CN1204642C - Zirconia electrolytic film material for solid oxide fuel cell and its prepn - Google Patents
Zirconia electrolytic film material for solid oxide fuel cell and its prepn Download PDFInfo
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Abstract
The present invention provides a stable zirconia ceramic thin film material with a large dimension. The length of the thin film material is at least from 50 to 300 millimeters, the width is at least from 50 to 300 millimeters, and the thickness is from 0.02 to 0.2 millimeters. The present invention also provides a method for preparing the stable zirconia ceramic thin film material, which comprises a shaping step and a sintering step. The method is characterized in that in the shaping step, nanometer powder, such as nanometer YSZ powder, is used as the raw material; the nanometer powder has the following performance: the particle size of a primary particle is from 15 to 50 nm, and the specific surface area is from 10 to 70m<2>/g; the particle size of 85% of secondary particles is between 0.10 and 0.60 mu m, and the main peak value is presented at 0.3 to 0.4 mu m points.
Description
Technical field
The present invention relates to a kind of large-sized zirconia ceramics thin-film material and its preparation method, more specifically, the present invention relates to be used for the zirconia electrolytic thin-membrane and its preparation method of Solid Oxide Fuel Cell (SOFC).
Background technology
Along with the ceramic-like thin-film material has increasing application in fields such as electronic devices, preparation large-size ceramic thin-film material becomes present focus.
Provided among the CN1277096A and adopted vacuum casting method to prepare the technology and the shaped device of electrolyte membrane tube, but the dielectric film of this method preparation only is only applicable to the tubular structure Solid Oxide Fuel Cell, does not appear in the newspapers for the solid-oxide fuel battery electrolyte film of plate armature.The Solid Oxide Fuel Cell of plate armature is because the power density height, production cost is low, caused worldwide common concern, it is the focus that develops both at home and abroad, wherein preparing large scale self-supporting electrolytic thin-membrane is one of key technology of its development, also is the prerequisite of the Solid Oxide Fuel Cell commercialized development of plate armature.
The ceramic-like thin-film material is widely used in industries such as capacitor, piezo at present, but its size is all very little.The electrolyte that fuel cell requires is very thin, and the thickness direction size can effectively reduce the electrolyte internal resistance like this at 30～150 microns, reduces the ohmic polarization in battery operated, the raising power density; Also require big work area simultaneously, the length and width size to obtain big power output, just has using value greater than each 50 millimeters.Large-size on the preparation two-dimensional direction, the relative very ceramic sheet of small scale structures of third dimension direction are the difficult point technology among the ceramic preparation technology always, and control requires very strict to the parameter among material property and the preparation technology for this.Because the fragility feature of ceramic material, ceramic membrane General Mechanics poor-performing is difficult to prepare large-area film, defectives such as film is easy to ftracture, warpage.
In summary, in the prior art, the large-size ceramic film still is difficult for producing, and the sintering temperature of ceramic membrane is too high, is difficult to contain by the co-firing technology preparation ceramic component of multiple thin-film component.Therefore, exist demand to the large-size ceramic film.
Summary of the invention
At problems of the prior art, the object of the present invention is to provide a kind of large-sized zirconia ceramics thin-film material and its preparation method, more specifically, the invention provides the stabilized zirconia film that can be used for Solid Oxide Fuel Cell (SOFC), another object of the present invention is to provide a kind of YSZ electrolyte thin membrane preparation technology of in enormous quantities, low-cost, stable performance, for the development of Solid Oxide Fuel Cell, improve and extensive use lays the foundation.In addition, the invention still further relates to a Solid Oxide Fuel Cell that adopts zirconia ceramics thin-film material of the present invention.
At present, along with the development of nanometer technology, adopt the nano powder preparation ceramic material to obtain paying attention to.But, be difficult for the preparation ceramic body by nano-powder, and the base substrate that nano-powder constitutes is strict to sintering process, therefore use the report of nano powder preparation ceramic membrane also fewer.The inventor passes through repetition test, unexpectedly find, employing has the large tracts of land ceramic membrane that the nano powder of characteristic powder property can obtain to have superior electrical performance and mechanical property, and by control moulding and sintering process, reduced the sintering temperature of ceramic membrane, the co-firing technology that helps this ceramic membrane and other thin-film component greatly, thus can the more excellent thin-film device of obtained performance.Wherein, the membrane blank profile that is obtained is smooth evenly, and thickness error is no more than 8%, can stablize placement, and Undeformable and indehiscent, does not ftracture at the smooth not warpage of the ceramic membrane behind the sintering.
