CN1560948A - Method of preparing solid electrolyte film - Google Patents

Method of preparing solid electrolyte film Download PDF

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Publication number
CN1560948A
CN1560948A CNA2004100135630A CN200410013563A CN1560948A CN 1560948 A CN1560948 A CN 1560948A CN A2004100135630 A CNA2004100135630 A CN A2004100135630A CN 200410013563 A CN200410013563 A CN 200410013563A CN 1560948 A CN1560948 A CN 1560948A
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supporter
30min
suspension
electrophoretic deposition
solid electrolyte
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CNA2004100135630A
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CN1242507C (en
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�吕
吕喆
苏文辉
贾莉
黄喜强
植柱
陈孔发
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

This invention discloses a method for preparing a densed oxide solid electrolyte film which is realized by the following steps: 1.preparing plate supporters, gravity sedimentation suspension and electrophoretic deposit soliquoid separately, 2. immersing the supporter into the slurry of the gravity sedimentation suspension for 0.5-4h, then taking out the tray together with the supporter form it to dry them for 6-12h in the shade, 3. putting the supporter with a deposited film in a muffle furnace to be sintered for 1-6h, which temperature rises to 800-1200deg.C with the rate of 5-20k/min, 4. repeating step 2 and 3 for 1-6times, 5 carrying out electric conduction process to the sintered supporter, 6. The processed supporter is adhered to a silver plate electrode for electrophoretic deposition to the film in electrophoretic deposit soliquoid. 7. The film body is sintered for 1-8h under 1300-1400deg.C to finish the film.

