CN1908046A - Composite pore-forming agent and method of preparing anode supporting body using the same - Google Patents

Composite pore-forming agent and method of preparing anode supporting body using the same Download PDF

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CN1908046A
CN1908046A CNA2006100102532A CN200610010253A CN1908046A CN 1908046 A CN1908046 A CN 1908046A CN A2006100102532 A CNA2006100102532 A CN A2006100102532A CN 200610010253 A CN200610010253 A CN 200610010253A CN 1908046 A CN1908046 A CN 1908046A
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pore
powder
anode
forming material
forming
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CN100419012C (en
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陈孔发
吕喆
胡金艳
艾娜
王嘉明
黄喜强
苏文辉
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Harbin Institute of Technology
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Harbin Institute of Technology
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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
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    • 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 invention discloses a compound pore-creating agent and preparing method of anode support through pore-creating agent, which comprises the following steps: first, blending primary anode powder; second, blending compound pore-creating agent; third, blending final anode powder; forth, preparing cathode support. the method is easy to control sintering contracting quantity and pore size, which improves film battery property effectively.

Description

A kind of composite pore-forming agent and utilize it to prepare the method for anode support
Technical field
The present invention relates to a kind ofly be used for the pore-forming material that anode powder preparing process adds and utilize it to prepare the method for anode support.
Background technology
Solid Oxide Fuel Cell (SOFC) is the electrochemical generating unit that a kind of chemical energy with fuel is converted into electric energy, has the energy transformation ratio height, advantages such as environmental protection.For the working temperature cold zone (500～800 ℃) from traditional high-temperature zone (800～1000 ℃) drop to battery, the focus of research is the electrolyte thin film battery of preparation anode-supported at present.And often there are the stress that does not match and occur because of contraction in anode and ionogen when co-sintering, cause battery to deform; Excessive stress causes electrolytic thin-membrane crackle and pore to occur easily when sintering; Stress also causes battery to break in test process easily, can't play the effect of separation gas, influences the raising of battery performance; Battery deforms has increased the difficulty of negative electrode and series of cells preparation.For addressing this is that, must select suitable anode, making it has sintering matched performance preferably with ionogen.
In order to increase the anodic porosity, in the preparation process of anode powder, add an amount of pore-forming material usually, as organism such as flour, starch, Semen Maydis powder, or carbon simple substance such as carbon dust, Graphite Powder 99.The adding of organic pore-forming agents also can be suitable adjustment anodic sintering shrinkage, but setting range is little; Carbon simple substance, as the adding of activated carbon powder pore-forming material, the change role of antianode porosity is little, but but can adjust the anodic shrinking percentage on a large scale.For this reason,, when improving the anodic porosity, can regulate the anodic shrinking percentage again, make it to have better sintering matching with electrolytic thin-membrane if organic and these two kinds of pore-forming material reasonable combination of carbon simple substance can be got up use.
Summary of the invention
For the electrolytic thin-membrane of the anode-supported that the solves ceramic methods preparation contraction mismatch problem when the co-sintering, a kind of composite pore-forming agent is provided and utilizes it to prepare the method for anode support.
Composite pore-forming agent of the present invention is that 0.5～50: 0～30 mixed forms by organism pore-forming material and carbon simple substance pore-forming material according to mass ratio.Utilize above-mentioned pore-forming material to prepare the method for anode support, it is characterized in that described method is:
One, the mixing of the initial powder of anode: with NiO, ionogen powder uniform mixing, wherein NiO accounts for 20～90% of the initial powder total mass of anode;
Two, the mixing of pore-forming material: with organism pore-forming material and carbon simple substance pore-forming material according to the described proportioning uniform mixing of claim 1;
Three, blending final anode powder: with the initial powder of anode and pore-forming material according to 100: the quality of (0.5～50) compares uniform mixing;
Four, the preparation of anode support: final anode powder is pressed into thick 0.05～3 millimeter anode base substrate, and 700～1500 ℃ of sintering 1～10 hour.
Present method simply is used by a kind of composite pore-forming agent, has realized the solution of the contraction mismatch problem of electrolytic thin-membrane when co-sintering of the anode-supported that ceramic methods prepares.Method of the present invention is simple, is easy to control the size that the anodic sintering shrinks total amount and porosity, and the electrolytic thin-membrane cell output of the anode-supported of preparation is superior.
Description of drawings
Fig. 1 is the sintering shrinkage curve of anode support and ionogen base substrate, and Fig. 2 is anode and electrolytical sintering shrinkage curve, and Fig. 3 is the I-V and the I-P rational curve of monocell.
Embodiment
Embodiment one: the composite pore-forming agent of present embodiment is that 0.5～50: 0～30 mixed forms by organism pore-forming material and carbon simple substance pore-forming material according to mass ratio.
The pore-forming material of organism described in the present embodiment refers to the powder that grain class crop makes, as: flour, W-Gum, potato powder, tapioca flour or Semen Maydis powder or the like.Carbon simple substance refers to the simple substance that carbons such as carbon dust, activated carbon powder or Graphite Powder 99 form.
Embodiment two: what present embodiment and embodiment one were different is that the mass ratio of organism pore-forming material and carbon simple substance pore-forming material is 0.5～50: 0.5～30.