To this, the present invention at first provides a kind of large-sized stabilization zirconium oxide ceramic thin-film material, the length of this thin-film material, width are respectively at least 50 millimeters, at least 50 millimeters, preferred length, width are respectively at least 100 millimeters, at least 100 millimeters, more preferably length, width are respectively at least 200 millimeters, at least 200 millimeters, and most preferably length, width are respectively at least 300 millimeters, at least 300 millimeters; The thickness of this film is 0.02～0.2 millimeter, preferred 0.1～0.2 millimeter, and more preferably 0.12～0.2 millimeter, most preferably 0.15～0.2 millimeter.It is worthy of note that above-mentioned length and width and gauge are separate, be used to the large tracts of land characteristic that illustrates that film of the present invention has, promptly the invention is not restricted to square, can also be rectangle or other shape.
Stabilization zirconium oxide ceramic thin-film material of the present invention is selected from the stable zirconia of yttrium, the zirconia of calcium stable, the stable zirconia of zirconia, Sc that Yb is stable.Though in an embodiment, be that example is set forth the present invention mainly with the stable zirconia of yttrium,, the present invention is not limited to the stable zirconia of yttrium, but applicable to various stabilizing zirconia materials.In a preferred embodiment, stabilization zirconium oxide ceramic thin-film material of the present invention has following composition: 8～12mol% yittrium oxide (Y
2O
3) and 88～92mol% zirconia (ZrO
2) (being designated as YSZ).
In one embodiment, the average grain size of stabilization zirconium oxide ceramic thin-film material of the present invention preferably is no more than 3 microns, more preferably no more than 2 microns, especially preferably less than 1 micron, its relative density is not less than 96%, preferably is not less than 98%, more preferably more than 99%.
In a preferred embodiment, stabilization zirconium oxide ceramic thin-film material of the present invention has the good mechanical performance, and bending strength is more than 120Mpa, especially more than 150Mpa, in addition, this film preferably has transparent, smooth, smooth outward appearance, and for example this film thickness is 150 microns, when length and width are 100 millimeters sheet form, flatness error preferably is not more than 10 microns, and slow stressed when crooked, amount of deflection reaches 25 millimeters and do not break.
In a further preferred embodiment, stabilization zirconium oxide ceramic thin-film material of the present invention, as the electrolyte of Solid Oxide Fuel Cell (SOFC), its 1000 ℃ of conductivity are 0.10-0.20Scm
-1, 0.12-0.20Scm especially
-1, 0.15-0.20Scm more especially
-1
On the other hand, the present invention also provides a kind of preparation method of large-sized zirconia ceramics thin-film material, and this method comprises moulding and sintering step, when moulding, adopt nano-powder for example nanometer YSZ powder be raw material, the nano-powder performance is: primary particle granularity 15～50nm, N
2Absorption specific surface 10～70m
2/ g; Offspring concentrates on more than 85% between 0.10～0.60 μ m micron, and presents the main peak value in 0.3～0.4 μ m place.
In addition, also preferred above-mentioned powder observes particle spherical in shape basically under TEM, can be in water stable suspersion more than 24 hours; Present a cube crystalline phase in the X-ray diffraction.
In the preparation method of stabilization zirconium oxide ceramic thin-film material of the present invention, can adopt and be selected from the multiple film that rolls film, spraying, curtain coating and form technology and obtain the zirconia film base substrate, gained base substrate relative density is more than 60%, be preferably greater than 65%, more preferably greater than 70%, gained base substrate profile is smooth evenly in addition, can stablize placement, Undeformable and indehiscent, the error of preferred thickness direction is no more than 8%.In a specific embodiments, adopt casting technique to prepare the base substrate of zirconia ceramics thin-film material.
In one embodiment, preparation method's sintering step of stabilization zirconium oxide ceramic thin-film material of the present invention divides following three phases to carry out: 200～400 ℃ low thermophase, 800～1100 ℃ middle thermophase, 1300～1450 ℃ hot stage.Temperature retention time is as follows: in the low thermophase: room temperature～200 ℃, heating-up time 1-2 hour; Between 200～400 ℃, every 50 ℃ of constant temperature 1-3 hours, during heating rate be controlled at and raise in 1-2 hour 50 ℃.At low temperature between the middle thermophase, control heating rate be the 2-5 degree/minute.In thermophase: at interval 50 ℃ constant temperature 1-3 hour, during heating rate control 20-30 degree/hour.In middle temperature between the hot stage, control heating rate be the 30-50 degree/hour.Hot stage constant temperature 1-48 hour.In a more particular embodiment, the sintering temperature of described hot stage is higher than 1450 ℃ most, preferably is not higher than 1400 ℃, is more preferably not to be higher than 1350 ℃ and be more preferably 1300 ℃.
The invention still further relates to stabilization zirconium oxide ceramic thin-film material of the present invention or stabilization zirconium oxide ceramic thin-film material obtained by the method for the present invention electrolytical purposes as Solid Oxide Fuel Cell (SOFC).
