CN108417872A - A kind of composite Y SZ electrolyte of solid oxide fuel cell and preparation method thereof - Google Patents
A kind of composite Y SZ electrolyte of solid oxide fuel cell and preparation method thereof Download PDFInfo
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- CN108417872A CN108417872A CN201810448929.9A CN201810448929A CN108417872A CN 108417872 A CN108417872 A CN 108417872A CN 201810448929 A CN201810448929 A CN 201810448929A CN 108417872 A CN108417872 A CN 108417872A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
The present invention provides a kind of composite Y SZ electrolyte of solid oxide fuel cell and preparation method thereof, and the composite Y SZ electrolyte is pressed successively by the first YSZ cast sheets, the 2nd YSZ cast sheets, the first YSZ cast sheets；The first YSZ curtain coatings on-chip array is laid with through-hole, and array laying is fluted on upper and lower two surface of the 2nd YSZ cast sheets.The present invention can ensure that battery has enough mechanical strengths while reducing SOFC electrolyte thickness, to reduce the Ohmic resistance of battery.In addition, this new structural electrolyte can expand the interfacial area of electrode/electrolyte, more active reaction points are provided for electrochemical reaction, to reduce the polarization resistance of battery.
Description
Technical field
The present invention relates to field of solid oxide fuel, and in particular to a kind of solid oxide fuel cell it is compound
YSZ electrolyte and preparation method thereof.
Technical background
The energy is the important foundation that human society is depended on for existence and development.In today's society, fossil energy coal, oil and
Natural gas is still most important energy resources, but these energy will be successively consumed nearly with the high speed development of human society
To the greatest extent.Moreover, fossil energy can give off a large amount of waste water, exhaust gas during burning, environmental pollution and greenhouse effect are exacerbated
It answers.Therefore, in order to realize the sustainable development of human society, it is extremely urgent to find a kind of new energy technology.Solid oxidation
Chemical energy in fuel can be converted into electric energy by object fuel cell (SOFC) as a kind of all solid state power generator,
It is not limited by Carnot cycle, therefore energy conversion efficiency is very high.With the development of battery thin film technology of preparing, electrode supporting
Type SOFC is increasingly becoming the hot spot of research, and being compared to traditional electrolyte-supported its sharpest edges can be by the thickness of electrolyte
It is reduced to 10-30 μm, thus greatly reduces the Ohmic resistance of battery.However, electrode-supported SOFC is in practical application mistake
Remain many problems in journey, for example unstable, electrode interior gas transport is limited etc. under redox condition.Phase
Instead, electrolyte-supporting type SOFC is highly stable under redox condition, and is not limited by electrode mass transport process.Therefore,
By the design to battery structure, prepares and have both the battery of electrolyte-supported advantage and electrode supporting advantage and seem and very must
It wants.
Invention content
The object of the present invention is to provide composite Y SZ electrolyte of a kind of solid oxide fuel cell and preparation method thereof,
The Ohmic resistance and polarization resistance of traditional electrolyte matter support type SOFC batteries can be greatly reduced, improve the output of single battery
Energy.
To achieve the above object, present invention employs following technical schemes：
A kind of composite Y SZ electrolyte of solid oxide fuel cell, the composite Y SZ electrolyte are flowed by the first YSZ
Prolong piece, the 2nd YSZ cast sheets, the first YSZ cast sheets to press successively；The first YSZ curtain coatings on-chip array is laid with logical
Hole, on upper and lower two surface of the 2nd YSZ cast sheets array lay it is fluted.
Further scheme, the through-hole be the size formed by laser micro-machining technology be 0.5~1mm, quantity be 4~
400 square through-holes；The groove be the size formed by laser micro-machining technology be 10~100 μm, quantity is
5000~20000 circular grooves.