Description

A kind of preparation method of solid electrolyte film
Technical field: the present invention relates to a kind of method for preparing the dense oxide solid electrolyte film, the electrolytic thin-membrane of this densification can be used to make Solid Oxide Fuel Cell or other electrochemical membrane reactors.
Background technology: traditional is electrolytical Solid Oxide Fuel Cell with yttria-stabilized zirconia (YSZ), has important use to be worth, and is the emphasis of current R﹠D work and make the YSZ filming.The method for preparing the YSZ film is a lot, mainly contains shaping method of ceramics such as electrochemical vapour deposition (EVD) (EVD), chemical vapor deposition (CVD), physical vapor deposition (PVD), spray pyrolysis, hot spray process, sol-gal process and slip casting, electrophoretic deposition (EPD), centrifugal casting, silk screen print method, doctor-blade casting process.Each method all respectively has pluses and minuses.Because YSZ is typical ceramic material, therefore adopt shaping method of ceramics to prepare the YSZ film, very big potential advantages are arranged on manufacture craft and production cost.
Summary of the invention: purpose of the present invention just provides the preparation method of the solid electrolyte film that a kind of manufacture craft is simple, production cost is lower.Technical scheme of the present invention is as follows: a kind of preparation method of solid electrolyte film, it is realized by following step: (one) prepares supporter, gravitational settling suspension-turbid liquid and the electrophoretic deposition suspension of sheet respectively.(1) with nickel oxide and rear-earth-doped oxidation zirconium or rear-earth-doped oxidation cerium electrolyte and a certain amount of organic pore former by (3~7): (3~7): the weight ratio of (1~2) consists of raw material, makes the nickel oxide anode composite material supporter of the sheet that is used for gravity-electrophoretic deposition successively through mixed grinding, dry-pressing formed and pre-sinter process.(2) adding 0.1~50g average grain diameter in the 1L organic solvent is 0.1 μ m~10 μ m oxide electrolyte powders, through stirring 5~30min,, leave standstill 1~30min through high-energy ultrasound fragmentation 1~30min, form the gravitational settling suspension-turbid liquid that disperses better, certain stability is arranged, be used for gravitational settling.(3) add less than 10g iodine (I in the 1L organic solvent 2) and 0.1~20g average grain diameter be 0.1 μ m~1 μ m oxide electrolyte powder, through stirring 5~30min,, form the electrophoretic deposition suspension that disperses better, certain stability is arranged through high-energy ultrasound fragmentation 1~30min.(2) the supporter sheet for preparing is placed on the dull and stereotyped pallet, pallet is immersed in the gravitational settling suspension-turbid liquid slip together with supporter, sedimentation time 0.5~4h after deposition is finished, takes out together with supporter pallet from suspension-turbid liquid, and 6~12h dries in the shade in air.(3) supporter that will deposit film places Muffle furnace, is warmed up to 800~1200 ℃ with the heating rate of 5~20K/min, and co-sintering 1h~6h takes out with the stove cool to room temperature.(4) repeating step (two) and step (three) 1~6 times successively.(5) the supporter conduction processing behind the sintering.(6) supporter after the conductionization processing is sticked to the electrophoretic deposition that carries out film on the silver strip electrode in electrophoretic deposition suspension.(7) the electrolytic thin-membrane base substrate of having finished gravity sedimentation and electrophoretic deposition is made electrolytic thin-membrane at last at 1300~1400 ℃ of co-sintering 1~8h.This patent adopts nickel oxide-electrolyte composite material (as NiO-YSZ) to make supporter.Utilize the character of particle meeting sedimentation under the self gravitation effect in suspension in the electrolyte to prepare the electrolytic thin-membrane base substrate, in sintering process subsequently, can obtain electrolytic thin-membrane.But, there are defectives such as more hole and crackle in this film, application performance is not good.Defectiveness film at the preparation of gravitational settling method carries out electrophoretic deposition process again, can eliminate this a large amount of class defectives, reaches the purpose of preparation dense electrolyte film.The route that in the soft substance system of suspension, adopts physics such as gravitational settling-electrophoretic deposition and co-sintering and chemical method to combine, have advantages such as technology is simple, with low cost, also be very suitable for the oxide solid electrolytic thin-membrane that is used for warm area work that large tracts of land is produced, have a good application prospect.