Description of drawings
The schematic diagram of accompanying drawing 1 zirconia film of the present invention is of a size of: length, width, thickness are respectively (100～300) millimeter, (100～300) millimeter, (0.02～0.2) millimeter
Accompanying drawing 2 zirconia films of the present invention bending within the specific limits do not break
Three kinds of zirconia electrolytic thin-membrane relative density data that prepare in accompanying drawing 3 examples
Three kinds of zirconia electrolytic thin-membrane bending strength data that prepare in accompanying drawing 4 examples
Embodiment describes the present invention and characteristics in detail below in conjunction with example and accompanying drawing.
Below be that example is introduced thin-film material of the present invention and preparation method with the YSZ nano-powder, but the invention is not restricted to the YSZ nano-powder.Adopting the YSZ nano-powder is raw material, and nano-powder small-size effect and high activity surface effect effectively reduce the solid phase reaction sintering temperature, realizes sintering under the material at low temperature, cuts down the consumption of energy, and saves cost; The nano-powder low-temperature sintering generates small-size grains (sub-micron), effectively reduces grain boundary resistance, improves the conductance of material; Generate small-size grains in the pottery, improved mechanical property, especially increased the toughness of thin-film material, obviously improved its reliability of applying.All electrolytical above-mentioned performances require all that the nano-powder granularity is little, specific surface is big.But such nano particle is easy to reunite, and is difficult for forming uniform and stable slurry dispersion, and the moulding process of film (casting technique for example, below be that example specify with the casting technique) moulding electrolytic thin-membrane is caused harmful effect.Require from casting molding processes, the nano particle specific surface is difficult for excessive, and distribution of particles will be concentrated, and the particle sphericity will be got well.Obviously the factor of above-mentioned two aspects is conflicting, the present invention passes through repetition test, take all factors into consideration various factors, unexpectedly find to use powder with following characteristic, can obtain zirconia ceramics film of the present invention, require the YSZ nanopowder should have following feature: TEM observation primary particle granularity 15～50nm down, N
2Absorption specific surface 10～70m
2/ g; Centrifugal sedimentation test offspring concentrates on more than 85% between 0.10～0.60 μ m micron, and presents the main peak value in 0.3～0.4 μ m place; Down the observation particle is spherical in shape basically for TEM, can be in water stable suspersion more than 24 hours; Present a cube crystalline phase in the X-ray diffraction.When exceeding above-mentioned scope, granularity is too little on the one hand, and when specific surface was excessive, particle agglomeration was serious, can not form the slurries of stable suspersion and membrane blank uniformly; Granularity is too big on the other hand, and when specific surface was too small, seed activity descended, and sintering temperature is too high.
Nano-powder with above-mentioned characteristic can adopt the method preparation of introducing among the embodiment.
In the present invention, membrane blank can adopt accomplished in many ways, for example rolls film, spraying, curtain coating or the like.These methods are known altogether in this area, for the ease of later sintering process, reduce sintering shrinkage to reduce the cracking and the warpage of film, require in the present invention the ceramic membrane base substrate have after the drying more than 60% blank density (except as otherwise noted, the relative density of base substrate is all to refer to dried relative density herein), drying condition is mediated according to the experiment situation, adjustable range is 20～40 ℃ of dryings 1～8 hour, the base substrate of criterion for obtaining, stable placement is more than 24 hours, the loss in weight is not more than 1% and is advisable, so the present invention is not limited to a certain concrete film build method.
CN99125697.2 discloses a kind of method that adopts The tape casting to prepare ceramic membrane, and it can be incorporated herein by reference in full.Below be example with the The tape casting, specifically introduce a kind of technology of forming ceramic membrane blank.Above-mentioned nano-powder (being example with the YSZ nanopowder here) and The suitable solvent, dispersant, binding agent and plasticiser are mixed, form the mud of even viscosity behind the ball milling.By 100 microns sieve apertures, under 0.2atm, carry out the emptying gas disposal, it is higher relatively to form solid content, and viscosity is suitable, good film-forming property, the mud of stable suspersion.Mixing mud being cast on the conveyer belt of a motion, is thin slice with thin scraper with its strickling.Usually scraper gap is 2: 1 with the biscuit thickness ratio of final drying.The viscosity of dry back biscuit thickness and mud, curtain coating speed, scraper gap setting and relation is arranged through the height of scraper rear slurry.Above-mentioned condition all is controlled, evenly can repeat thin slice to guarantee acquisition.Behind the mud casting film-forming, put into drying box and get rid of solvent, drying condition depends on casting machine length, solvent species, heating-up temperature and film forming thickness etc. will accurately be controlled above-mentioned condition, with prevent and reduce curling, crackle and add and wrap up in bubble.Adopt casting technique moulding electrolytic thin-membrane base substrate, the base substrate relative density is more than 60%, and profile is smooth evenly can stablize placement, not the modification cracking.