Another goal of the invention of the present invention is to provide above-mentioned composite Y SZ electrolyte preparing methods comprising following step
Suddenly：
(1) the tape casting is used to prepare YSZ electrolyte cast sheets：
(2) by laser micro-machining technology, the square that array laying is processed into a collection of YSZ electrolyte cast sheet is logical
Hole, as the first YSZ cast sheets；It is processed into array laying in upper and lower two surface in another batch of YSZ electrolyte cast sheet
Circular groove, as the 2nd YSZ cast sheets；
(3) the first YSZ cast sheets, the 2nd YSZ cast sheets and the first YSZ cast sheets are sequentially superimposed and are put together, so
YSZ electrolyte raw cooks are made after pressurizeing on tablet press machine afterwards；
(4) YSZ electrolyte raw cooks are put into high temperature furnace and are calcined, being made has new structural SOFC electrolyte.
Further scheme, the preparation process of YSZ electrolyte cast sheets is as follows in step (1)：First by YSZ (stabilized with yttrium oxide
Zirconium oxide) after powder mixes with triethanolamine, it is dissolved in the mixed solution of alcohol and dimethylbenzene and carries out ball milling into slurry；In slurry
Middle addition organic additive, and alcohol and dimethylbenzene continuation ball milling is added；Then YSZ slurries are put into vacuum pump and take out very
Empty de-bubble processing；Finally the YSZ slurries after de-bubble are cast on polyester film, YSZ electrolyte cast sheets are obtained after dry；
Further scheme, the mass ratio of alcohol and dimethylbenzene is 1 in the mixed solution:1~3：1；
The organic additive be one kind in polyvinyl butyral, polyethylene glycol, dibutyl phthalate etc. or
Person is a variety of；
It is described to vacuumize de-bubble processing time as 10~60min；
The temperature of the drying is room temperature, and the time is 1~2 day.
The thickness of further scheme, the YSZ electrolyte cast sheets described in step (1) is 100~150 μm.
Further scheme, the pressure of the tablet press machine described in step (3) are 20~100MPa, the dwell time is 5~
10min。
Further scheme, the calcination temperature described in step (4) is 1300~1600 DEG C, calcination time is 1~5h.
Surface is had reeded 2nd YSZ cast sheets and is placed in two the first YSZ cast sheets with through-hole by the present invention
Between at sandwich style pressing form SOFC electrolyte, wherein the through-hole structure of the first YSZ cast sheets can reduce SOFC electrolysis
Ensure that battery there are enough mechanical strengths while matter thickness, to reduce the Ohmic resistance of battery.2nd YSZ cast sheets it is recessed
Slot structure can expand the interfacial area of electrode-electric solution matter, more active reaction points be provided for electrochemical reaction, to reduce
The polarization resistance of battery.
So the composite Y SZ electrolyte of the present invention can not only reduce the polarization resistance of traditional electrolyte matter support type SOFC,
The Ohmic resistance of battery can also be reduced in the case where ensureing that battery has sufficient mechanical strength；Monomer can also be greatly improved
The output power of battery provides power-assisted for the commercialization process of SOFC.
Description of the drawings
Fig. 1 is that composite Y SZ electrolyte splits schematic diagram in the present invention；
Fig. 2 is exchanging under 800 DEG C of open-circuit conditions after four embodiments are prepared into monocell with comparative sample in the present invention
Impedance spectrum.
Specific implementation mode
In order to make goal of the invention, technical solution and the advantageous effects of the present invention be more clear, with reference to embodiments
The present invention will be described in further detail.
As shown in Figure 1, a kind of composite Y SZ electrolyte of solid oxide fuel cell, the composite Y SZ electrolyte be by
First YSZ cast sheets 1, the 2nd YSZ cast sheets 3, the first YSZ cast sheets 1 press successively；In the first YSZ cast sheets 1
Array is laid with through-hole 2, and array lays fluted 4 on upper and lower two surface of the 2nd YSZ cast sheets 3.
Further scheme, the through-hole 2 be the size formed by laser micro-machining technology be 0.5~1mm, quantity 4
~400 square through-holes；The groove 4 be the size formed by laser micro-machining technology be 10~100 μm, quantity is
5000~20000 circular grooves.
First YSZ cast sheets 1, the 2nd YSZ cast sheets 3 thickness be 100~150 μm.
