CN1960048A - Structure of low temperature solid oxide fuel cell supported by porous metal - Google Patents
Structure of low temperature solid oxide fuel cell supported by porous metal Download PDFInfo
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- CN1960048A CN1960048A CNA2006101186658A CN200610118665A CN1960048A CN 1960048 A CN1960048 A CN 1960048A CN A2006101186658 A CNA2006101186658 A CN A2006101186658A CN 200610118665 A CN200610118665 A CN 200610118665A CN 1960048 A CN1960048 A CN 1960048A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
一种燃料电池技术领域的多孔金属支撑的低温固体氧化物燃料电池的结构，包括：多孔阳极薄膜、致密固体电解质薄膜、反应阻挡层、阴极活化层、阴极接触层，多孔不锈钢支撑体、重整催化剂，多孔阳极薄膜、致密固体电解质、反应阻挡层、阴极活化层、阴极接触层由下而上依次紧密连接，构成固体氧化物燃料电池的单体电池，载有重整催化剂的多孔不锈钢支撑体置于多孔阳极薄膜的下侧。本发明增加了电池结构的稳定性，提高了阳极的电催化性能；提高了整个电池温度的热均匀性，进而提高电池的性能和寿命；整个系统结构更加紧凑，效率更高。这对于解决固体氧化物燃料电池在发电系统应用方面面临的关键问题具有非常重要的意义。
A structure of a porous metal-supported low-temperature solid oxide fuel cell in the field of fuel cell technology, comprising: a porous anode film, a dense solid electrolyte film, a reaction barrier layer, a cathode activation layer, a cathode contact layer, a porous stainless steel support, and a reforming Catalyst, porous anode film, dense solid electrolyte, reaction barrier layer, cathode activation layer, and cathode contact layer are closely connected from bottom to top to form a single cell of a solid oxide fuel cell, and a porous stainless steel support carrying a reforming catalyst placed on the underside of the porous anode membrane. The invention increases the stability of the battery structure, improves the electrocatalytic performance of the anode, improves the thermal uniformity of the temperature of the whole battery, and further improves the performance and service life of the battery; the structure of the whole system is more compact and the efficiency is higher. This is of great significance for solving the key problems faced by solid oxide fuel cells in the application of power generation systems.
Description
Technical field
What the present invention relates to is the battery in a kind of fuel cell technology field, specifically is a kind of structure of low-temperature solid oxide fuel cell of porous metals support.
Background technology
The major obstacle that Solid Oxide Fuel Cell enters commercialized development is battery pile lifetime of system and system price, and the Solid Oxide Fuel Cell working temperature is the key factor of this two aspect of decision.In the world many at present research and development units develop actively intermediate temperature solid oxide fuel cell is about to 950 ℃ of conventional left and right sides working temperatures and is reduced to 700-800 ℃.Wherein, (YSZ: yttrium stable zirconium oxide) the anode-supported intermediate temperature solid oxide fuel cell has obtained paying attention to widely Ni-YSZ in recent years in the world, its working temperature is 700-800 ℃, the also existing report of good stack performance, the part unit of research and development has possessed fairly large production capacity, but the problem relevant with thick anode support also needs to be resolved.The porous anode supporter is lower mechanical strength, is difficult to resist heat and mechanical stress.In addition, in redox cycle, metallic nickel in the porous anode supporter is oxidized to NiO, then NiO is reduced into metallic nickel, porous anode supporter experience change in volume, thereby easily cause the electrolyte cracking, therefore cause supply of fuel to interrupt easily causing, cause the Solid Oxide Fuel Cell of Ni-YSZ anode-supported to be damaged because of air enters the anode chamber if system breaks down.Simultaneously, in this humidity province, the oxide etch problem of metal connector is also comparatively serious.
Find through literature search prior art, by the disclosed patent WO2005122300 title of World Intellectual Property Organization's international office is " Solid Oxide Fuel Cell " (Solid Oxide Fuel Cell), this patent has proposed to replace with metal support the method for Ni-YSZ anode support, think the employing metal support, can strengthen the mechanical strength of supporter, guarantee the redox stability of supporter simultaneously.The method that this patent has proposed the gradient metal ceramic structure and flooded porous anode with metallic compound, avoided the problem that adopts metal support to cause effectively, promptly in the high-temperature sintering process of preparation electrode, metal in the anode can be diffused in the metal support, causes the change of metallic support bulk structure.But, in this patent, only rely on the very thin active anode of one deck (thickness is 10 μ m), should participate in the electrochemical reaction of anode, carry out the reaction of cracking hydrocarbon again, influence the electrochemical reaction performance of battery possibly, also can cause carbon to deposit simultaneously, thereby influence the life-span of battery at anode surface.
