CN100355137C - Filtering coating preparing method of solid oxide electrolytic film - Google Patents
Filtering coating preparing method of solid oxide electrolytic film Download PDFInfo
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- CN100355137C CN100355137C CNB2005100104196A CN200510010419A CN100355137C CN 100355137 C CN100355137 C CN 100355137C CN B2005100104196 A CNB2005100104196 A CN B2005100104196A CN 200510010419 A CN200510010419 A CN 200510010419A CN 100355137 C CN100355137 C CN 100355137C
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- buchner funnel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention discloses a preparing method of an electrolyte film of a solid oxide fuel battery, particularly a filtering and preparing method of an electrolyte film of solid oxide. The preparing method overcomes the defects of high cost, complicated film producing process or low battery performance in the existing preparing methods. The preparing method comprises the steps that a plate-shaped anode supporting body is prepared; ethanol or isopropanol is used as dissolvent, and YSZ powder and dispersant or gel forming agents are added into the dissolvent and are stirred to obtain stable suspension; a Buchner funnel with a flat bottom is used, filter paper is placed into the funnel, the anode supporting body is horizontally placed into the Buchner funnel, a glass rod is used for guiding the suspension into the Buchner funnel, and a layer of smooth YSZ film billet is formed on the surface of the anode supporting body following the entire subsidence of filtering liquid; the smooth YSZ film billet is sintered at high temperature to obtain a YSZ film. The filtering and preparing method has the advantages of low cost, simple method, high film forming efficiency, controllable film thickness, high ultimate electric performance, etc.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the electrolytic thin-membrane of Solid Oxide Fuel Cell (SOFC).
Background technology
Fuel cell has the energy conversion efficiency height, simplicity of design, configuration is flexible and varied, fuel tolerance is strong, and noxious gas emission is few and noise is little, be beneficial to plurality of advantages such as environmental protection, and extremely national governments and researcher's concern in recent years develops very fast.In the world wide, the SOFC group from several watts of levels to hundreds of multikilowatts has all designed success and has been put to be used at present.In order to reduce operating temperature, the design of SOFC also transforms from the electrolyte thin membranous type of electrolyte-supporting type to electrode supporting.Research at present is the widest, and the thin-film electrolyte that practicality is the strongest is the zirconia (YSZ) of stabilized with yttrium oxide.
In present high performance YSZ battery, Souza etc. (J.Elect rochem.Soc.1441997 L35) adopt colloidal deposition (colloidal deposition) technology to prepare the thick anode support type 8YSZ electrolytic thin-membrane of 10 μ m, and peak power output has reached 1.9Wcm in the time of 800 ℃
-2Kim etc. (J.Electrochem.Soc.146 1,999 69) adopt slurry cladding process (slurry coating) to prepare the thick electrolytic thin-membrane of 10 μ m, have obtained similar performance.In addition, it is 18 μ m dielectric films that Leng etc. (J.Power Sources) adopt spraying process (spray coating) to obtain thickness, and peak power output has reached 0.98Wcm in the time of 800 ℃
-2These are higher electrolytic thin-membranes of performance of reporting at present.Except above-mentioned several film techniques, use at present wider The tape casting (tape casting) and the silk screen print method (screenprinting) etc. of being mainly.These method costs are lower, yet these methods only are applicable to the small size battery, and (diameter＞10cm) was accompanied by the pyrolysis of dispersants a large amount of in the slurry or gelling agent and causes bigger contraction when area was big, make the battery gross distortion, thereby influence filming performance and application.Also has sol-gel process (sol-gel) in addition, spray pyrolysis (spray pyrolysis), electrophoresis (electrophoresis), plasma spraying method (plasma spraying), dip coating (dipcoating), spin-coating method (spin coating), chemistry or electrochemical vapor deposition (CVD or EVD) etc.Though these methods can be prepared the film of different-thickness, these methods or cost costliness, perhaps film-forming process is loaded down with trivial details, and the film-forming process step is many, wastes time and energy, and battery performance is lower.
Summary of the invention
The filtering coating preparation method that the purpose of this invention is to provide solid oxide electrolytic film, to overcome prior preparation method or cost costliness, perhaps film-forming process is loaded down with trivial details, and the film-forming process step is many, wastes time and energy the defective that battery performance is lower.The present invention realizes by following steps: one, the anode support of preparation sheet; Two, adopt ethanol or isopropyl alcohol as solution, stir the acquisition steady suspension thereby add YSZ powder and dispersant or gelling agent; Three, adopt flat Buchner funnel, filter paper is placed in the inside of funnel, anode support is kept flat in the Buchner funnel, the steady suspension that is mixed with in the step 2 is joined in the Buchner funnel with the glass bar drainage, suspension diameter be subsidence velocity by volume in 5.5 centimetres the Buchner funnel calculate for the 1-200 milliliter/hour; Along with filtrate is all sunk, YSZ particle wherein stayed on the anode-supported surface and filter paper on, on the anode-supported surface, formed the smooth YSZ film base of one deck; Four, this film base sintering at high temperature obtains the YSZ film, and in the step 4, coexist under 1200-1600 ℃ high temperature sintering 2～10 hours of film base and the anode support one that supports it obtains the YSZ film.