The preparation process of YSZ electrolyte cast sheet is as follows in the present invention：First by YSZ (yttria-stabilized zirconia) powders with
After triethanolamine mixing, it is 1 in mass ratio to be dissolved in by alcohol and dimethylbenzene:1~3：Ball milling is carried out in 1 mixed solution to be slurried
Material；Organic additive is added in the slurry, and alcohol and dimethylbenzene continuation ball milling is added；Then YSZ slurries are put into vacuum pump
In vacuumize de-bubble and handle 10~60min；Finally the YSZ slurries after de-bubble are cast on polyester film, are placed in room temperature
Under the conditions of obtain YSZ electrolyte cast sheets after drying in 1~2 day；
The wherein described organic additive is one in polyvinyl butyral, polyethylene glycol, dibutyl phthalate etc.
Kind is a variety of.
Further scheme, the pressure of the tablet press machine described in step (3) are 20~100MPa, the dwell time is 5~
10min。
Further scheme, the calcination temperature described in step (4) is 1300~1600 DEG C, calcination time is 1~5h.
Embodiment 1：
Composite Y SZ electrolyte preparing methods comprising following steps：
(1) the tape casting is used to prepare YSZ electrolyte cast sheets：
(2) by laser micro-machining technology, the laying of 4 × 4 arrays is cut into a collection of YSZ electrolyte cast sheet
The length of side of square through-hole, square through-hole is 0.8mm, and the spacing between adjacent through-holes is 2.26mm, is cast as the first YSZ
Piece；Square through-hole area accounts for the 10% of the first YSZ cast sheet areas.
The circular groove of array laying is processed on upper and lower two surface in another batch of YSZ electrolyte cast sheet, as
2nd YSZ cast sheets；
(3) the first YSZ cast sheets, the 2nd YSZ cast sheets and the first YSZ cast sheets are sequentially superimposed and are put together, so
YSZ electrolyte raw cooks are made after being forced into 50MPa pressurizes 8min on tablet press machine afterwards；
(4) YSZ electrolyte raw cooks are put into high temperature furnace and calcine 2h at 1500 DEG C, being made has new structural SOFC
Electrolyte.
Embodiment 2：
Composite Y SZ electrolyte preparing methods comprising following steps：
(1) the tape casting is used to prepare YSZ electrolyte cast sheets：
(2) by laser micro-machining technology, the laying of 6 × 6 arrays is cut into a collection of YSZ electrolyte cast sheet
The length of side of square through-hole, square through-hole is 0.8mm, and the spacing between adjacent through-holes is 1.04mm, is cast as the first YSZ
Piece；Square through-hole area accounts for the 23% of the first YSZ cast sheet areas.
The circular groove of array laying is processed on upper and lower two surface in another batch of YSZ electrolyte cast sheet, as
2nd YSZ cast sheets；
(3) the first YSZ cast sheets, the 2nd YSZ cast sheets and the first YSZ cast sheets are sequentially superimposed and are put together, so
YSZ electrolyte raw cooks are made after being forced into 20MPa pressurizes 10min on tablet press machine afterwards；
(4) YSZ electrolyte raw cooks are put into high temperature furnace and calcine 2h at 1500 DEG C, being made has new structural SOFC
Electrolyte.
Embodiment 3：
Composite Y SZ electrolyte preparing methods comprising following steps：
(1) the tape casting is used to prepare YSZ electrolyte cast sheets：
(2) by laser micro-machining technology, the laying of 8 × 8 arrays is cut into a collection of YSZ electrolyte cast sheet
The length of side of square through-hole, square through-hole is 0.8mm, and the spacing between adjacent through-holes is 0.51mm, is cast as the first YSZ
Piece；Square through-hole area accounts for the 41% of the first YSZ cast sheet areas.
The circular groove of array laying is processed on upper and lower two surface in another batch of YSZ electrolyte cast sheet, as
2nd YSZ cast sheets；
(3) the first YSZ cast sheets, the 2nd YSZ cast sheets and the first YSZ cast sheets are sequentially superimposed and are put together, so
YSZ electrolyte raw cooks are made after being forced into 100MPa pressurizes 5min on tablet press machine afterwards；
(4) YSZ electrolyte raw cooks are put into high temperature furnace and calcine 5h at 1300 DEG C, being made has new structural SOFC
Electrolyte.