Embodiment one: it is realized by following step: (one) prepares supporter, gravitational settling suspension-turbid liquid and the electrophoretic deposition suspension of sheet respectively.(1) with nickel oxide (NiO) and rear-earth-doped oxidation zirconium (as Zr 1-xLn xO 2-x/2) or rear-earth-doped oxidation cerium (Ce 1-xLn xO 2-x/2), (Ln=Y wherein, La, Sm, Nd, Pr, Gd etc., x=0.05~0.4) electrolyte and a certain amount of organic pore former are by (3~7): (3~7): the weight ratio of (1~2) consists of raw material, makes the nickel oxide anode composite material supporter of the sheet that is used for gravity-electrophoretic deposition successively through mixed grinding, dry-pressing formed and pre-sinter process.(2) adding 0.1~50g average grain diameter in the 1L organic solvent is 0.1 μ m~10 μ m oxide electrolyte powders, through stirring 5~30min,, leave standstill 1~30min through high-energy ultrasound fragmentation 1~30min, form the gravitational settling suspension-turbid liquid that disperses better, certain stability is arranged, be used for gravitational settling.(3) add less than 10g iodine (I in the 1L organic solvent 2) and 0.1~20g average grain diameter be 0.1 μ m~1 μ m oxide electrolyte powder, through stirring 5~30min,, form the electrophoretic deposition suspension that disperses better, certain stability is arranged through high-energy ultrasound fragmentation 1~30min.(2) the supporter sheet for preparing is placed on the dull and stereotyped pallet, pallet is immersed in appropriate location in the gravitational settling suspension-turbid liquid slip (apart from liquid level 2~6cm) together with supporter.The slowly sedimentation under the effect of self gravitation of oxide electrolyte particle deposits thin film gradually at the supporter upper surface in the suspension.Sedimentation time 0.5~4h determines according to the subsidence curve data of determining concentration and the thickness of needs.After deposition is finished, pallet is taken out from suspension-turbid liquid together with supporter, 6~12h dries in the shade in air.(3) supporter that will deposit film places Muffle furnace, is warmed up to 800~1200 ℃ with the heating rate of 5~20K/min, and co-sintering 1h~6h takes out with the stove cool to room temperature.(4) repeating step (two) and step (three) 1~6 times successively.(5) the supporter conduction processing behind the sintering.(6) supporter after the conductionization processing is sticked to the electrophoretic deposition that carries out film on the silver strip electrode in electrophoretic deposition suspension.(7) the electrolytic thin-membrane base substrate of having finished gravity sedimentation and electrophoretic deposition is made electrolytic thin-membrane at last at 1300~1400 ℃ of co-sintering 1~8h.
Embodiment two: the difference of present embodiment and execution mode one is, organic pore former is starch or carbon dust, and organic solvent is ethanol, acetone, acetylacetone,2,4-pentanedione or isopropyl alcohol, and the oxide electrolyte powder is oxide stabilizing zirconia (YSZ) powder.Other step is identical with execution mode one.