Method of the present invention adopts diafiltration to be coated with membrane technology (filter is coated with) on anode support, by regulating the speed that suspension concentration, height and suspension sink, along with finishing of suspension diafiltration, on anode support, obtain the dielectric film base of one deck controllable thickness, this film base drying and behind the uniform temperature sintering just forms the film of skim even compact on the anode support substrate.Therefore greatly guaranteed ionic conductivity and the ion transport passage that electrolyte is high, stoped the infiltration of gas effectively, battery performance is greatly improved.Filter of the present invention is coated with the film technique method and has the quality of forming film height, and is with low cost, controllable film thickness (minimum 5 μ m), simple advantage such as efficient.Compare with other film technique, this process is simple, repeatable strong, the film densification that makes, battery output power density height can guarantee to carry out industrialization production under the product quality premise fully, and the present invention is guaranteeing under the battery performance condition with higher, can greatly reduce the cost of manufacture of battery, have very high practical value.Method of the present invention also is used in other oxide electrolytic films that preparation electrochemical membrane reactor is used on the porous supporting body.
Description of drawings
Fig. 1 and Fig. 2 are that the diafiltration coating device and the diafiltration of the inventive method step 3 is coated with the membrane process schematic diagram, Fig. 3 is ' composite anode supporter/8YSZ electrolytic thin-membrane/composite cathode ' Trinity structure section schematic diagram that adopts the inventive method to make, Fig. 4 is the sem photograph of electrolyte membrane surface, and Fig. 5 is the battery output characteristic curve that adopts zirconia (YSZ) film of stabilized with yttrium oxide of 7 μ m thickness of the present invention's preparation to test as Solid Oxide Fuel Cell (SOFC) electrolyte.
Embodiment
Embodiment one: this embodiment prepares the anode support type electrolytic thin-membrane and may further comprise the steps: one, the anode support of preparation sheet; Two, adopt ethanol or isopropyl alcohol as solution, stir the acquisition steady suspension thereby add YSZ powder and dispersant or gelling agent; Three, adopt flat Buchner funnel, the inner filter paper of placing of funnel, anode support is kept flat in the Buchner funnel, the steady suspension that is mixed with in the step 2 is joined in the Buchner funnel with the glass bar drainage, suspension diameter be subsidence velocity by volume in 5.5 centimetres the Buchner funnel calculate for the 1-200 milliliter/hour; Along with filtrate is all sunk, YSZ particle wherein stayed on the anode-supported surface and filter paper on, on the anode-supported surface, formed the smooth YSZ film base of one deck; Four, this film base sintering at high temperature obtains the YSZ film, and in the step 4, coexist under 1200-1600 ℃ high temperature sintering 2～10 hours of film base and the anode support one that supports it obtains the YSZ film.The filtrate subsidence velocity is controlled by filter paper thickness.When the filter paper number of plies was less, the filtrate subsidence velocity was too fast, made to become living embryophoric membrane deposition to tail off on the anode substrate, and quality of forming film is relatively poor.Therefore must control the filtrate subsidence velocity well.