The sintering process of electrolytic thin-membrane base substrate divided for three steps carried out: 200～400 ℃ low thermophase, 800～1100 ℃ middle thermophase, 1300～1450 ℃ hot stage.The heating rate of strict control different phase.Low thermophase: room temperature～200 ℃, heating-up time 1-2 hour; Between 200～400 ℃, every 50 ℃ of constant temperature 1-3 hours, during heating rate be controlled at and raise in 1-2 hour 50 ℃.At low temperature between the middle thermophase, control heating rate be the 2-5 degree/minute.In thermophase: at interval 50 ℃ constant temperature 1-3 hour, during heating rate control 20-30 degree/hour.In middle temperature between the hot stage, control heating rate be the 30-50 degree/hour.Hot stage constant temperature 1-48 hour.
It is transparent, smooth, smooth to obtain electrolytic thin-membrane at last, is 150 microns with thickness, and length and width are that 100 millimeters electrolyte sheet is an example, and flatness error is not more than 10 microns, and relative density is preferred more than 98%, and 1000 ℃ of conductivity are preferably at 0.15Scm
-1More than, above-mentioned size thin-film material is slow stressed when crooked, and amount of deflection reaches 25 millimeters and does not break, referring to Fig. 2.
Embodiment
The preparation nano-powder
According to the method for following example 1-6, prepare three kinds of powder 8YSZ-KD, 8YSZ-HW1,8YSZ-TH.Adopt following method to measure the performance of powder:
Utilize ultrasonic oscillator that the zirconia powder is scattered in the absolute ethyl alcohol, use the suction pipe adsorbent solution, drop on the copper mesh with little grid film, under JEOL-2000FX and HITACHI-H8100 transmission electron microscope, observe microscopic appearance, the distribution of pores of powder, the granularity of test powder adopts supporting Philips DX-4 energy dispersive spectrometry to analyze its composition simultaneously.
In being added with the aqueous solution of dispersant, disperse powder, adopt the degree of aggregation of SA-CP3 centrifugal sedimentation particle size analyzer powder.
Adopt the Autosorb-1 nitrogen adsorption instrument of Quanta Chrome company to measure the nitrogen adsorption condition
Under the powder specific area and pore size distribution and the aperture size in the powder.
Utilize the crystal structure and the cell parameter of the D/MAX-RC XRD analysis instrument test powder of Japanese Rigaku Denki Co., Ltd.The instrument condition of work is: the copper target, 50KV voltage and 60mA operating current, sweep speed be 8 the degree/minute, scanning angle is the 20-100 degree.
Example 1 configuration cushioning liquid
Getting concentration in 1: 1 in molar ratio respectively is the NH4HCO3 solution of 0.5M and the NH4OH solution of 0.5M, NH4HCO3 solution is progressively joined in the NH4OH solution, and mixing and stirring, adjusting PH is about 9.0, is employed cushioning liquid.
Example 2 configuration cushioning liquid
Got sucrose solution that concentration is 0.5M and the NH4OH solution of 0.5M in 1: 1 in molar ratio respectively, sucrose solution is progressively joined in the NH4OH solution, mixing and stirring, adjusting PH is about 8.0～10.0, is employed cushioning liquid.
Example 3 configuration titrating solutions
The zirconium oxychloride of 322.0g is dissolved in the distilled water, is mixed with the solution that concentration is 1M.The yittrium oxide of 226.0g is dissolved in the hydrochloric acid, is mixed with the solution that concentration is 0.5M.Press Y
2O
3And ZrO
2Mol ratio is above-mentioned two kinds of solution to be hybridly prepared into titrating solution in 8: 92.
Example 4:
With the titrating solution that is mixed with in the example 3, splash in the cushioning liquid that is mixed with in the example 1, rate of titration is 0.3～0.5l/h, adds 5～8 n-butanol during titration in cushioning liquid.Mix simultaneously, mixing speed is 80～150r/min.Use distilled water filtering and washing sediment 2～3 times earlier, use absolute ethanol washing again 1～2 time,, cross 80 mesh sieves 60～70 ℃ of oven dry.At 500 ℃ of insulation 1h, 800 ℃ of insulation 2h, cooling back ball milling 24～54h, oven dry is sieved and is surveyed its performance.This sample number into spectrum is 8YSZ-KD, and performance index see Table 1 and table 2.
