CN103165930A - Method for Improving Sintering Performance of Proton Conductor Solid Oxide Fuel Cell Electrolyte - Google Patents
Method for Improving Sintering Performance of Proton Conductor Solid Oxide Fuel Cell Electrolyte Download PDFInfo
- Publication number
- CN103165930A CN103165930A CN2013100987663A CN201310098766A CN103165930A CN 103165930 A CN103165930 A CN 103165930A CN 2013100987663 A CN2013100987663 A CN 2013100987663A CN 201310098766 A CN201310098766 A CN 201310098766A CN 103165930 A CN103165930 A CN 103165930A
- Authority
- CN
- China
- Prior art keywords
- sintering
- sintering aid
- electrolyte
- base substrate
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005245 sintering Methods 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000003792 electrolyte Substances 0.000 title claims abstract description 42
- 239000004020 conductor Substances 0.000 title claims abstract description 31
- 239000000446 fuel Substances 0.000 title claims abstract description 17
- 239000007787 solid Substances 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002001 electrolyte material Substances 0.000 abstract 2
- 239000013354 porous framework Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 34
- 238000007598 dipping method Methods 0.000 description 33
- 239000000463 material Substances 0.000 description 25
- 210000000988 bone and bone Anatomy 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000000280 densification Methods 0.000 description 7
- 238000003980 solgel method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 230000000536 complexating effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910002741 Ba0.5Sr0.5Co0.8Fe0.2O3-δ Inorganic materials 0.000 description 1
- 229910002742 Ba0.5Sr0.5Co0.8Fe0.2O3−δ Inorganic materials 0.000 description 1
- 229910002939 BaZr0.8Y0.2O3−δ Inorganic materials 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Conductive Materials (AREA)
Abstract
The invention belongs to the field of Solid Oxide Fuel Cell (SOFC) electrolyte materials, and particularly relates to a method for improving the sintering performance of a proton conductor oxide fuel cell electrolyte, which can be used for preparing a dense electrolyte of a high-temperature proton conductor. The method comprises the following specific steps: A. preparing electrolyte powder into a high-temperature proton conductor blank with a porous framework structure by a dry pressing method; B. preparing a sintering aid solution, and soaking the sintering aid solution into the high-temperature proton conductor blank prepared in the step A by using a micro-injector; C. and (3) putting the high-temperature proton conductor blank impregnated with the sintering aid solution into a muffle furnace for roasting to obtain a compact electrolyte layer. The method has simple manufacturing process, avoids the step of preparing the porous framework by high-temperature sintering, saves energy and preparation time, saves the step of adding the sintering aid for premixing in the powder synthesis process in the traditional method, and can ensure that the sintering aid is uniformly dispersed in the proton conductor electrolyte material.
Description
Technical field
The invention belongs to field of solid oxide fuel, a kind of method that improves proton conductor oxide fuel battery electrolyte sintering character can be used for preparing the electrolyte of the densification of high-temperature proton-conductor.
Background technology
Solid Oxide Fuel Cell (SOFC) is a kind of energy conversion device of efficient, cleaning.It is electrolyte that traditional SOFC technology is based on YSZ, and this needs higher operating temperature greatly about 800～1000 ° of C.This higher operating temperature has been brought larger obstruction to the practical application of SOFC, such as the demand to expensive material, and long start-up time and higher heat energy life-span that can reduce battery.So the research tendency in this field is to pursue temperatureization in operating temperature, with all technology and the material difficulty that overcomes conventional high-temperature SOFC.The operating temperature that reduces SOFC not only can also be conducive to develop portable SOFC by Cost reduction.In attempting developing the SOFC process that to work in mesophilic range (500～700 ° of C), need to reduce electrolytical ohmage.Therefore, High-temperature proton conductor material has caused every researcher's great interest in the last few years.The high-temperature proton-conductor electrolyte has higher proton conductivity in the atmosphere of hydrogen or humidification hydrogen, especially have lower activation energy at the traditional oxygen ion conductor of mesophilic range internal ratio.