Summary of the invention
The present invention is directed to the weak point of above-mentioned technology, proposed a kind of structure of low-temperature solid oxide fuel cell of porous metals support.The present invention adopts porous stainless steel as supporter, and in the loose structure of this supporter, add can the various fuel gas of catalytic reforming catalyst, reforming catalyst with to carry out the anode electrochemical catalyst for reaction placed apart, particularly reforming catalyst is placed on the interior reformation of carrying out fuel in the porous stainless steel supporter, can improve the ability of fuel treatment, the structure of simplified system, improve the performance of battery and extend the life of a cell, solving at present with electrolyte or anode is key issue, promptly high cost and low stability and the life-span that the Solid Oxide Fuel Cell of supporting body structure exists.
The present invention is achieved by the following technical solutions, the low-temperature solid oxide fuel cell that porous metals of the present invention support, with the general similar part of Solid Oxide Fuel Cell be that the critical piece of battery also is made up of anode, solid electrolyte and negative electrode.Characteristic of the present invention is that these parts have all been carried out the filming processing, and by the battery that thin film component is formed, energy density can be higher, more can tolerate the impact of heat.
Therefore, the present invention with the porous anode film as anode, with fine and close solid electrolyte film as solid electrolyte, negative electrode is made up of activation of cathode layer and cathode contact layer, simultaneously, between solid electrolyte and negative electrode, add one deck reaction barrier layers, influenced the life-span of battery to prevent highly active negative electrode and solid electrolyte from reacting.
The present invention from bottom to top stacks porous anode film, compact solid electrolytic thin-membrane, reaction barrier layers, activation of cathode layer and cathode contact layer in turn, when the negative electrode bubbling air, when anode feeds hydrogen, following reaction just takes place:
Negative electrode:
(1)
Anode:
(2)
In above-mentioned reaction equation, the oxygen of negative electrode is reduced to oxonium ion, is delivered to anode and hydrogen reacts through solid electrolyte (oxygen ion conductor), generates water, and the electronics that discharges through external circuit, is transferred to negative electrode.
The point of innovation of the present invention is the downside at anode, has increased the porous stainless steel supporter, in the hole of this porous stainless steel supporter, and impregnated catalyst, the effect of this catalyst is to reform or the various fuel gas of cracking and catalyzing.When cathode gas remains air, and anodic gas is when adopting natural gas, coal gas, methyl alcohol, alcohol, gasoline, diesel oil and biogas etc. to act as a fuel gas, anodic gas at first passes through the porous metals supporter, after being present in the catalyst reformation in the porous body, become the anodic gas that is rich in hydrogen and entered anode, and then above-mentioned electrochemical reaction takes place on negative electrode and anode and generated electricity.Reforming catalyst has relevant commodity selling for existing mature technology, can select according to concrete gas componant.
The present invention adopts the porous stainless steel supporter, can increase on the one hand the mechanical strength of supporter, has reduced the suffered stress of anode, has increased the stability of battery structure, allows anode also can do the processing of filming, has improved the electrocatalysis characteristic of anode; On the other hand, utilizing metal is the characteristic of the good conductor of heat, can improve the thermal uniformity of entire cell temperature, and then improves the performance and the life-span of battery; In addition, can reduce by an outer device of reforming in whole solid oxide fuel cell power generating system, various fuel gas can directly enter battery and generate electricity, and make the whole system structure compact more, and efficient is higher.This has very important significance in the key issue that the electricity generation system application facet faces for solving Solid Oxide Fuel Cell.
Description of drawings
Fig. 1 is a structural representation of the present invention
Among the figure: porous stainless steel supporter 1, reforming catalyst 2, porous anode film 3, compact solid electrolytic thin-membrane 4, reaction barrier layers 5, activation of cathode layer 6, cathode contact layer 7.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment has provided detailed execution mode being to implement under the prerequisite with the technical solution of the present invention, but that protection scope of the present invention is not limited to is following
Embodiment.
As shown in Figure 1, present embodiment comprises: porous stainless steel supporter 1, reforming catalyst 2, porous anode film 3, compact solid electrolytic thin-membrane 4, reaction barrier layers 5, activation of cathode layer 6, cathode contact layer 7.