Example 5:
With the titrating solution that is mixed with in the example 3, splash in the cushioning liquid that is mixed with in the example 1, rate of titration is 1.5～2.0l/h, adds 5～8 n-butanol during titration in cushioning liquid.Mix simultaneously, mixing speed is 80～150r/min.Use distilled water filtering and washing sediment 2～3 times earlier, use absolute ethanol washing again 1～2 time,, cross 80 mesh sieves 60～70 ℃ of oven dry.At 800 ℃ of insulation 2h, cooling back ball milling 24～54h, oven dry is sieved and is surveyed its performance.This sample number into spectrum is 8YSZ-HW1, and performance index see Table 1 and table 2.
Example 6:
With the titrating solution that is mixed with in the example 3, splash in the cushioning liquid that is mixed with in the example 2, rate of titration is 1.5～2.0l/h.Mix, mixing speed is 80～150r/min.Use distilled water filtering and washing sediment 2～3 times earlier, use absolute ethanol washing again 1～2 time,, cross 80 mesh sieves 60～70 ℃ of oven dry.At 800 ℃ of insulation 2h, cooling back ball milling 24～54h, oven dry is sieved and is surveyed its performance.This sample number into spectrum is 8YSZ-TH, and performance index see Table 1 and table 2.
The sintering of preparation membrane blank and base substrate
The film sample that obtains behind the membrane blank sintering of preparation adopts following method to measure its various performances: the base substrate relative density is measured in the following ways: utilize Archimedes principle, weight method is measured porcelain body density in the water.Concrete operations are as follows: test specimen is cleaned out, dried to constant weight in 100 ℃ of baking ovens, put into drier and be cooled to room temperature, take by weighing weight G
1In the paraffin with the fusing of test specimen input, and take out rapidly, make test specimen surface-coated skim (being not more than 1 millimeter) paraffin, notice that the wax layer can not have bubble, takes by weighing weight G
2Tie down the test specimen of waxing with fine rule, be suspended on day plain hook, weighing in filling the beaker of pure water requires test specimen to be submerged in the water fully, but can not contact beaker bottom, obtains weight G
3Obtain the bulk density of porcelain body according to formula (1).
F in the formula
0=0.93g/cm
3, be the density of paraffin.
Thermal coefficient of expansion: prepared the test specimen of 3 * 4 * 35mm in the experiment by dry-pressing formed mode, adopted Netzsch Dil402C type thermal performance analysis instrument to measure the thermal coefficient of expansion of electrolyte.Bending strength: the test specimen that has prepared 3 * 4 * 35mm in the experiment by dry-pressing formed mode, adopt the mode of three-point bending, the bending strength of test electrolyte on the servo fatigue system tester of Tianjin, island GSM10KN high temperature, length of support 25mm, loading velocity 0.0001mm/s.
Conductivity: according to grace measuring principle suddenly, measure the electrolyte conductivity by the four electrode method of Van De Pauw development, the sample that adopts in this test is thin disk, and its contact electrode position is the edge of the ceramics divided equally.
Amount of deflection: the thin slice of 100～100～0.15mm of Experiment Preparation, be placed on the soft belt, be that the roller of 400mm slowly presses down with diameter, cause the ceramic sheet bending, when the maximum camber place reaches 25mm, ceramics do not break promptly regard as qualified, as Fig. 2.
Flatness error adopts screw-thread micrometer to measure thickness immediately at the different surfaces place, and density measurement is for being not less than 10 points/cm
2, carry out statistical average then.
Crystallite dimension adopts scanning electron microscopy (SEM) observation down.At first sample is polished polishing, sintering placed SEM observation granule size and distribution down after 15～30 minutes in being lower than 50～100 ℃ of scopes of firing temperature then.
Example 7:
With the 8YSZ-TH sample that 100g prepares in nano powder example 6, join 20ml and contain in the water of dispersant ball milling 24h.Add the PVA solution of 9.5wt%, the alcoholysis degree of PVA is 50%, adds propylene glycol and PVP, wherein, the binding agent gross mass is 6.20g, and the quality of PVP is 20% of a binding agent gross mass, and the quality of propylene glycol is 1/2 of PVA, 1, the quality of ammediol is 100% of a propylene glycol, continues ball milling 24h.With the slurries filtration that obtains, vacuum degassing, curtain coating then, air dry 8h.
Example 8:
With the 8YSZ-HW1 sample that 100g prepares in nano powder example 5, join in the mixed solution of the methyl ethyl ketone of 18ml and ethanol, add the olein of 3ml simultaneously, ball milling 18～24h.Afterwards, add polyvinyl butyral resin 3～8g, and diethyl phthalate 3～8g, ball milling 24h continued.With the slurries filtration that obtains, vacuum degassing, curtain coating then, air dry 4h.