BaZrO
3Base oxide is a kind of electrolyte with development prospect of proton conductor oxide fuel cell, and it has higher ionic conductivity and for the CO in fuel atmosphere
2And H
2O has chemical stability preferably.In order to reduce BaZrO
3The sintering temperature of base oxide material, researchers have taked a lot of methods to improve its sintering character, such as other elements of doping reduce the ratio of Zr element, appropriate Ba is more than needed or defective, to BaZrO
3Add the methods such as sintering aid in base oxide material.Structure, double-layer tablet sintering character that but there is complex manufacturing process in above method, can destroy material such as do not mate at the shortcoming.Sintering aid commonly used has ZnO, CuO and NiO etc.Studies show that adding a small amount of metal oxide can reduce by 150～250 ° of C with its sintering temperature in the middle of material.Wherein Zn is considered to a kind of and can improves BaZrO
3The desirable auxiliary agent of base oxide High-temperature proton conductor material sintering character.But, directly use preparation method's more complicated of the method interpolation sintering aid of metal oxide and electrolyte mechanical mixture, the electrolyte for preparing easily ftractures later on through roasting, and metal ion can enter into the lattice of electrolyte, thereby reduces the conductivity of electrolyte.
Summary of the invention
The objective of the invention is in order to solve BaZrO
3The sintering character of base high-temperature proton-conductor electrolyte is poor, and the electrolyte densified sintering product needs higher temperature, and a kind of method that improves proton conductor oxide fuel battery electrolyte sintering character.And the method is not used other auxiliary equipment complicated and high price in preparation process, thereby technique simply is easy to repeat preparation.
Technical scheme of the present invention is: a kind of method that improves proton conductor oxide fuel battery electrolyte sintering character, can be used for preparing the electrolyte of the densification of high-temperature proton-conductor, its concrete steps are as follows: A, the electrolyte powder body is prepared into the high-temperature proton-conductor base substrate with porous skeleton structure with the method for dry-pressing; B, preparation sintering aid solution, and impregnation sintering compounding agent solution in the high-temperature proton-conductor base substrate that makes to steps A with micro syringe; C, the high-temperature proton-conductor base substrate of impregnation sintering compounding agent solution is put into Muffle furnace carry out roasting, obtained fine and close dielectric substrate.
The structural formula of preferred described electrolyte powder is BaZrO
3Or BaZr
0.8-xM
xY
0.2O
3-δ, wherein M=La, Ce, Pr, Nd, Sm, Eu, Gd, Yb, In, 0≤x≤0.8.
Preferred sintering aid solution is Zn (NO
3)
2, Cu (NO
3)
2Or Ni (NO
3)
2Ethanol solution, wherein to belong to the concentration of ion be 0.02～0.2mol L to the sintering aid GOLD FROM PLATING SOLUTION
-1It is characterized in that making solvent with absolute ethyl alcohol volatile, and the wetability of ethanol is good, large in the contact angle of solid phase surface, more easily be penetrated among porous skeleton structure, sintering aid is distributed more even.The pickup of sintering aid solution is 3%～8% of green body quality for the quality of controlling metal ion in sintering aid.
The pressure position 150～300MPa of preferred dry pressing pressing blank.The porosity of the high-temperature proton-conductor base substrate of dry-pressing formed porous skeleton structure is 65%～75%.
The sintering temperature of preferred high-temperature proton-conductor base substrate is 1150～1400 ° of C, and roasting time is 2～6 hours.
Immersion tool of the present invention is to use market accurate micro syringe on sale.
High-temperature proton-conductor oxide of the present invention, its synthetic method are sol-gel process, and its detailed process can be referring to document (W.Zhou, Z.P.Shao, R.Ran, R.Cai, Novel, Electrochem.Commun.10 (2008).