Assembling and the performance test of the anode support type electrolytic thin-membrane that makes being carried out monocell are as follows: adopt glycine-nitrate process to prepare strontium lanthanum manganese oxide (La
0.85Sr
0.15MnO
3, LSM), it is mixed with 8YSZ and glycerine or terpinol etc. makes mixed slurry.Adopt the slurry cladding process on electrolytic thin-membrane, to be coated with the last layer negative electrode in this slurry.With scribbling diaphragm 1000-1400 ℃ of roasting 1-5h in Muffle furnace of negative electrode, obtain ' composite anode supporter/8YSZ electrolytic thin-membrane/composite cathode ' Trinity structure.Be tiled in each one deck of cathode and anode as current collector with silver conductive adhesive, use filamentary silver as lead.With silver conductive adhesive it is packaged into battery simultaneously, acts as a fuel with the hydrogen of mixing 3mol% steam, still air is tested as cathode oxidant.As shown in Figure 5, the open circuit voltage of the battery of surveying when temperature is 700-900 ℃ near 1.1V more than, illustrate that the electrolyte densification is airtight.In temperature is 800 ℃, and power density has reached 1.05,1.31 respectively, 1.46Wcm when 850 ℃ and 900 ℃
-2, reach or the approaching higher power level of having delivered in the world, illustrate that the battery that is made by diafiltration (filter is coated with) method of filming has very perfect performance.Fig. 3 and Fig. 4 by the sem photograph of survey battery.As can be seen from Figure 3, the surface of film is arranged smooth, does not almost have the gap and occurs, and shows that the compactness of film is better.As can be seen from Figure 4, thickness is 7 μ m, no air-vent or fracture occur, has only a small amount of closed pore, therefore guarantee ionic conductivity and the ion transport passage that electrolyte is high, effectively stoped the mutual expansion of anode and cathode gas to be oozed, greatly reduced the Ohmic resistance of battery, therefore make battery have higher power output, battery performance is greatly improved.To be coated with the film technique method simple in filter, and the quality of forming film height is with low cost, can carry out amplification test fully and make film have reliable quality equally, has certain application prospect.Adopt the ceramic membrane of other material, equally in protection scope of the present invention with the present invention's preparation.
Embodiment two: the difference of present embodiment and execution mode one is: in step 1, Nio powder that at first sluggish precipitation is made and YSZ powder and pore creating material mix, three's mass ratio is a pore creating material: the NiO powder: YSZ powder=1: 1: 1 to 1: 8: 8, then pore creating material, NiO powder and YSZ powder are mixed with ethanol or isopropyl alcohol, in ball mill, in baking oven, dry behind the ball milling 1-20h then, after being pressed into sheet, roasting becomes anode support.The YSZ powder selects for use commercial Zirconium oxide powder and pore creating material with 8YSZ (8mol%) stabilized with yttrium oxide to mix.Mechanical milling process can make each material mixing more even, and the surface behind the compressing tablet is more smooth, and film sprawls when helping film forming.
Embodiment three: present embodiment with the difference of execution mode two is: pore creating material is that in starch, active carbon or the flour one or more mix interpolation.The interpolation of pore creating material had both guaranteed that electrode had certain porosity, the diffusion of fuel gas and transport passage when helping as anode again.Pore creating material scalable anode support shrinkage degree is complementary anode support and electrolyte simultaneously, and shrinkage degree is identical as far as possible, and it is crooked that the back is burnt in minimizing altogether, and is smooth with assurance anode-supported plate shaped battery.
Embodiment four: the difference of present embodiment and execution mode two is: the mixed-powder after the oven dry is pressed into diameter 13mm under the pressure of 100-350MPa, and thickness is the anode strip of 0.15-3mm.This anode strip is become anode support at 400-1200 ℃ roasting temperature 0.5-5h, and organic substance is removed in roasting, makes anode strip have certain mechanical strength simultaneously.
Embodiment five: the difference of present embodiment and execution mode one is: the preparation steps of stable suspension is: adopt ethanol or isopropyl alcohol as solution, add the YSZ powder, make YSZ suspension, solid concentration is 1-30g/L in the suspension, add dispersant or gelling agent then, as PVA (polyvinyl alcohol), PVB (polyvinyl butyral resin) or PEG (polyethylene glycol) etc., the weight ratio of dispersant or gelling agent and YSZ powder is 1: 20～1: 250, and even also ultrasonic dispersion 1-20min obtains stable suspension through magnetic agitation.The granularity that the YSZ powder selects for use Japanese Tosoh product 8YSZ (particle diameter 0.1-2 μ m) of company or China Building Materials Academy to produce is the zirconia of the 8mol% stabilized with yttrium oxide of 1-5 μ m.The preparation of suspension and powder suspension degree of stability and degree of scatter cut much ice to forming the even compact film.The method of present embodiment helps to obtain fine and close, the second best in quality YSZ film.The adding of dispersant or gelling agent had both prevented the flocculation of suspension, can make again become dielectric film smooth, densification, it is tightr that film is combined with anode support.
Embodiment seven: the difference of present embodiment and execution mode one is: in the step 3,1-10 metafiltration paper in shop makes the filter paper face smooth and make liquid level maintenance level in the Buchner funnel to regulate the filtrate subsidence velocity in the Buchner funnel.Stable suspension adopts normal pressure to sink naturally in the sinking of Buchner funnel liquid level, needing no vacuum suction filtration device, thus equipment is oversimplified more.
Embodiment eight: the difference of present embodiment and execution mode one is: in the step 3, the attachment with the flushing of anode-supported body and function alcohol goes to the surface to exist keeps flat in the Buchner funnel afterwards.The stable suspension for preparing is introduced in the Buchner funnel with glass bar, funnel top is covered with paper, enter to prevent dust or other foreign material.