Example 9:
With the 8YSZ-KD nano-powder of preparation in the example 4, according to the method that example 7 provides, flow casting molding prepares base substrate, base substrate relative density 60%.Low thermophase at 200～400 ℃, 850 ℃, 900 ℃, 950 ℃ and 1000 ℃ are constant temperature 2 hours respectively, 1300 ℃ hot stage constant temperature 1-6 hour, obtain electrolytic thin-membrane, the relative density data are seen Fig. 3, bending strength data such as Fig. 4, conductivity data sees Table 3 and 4, and thermal coefficient of expansion is 10.1988 * 10 in the 100-1000 ℃ of scope
-6Cm/cm.K.
Example 10:
With the 8YSZ-HW1 curtain coating base substrate of preparation in the example 8, base substrate relative density 65%.Low thermophase at 200～400 ℃, 950 ℃, 1000 ℃ and 1050 ℃ are constant temperature 2 hours respectively, 1350 ℃ hot stage constant temperature 1-6 hour, obtain electrolytic thin-membrane, the relative density data are seen Fig. 3, bending strength data such as Fig. 4, conductivity data sees Table 3 and 4, and thermal coefficient of expansion is 10.6922 * 10 in the 100-1000 ℃ of scope
-6Cm/cm.K.
Example 11:
8YSZ-TH nano-powder with preparation in the example 7 prepares slip with various function additive mixing and ball milling, flow casting molding base substrate, base substrate relative density 70%.Low thermophase at 200～400 ℃, 1000 ℃ and 1100 ℃ are constant temperature 2 hours respectively, 1450 ℃ hot stage constant temperature 1-6 hour, obtain electrolytic thin-membrane, the relative density data are seen Fig. 3, bending strength data such as Fig. 4, conductivity data sees Table 3 and 4, and thermal coefficient of expansion is 10.5117 * 10 in the 100-1000 ℃ of scope
-6Cm/cm.K.
Table 1 8YSZ nanopowder performance index
| Example | The name of an article | Primary particle (nm) | Offspring (μ m) | Specific surface (m 2/g) | Powder density (g/cm 3) | Crystal formation | Pattern | |
| Meso-position radius Dmed | Peak value is through | |||||||
| 4 | 8YSZ-KD | 10-20 | 0.99 | 0.71 | 64.2 | 5.42 | Cubic | Approximate ball- |
| 5 | 8YSZ-HW1 | 30 | 1.05 | 0.75 | 24.9 | 5.87 | Cubic | Part is spherical |
| 6 | 8YSZ-TH | 50 | 0.49 | 0.45 | 14.3 | 5.70 | Cubic | Ball-type and polygon build |
Table 2 8YSZ nanopowder chemical composition (atomic ratio, at%)
| Example | The name of an article | ZrO 2 | Y 2O 3 | HfO 2 | Cs 2O | Ra |
| 4 | 8YSZ-KD | 89.55 | 8.93 | 0.87 | 0.64 | - |
| 5 | 8YSZ-HW1 | 90.56 | 8.02 | 0.87 | 0.54 | - |
| 6 | 8YSZ-TH | 90.82 | 7.64 | 0.935 | 0.598 | - |
Table 3 8YSZ sample is at 800 ℃ conductivity values (Scm
-1)
| Constant temperature time (h) | 1 | 2 | 4 | 6 |
| 8YSZ-KD | 0.026 | 0.0286 | 0.0425 | 0.0342 |
| 8YSZ-HW1 | 0.0271 | 0.0325 | 0.0416 | 0.0249 |
| 8YSZ-TH | 0.0347 | 0.0382 | 0.0474 | 0.0371 |
Table 4 8YSZ sample is at 1000 ℃ conductivity values (Scm
-1)
| Constant temperature time (h) | 1 | 2 | 4 | 6 |
| 8YSZ-KD | 0.128 | 0.160 | 0.183 | 0.142 |
| 8YSZ-HW1 | 0.131 | 0.134 | 0.142 | 0.126 |
| 8YSZ-TH | 0.154 | 0.150 | 0.158 | 0.142 |
In above-mentioned example 8～11, the inventor adopts different casting machine parameters, the stabilization zirconium oxide ceramic membrane blank and the sintered film of different size have been obtained respectively, length, width that the test discovery can successfully obtain the sintered film material are respectively at least 50 millimeters, at least 50 millimeters, be respectively at least 100 millimeters, at least 100 millimeters with length, width, be respectively at least 200 millimeters, at least 200 millimeters with length, width, and length, width are respectively at least 300 millimeters, at least 300 millimeters film.And the thickness of this film is 0.02～0.2 millimeter, and especially 0.1～0.2 millimeter more specifically is 0.12～0.2 millimeter and 0.15～0.2 millimeter.Wherein, by regulating the sintered film that edge of a knife height can obtain any thickness in 0.02～0.2 millimeter scope.
