperature (29 ℃), stir and dissolve fully until nickel acetate, add lanthanum nitrate then and under agitation be warming up to 70 ℃ and add deionized water, after lanthanum nitrate dissolves fully, under agitation be warming up to 80 ℃ and add polyvinyl alcohol, the addition of polyvinyl alcohol is a benchmark with the solution that nickel acetate, lanthanum nitrate, deionized water, glacial acetic acid form, and every liter of described solution adds polyvinyl alcohol 10g; After polyvinyl alcohol dissolved fully, by the concentration that the mode of evaporating solvent or interpolation solvent is regulated described solution, making the content of LNO in the described solution was 0.1mol/L, continues after 0.2 micron filter filters out impurities, and promptly obtains the LNO precursor solution of green transparent; It is pure that above-mentioned raw materials is analysis.
The preparation of (3) first kinds of cell cubes
The shape of first kind of cell cube and structure as shown in Figure 3, Figure 4, by potsherd 1, cover the LNO conductive buffer layer 2 on the potsherd both ends of the surface and cover an Ag electrode layer 3 on the LNO conductive buffer layer and form respectively;
1. adopt the rotation lacquering technique LNO precursor solution that step (2) is prepared to be coated in and on the both ends of the surface of the potsherd after step (1) processing, form the LNO wet film and heat-treat formation LNO conductive buffer layer, even glue speed 3500rpm, even glue time 20s, the method of successively handling is adopted in heat treatment, be that every coating one deck LNO wet film carries out a heat treatment, the heat treatment operation of every layer of LNO wet film is identical, be: successively at 150 ℃ of following dry 20min, 300 ℃ of following decomposing organic matter 20min, 500 ℃ of following preliminary treatment 5min; Rotation whirl coating and heat treated number of times reach 200 nanometers with the thickness of LNO film and exceed, and after last heat treatment is finished, are incubated 60min at 600 ℃, cool to room temperature then with the furnace;
2. by silver powder, solvent and bonding agent preparation silver slurry slurry, the mass parts of silver powder is 100 parts, the mass parts of solvent is 5 parts, and the mass parts of bonding agent is 60 parts, and described solvent is a bismuth oxide, described bonding agent is made up of terpinol, turpentine oil, nitrocotton, cyclohexanone and dibutyl phthalate, the mass parts of terpinol is 4.5, and terebinthine mass parts is 2.6 parts, and the mass parts of nitrocotton is 1.3 parts, the mass parts of cyclohexanone is 16.0 parts, and the mass parts of dibutyl phthalate is 4.2 parts; To be ground to the fineness≤6 μ m of slurry, be 12 * 10 with three-roll grinder by silver powder, solvent and the bonding agent of the metering of above-mentioned mass parts 25 ℃ viscosity viscosity
4MPas; Above-mentioned raw materials all adopts analysis pure.
Adopt the printing of 300 order silk screen gross areas to a LNO conductive buffer layer in the silver slurry slurry of being prepared, every printing once, wet sheet is obtained at 100 ℃ of dry 5min down in this time printshop, the number of times of printing and the dry number of times of wet sheet is reached 50 microns with the thickness of Ag electrode layer exceed; The unnecessary Ag/LNO material that the potsherd periphery overflows is handled by sanding and polishing;
The preparation of (4) second kinds of cell cubes
The shape of second kind of cell cube and structure be as Fig. 5, shown in Figure 6, by potsherd 1, cover the LNO conductive buffer layer 2 on the potsherd both ends of the surface respectively and the Ag electrode layer 3 that covers respectively on the two LNO conductive buffer layers is formed;
1. the method at the both ends of the surface covering LNO of potsherd 1 conductive buffer layer 2 is identical with first kind of cell cube of above-mentioned steps (3) preparation;
2. the used silver powder of preparation silver slurry slurry, solvent and bonding agent and first kind of cell cube of operation and above-mentioned steps (3) preparation thereof are identical; Adopt the printing of 300 order silk screen gross areas to two LNO conductive buffer layers in the silver slurry slurry of being prepared, every printing once, wet sheet is obtained at 100 ℃ of dry 15min down in this time printshop, the number of times of printing and the dry number of times of wet sheet is reached 50 microns with the thickness of Ag electrode layer exceed; The unnecessary Ag/LNO material that the potsherd periphery overflows is handled by sanding and polishing;
(5) combination of cell cube and sintering
With Fig. 5, second kind of cell cube shown in Figure 6 is egative film, two Fig. 3, first kind of cell cube shown in Figure 4 is overlayed the base substrate that forms three layers of ceramic gross area LNO/Ag/LNO combination electrode on described second kind of cell cube; Make up the base substrate of six described three layers of ceramic gross area LNO/Ag/LNO combination electrodes.