Beneficial effect:
The density of the resulting high-temperature proton-conductor electrolyte of the present invention has reached 93%～98%, and the temperature of material densified sintering product has been reduced by 150～250 ° of C, prepared the thin-film electrolyte structure of anode support type by the method for infusion process and multiple dry-pressing.
Description of drawings
Fig. 1 is that the later BZCY1 material of the dipping Zn of embodiment 1 is at 1150 ° of XRD collection of illustrative plates that the C roasting is later;
The section S EM figure that Fig. 2 is the later BZCY4 base substrate of the dipping Zn sintering aid of embodiment 1 after 1150 ° of C roastings 5 hours;
Fig. 3 is the section S EM figure take the later BZCY4 of dipping Zn as the Solid Oxide Fuel Cell of electrolytical anode support type of embodiment 4;
Fig. 4 is the battery performance figure take the later BZCY4 of dipping Zn as the Solid Oxide Fuel Cell of electrolytical anode support type of embodiment 4;
Fig. 5 is the Solid Oxide Fuel Cell chemical impedance spectrum take the later BZCY4 of dipping Zn as electrolytical anode support type of embodiment 4;
Fig. 6 be embodiment 5 for not flooding the sintering curre of BZCY6 material of Zn and dipping 4wt%Zn.
Embodiment
Method involved in the present invention comprises but is not limited to material in following examples.
Embodiment 1: with BaZr
0.1Ce
0.7Y
0.2O
3-δ(BZCY1) material is bone porous base substrate, adds the Zn sintering aid with the method for dipping to it.
(1) prepare BaZr with sol-gel process
0.1Ce
0.7Y
0.2O
3-δPowder: the preparation method of powder adopts sol-gel complexing method commonly used, its detailed process can be referring to document (W.Zhou, Z.P.Shao, R.Ran, R.Cai, Novel, Electrochem.Commun.10 (2008) 1647 – 1651), recently determine the consumption of raw material according to the stoichiometry of BZCY1 material.
(2) preparation Zn (NO
3)
2Ethanolic solution: take appropriate Zn (NO
3)
2Join in beaker, then add absolute ethyl alcohol in beaker, use at last the volumetric flask constant volume, the solubility of solution is 0.02mol L
-1
(3) the bone porous electrolyte base substrate of preparation: the BZCY1 powder of getting 0.5g is put in stainless cylindrical mould, is pressed into columniform porous green compact body under 300MPa, and relative density is 70%.
(4) dipping Zn sintering aid solution is to having in bone porous base substrate: the stephanoporate framework base substrate of BZCY1 is placed on experimental bench, then uses the accurate syringe of trace with Zn (NO
3)
2Ethanolic solution join in the middle of stephanoporate framework, the quality of the Zn of dipping is 3% of green body quality, after the alcohol solvent volatilization is complete, the base substrate that dipping is completed is put into Muffle furnace obtains densification after roasting 5h under 1150 ° of C electrolyte sheet, and the relative density that uses Archimedes's draining measurement to record is 97.6%.
Fig. 1 shows that for the base substrate later XRD spectra of roasting 5h under 1150 ° of C of the BZCY1 after flooding material has still kept stable perovskite structure, does not destroy original structure because of adding of Zn.
Fig. 2 floods the section S EM figure of the later BZCY1 base substrate of Zn sintering aid after 1150 ° of C roastings 5 hours, show to add 3wt%Zn can increase substantially the sintering character of material as sintering aid in BZCY1, just can obtain fine and close electrolyte sheet at 1150 ° of C.
Embodiment 2: with BaZr
0.1Ce
0.7Y
0.2O
3-δ(BZCY1) material is bone porous base substrate, adds the Ni sintering aid with the method for dipping to it.
(1) with the method in embodiment 1 (1).
(2) preparation Ni (NO
3)
2Ethanolic solution: take appropriate Ni (NO
3)
2Join in beaker, then add absolute ethyl alcohol in beaker, use at last the volumetric flask constant volume, the solubility of solution is 0.01mol L
-1.