Embodiment three: the difference of present embodiment and execution mode two is, in step (), (1) by 1: 1 weight ratio take by weighing the NiO micro mist (coprecipitation makes, average grain diameter be 8~14nm) with the electrolyte ((ZrO of micron grain size 2) 0.92(Y 2O 3) 0.08Powder, the pore former (starch, carbon dust etc.) of adding 10%, in agate mortar or ball grinder, add absolute ethyl alcohol and grind 30min, after the oven dry, powder is put into the axial compressive force of steel mold with about 200MPa, be pressed into the thin slice that thickness is 0.1~1mm,, obtain being used for the composite material supporter of deposit film sheet 800 ℃~1200 ℃ roasting 1~5h in high-temperature electric resistance furnace that press.(2) gravitational settling is with the preparation of suspension-turbid liquid: with 0.1~50g average grain diameter is that 0.1 μ m~10 μ m oxide electrolyte powders (producing average grain diameter as Japanese Tosoh is the 8YSZ of 0.2 μ m) join in the 1L organic solvent (ethanol, acetone, acetylacetone,2,4-pentanedione or isopropyl alcohol), through magnetic agitation 5~30min, high-energy ultrasound fragmentation 1~30min with the ultrasonic-wave crushing machine, leave standstill 1~30min, the suspension-turbid liquid that form to disperse better and can spontaneous slow sedimentation (metastable) is used for gravitational settling.(3) press the iodine (I that adds in the 1L organic solvent (ethanol, acetone, acetylacetone,2,4-pentanedione or isopropyl alcohol) less than 10g 2) and 0.1~20g average grain diameter be the ratio batching of 0.1 μ m~1 μ m oxide electrolyte powder, with magnetic stirrer 5~30min, use ultrasonic-wave crushing machine high-energy ultrasound fragmentation 1~30min subsequently, form and disperse better, stable electrophoretic deposition suspension, be used for electrophoretic deposition.Other step is identical with execution mode two.
Embodiment four: the difference of present embodiment and execution mode one is that in step (two), gravity sedimentation uses the hanging scaffold electronic balance that has the computer data acquiring function to carry out the THICKNESS CONTROL of film.Utilize the electronic balance of band computer interface to measure the subsidence curve of YSZ particle in suspension.Pallet is hung on the suspension hook of balance, pallet is placed in the middle of the suspension for preparing, press " peeling " key the zero clearing of balance registration.When particle when the action of gravity deposit is to substrate, can measure the quality of deposited particles on the pallet by balance, the measured qualitative data of balance is by RS-232C serial line interface computer-automatic collection, acquisition subsidence curve data.According to subsidence curve, the film quality that deposits on the unit are of any time after just can determining to begin.Film thickness can calculate according to following formula:
h = m ( t ) ( ρ p - ρ 0 ) · D
H is a film thickness in the formula; M (t) is the subsidence curve data; ρ pDensity for particle; ρ 0Be the suspension averag density; D is density coefficient (0~1), when forming absolute dense film, and D=1.Other step is identical with execution mode one.
Embodiment five: the difference of present embodiment and execution mode one is in step (five), the supporter behind the sintering to be placed boiler tube, feeding N 2And H 2Reduce and sintering at 500~800 ℃, obtain the supporter that has conductivity in room temperature.Other step is identical with execution mode one.
Embodiment six: the difference of present embodiment and execution mode one is, in step (five), and will be than the supporter behind the loose sintering at Li 2CO 3Boil in the saturated solution, oven dry back is at 700~900 ℃ of roasting 1~4h, 2~4 times repeatedly, utilizes its absorption and the Li that dissolves in appraises at the current rate part Ni and reduces the resistivity of material.After the said method processing, the supporter resistance drop is to below tens of kilohms.Other step is identical with execution mode one.
Embodiment seven: the difference of present embodiment and execution mode one is, in step (six), electrophoretic deposition uses silver (Ag) plate electrode, the horizontal or vertical layout of the plate electrode that is parallel to each other, the supporter after the conductionization processing is with on the gluing Ag of the being attached to sheet of the carbonaceous conductive negative electrode (connecing power cathode).Electrode spacing 5~20mm, inter-electrode voltage 5~500V adopts constant voltage or current constant mode to carry out electrophoresis, time 5~120min.The time of electrophoresis process, electric current and voltage signal be with the automatic record of computer, and as the Control Parameter of producing in batches.Other step is identical with execution mode one.

