TWI409982B - Interconnector of solid oxide fuel cell - Google Patents

Abstract

An interconnector of a solid oxide fuel cell is provided. The device includes a gas distributor which has a curved delivery to deliver a fuel and air (the oxidant), and the gas distributor is a glass module. A current collector mounted on the gas distributor is used to collect a current produced by the cell at intermediate operation temperatures (500-650 DEG C ).

Description

Solid oxide fuel cell connector

The invention relates to a connector of a solid oxide fuel cell (SOFC), in particular to a connector of a solid oxide fuel cell of a glass template having a curved flow channel.

Since hydrogen fuel can be used in fuel cells, it is recognized as the most important new energy technology in this century due to its high efficiency, low pollution, no noise, no need for charging, and no mechanical motor rotating parts. Hydrogen energy is used. The long-term planning goal of international energy use in the future, the production cost of hydrogen and other hydrogen-containing small molecule fuels is very competitive, and the purification of hydrogen-related bio-gas and coal syngas, The storage and energy conversion technologies have been researched and developed [DOE report, US, 2000/10]. The above-mentioned gas phase fuels are highly valued as energy carriers.

Since high-temperature power generation components can directly use liquid fuels, such as solid-state fuel cells (SOFC), alcohol is used, and compared to Proton Exchange Membrane (PEM) or Direct-methanol fuel cells (DMFC). % conversion efficiency, SOFC energy efficiency is 45%, and the energy output per unit area can be as high as 1.8W/cm ² . [Kim et al., US 6,228,521, 2001]. The high-temperature power generation component, such as a solid oxide fuel cell stack (SOFC stack), includes (1) an electrode, a solid electrolyte, called a power generating component, and (2) a gas flow conduit between the components, which can provide fuel and oxygen required for the reaction. An anode or cathode that needs to be distributed to the power generating component; and (3) a current collector that has a conductive line for directing current.

The SOFC type is divided into tubular (Tubular) and flat (Planar) [Minh, 1993], tubular ceramic parts generally use extrusion technology, the smallest anode tube (or zirconia tube) has a diameter as small as 0.8mm, The wall thickness can be less than 0.2 mm [Susuki, 2007]. Most of the flat ceramic substrates are formed by a tape casting method to produce a sheet electrolyte or an electrode. Further, the sandwich structure of the electrode and the electrolyte is mass-produced by a tape calendaring method [Schroeder and Anderson, US 4,957,673]. As for the three-layer or multi-layer structure, the above electrolyte ceramics can be fabricated using various physical or chemical methods including screen printing, spin coating, die-pressing, and sintering. Films and blocks [Mitterdorfer et al., 2000]. Recently, in response to the volumetric efficiency requirements of batteries, the application of vapor chemical deposition technology in the production of thin film electrolyte layers has received increasing attention, but due to the high cost, there has been no significant use.

Taking a solid electrolyte fuel cell as an example, in order to smoothly perform the function of electric energy conversion, the following components are required:

(1) An electrochemical converter consisting of a solid electrolyte and a cathode of yin and yang. This device is simplified to a tubular or flat shape for the purpose of manufacturing. In the current electrolyte material, yttrium-doped zirconia (Yttria-stabilized) ZrO ₂ , YSZ) is the most mature in development, and currently the electrolyte based on cerium oxide (CeO ₂ ) is the best choice;

(2) Evaporation device and recombiner for gaseous fuel, which can smoothly evaporate the fuel and then convert it into small molecules, such as methane or hydrogen, usually attached to the front end of the stack of the battery, and must be heated at 400-500 °C. Catalytic, which can be converted using the heat generated by the operation of the fuel cell;

(3) The sensor can be used to detect the temperature, current, and oxygen partial pressure of the battery, and generally output as a voltage;

(4) Thermal control devices such as insulation, coolers and ventilation systems;

(5) The battery or battery stack housing is expected to operate at near room temperature; therefore, commercial metal alloys, such as stainless steel 304, are used to reduce manufacturing costs.

Recently, regarding the operating temperature of the medium temperature SOFC, the TOTO release message [ http://nikkeibp.co.jp ] has dropped to between 500 °C. In the past, Yang Zhizhong's paper [Yang et al., 2003] used thin film technology to make an ultrathin (about 1 μm) electrolyte layer, which is expected to be operated at 600 °C.

A gas and fuel delivery conduit (or gas distributor) is required between the aforementioned components, and a current is collected, which is called an interconnector. The connector has a joint to connect a power generating component, and the gas delivery conduit of the connector can also be used on the surface of the electrolyte. For example, Badding et al. (US 7,531,261 B2, 2009) proposes to use gear imprinting to manufacture Specially textured electrolyte membrane that provides the function of a gas flow path. A similar U.S. Patent No. 7,550,221,2009 teaches the use of ceramic extrusion to produce a zirconia electrolyte substrate having a gas delivery array that can be used to conduct gas.