The inventor carries out electron microscopy observation to resultant film, and resulting film has uniform grainiess, and average grain size is generally below 3 microns, especially can be by low-temperature sintering below 2 microns, even below 1 micron.
In the test, also find, by the control process conditions, the stabilization zirconium oxide ceramic thin-film material has the good mechanical performance, bending strength can be increased to more than the 120Mpa, especially more than 150Mpa, in addition, this film preferably has transparent, smooth, smooth outward appearance, for example this film thickness is 150 microns, and when length and width were 100 millimeters sheet form, flatness error preferably was not more than 10 microns, and slow stressed when crooked, amount of deflection reaches 25 millimeters and does not break.
In addition, as can be seen, be controlled at 3～5 hours, can obtain higher bending strength and higher conductivity by temperature retention time with hot stage.
Thin-film material of the present invention has good performance, is very suitable for being used for Solid Oxide Fuel Cell as electrolyte.
Though more than be that example has been introduced film of the present invention and its preparation method with YSZ, those of ordinary skill in the art can understand fully, according to instruction of the present invention, design of the present invention and method can be applied to other various stabilizing zirconia materials fully.
Claims (28)
1. stabilization zirconium oxide ceramic thin-film material, the length of this thin-film material, width are respectively 50-300 millimeter, 50-300 millimeter, the thickness of this film is 0.02～0.2 millimeter, and this thin-film material average grain size is no more than 3 microns, and bending strength is more than 120Mpa.
2. stabilization zirconium oxide ceramic thin-film material as claimed in claim 1 is characterized in that, the length of this thin-film material, width are respectively 100-300 millimeter and 100-300 millimeter millimeter.
3. stabilization zirconium oxide ceramic thin-film material as claimed in claim 1 is characterized in that, the length of this thin-film material, width are respectively 200-300 millimeter and 200-300 millimeter.
4. stabilization zirconium oxide ceramic thin-film material as claimed in claim 1 is characterized in that, the thickness of this thin-film material is 0.1～0.2 millimeter.
5. stabilization zirconium oxide ceramic thin-film material as claimed in claim 1 is characterized in that, the thickness of this thin-film material is 0.12～0.2 millimeter.
6. stabilization zirconium oxide ceramic thin-film material as claimed in claim 1 is characterized in that, the thickness of this thin-film material is 0.15～0.2 millimeter.
7. as each described stabilization zirconium oxide ceramic thin-film material among the claim 1-6, it is characterized in that this stabilizing zirconia is selected from the stable zirconia of yttrium, the zirconia of calcium stable, the stable zirconia of zirconia, Sc that Yb is stable.
8. as each described stabilization zirconium oxide ceramic thin-film material among the claim 1-6, it is characterized in that this stabilizing zirconia has following composition: 8～12mol% yittrium oxide and 88～92mol% zirconia.
9. as each described stabilization zirconium oxide ceramic thin-film material among the claim 1-6, it is characterized in that this stabilization zirconium oxide ceramic thin-film material average grain size is no more than 2 microns, its relative density is not less than 96%.
10. stabilization zirconium oxide ceramic thin-film material as claimed in claim 9 is characterized in that, this stabilization zirconium oxide ceramic thin-film material average grain size is less than 1 micron, and its relative density is not less than 98%.
11. stabilization zirconium oxide ceramic thin-film material as claimed in claim 10 is characterized in that the relative density of this stabilization zirconium oxide ceramic thin-film material is more than 99%.
12., it is characterized in that the bending strength of this stabilization zirconium oxide ceramic thin-film material is more than 150Mpa as each described stabilization zirconium oxide ceramic thin-film material among the claim 1-6.
13., it is characterized in that this thin-film material has transparent, smooth, smooth outward appearance as each described stabilization zirconium oxide ceramic thin-film material among the claim 1-6.
14. stabilization zirconium oxide ceramic thin-film material as claimed in claim 13 is characterized in that, this thin-film material is that thickness is 150 microns, and when length and width were 100 millimeters sheet form, flatness error was not more than 10 microns.
15., it is characterized in that adopting thickness is 0.15 millimeter as each described stabilization zirconium oxide ceramic thin-film material among the claim 1-6, length and width are that the thin-film material of 100 millimeters sheet is tested, the amount of deflection of this thin-film material reaches 25 millimeters and does not break.