(3) with the method in embodiment 1 (3).
(4) dipping Ni sintering aid solution is to having in bone porous base substrate: the stephanoporate framework base substrate of BZCY1 is placed on experimental bench, then uses the accurate syringe of trace with Ni (NO
3)
2Ethanolic solution join in the middle of stephanoporate framework, the quality of the Ni of dipping is 4% of green body quality, after the alcohol solvent volatilization is complete, the base substrate that dipping is completed is put into Muffle furnace obtains densification after roasting 5h under 1150 ° of C electrolyte sheet, and the relative density that uses Archimedes's draining measurement to record is 96.8%.。
Embodiment 3: with BaZr
0.8Y
0.2O
3-δ(BZY8) material is bone porous base substrate, adds the Cu sintering aid with the method for dipping to it.
(1) prepare BaZr with sol-gel process
0.8Y
0.2O
3-δPowder: the preparation method of powder adopts sol-gel complexing method commonly used, its detailed process can be referring to document (W.Zhou, Z.P.Shao, R.Ran, R.Cai, Novel, Electrochem.Commun.10 (2008) 1647 – 1651), recently determine the consumption of raw material according to the stoichiometry of BZY8 material.
(2) preparation Cu (NO
3)
23H
2The ethanolic solution of O: take appropriate Cu (NO
3)
2Join in beaker, then add absolute ethyl alcohol in beaker, use at last the volumetric flask constant volume, the solubility of solution is 0.2mol L
-1
(3) the bone porous electrolyte base substrate of preparation: the BZY8 powder of getting 0.5g is put in stainless cylindrical mould, is pressed into columniform porous green compact body under 150MPa, and relative density is 65%.
(4) dipping Cu sintering aid solution is to having in bone porous base substrate: the stephanoporate framework base substrate of BZY8 is placed on experimental bench, then uses the accurate syringe of trace with Cu (NO
3)
2Ethanolic solution join in the middle of stephanoporate framework, the quality of the Cu of dipping is 8% of green body quality, after the alcohol solvent volatilization is complete, the base substrate that dipping is completed is put into Muffle furnace obtains densification after roasting 3h under 1400 ° of C electrolyte sheet, and the relative density that uses Archimedes's draining measurement to record is 95.7%.。
Embodiment 4: with the BaZr of dipping Zn sintering aid
0.4Ce
0.4Y
0.2O
3-δ(BZCY4) be the application of electrolytical proton conductor oxide fuel cell
(1) preparation of anode-supported monocell: the anode support type monocell adopts the method preparation of dry-pressing-co-sintering.Now the BZCY4 powder mixed according to the ratio of mass ratio 4:6 and adds appropriate ethanol with the NiO powder, taking out and dry after the rotating speed ball milling 30min with 400rmp in high-energy ball milling, obtaining required anode powder.Taking 0.4g anode powder is to be to suppress under 100MPa at pressure in the stainless steel mould of 15mm at diameter, then the BZCY4 electrolyte powder that takes 0.02g is layered on anode substrate equably, presses altogether the anode that obtains anode support type-double-deck base substrate of electrolyte under 300MPa pressure.
(2) preparation Zn (NO
3)
2Ethanolic solution: take appropriate Zn (NO
3)
2Join in beaker, then add absolute ethyl alcohol in beaker, use at last the volumetric flask constant volume, the solubility of solution is 0.1mol L
-1
(3) base substrate with preparation in step (1) is placed on smooth experimental bench, then thinks base substrate electrolyte one side dipping Zn (NO with accurate micro syringe
3)
2Ethanolic solution, in the sintering aid of dipping, the quality of Zn is the 5wt% of electrolyte quality, after alcohol solvent volatilization was complete, the base substrate that dipping is completed was put into Muffle furnace and is being obtained the bilayer cells sheet after roasting 5h under 1400 ° of C.