The annexation of each parts is: in porous stainless steel supporter 1 the inside, dipping reforming catalyst 2, be used for different types of fuel, catalytic reforming becomes to be rich in the anodic gas of hydrogen, on porous stainless steel supporter 1, go up porous anode film 3 by spraying or silk screen print method deposition, then, compact solid electrolytic thin-membrane 4 on spraying or silk screen print method deposition on the porous anode film 3, then, depositing reaction barrier layers 5 by spraying or silk screen printing on the compact solid electrolytic thin-membrane 4, continue activation of cathode layer 6 in spraying or silk screen printing on the reaction barrier layers 5, at last, cathode contact layer 7 in spraying or silk screen printing on the activation of cathode layer 6.Like this, constituted the structure of the cell of the low-temperature solid oxide fuel cell that porous metals support.Repeat said structure, just constituted the electric pile structure of the low-temperature solid oxide fuel cell of porous metals supports.
Described porous stainless steel supporter 1, thickness are between the 0.5-1mm, and aperture 5-10 μ m between the voidage 50-70%, makes with The tape casting.In this porous stainless steel, optionally flood reforming catalyst 2, thereby make prepared battery have suitability of fuel widely, eliminated outer reformer, reduced the cost of system effectively, also realized the thermal uniformity of battery pile simultaneously because of the high-termal conductivity of porous stainless steel.
Described porous anode film 3, be deposited on the surface of porous stainless steel supporter 1 by spraying or silk screen print method with NiO-ScSZ or CGO powder, thickness is between 10-50 μ m, between the porosity 30-50%, the aperture is 1-3 μ m, the NiO in-situ reducing becomes Ni under battery operated condition, and metal Ni provides electronic conductor for electrode on the one hand, is the eelctro-catalyst of anode of solid oxide fuel cell on the other hand.
Described compact solid electrolytic thin-membrane 4 is made up of ScSZ (scandium doped zirconia) powder, is deposited on porous anode film 3 surfaces by spraying or silk screen printing, and thickness is between 10-30 μ m, and ScSZ is good oxygen ion conductor.
Described reaction barrier layers 5, form by CGO (gadolinium doped cerium oxide) powder, be deposited on compact solid electrolytic thin-membrane 4 surfaces by spraying or silk screen printing, thickness is between 5-10 μ m, CGO is good oxygen ion conductor, simultaneously can stop that high performance cathodes and ScSZ electrolyte react, thereby improve the life-span of battery.
Described activation of cathode layer 6, thickness are between 5-20 μ m, and this activation of cathode layer 6 is by the LSFC (La of 50% (percentage by weight)
0.58Sr
0.4Fe
0.8Co
0.2O
3-δ) and the mixture of the CGO of 50% (percentage by weight) form.
Described cathode contact layer 7 is thickness single-phase LSFC layers about 50 μ m.
Claims (8)
1, the structure of the low-temperature solid oxide fuel cell that a kind of porous metals support, comprise: the porous anode film, the compact solid electrolytic thin-membrane, reaction barrier layers, the activation of cathode layer, cathode contact layer, it is characterized in that, also comprise: the porous stainless steel supporter, reforming catalyst, the porous anode film, the compact solid electrolyte, reaction barrier layers, the activation of cathode layer, cathode contact layer from bottom to top closely connects successively, constitute the cell of Solid Oxide Fuel Cell, the porous stainless steel supporter that is loaded with reforming catalyst places the downside of porous anode film.
2, the structure of the low-temperature solid oxide fuel cell of porous metals support according to claim 1 is characterized in that described porous stainless steel supporter, thickness are between the 0.5-1mm, and aperture 5-10 μ m is between the voidage 50-70%.
3, the structure of the low-temperature solid oxide fuel cell of porous metals support according to claim 1 is characterized in that described porous anode film, thickness are between 10-50 μ m, and between the porosity 30-50%, the aperture is 1-3 μ m.
4, the structure of the low-temperature solid oxide fuel cell of porous metals support according to claim 1 is characterized in that, described compact solid electrolytic thin-membrane, and thickness is between 10-30 μ m.
5, the structure of the low-temperature solid oxide fuel cell of porous metals support according to claim 1 is characterized in that, described reaction barrier layers, and thickness is between 5-10 μ m.
6, the structure of the low-temperature solid oxide fuel cell of porous metals support according to claim 1 is characterized in that, described activation of cathode layer, and thickness is between 5-20 μ m.