Embodiment nine: the difference of present embodiment and execution mode one is: in the step 4, coexist under 1200-1600 ℃ high temperature sintering 2～10 hours of film base and the anode support one that supports it, obtain the second best in quality YSZ film, its controllable thickness is built in 5-50 μ m.
Claims (6)
1, the filtering coating preparation method of solid oxide electrolytic film is characterized in that it may further comprise the steps: one, the anode support of preparation sheet; Two, adopt ethanol or isopropyl alcohol as solution, stir the acquisition steady suspension thereby add YSZ powder and dispersant or gelling agent; Three, adopt flat Buchner funnel, the inner filter paper of placing of funnel, anode support is kept flat in the Buchner funnel, the steady suspension that is mixed with in the step 2 is joined in the Buchner funnel with the glass bar drainage, suspension diameter be subsidence velocity by volume in 5.5 centimetres the Buchner funnel calculate for the 1-200 milliliter/hour; Along with filtrate is all sunk, YSZ particle wherein stayed on the anode-supported surface and filter paper on, on the anode-supported surface, formed the smooth YSZ film base of one deck; Four, this film base sintering at high temperature obtains the YSZ film, and in the step 4, coexist under 1200-1600 ℃ high temperature sintering 2～10 hours of film base and the anode support one that supports it obtains the YSZ film.
2, the filtering coating preparation method of solid oxide electrolytic film according to claim 1 is characterized in that in step 2 solid concentration is 1-30g/L in the YSZ suspension.
3, the filtering coating preparation method of solid oxide electrolytic film according to claim 1 is characterized in that the gelling agent that suspension adds in step 2 is PVA, PVB or PEG, and they and YSZ weight ratio are 1: 20～1: 250.
4, the filtering coating preparation method of solid oxide electrolytic film according to claim 1, it is characterized in that in step 2 YSZ powder and dispersant or gelling agent through magnetic agitation evenly and ultrasonic dispersion 1-20min obtain stable suspension.
5, the filtering coating preparation method of solid oxide electrolytic film according to claim 1 is characterized in that in the step 3, and 1-10 metafiltration paper in shop makes the filter paper face smooth and make liquid level maintenance level in the Buchner funnel to regulate the filtrate subsidence velocity in the Buchner funnel.
6, the filtering coating preparation method of solid oxide electrolytic film according to claim 1, it is characterized in that in the step 3, the attachment of surface existence is removed in the flushing of anode-supported body and function alcohol, keep flat in the Buchner funnel afterwards, the stable suspension for preparing is introduced in the Buchner funnel with glass bar, funnel top is covered with paper, enter to prevent dust or other foreign material.
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| CN100355137C true CN100355137C (en) | 2007-12-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100419012C (en) * | 2006-07-05 | 2008-09-17 | 哈尔滨工业大学 | Composite pore-forming agent and method of preparing anode supporting body using the same |
| CN103682388A (en) * | 2012-09-17 | 2014-03-26 | 中国科学院上海硅酸盐研究所 | Vacuum impregnation coating method and device for planar solid oxide fuel cell (SOFC) electrolyte |
| CN109346753A (en) * | 2017-08-01 | 2019-02-15 | 清华大学深圳研究生院 | A kind of preparation method of flat-plate solid-oxide fuel battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5147943B2 (en) * | 1973-12-17 | 1976-12-17 | ||
| CN1271969A (en) * | 1999-04-22 | 2000-11-01 | 中国科学院大连化学物理研究所 | Anode load type solid electrolyte of yttrium oxide stabilized zirconium oxide and its preparing process |
| US20050026017A1 (en) * | 2001-07-02 | 2005-02-03 | Seabaugh Matthew M. | Ceramic electrolyte coating and methods |
| CN1641919A (en) * | 2004-12-22 | 2005-07-20 | 哈尔滨工业大学 | Method for preparing anode-support type yttrium oxide stable zirconium oxide electrolyte membrane |
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2005
- 2005-10-11 CN CNB2005100104196A patent/CN100355137C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5147943B2 (en) * | 1973-12-17 | 1976-12-17 | ||
| CN1271969A (en) * | 1999-04-22 | 2000-11-01 | 中国科学院大连化学物理研究所 | Anode load type solid electrolyte of yttrium oxide stabilized zirconium oxide and its preparing process |
| US20050026017A1 (en) * | 2001-07-02 | 2005-02-03 | Seabaugh Matthew M. | Ceramic electrolyte coating and methods |
| CN1641919A (en) * | 2004-12-22 | 2005-07-20 | 哈尔滨工业大学 | Method for preparing anode-support type yttrium oxide stable zirconium oxide electrolyte membrane |
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