(4) Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3-δ(BSCF) preparation of cathode slurry and spraying: a certain amount of ethylene glycol, isopropyl alcohol and glycerine are joined in BSCF cathode powder with sol-gel process preparation, with in high-energy ball milling under the rotating speed of 400rmp ball milling 40min make cathode slurry.Then pulp spraying is coated in the electrolyte one side of the double-layer tablet of preparation in step (3), and under 1000 ° of C roasting 2h.Use the elargol of dilution and silver-colored line respectively as current collector and the wire of electrode.
(5) test of battery: the marking of cell piece is exposed in air, act as a fuel with the wet hydrogen of humidification 3% and pass into anode one side, the digital instrument that adopts computer to control records I-V and the I-P curve of battery, the flow of hydrogen is controlled by flow controller, with the AC impedance spectrogram of Impedance Analysis instrument test electrical measurement under open circuit.
Fig. 3 can find out that for the section S EM figure after testing take 5%Zn-BZCY4 as electrolytical monocell dielectric substrate is very fine and close, can satisfy the requirement of battery testing.
Fig. 4 is I-V and I-P curve take 5wt%Zn-BZCY4 as electrolytical monocell, and when 700 ° of C, the OCV of battery is 0.96V, and performance is 325mW cm
-2
Fig. 5 is take 5wt%Zn-BZCY4 as electrolytical monocell electrochemical impedance spectrogram.
Embodiment 5: the BaZr of dipping Zn sintering aid
0.6Pr
0.2Y
0.2O
3-δ(BZPY6) sintering curre after
(1) prepare BaZr with sol-gel process
0.6Pr
0.2Y
0.2O
3-δPowder: the preparation method of powder adopts sol-gel complexing method commonly used, its detailed process can be referring to document (W.Zhou, Z.P.Shao, R.Ran, R.Cai, Novel, Electrochem.Commun.10 (2008) 1647 – 1651), recently determine the consumption of raw material according to the stoichiometry of BZPY6 material.
(2) preparation Zn (NO
3)
2Ethanolic solution: take appropriate Zn (NO
3)
2Join in beaker, then add absolute ethyl alcohol in beaker, use at last the volumetric flask constant volume, the solubility of solution is 0.2mol L
-1
(3) the bone porous electrolyte base substrate of preparation: the BZPY6 powder of getting 0.5g is put in stainless cylindrical mould, is pressed into columniform porous green compact body under 150MPa, and relative density is 71%.
(4) dipping Zn sintering aid solution is to having in bone porous base substrate: the stephanoporate framework base substrate of BZCY6 is placed on experimental bench, then uses the accurate syringe of trace with Zn (NO
3)
2Ethanolic solution join in the middle of stephanoporate framework, the quality of the Zn of dipping is 7% of green body quality.
(5) test of sintering curre: the BZCY6 base substrate that will flood the Zn sintering aid and not flood the Zn sintering aid adopts thermal dilatometer to study its sintering curre, and temperature range is by room temperature to 1400 ° C, and sintering time is 5 hours.
Fig. 6 is the sintering curre that flooded the Zn sintering aid and do not flood Zn sintering aid BZCY6 base substrate, can find to have increased significantly through the sintering character of BZCY6 material after flooding.
Embodiment 6: with BaZrO
3Material is bone porous base substrate, adds the Zn sintering aid with the method for dipping to it.
(1) use sol-gel process BaZrO
3Powder: the preparation method of powder adopts sol-gel complexing method commonly used, its detailed process can be referring to document (W.Zhou, Z.P.Shao, R.Ran, R.Cai, Novel, Electrochem.Commun.10 (2008) 1647 – 1651), recently determine the consumption of raw material according to the stoichiometry of powder body material.
(2) preparation Zn (NO
3)
2Ethanolic solution: take appropriate Zn (NO
3)
2Join in beaker, then add absolute ethyl alcohol in beaker, use at last the volumetric flask constant volume, the solubility of solution is 0.02mol L
-1
(3) the bone porous electrolyte base substrate of preparation: the BaZrO that gets 0.5g
3Powder is put in stainless cylindrical mould, is pressed into columniform porous green compact body under 150MPa, and relative density is 70%.