Six described base substrates are put into the sintering furnace (described mechanical press device is identical with embodiment 1) of band mechanical press device, per three base substrates are one group, to three assembly axons to applying 1Mpa, 2Mpa, 3MPa mechanical pressure respectively, under exerting pressure, be warming up to 750 ℃ of sintering 60min then, continue after cool to room temperature with the furnace, promptly obtain six three layers ceramic gross area LNO/Ag/LNO combination electrode.
Three layers of ceramic gross area LNO/Ag/LNO combination electrode that present embodiment is prepared carry out performance test, and testing equipment is identical with embodiment 1, and operating voltage is-300～+ 300V, the counter-rotating test frequency is 1.5 * 10
4Hz, 6 hours rear electrode not damageds of follow-on test.The resistivity measurement result is as follows:
| Sintering pressure | 1Mpa | 2Mpa | 3MPa |
| The electrode resistance rate | 0.67mΩ·cm | 0.56mΩ·cm | 0.48mΩ·cm |
Claims (10)
1. multi-layer ceramics gross area LNO/Ag/LNO combination electrode, it is characterized in that comprising the potsherd (1) of at least two overlapping placements, between adjacent two potsherds (1) " LNO conductive buffer layer (2)/Ag electrode layer (3)/LNO conductive buffer layer (2) ", potsherd (1) surface that is positioned at top and bottom covers LNO conductive buffer layer (2) successively, Ag electrode layer (3), the shape of LNO conductive buffer layer (2) end face is identical with the shape and the area of potsherd (1) end face with area, the shape of Ag electrode layer (3) end face is identical with the shape and the area of LNO conductive buffer layer (2) end face with area, between described potsherd (1) and the LNO conductive buffer layer (2), between LNO conductive buffer layer (2) and the Ag electrode layer (3) by being sintered into integral structure.
2. multi-layer ceramics gross area LNO/Ag/LNO combination electrode according to claim 1, the thickness that it is characterized in that LNO conductive buffer layer (2) is 200 nanometers～300 nanometers.
3. multi-layer ceramics gross area LNO/Ag/LNO combination electrode according to claim 1 and 2, the thickness that it is characterized in that Ag electrode layer (3) is 20 microns～100 microns.
4. multi-layer ceramics gross area LNO/Ag/LNO combination electrode according to claim 1 and 2 is characterized in that potsherd (1) is by lead lanthanum zirconate titanate or lead zirconate titanate making.
5. multi-layer ceramics gross area LNO/Ag/LNO combination electrode according to claim 3 is characterized in that potsherd (1) is by lead lanthanum zirconate titanate or lead zirconate titanate making.
6. the preparation method of a multi-layer ceramics gross area LNO/Ag/LNO combination electrode is characterized in that processing step is as follows:
(1) surface treatment of potsherd
At first potsherd is polished, carry out craft then successively and clean and ultrasonic waves for cleaning;
(2) preparation of LNO precursor solution
Be solute, be solvent, be chelating agent preparation LNO precursor solution with the polyvinyl alcohol that with deionized water and glacial acetic acid the mol ratio of nickel acetate and lanthanum nitrate is 1: 1 that with nickel acetate and lanthanum nitrate the volume ratio of deionized water and glacial acetic acid is 1: 3～5; Nickel acetate is put into reaction vessel and added glacial acetic acid, under normal pressure, room temperature, stir and dissolve fully until nickel acetate, add lanthanum nitrate then and under agitation be warming up to 60 ℃～70 ℃ and add deionized water, after lanthanum nitrate dissolves fully, under agitation be warming up to 70 ℃～80 ℃ and add polyvinyl alcohol, the addition of polyvinyl alcohol is a benchmark with the solution that nickel acetate, lanthanum nitrate, deionized water, glacial acetic acid form, and every liter of described solution adds polyvinyl alcohol 10g～45g; After polyvinyl alcohol dissolved fully, by the concentration that the mode of evaporating solvent or interpolation solvent is regulated described solution, making the content of LNO in the described solution was 0.1mol/L～0.3mol/L, continues after filtering and impurity removing promptly obtains LNO precursor solution;
The preparation of (3) first kinds of cell cubes
First kind of cell cube is by potsherd, cover the LNO conductive buffer layer on the potsherd both ends of the surface and cover an Ag electrode layer on the LNO conductive buffer layer and form respectively;