16., it is characterized in that this stabilization zirconium oxide ceramic thin-film material is as the electrolyte of Solid Oxide Fuel Cell as each described stabilization zirconium oxide ceramic thin-film material among the claim 1-6, its 1000 ℃ of conductivity are 0.10-0.20Scm
-1
17. stabilization zirconium oxide ceramic thin-film material as claimed in claim 16 is characterized in that, this stabilization zirconium oxide ceramic thin-film material is 0.12-0.20Scm 1000 ℃ of conductivity
-1
18. stabilization zirconium oxide ceramic thin-film material as claimed in claim 17 is characterized in that, this stabilization zirconium oxide ceramic thin-film material is 0.15-0.20Scm 1000 ℃ of conductivity
-1
19. preparation is as the method for each described stabilization zirconium oxide ceramic thin-film material among the claim 1-18, this method comprises moulding and sintering step, it is characterized in that when moulding adopting nano-powder for example nanometer YSZ powder be raw material, the nano-powder performance is: primary particle granularity 15～50nm, specific surface 10～70m
2/ g; Offspring concentrates on more than 85% between 0.10～0.60 μ m micron, and present the main peak value in 0.3～0.4 μ m place, film sintered process divided for three steps carried out: 200～400 ℃ low thermophase, 800～1100 ℃ middle thermophase, 1300～1450 ℃ hot stage, temperature retention time is as follows: in the low thermophase: room temperature～200 ℃, heating-up time 1-2 hour; Between 200～400 ℃, every 50 ℃ of constant temperature 1-3 hours, during heating rate be controlled at and raise in 1-2 hour 50 ℃, at low temperature between the middle thermophase, the control heating rate be the 2-5 degree/minute; In thermophase: at interval 50 ℃ constant temperature 1-3 hour, during heating rate control 20-30 degree/hour, in middle temperature between the hot stage, the control heating rate be the 30-50 degree/hour; Hot stage constant temperature 1-48 hour.
20. the preparation method of stabilization zirconium oxide ceramic thin-film material as claimed in claim 19 is characterized in that in forming step, adopts and is selected from the technological forming electrolytic thin-membrane base substrate that rolls film, spraying, curtain coating, gained base substrate relative density is more than 60%.
21. the preparation method of stabilization zirconium oxide ceramic thin-film material as claimed in claim 19 is characterized in that in forming step, adopts casting technique moulding electrolytic thin-membrane base substrate, gained base substrate relative density is greater than 65%.
22. the preparation method of stabilization zirconium oxide ceramic thin-film material as claimed in claim 19 is characterized in that in forming step, adopts casting technique moulding electrolytic thin-membrane base substrate, gained base substrate relative density is greater than 70%.
23. the preparation method as each described stabilization zirconium oxide ceramic thin-film material among the claim 19-22 is characterized in that, the error of gained base substrate thickness direction, and promptly evenness is no more than 8%.
24. as the preparation method of each described stabilization zirconium oxide ceramic thin-film material among the claim 19-22, the sintering temperature that it is characterized in that described hot stage is 1300-1400 ℃.
25. the preparation method of stabilization zirconium oxide ceramic thin-film material as claimed in claim 24, the sintering temperature that it is characterized in that described hot stage is 1300-1350 ℃.
26. the preparation method of stabilization zirconium oxide ceramic thin-film material as claimed in claim 24, the sintering temperature that it is characterized in that described hot stage are 1300 ℃.
27. as each described stabilization zirconium oxide ceramic thin-film material among the claim 1-18 as the electrolytical purposes of Solid Oxide Fuel Cell.
28. the stabilization zirconium oxide ceramic thin-film material that obtains as each method among the claim 19-26 is as the electrolytical purposes of Solid Oxide Fuel Cell.
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| CN100423346C (en) * | 2004-06-18 | 2008-10-01 | 中国科学院过程工程研究所 | Method for low-temp. preparing nano-crystal zirconium-oxide base solid electrolyte |
| CN100432013C (en) * | 2005-04-12 | 2008-11-12 | 中国矿业大学（北京校区） | Sub-micron zirconium oxide electrolyte film material and its prepn process |
| CN103183513B (en) * | 2011-12-29 | 2015-01-21 | 北京有色金属研究总院 | Preparation method of proton conductive ceramic electrolyte film |
| CN102584223A (en) * | 2012-01-18 | 2012-07-18 | 苏州华清京昆新能源科技有限公司 | Casting slurry for preparing electrolyte layer in fuel cell |
| CN104418589B (en) * | 2013-08-23 | 2016-09-21 | 张锡薰 | The preparation method of the base material unit of tool thin film and the base material unit of tool thin film |
| CN107910148A (en) * | 2017-10-23 | 2018-04-13 | 孝感华工高理电子有限公司 | A kind of auto heater large scale PTC chip production method |
| CN111348912A (en) * | 2020-03-20 | 2020-06-30 | 四川轻化工大学 | Solid oxide fuel cell dense electrolyte and preparation method thereof |
| CN115259874B (en) * | 2021-04-29 | 2023-11-17 | 中国科学院福建物质结构研究所 | Toughened and conductive MXene-zirconia composite ceramic and preparation method thereof |
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