(4) dipping Zn sintering aid solution is to having in bone porous base substrate: with BaZrO
3The stephanoporate framework base substrate be placed on experimental bench, then use the trace accurate syringe with Zn (NO
3)
2Ethanolic solution join in the middle of stephanoporate framework, the quality of the Zn of dipping is 3% of green body quality, after the alcohol solvent volatilization is complete, the base substrate that dipping is completed is put into Muffle furnace obtains densification after roasting 3h under 1400 ° of C electrolyte sheet, and the relative density that uses Archimedes's draining measurement to record is 96.3%.
Embodiment 7: with BaZr
0.7Nd
0.1Y
0.2O
3-δ(BZNY7) material is bone porous base substrate, adds the Ni sintering aid with the method for dipping to it.
(1) prepare BaZr with sol-gel process
0.7Nd
0.1Y
0.2O
3-δPowder: the preparation method of powder adopts sol-gel complexing method commonly used, its detailed process can be referring to document (W.Zhou, Z.P.Shao, R.Ran, R.Cai, Novel, Electrochem.Commun.10 (2008) 1647 – 1651), recently determine the consumption of raw material according to the stoichiometry of BZNY7 material.
(2) preparation Ni (NO
3)
2Ethanolic solution: take appropriate Ni (NO
3)
2Join in beaker, then add absolute ethyl alcohol in beaker, use at last the volumetric flask constant volume, the solubility of solution is 0.01mol L
-1.
(3) with the method in embodiment 1 (3).
(4) dipping Ni sintering aid solution is to having in bone porous base substrate: the stephanoporate framework base substrate of BZNY7 is placed on experimental bench, then uses the accurate syringe of trace with Ni (NO
3)
2Ethanolic solution join in the middle of stephanoporate framework, the quality of the Ni of dipping is 4% of green body quality, after the alcohol solvent volatilization is complete, the base substrate that dipping is completed is put into Muffle furnace obtains densification after roasting 6h under 1350 ° of C electrolyte sheet, and the relative density that uses Archimedes's draining measurement to record is 95.8%.
Claims (6)
1. method that improves proton conductor oxide fuel battery electrolyte sintering character, its concrete steps are as follows: A, the electrolyte powder body is prepared into the high-temperature proton-conductor base substrate with porous skeleton structure with the method for dry-pressing; B, preparation sintering aid solution, and impregnation sintering compounding agent solution in the high-temperature proton-conductor base substrate that makes to steps A with micro syringe; C, the high-temperature proton-conductor base substrate of impregnation sintering compounding agent solution is carried out roasting, obtained fine and close dielectric substrate.
2. method according to claim 1, the structural formula that it is characterized in that described electrolyte powder is BaZrO
3Or BaZr
0.8-xM
xY
0.2O
3-δ, wherein M=La, Ce, Pr, Nd, Sm, Eu, Gd, Yb, In, 0≤x≤0.8.
3. method according to claim 1, is characterized in that sintering aid solution is Zn (NO
3)
2, Cu (NO
3)
2Or Ni (NO
3)
2Ethanol solution, wherein to belong to the concentration of ion be 0.02～0.2mol L to the sintering aid GOLD FROM PLATING SOLUTION
-1
4. method according to claim 1, is characterized in that the pickup of sintering aid solution is 3%～8% of green body quality for the quality of controlling metal ion in sintering aid.
5. method according to claim 1, the sintering temperature that it is characterized in that the high-temperature proton-conductor base substrate is 1150～1400 ° of C, roasting time is 2～6 hours.