1. adopt the rotation lacquering technique LNO precursor solution that step (2) is prepared to be coated in and on the both ends of the surface of the potsherd after step (1) processing, form the LNO wet film and heat-treat formation LNO conductive buffer layer, the method of successively handling is adopted in heat treatment, be that every coating one deck LNO wet film carries out a heat treatment, the heat treatment operation of every layer of LNO wet film is identical, rotation whirl coating and heat treated number of times reach 200 nanometers～300 nanometers with the thickness of LNO film and exceed, after last heat treatment is finished, at 600 ℃～850 ℃ insulation 20min～60min, cool to room temperature then with the furnace;
2. the silver slurry is adopted 300 orders～350 order silk screen gross areas to print to a LNO conductive buffer layer, every printing once, wet sheet is obtained at 80 ℃～100 ℃ dry 5min～15min down in this time printshop, the number of times of printing and the dry number of times of wet sheet is reached 20 microns～100 microns with the thickness of Ag electrode layer exceed;
The preparation of (4) second kinds of cell cubes
Second kind of cell cube by potsherd, cover the LNO conductive buffer layer on the potsherd both ends of the surface respectively and the Ag electrode layer that covers respectively on the two LNO conductive buffer layers is formed;
1. adopt the rotation lacquering technique LNO precursor solution that step (2) is prepared to be coated in and on the both ends of the surface of the potsherd after step (1) processing, form the LNO wet film and heat-treat formation LNO conductive buffer layer, the method of successively handling is adopted in heat treatment, be that every coating one deck LNO wet film carries out a heat treatment, the heat treatment operation of every layer of LNO wet film is identical, rotation whirl coating and heat treated number of times reach 200 nanometers～300 nanometers with the thickness of LNO film and exceed, after last heat treatment is finished, at 600 ℃～850 ℃ insulation 20min～60min, cool to room temperature then with the furnace;
2. the silver slurry is adopted 300 orders～350 order silk screen gross areas to print to two LNO conductive buffer layers, every printing once, wet sheet is obtained at 80 ℃～100 ℃ dry 5min～15min down in this time printshop, the number of times of printing and the dry number of times of wet sheet is reached 20 microns～100 microns with the thickness of Ag electrode layer exceed;
(5) combination of cell cube and sintering
With second kind of cell cube is egative film, one or more first kind of cell cube overlayed the base substrate that forms multi-layer ceramics gross area LNO/Ag/LNO combination electrode on second kind of cell cube, then described base substrate is put into the sintering furnace of band pressure apparatus, under the condition that axially applies 1MPa～3MPa pressure to base substrate, be warming up to 750 ℃～850 ℃ sintering 20min～60min, continue after cool to room temperature with the furnace, promptly obtain multi-layer ceramics gross area LNO/Ag/LNO combination electrode.
7. according to the preparation method of claim 6 multi-layer ceramics gross area LNO/Ag/LNO combination electrode, the heat treatment operation that it is characterized in that the LNO wet film is: successively at 150 ℃～200 ℃ following dry 10min～20min, 300 ℃～400 ℃ following decomposing organic matter 10min～20min, 500 ℃～600 ℃ following pre-crystallization treatment 1min～5min.
8. according to the preparation method of claim 6 or 7 multi-layer ceramics gross area LNO/Ag/LNO combination electrodes, it is characterized in that silver slurry slurry is formulated by silver powder, solvent and bonding agent, the mass parts of silver powder is 100 parts, the mass parts of solvent is 4 parts～6 parts, the mass parts of bonding agent is 10 parts～60 parts, to grind by silver powder, solvent and the bonding agent of above-mentioned mass parts metering, the time of grinding is with the fineness≤6 μ m of silver slurry slurry, reach 8 * 10 25 ℃ viscosity
4MPas～12 * 10
4MPas exceeds; Described solvent is a bismuth oxide, described bonding agent is made up of terpinol, turpentine oil, nitrocotton, cyclohexanone and dibutyl phthalate, the mass parts of terpinol is 3.8 parts～4.5 parts, terebinthine mass parts is 1.7 parts～2.6 parts, the mass parts of nitrocotton is 1.3 parts～1.6 parts, the mass parts of cyclohexanone is 14.3 parts～16.2 parts, and the mass parts of dibutyl phthalate is 3.1 parts～4.2 parts.
9. according to the preparation method of claim 6 or 7 described multi-layer ceramics gross area LNO/Ag/LNO combination electrodes, it is characterized in that potsherd is by lead lanthanum zirconate titanate or lead zirconate titanate making.
10. according to the preparation method of claim described 8 described multi-layer ceramics gross area LNO/Ag/LNO combination electrodes, it is characterized in that potsherd is by lead lanthanum zirconate titanate or lead zirconate titanate making.
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