Embodiment three: present embodiment prepares anode support according to following steps:
The mixing of step 1, the initial powder of anode: with NiO, oxide electrolyte powder uniform mixing, wherein NiO accounts for 20～90% of the initial powder total mass of anode.
Step 2, blending compound pore-creating: with organism pore-forming material and carbon simple substance pore-forming material according to (0.5～50): the quality of (0～30) compares uniform mixing.
Step 3, blending final anode powder: with the initial powder of anode and composite pore-forming agent according to 100: the quality of (0.5～50) compares uniform mixing.
The preparation of step 4, anode support: final anode powder is pressed into thick 0.05～3 millimeter anode base substrate, and 700～1500 ℃ of sintering 1～10 hour.So far, the preparation process of adding the anode support of composite pore-forming agent finishes.
Embodiment four: what present embodiment and embodiment three were different is,
Adopt the precipitator method to prepare the NiO powder in the step 1: the ionogen powder adopts 8mol%Y 2O 3Stable ZrO 2(YSZ), produce by Chinese building material institute; The mass ratio of NiO and YSZ is 5: 5.
The organic pore-forming agents that step 2 adopts is a flour, and carbon simple substance is activated carbon powder, and the mass ratio of the two is 25: 5.
The mass ratio of initial powder of the anode of step 3 and composite pore-forming agent is 100: 30.
Final anode powder depresses to the disk of 13mm at the pressure of 200MPa in the step 4, and the thick about 0.7mm of disk 1000 ℃ of sintering 2 hours, makes the NiO-YSZ anode support.
The ionogen of step 1 refers to the solid electrolyte material that Solid Oxide Fuel Cell can be used in the present embodiment, as stable zirconium oxide base electrolyte material, and doping of cerium oxide base electrolyte material etc.The organism pore-forming material refers to the powder that grain class crop makes in the step 2, as: flour, W-Gum, potato powder, tapioca flour or Semen Maydis powder or the like.Carbon simple substance refers to carbon dust, comprises the simple substance that carbons such as activated carbon powder or Graphite Powder 99 form.
Embodiment five: what present embodiment and embodiment four were different is, step 4 is changed into the cylinder that final anode powder is pressed into 6mm, and measure the sintering curre of YSZ (TZ-8YS) the ionogen base substrate that this anode and Japanese Tosoh company produce with Netzsch DIL 402C/3/G elevated temperature heat dilatometer, probe temperature is 50～1400 ℃, temperature rise rate is 5K/min, the air of the logical 50mL/min of test process.The result as shown in Figure 1.Anode and YSZ base substrate have shunk 20.4% and 19.6% respectively at 1000～1400 ℃, and the linear shrinkage amount of the two is basic identical, illustrate that the present invention is fruitful.As a comparison, Fig. 2 has provided the sintering curre of anode 1, anode 2 base substrates and ionogen base substrate, and wherein anode 1 is for only adding 25% flour NiO-YSZ anode, and anode 2 is for only adding the NiO-YSZ anode of 20% carbon dust.Anode 1 and anode 2 base substrates have shunk 15.6% and 29.4% respectively at 1000～1400 ℃.Lacking 4% and many 9.8% than the YSZ ionogen respectively, is unmatched with electrolytical contraction all.
Embodiment six: adopt the anode support of embodiment four preparations, prepare the YSZ film of the about 10 μ m of a bed thickness with the slurry for rotary coating method in the above.With La 0.7Sr 0.3MnO 3(LSM) cathode coverage is on the YSZ film, and 1100 ℃ of sintering 2 hours; Then with Sm 0.2Ce 0.8(NO 3) xSolution impregnation 850 ℃ of sintering 1 hour, repeats twice to the LSM negative electrode.Packaged battery is tested monocell with four electrode method.Measure the I-V rational curve of monocell with SI 1287 electrochemical interfaces of Britain Solartron company production.The dry hydrogen of the logical 200mL/min of anode, negative electrode is in the immobilized ambient air, and the monocell test result is as shown in Figure 3.Open circuit voltage (OCV) during 800 ℃ on battery is 1.08V, illustrates that electrolytic thin-membrane is very fine and close, illustrates that also the improvement of anode and electrolytical co-sintering matching optimized the performance of film.The maximum power output density that monocell is 800 ℃ is respectively 1120mW/cm 2, reached a higher output performance at middle warm area.Tangible concentration polarization phenomenon does not appear in discharge curve near short-circuit current, illustrate that the anodic porosity is rational.This result shows that generally the adding of composite pore-forming agent is mated the co-sintering of anode-electrolytic thin-membrane more, and the anodic porosity is also unaffected simultaneously, and the output performance of battery is also secure.
Embodiment seven: what present embodiment and embodiment four were different is, the YSZ (TZ-8YS) that the ionogen powder of step 1 adopts Japanese Tosoh company to produce.
Embodiment eight: what present embodiment and embodiment four were different is that the ionogen powder of step 1 adopts 8mol%Y 2O 3Stable ZrO 2(YSZ), by glycine-nitrate process preparation, and at 600～1000 ℃ of sintering 2h.
Embodiment nine: what present embodiment and embodiment three were different is:
The NiO powder of step 1 adopts precipitator method preparation, and the ionogen powder adopts 10mol%Sm 2O 3Adulterated CeO 2(Sm 0.2Ce 0.8O 1.9, SDC), adopt glycine-nitrate process preparation; The mass ratio of NiO and SDC is 65: 35.
The organic pore-forming agents that step 2 adopts is a flour, and carbon simple substance is activated carbon powder, and the mass ratio of the two is 20: 5.
The mass ratio of initial powder of the anode of step 3 and composite pore-forming agent is 100: 25.
Step 4, final anode powder depress to the disk of 13mm at the pressure of 200MPa, and the thick about 0.7mm of disk 1000 ℃ of sintering 2 hours, makes the NiO-SDC anode support.
Embodiment ten: what present embodiment and embodiment three were different is, the organic pore-forming agents that step 2 adopts is a W-Gum, and carbon simple substance is Graphite Powder 99, and the mass ratio of the two is 30: 10.
Embodiment 11: what present embodiment and embodiment three were different is, the organic pore-forming agents that step 2 adopts is a flour, and carbon simple substance is activated carbon powder, and the mass ratio of the two is 50: 15.