6. method according to claim 1 is characterized in that the pressure position 150～300MPa of dry pressing pressing blank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100987663A CN103165930A (en) | 2013-03-25 | 2013-03-25 | Method for Improving Sintering Performance of Proton Conductor Solid Oxide Fuel Cell Electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100987663A CN103165930A (en) | 2013-03-25 | 2013-03-25 | Method for Improving Sintering Performance of Proton Conductor Solid Oxide Fuel Cell Electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103165930A true CN103165930A (en) | 2013-06-19 |
Family
ID=48588816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100987663A Pending CN103165930A (en) | 2013-03-25 | 2013-03-25 | Method for Improving Sintering Performance of Proton Conductor Solid Oxide Fuel Cell Electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103165930A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103825039A (en) * | 2014-02-27 | 2014-05-28 | 盐城工学院 | Electrolyte material and preparation method for intermediate and low-temperature solid oxide fuel cells |
| CN106602136A (en) * | 2016-12-22 | 2017-04-26 | 中国矿业大学 | Barium zirconate-based electrolyte material system and preparation method thereof |
| CN109346752A (en) * | 2018-09-11 | 2019-02-15 | 山西大学 | A kind of preparation method of the solid oxide fuel cell zirconium base electrolytic thin-membrane of electrolyte-supported |
| CN110224146A (en) * | 2019-05-23 | 2019-09-10 | 湖北大学 | A kind of online densifying method of fuel-cell electrolyte low temperature |
| CN111732434A (en) * | 2020-07-07 | 2020-10-02 | 韶关学院 | Ceramic preparation method using in-situ generated oxide as sintering aid |
| WO2024012802A1 (en) * | 2022-07-11 | 2024-01-18 | Forschungszentrum Jülich GmbH | Production of a component with a gas-tight ion-conducting functional layer, and component |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1622378A (en) * | 2003-11-28 | 2005-06-01 | 三洋电机株式会社 | Materials for solid oxide electrolyte and method for preparing solid oxide electrolyte |
| CN102531587A (en) * | 2012-01-06 | 2012-07-04 | 天津大学 | Yttrium-doped barium zirconate-cerate/inorganic salt complex phase-structured proton conductor material and preparation method thereof |
-
2013
- 2013-03-25 CN CN2013100987663A patent/CN103165930A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1622378A (en) * | 2003-11-28 | 2005-06-01 | 三洋电机株式会社 | Materials for solid oxide electrolyte and method for preparing solid oxide electrolyte |
| CN102531587A (en) * | 2012-01-06 | 2012-07-04 | 天津大学 | Yttrium-doped barium zirconate-cerate/inorganic salt complex phase-structured proton conductor material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YU LIU ET AL.: "A novel approach for substantially improving the sinterability of BaZr0.4Ce0.4Y0.2O3-δ electrolyte for fuel cells by impregnating the green membrane with zinc nitrate as a sintering aid", 《JOURNAL OF MEMBRANE SCIENCE》, vol. 437, 21 March 2013 (2013-03-21), pages 189 - 195 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103825039A (en) * | 2014-02-27 | 2014-05-28 | 盐城工学院 | Electrolyte material and preparation method for intermediate and low-temperature solid oxide fuel cells |
| CN106602136A (en) * | 2016-12-22 | 2017-04-26 | 中国矿业大学 | Barium zirconate-based electrolyte material system and preparation method thereof |
| CN109346752A (en) * | 2018-09-11 | 2019-02-15 | 山西大学 | A kind of preparation method of the solid oxide fuel cell zirconium base electrolytic thin-membrane of electrolyte-supported |
| CN110224146A (en) * | 2019-05-23 | 2019-09-10 | 湖北大学 | A kind of online densifying method of fuel-cell electrolyte low temperature |