Embodiment 4：
Composite Y SZ electrolyte preparing methods comprising following steps：
(1) the tape casting is used to prepare YSZ electrolyte cast sheets：
(2) by laser micro-machining technology, the laying of 10 × 10 arrays is cut into a collection of YSZ electrolyte cast sheet
Square through-hole, the length of side of square through-hole is 0.8mm, and the spacing between adjacent through-holes is 0.22mm, is flowed as the first YSZ
Prolong piece；Square through-hole area accounts for the 64% of the first YSZ cast sheet areas.
The circular groove of array laying is processed on upper and lower two surface in another batch of YSZ electrolyte cast sheet, as
2nd YSZ cast sheets；
(3) the first YSZ cast sheets, the 2nd YSZ cast sheets and the first YSZ cast sheets are sequentially superimposed and are put together, so
YSZ electrolyte raw cooks are made after being forced into 80MPa pressurizes 5min on tablet press machine afterwards；
(4) YSZ electrolyte raw cooks are put into high temperature furnace and calcine 1h at 1600 DEG C, being made has new structural SOFC
Electrolyte.
By the two sides of SOFC electrolyte and traditional structure electrolyte prepared by above-described embodiment 1-5 be respectively coated it is identical just
Monocell is made in negative material after calcining.Each monocell is analyzed under open-circuit condition using electrochemical alternate impedance spectrum (EIS)
Impedance, test temperature are 800 DEG C.Test results are shown in figure 2, monocell made of SOFC electrolyte in the embodiment of the present application 1
4.15% is reduced in 800 DEG C of Ohmic resistances, polarization resistance reduces 29.7%；In embodiment 2 made of SOFC electrolyte
Monocell reduces 12.4% in 800 DEG C of Ohmic resistance, and polarization resistance reduces 32.7%；SOFC electrolyte in embodiment 3
Manufactured monocell reduces 24.4% in 800 DEG C of Ohmic resistance, and polarization resistance reduces 36.2%；SOFC in embodiment 4
Monocell made of electrolyte reduces 40.9% in 800 DEG C of Ohmic resistance, and polarization resistance reduces 45.3%.From upper analysis
It is found that composite Y SZ electrolyte prepared by the present invention significantly reduces the Ohmic resistance and polarization resistance of battery.
Applicant declares, and the invention is not limited in the specific implementation modes that above-described embodiment is disclosed and described, to this hair
Some bright modifications and changes should also be as falling into the scope of the claims of the present invention.
Claims (8)
1. a kind of composite Y SZ electrolyte of solid oxide fuel cell, it is characterised in that：The composite Y SZ electrolyte be by
First YSZ cast sheets, the 2nd YSZ cast sheets, the first YSZ cast sheets press successively；First YSZ is cast on-chip array
It is laid with through-hole, array laying is fluted on upper and lower two surface of the 2nd YSZ cast sheets.
2. composite Y SZ electrolyte according to claim 1, it is characterised in that：The through-hole is by Laser Micro-Machining skill
Art formed size be 0.5 ~ 1 mm, the square through-hole that quantity is 4 ~ 400；The groove is to pass through laser micro-machining technology
The circular groove that the size of formation is 10 ~ 100 μm, quantity is 5000 ~ 20000.
3. composite Y SZ electrolyte preparing methods as described in claim 1, it is characterised in that：Include the following steps：
（1）YSZ electrolyte cast sheets are prepared using the tape casting：
（2）By laser micro-machining technology, the square through-hole of array laying is processed into a collection of YSZ electrolyte cast sheet,
As the first YSZ cast sheets；It is processed into the circle of array laying in upper and lower two surface in another batch of YSZ electrolyte cast sheet
Connected in star, as the 2nd YSZ cast sheets；
（3）First YSZ cast sheets, the 2nd YSZ cast sheets and the first YSZ cast sheets are sequentially superimposed and are put together, is then existed
YSZ electrolyte raw cooks are made after pressurizeing on tablet press machine；
（4）YSZ electrolyte raw cooks are put into high temperature furnace and are calcined, being made has new structural SOFC electrolyte.