Claims (7)

1, a kind of preparation method of solid electrolyte film, it is characterized in that it realizes by following step: (one) prepares the supporter of sheet respectively, gravitational settling suspension-turbid liquid and electrophoretic deposition suspension, (1) with nickel oxide and rear-earth-doped oxidation zirconium or rear-earth-doped oxidation cerium electrolyte and a certain amount of organic pore former by (3~7): (3~7): the weight ratio of (1~2) consists of raw material, pass through mixed grinding successively, dry-pressing formed and pre-sinter process is made the nickel oxide anode composite material supporter of the sheet that is used for gravity-electrophoretic deposition, (2) adding 0.1~50g average grain diameter in the 1L organic solvent is 0.1 μ m~10 μ m oxide electrolyte powders, through stirring 5~30min, through high-energy ultrasound fragmentation 1~30min, leave standstill 1~30min, form the gravitational settling suspension-turbid liquid, add less than 10g iodine (I in (3) 1L organic solvent 2) and 0.1~20g average grain diameter be 0.1 μ m~1 μ m oxide electrolyte powder, through stirring 5~30min,, form electrophoretic deposition suspension through high-energy ultrasound fragmentation 1~30min; (2) the supporter sheet for preparing is placed on the dull and stereotyped pallet, pallet is immersed in the gravitational settling suspension-turbid liquid slip together with supporter, sedimentation time 0.5~4h after deposition is finished, takes out together with supporter pallet from suspension-turbid liquid, and 6~12h dries in the shade in air; (3) supporter that will deposit film places Muffle furnace, is warmed up to 800~1200 ℃ with the heating rate of 5~20K/min, and co-sintering 1h~6h takes out with the stove cool to room temperature; (4) repeating step (two) and step (three) 1~6 times successively; (5) the supporter conduction processing behind the sintering; (6) supporter after the conductionization processing is sticked to the electrophoretic deposition that carries out film on the silver strip electrode in electrophoretic deposition suspension; (7) the electrolytic thin-membrane base substrate of having finished gravity sedimentation and electrophoretic deposition is made electrolytic thin-membrane at last at 1300~1400 ℃ of co-sintering 1~8h.
2, the preparation method of a kind of solid electrolyte film according to claim 1, it is characterized in that organic pore former is starch or carbon dust, organic solvent is ethanol, acetone, acetylacetone,2,4-pentanedione or isopropyl alcohol, and the oxide electrolyte powder is an oxide stabilizing zirconia powder.
3, the preparation method of a kind of solid electrolyte film according to claim 1 is characterized in that in step () (1) takes by weighing the electrolyte (ZrO of NiO micro mist and micron grain size by 1: 1 weight ratio 2) 0.92(Y 2O 3) 0.08Powder, the pore former of adding 10%, in agate mortar or ball grinder, add absolute ethyl alcohol and grind 30min, after the oven dry, powder is put into steel mold, be pressed into the thin slice that thickness is 0.1~1mm,, obtain being used for the composite material supporter of deposit film sheet 800 ℃~1200 ℃ roasting 1~5h in high-temperature electric resistance furnace that press; (2) gravitational settling is with the preparation of suspension-turbid liquid: with 0.1~50g average grain diameter is that 0.1 μ m~10 μ m oxide electrolyte powders join in the 1L organic solvent, through magnetic agitation 5~30min, high-energy ultrasound fragmentation 1~30min with the ultrasonic-wave crushing machine, leave standstill 1~30min, the suspension-turbid liquid that form to disperse better and can spontaneous slow sedimentation is used for gravitational settling; (3) press in the 1L organic solvent and to add less than 10g iodine (I 2) and 0.1~20g average grain diameter be the ratio batching of 0.1 μ m~1 μ m oxide electrolyte powder, with magnetic stirrer 5~30min, use ultrasonic-wave crushing machine high-energy ultrasound fragmentation 1~30min subsequently, form and disperse better, stable electrophoretic deposition suspension, be used for electrophoretic deposition.
4, the preparation method of a kind of solid electrolyte film according to claim 1 is characterized in that in step (two), and gravity sedimentation uses the hanging scaffold electronic balance that has the computer data acquiring function to carry out the THICKNESS CONTROL of film.
5, the preparation method of a kind of solid electrolyte film according to claim 1 is characterized in that in step (five) supporter behind the sintering being placed boiler tube, feeds N 2And H 2Reduce and sintering at 500~800 ℃.
6, the preparation method of a kind of solid electrolyte film according to claim 1 is characterized in that in step (five), will be than the supporter behind the loose sintering at Li 2CO 3Boil in the saturated solution, dry the back at 700~900 ℃ of roasting 1~4h, 2~4 times repeatedly.
7, the preparation method of a kind of solid electrolyte film according to claim 1, it is characterized in that in step (six), electrophoretic deposition uses silver (Ag) plate electrode, the horizontal or vertical layout of the plate electrode that is parallel to each other, the supporter after the conductionization processing is attached on the Ag sheet negative electrode with carbonaceous conductive is gluing; Electrode spacing 5~20mm, inter-electrode voltage 5~500V adopts constant voltage or current constant mode to carry out electrophoresis, time 5~120min.
CNB2004100135630A 2004-02-18 2004-02-18 Method of preparing solid electrolyte film Expired - Fee Related CN1242507C (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100419462C (en) * 2006-11-06 2008-09-17 北京科技大学 Process of nickel oxide optical film dispersed nanometer silver grains
CN100495793C (en) * 2006-12-15 2009-06-03 华南理工大学 Solid porous supporting body flat-plate series micro solid oxide fuel battery
CN101740819B (en) * 2008-11-25 2012-07-11 中国电子科技集团公司第十八研究所 Method for preparing lithium ion solid electrolyte conducting film
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
CN104011926A (en) * 2011-11-02 2014-08-27 I-Ten公司 Method for the production of thin films of solid electrolyte for lithium ion batteries
CN116914173A (en) * 2023-09-05 2023-10-20 中石油深圳新能源研究院有限公司 Compact isolation layer, preparation method thereof and solid oxide fuel cell
US11967694B2 (en) 2018-05-07 2024-04-23 I-Ten Porous electrodes for electrochemical devices

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100419462C (en) * 2006-11-06 2008-09-17 北京科技大学 Process of nickel oxide optical film dispersed nanometer silver grains
CN100495793C (en) * 2006-12-15 2009-06-03 华南理工大学 Solid porous supporting body flat-plate series micro solid oxide fuel battery
CN101740819B (en) * 2008-11-25 2012-07-11 中国电子科技集团公司第十八研究所 Method for preparing lithium ion solid electrolyte conducting film
CN104011926A (en) * 2011-11-02 2014-08-27 I-Ten公司 Method for the production of thin films of solid electrolyte for lithium ion batteries
CN104011926B (en) * 2011-11-02 2017-11-14 I-Ten公司 The method for preparing the solid electrolyte film for lithium ion battery
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
US11967694B2 (en) 2018-05-07 2024-04-23 I-Ten Porous electrodes for electrochemical devices
CN116914173A (en) * 2023-09-05 2023-10-20 中石油深圳新能源研究院有限公司 Compact isolation layer, preparation method thereof and solid oxide fuel cell
CN116914173B (en) * 2023-09-05 2023-11-24 中石油深圳新能源研究院有限公司 Compact isolation layer, preparation method thereof and solid oxide fuel cell

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