7, the structure of the low-temperature solid oxide fuel cell of porous metals support according to claim 1 is characterized in that described at cathode contact layer, thickness is 50 μ m.
8, the structure of the low-temperature solid oxide fuel cell of porous metals support according to claim 1 is characterized in that described reforming catalyst is the reforming catalyst of natural gas, coal gas, methyl alcohol, alcohol, gasoline, diesel oil and biogas.
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| CNA2006101186658A CN1960048A (en) | 2006-11-23 | 2006-11-23 | Structure of low temperature solid oxide fuel cell supported by porous metal |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101304093B (en) * | 2007-05-11 | 2010-12-01 | 中国科学院大连化学物理研究所 | A low-temperature solid oxide fuel cell three-in-one component MEA and its preparation |
| CN102437358A (en) * | 2011-11-30 | 2012-05-02 | 中国科学技术大学 | Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof |
| CN102460793A (en) * | 2009-05-11 | 2012-05-16 | 法国原子能及替代能源委员会 | Cells for High Temperature Fuel Cells with Internal Hydrocarbon Reforming |
| CN104157893A (en) * | 2013-05-13 | 2014-11-19 | 中国科学院大连化学物理研究所 | Low temperature solid oxide fuel cell supported by porous metal and preparation method thereof |
| CN104638277A (en) * | 2015-01-30 | 2015-05-20 | 陕西煤业化工技术研究院有限责任公司 | Gradient functional anode electrode for carbon-based solid oxide fuel battery and preparation method of gradient functional anode electrode |
| TWI634696B (en) * | 2013-05-21 | 2018-09-01 | 攀時組成物質有限公司 | Multi-layered layer arrangement for a solid electrolyte |
| CN109755616A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院宁波材料技术与工程研究所 | Hollow symmetrical structure double cathode solid state fuel cell with internal reforming characteristics and preparation method thereof |
| CN114023979A (en) * | 2021-10-29 | 2022-02-08 | 华中科技大学 | Metal support solid oxide fuel cell and preparation method thereof |
-
2006
- 2006-11-23 CN CNA2006101186658A patent/CN1960048A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101304093B (en) * | 2007-05-11 | 2010-12-01 | 中国科学院大连化学物理研究所 | A low-temperature solid oxide fuel cell three-in-one component MEA and its preparation |
| CN102460793A (en) * | 2009-05-11 | 2012-05-16 | 法国原子能及替代能源委员会 | Cells for High Temperature Fuel Cells with Internal Hydrocarbon Reforming |
| CN102437358A (en) * | 2011-11-30 | 2012-05-02 | 中国科学技术大学 | Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof |
| CN102437358B (en) * | 2011-11-30 | 2013-12-11 | 中国科学技术大学 | Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof |
| CN104157893B (en) * | 2013-05-13 | 2016-12-28 | 中国科学院大连化学物理研究所 | Low-temperature solid oxide fuel cell that a kind of porous metals support and preparation method thereof |
| CN104157893A (en) * | 2013-05-13 | 2014-11-19 | 中国科学院大连化学物理研究所 | Low temperature solid oxide fuel cell supported by porous metal and preparation method thereof |
| TWI634696B (en) * | 2013-05-21 | 2018-09-01 | 攀時組成物質有限公司 | Multi-layered layer arrangement for a solid electrolyte |
| US10312540B2 (en) | 2013-05-21 | 2019-06-04 | Plansee Composite Materials Gmbh | Multi-layered layer arrangement for a solid electrolyte |
| CN104638277A (en) * | 2015-01-30 | 2015-05-20 | 陕西煤业化工技术研究院有限责任公司 | Gradient functional anode electrode for carbon-based solid oxide fuel battery and preparation method of gradient functional anode electrode |
| CN104638277B (en) * | 2015-01-30 | 2017-03-22 | 陕西煤业化工技术研究院有限责任公司 | Gradient functional anode electrode for carbon-based solid oxide fuel battery and preparation method of gradient functional anode electrode |
| CN109755616A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院宁波材料技术与工程研究所 | Hollow symmetrical structure double cathode solid state fuel cell with internal reforming characteristics and preparation method thereof |
| CN109755616B (en) * | 2017-11-08 | 2022-05-13 | 中国科学院宁波材料技术与工程研究所 | Hollow symmetrical structure double-cathode solid fuel cell with internal reforming characteristic and preparation method thereof |
| CN114023979A (en) * | 2021-10-29 | 2022-02-08 | 华中科技大学 | Metal support solid oxide fuel cell and preparation method thereof |
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