4. preparation method according to claim 3, it is characterised in that：Step（1）The preparation of middle YSZ electrolyte cast sheet
Journey is as follows：First by YSZ（Yttria-stabilized zirconia）After powder is mixed with triethanolamine, the mixing for being dissolved in alcohol and dimethylbenzene is molten
Ball milling is carried out in liquid into slurry；Organic additive is added in the slurry, and alcohol and dimethylbenzene continuation ball milling is added；Then will
YSZ slurries, which are put into vacuum pump, vacuumize de-bubble processing；Finally the YSZ slurries after de-bubble are cast on polyester film,
YSZ electrolyte cast sheets are obtained after drying.
5. preparation method according to claim 4, it is characterised in that：The quality of alcohol and dimethylbenzene in the mixed solution
Than being 1:1~3：1；
The organic additive is a kind of or more in polyvinyl butyral, polyethylene glycol, dibutyl phthalate etc.
Kind；
It is described to vacuumize de-bubble processing time as 10 ~ 60 min；
The temperature of the drying is room temperature, and the time is 1 ~ 2 day.
6. preparation method according to claim 3, it is characterised in that：Step（1）Described in YSZ electrolyte cast sheets
Thickness is 100 ~ 150 μm.
7. preparation method according to claim 3, it is characterised in that：Step（3）Described in tablet press machine pressure be 20 ~
100 MPa, dwell time are 5 ~ 10 min.
8. preparation method according to claim 3, it is characterised in that：Step（4）Described in calcination temperature be 1300 ~
1600 DEG C, calcination time be 1 ~ 5 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810448929.9A CN108417872B (en) | 2018-05-11 | 2018-05-11 | Composite YSZ electrolyte of solid oxide fuel cell and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810448929.9A CN108417872B (en) | 2018-05-11 | 2018-05-11 | Composite YSZ electrolyte of solid oxide fuel cell and preparation method thereof |
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| CN108417872A true CN108417872A (en) | 2018-08-17 |
| CN108417872B CN108417872B (en) | 2021-04-09 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094123A (en) * | 2021-11-17 | 2022-02-25 | 合肥国轩高科动力能源有限公司 | Anode/electrolyte half cell, anode-supported solid oxide fuel cell and method for manufacturing the same |
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| US20020012825A1 (en) * | 2000-05-08 | 2002-01-31 | Jun Sasahara | Fuel cell with patterned electrolyte/electrode interface |
| CN1409427A (en) * | 2001-09-18 | 2003-04-09 | 中国科学技术大学 | PEN multilayer film of middle temperature solid oxide fuel cell and its producing method |
| CN101536235A (en) * | 2006-10-31 | 2009-09-16 | 康宁股份有限公司 | Micromachined electrolyte sheet, fuel cell devices utilizing such, and micromachining method for making fuel cell devices |
| CN103811789A (en) * | 2012-11-07 | 2014-05-21 | 中国科学院上海硅酸盐研究所 | Solid oxide fuel cell with symmetrical electrodes, and preparation method and application thereof |
| JP2016126884A (en) * | 2014-12-26 | 2016-07-11 | 株式会社日本触媒 | Electrolyte sheet for solid oxide fuel cell |
-
2018
- 2018-05-11 CN CN201810448929.9A patent/CN108417872B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020012825A1 (en) * | 2000-05-08 | 2002-01-31 | Jun Sasahara | Fuel cell with patterned electrolyte/electrode interface |
| CN1409427A (en) * | 2001-09-18 | 2003-04-09 | 中国科学技术大学 | PEN multilayer film of middle temperature solid oxide fuel cell and its producing method |
| CN101536235A (en) * | 2006-10-31 | 2009-09-16 | 康宁股份有限公司 | Micromachined electrolyte sheet, fuel cell devices utilizing such, and micromachining method for making fuel cell devices |
| CN103811789A (en) * | 2012-11-07 | 2014-05-21 | 中国科学院上海硅酸盐研究所 | Solid oxide fuel cell with symmetrical electrodes, and preparation method and application thereof |
| JP2016126884A (en) * | 2014-12-26 | 2016-07-11 | 株式会社日本触媒 | Electrolyte sheet for solid oxide fuel cell |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094123A (en) * | 2021-11-17 | 2022-02-25 | 合肥国轩高科动力能源有限公司 | Anode/electrolyte half cell, anode-supported solid oxide fuel cell and method for manufacturing the same |
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