Claims (9)

1, a kind of composite pore-forming agent is characterized in that described pore-forming material is that 0.5～50: 0～30 mixed forms by organism pore-forming material and carbon simple substance pore-forming material according to mass ratio.
2, composite pore-forming agent according to claim 1 is characterized in that described organism pore-forming material is the powder that grain class crop makes.
3, composite pore-forming agent according to claim 1 and 2 is characterized in that described organism pore-forming material is flour, W-Gum, potato powder, tapioca flour or Semen Maydis powder.
4, composite pore-forming agent according to claim 1 is characterized in that described carbon simple substance pore-forming material is a carbon dust.
5,, it is characterized in that described carbon simple substance pore-forming material is activated carbon powder or Graphite Powder 99 according to claim 1 or 4 described composite pore-forming agents.
6, a kind of method of utilizing the described composite pore-forming agent of claim 1 to prepare anode support is characterized in that described method is:
One, the mixing of the initial powder of anode: with NiO, ionogen powder uniform mixing, wherein NiO accounts for 20～90% of the initial powder total mass of anode;
Two, the mixing of pore-forming material: with organism pore-forming material and carbon simple substance pore-forming material according to the described proportioning uniform mixing of claim 1;
Three, blending final anode powder: with the initial powder of anode and pore-forming material according to 100: the quality of (0.5～50) compares uniform mixing;
Four, the preparation of anode support: final anode powder is pressed into thick 0.05～3 millimeter anode base substrate, and 700～1500 ℃ of sintering 1～10 hour.
7, the method for utilizing composite pore-forming agent to prepare anode support according to claim 6 is characterized in that described organism pore-forming material is flour, W-Gum, potato powder, tapioca flour or Semen Maydis powder.
8, the method for utilizing composite pore-forming agent to prepare anode support according to claim 6 is characterized in that described carbon simple substance is carbon dust, activated carbon powder or Graphite Powder 99.
9, the method for utilizing composite pore-forming agent to prepare anode support according to claim 6 is characterized in that described ionogen is stable zirconium oxide base electrolyte material or doping of cerium oxide base electrolyte material.
CNB2006100102532A 2006-07-05 2006-07-05 Composite pore-forming agent and method of preparing anode supporting body using the same Expired - Fee Related CN100419012C (en)

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CN103474670A (en) * 2012-06-08 2013-12-25 中国科学技术大学 High efficiency and low cost carbon deposition resistance anode and preparation method thereof

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CN109216740A (en) * 2017-07-07 2019-01-15 中国科学院宁波材料技术与工程研究所 A kind of anode support and preparation method thereof of hollow symmetrical SOFC battery

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US6719946B2 (en) * 2001-12-20 2004-04-13 Fuelcell Energy, Inc. Anode support for carbonate fuel cells
CN1279643C (en) * 2004-12-22 2006-10-11 哈尔滨工业大学 Method for preparing anode-support type yttrium oxide stable zirconium oxide electrolyte membrane
CN1747211A (en) * 2005-09-14 2006-03-15 哈尔滨工业大学 Production of mesh printing with yttria and stabilized zirconia electrolytic thin-membrane
CN100355137C (en) * 2005-10-11 2007-12-12 哈尔滨工业大学 Filtering coating preparing method of solid oxide electrolytic film

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CN103474670A (en) * 2012-06-08 2013-12-25 中国科学技术大学 High efficiency and low cost carbon deposition resistance anode and preparation method thereof
CN103474670B (en) * 2012-06-08 2015-11-18 中国科学技术大学 Anti-carbon anode of a kind of efficient, low cost and preparation method thereof

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