| CN111732434A (en) * | 2020-07-07 | 2020-10-02 | 韶关学院 | Ceramic preparation method using in-situ generated oxide as sintering aid |
| WO2024012802A1 (en) * | 2022-07-11 | 2024-01-18 | Forschungszentrum Jülich GmbH | Production of a component with a gas-tight ion-conducting functional layer, and component |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Evaluation of SrSc0. 175Nb0. 025Co0. 8O3-δ perovskite as a cathode for proton-conducting solid oxide fuel cells: the possibility of in situ creating protonic conductivity and electrochemical performance | |
| Yang et al. | Lattice incorporation of Cu2+ into the BaCe0. 7Zr0. 1Y0. 1Yb0. 1O3− δ electrolyte on boosting its sintering and proton-conducting abilities for reversible solid oxide cells | |
| CN111900449B (en) | Solid oxide fuel cell, method for producing same and use thereof | |
| CN103390739B (en) | A kind of Solid Oxide Fuel Cell ceria-based electrolyte interlayer and preparation thereof | |
| Zhang et al. | BaCo0. 4Fe0. 4Zr0. 2O3-δ: evaluation as a cathode for ceria-based electrolyte IT-SOFCs | |
| Yang et al. | (La0. 8Sr0. 2) 0.98 MnO3-δ-Zr0. 92Y0. 16O2-δ: PrOx for oxygen electrode supported solid oxide cells | |
| CN100449834C (en) | Anode-electrolyte-cathode assembly of middly temp SOFC and preparation method thereof | |
| CN103811789A (en) | Solid oxide fuel cell with symmetrical electrodes, and preparation method and application thereof | |
| CN103165930A (en) | Method for Improving Sintering Performance of Proton Conductor Solid Oxide Fuel Cell Electrolyte | |
| CN101577340A (en) | Method for preparing cathode-supported tubular solid oxide fuel cells | |
| CN104409742A (en) | BaCoO3-delta base B-position Bi2O3-Nb2O5 co-doped cathode material of solid oxide fuel cell, preparation method and applications thereof | |
| CN105742646B (en) | Cathode material for solid-oxide fuel cell and preparation with pomegranate fruit structure | |
| Chen et al. | Interlayer-free electrodes for IT-SOFCs by applying Co3O4 as sintering aid | |
| Zhang et al. | High-performance low-temperature solid oxide fuel cells using thin proton-conducting electrolyte with novel cathode | |
| Yang et al. | Tuning Ba0. 5Sr0. 5Co0. 8Fe0. 2O3-δ cathode to high stability and activity via Ce-doping for ceramic fuel cells | |
| Cao et al. | Novel reduction-resistant Ba (Ce, Zr) 1− xGdxO3− δ electron-blocking layer for Gd0. 1Ce0. 9O2− δ electrolyte in IT-SOFCs | |
| CN112687929A (en) | Lithium oxide electrode micro-molten salt ceramic fuel cell and preparation method thereof | |
| Hao et al. | Co-tape casting fabrication, field assistant sintering and evaluation of a coke resistant La0. 2Sr0. 7TiO3–Ni/YSZ functional gradient anode supported solid oxide fuel cell | |
| CN104037425A (en) | Medium-temperature SOFC (solid oxide fuel cell) flat-plate anode-supported monocell anode structure and preparation method thereof | |
| CN111416138A (en) | Proton ceramic membrane fuel cell and preparation method thereof | |
| Fu | Electrochemical performance of La0. 9Sr0. 1Co0. 8Ni0. 2O3− δ–Ce0. 8Sm0. 2O1. 9 composite cathode for solid oxide fuel cells | |
| Yang et al. | Sr-substituted SmBa0. 75Ca0. 25CoFeO5+ δ as a cathode for intermediate-temperature solid oxide fuel cells | |
| Xi et al. | Fabrication and evaluation of Sm0. 5Sr0. 5CoO3− δ impregnated PrBaCo2O5+ δ composite cathode for proton conducting SOFCs | |
| Ning et al. | Fabrication and characterization of anode support low-temperature solid oxide fuel cell based on the samaria-doped ceria electrolyte | |
| Jing et al. | Cone-shaped cylindrical Ce0. 9Gd0. 1O1. 95 electrolyte prepared by slip casting and its application to solid oxide fuel cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C05 | Deemed withdrawal (patent law before 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130619 |