In addition to good electrical conductivity, the material used in the connector must also match the coefficient of thermal expansion (CTE) of the oxide electrolyte. The smaller the difference between the two, the thermal stress generated during heating and cooling. It will be the smallest. In the past, U.S. Patent No. 4,476,196 discloses the use of high conductivity lanthanum chromite (LaCrO ₃ ) as a material. If a small amount of strontium (Sr) or calcium (Ca) is substituted for strontium, the conductivity of the tyrosine will be greatly improved. [Tanasescu et al., 2005], but strontium chromate oxides need to be sintered at higher temperatures (>1400 °C) [Rivas-Vazquez et al., 2006], and the chromium oxide component will gradually become in use. Gasification, the connector's conductivity gradually deteriorates, causing battery failure.

The connector can also be made of metal alloy. Due to the demand of CTE, only a few very expensive iron-chromium alloys, such as Crofer 22 alloy, can have similar CTE properties to zirconia electrolytes at operating temperatures of 500-1000 °C. Excellent oxidation resistance, which can be used to deliver gaseous reactants. Similar alloys, such as the Ni-Cr alloy disclosed in U.S. Patent No. 6,054,231, or a Co-based alloy, or a chromium-based alloy (94 wt% Cr-5) as taught in U.S. Patent No. 6,280,868. %Fe-1%Y ₂ O ₃ ), although these alloys have acceptable oxidation resistance and suitable CTE values, they are still not widely available because they contain a large amount of cobalt or nickel.

The fuel cell single cell produces a voltage of about 1.0 volts. When the current is generated, the voltage gradually drops to 0.5-0.7 volts. The current output is proportional to the reaction area, and the current density is about 0.5-1.8 W/cm ² . The current produced by the battery needs to be collected, which is derived from metal wires (made of precious metals) or oxides with good electronic conductivity. Connectors used in the past have been made of metal, metal alloys, strontium chromate-based ceramics, or bismuth cobaltate-based ceramics, such as Cable et al. (US 6,949, 307, 2005), which utilizes a flat structure, multi-layer stacking. The way to make a joint plate module with a gas flow path reveals how to create a flow path by punching. However, the choice of conductive material is limited to nickel, chromium, conductive ceramics and ceramic-metal complex. material. Limited to processing technology or material costs, connectors in the past were a very challenging project in high temperature fuel cell stack manufacturing technology.

Therefore, how to improve the temperature required for the chromic acid strontium material of the connector to be high in sintering density, the gradual gasification of the chromium oxide component during use, and the deterioration of the electrical conductivity of the connector are gradually tested by the inventors, and tested and tested. After the research, the connector of a solid oxide fuel cell was finally obtained. In addition to effectively solving the disadvantages of high temperature, vaporization of components and deterioration of conductivity, it was also able to obtain the effect of not changing the coefficient of thermal expansion of the crystal. That is, the problem to be solved by the present invention is how to overcome the problems of high temperature, composition gasification, conductivity deterioration and too simple flow path of the gas distributor, so that the gas distributor can have a lower temperature. , the composition and conductivity are more stable, easy to shape and shape, and how to overcome the problem that the second and third glass sheets need to be connected to each other, and how to overcome the laminated glass flakes by polymer burning and There are still problems with pores after high temperature sintering.

The present invention is a solid oxide fuel cell connector comprising a gas distributor having a curved flow path for delivering a fuel, and the gas distributor is a glass module and a current A collector is disposed on the gas distributor for collecting a current generated by the operation of the battery at a medium temperature (500-650 ° C) for output.

Preferably, the curved flow path of the connector is a conveying pipe for conveying a gas and deriving one of the exhaust gas after the reaction of the fuel, the gas is used for burning the fuel, and the connector has a more a joint for connecting a power generating component, and the material of the glass template comprises cerium oxide, boron oxide, cerium oxide and aluminum oxide, and the glass stencil is used for external connection of a medium temperature solid oxide fuel cell, and the current collecting device There is a conductive line, the material of the conductive line is silver, copper, nickel or aluminum, and the conductive line uses a screen printing method or an inkjet printing method to make a line image, the screen printing method uses silver, copper, nickel or a paste of aluminum, the inkjet printing method uses a dispersion of silver, copper, nickel or aluminum, the glass template comprises a first glass sheet, and the glass template further comprises a second, a third and a fourth a glass sheet and lamination of the first, second, third and fourth glass sheets.

Preferably, the second glass sheet of the connector has a left flow channel, the third glass sheet has a rear flow passage, and the left end of the left flow passage communicates with one of the backward flow passages. The end portion, and the glass template has a cerium oxide content of 26 to 46 mol%, a boron oxide content of 19 to 23 mol%, a cerium oxide content of 30 to 47 mol%, and an alumina of 0.5 to 6 mol%. content.

Of course, the second glass sheet of the connector may have an upper semicircular flow path, the third glass sheet having a lower semicircular flow path, and the upper semicircular flow path and the lower semicircular flow The channel is a semi-circular flow channel. The glass template is a first type glass. The first type glass has a cerium oxide content of 46±1 mol%, a cerium oxide content of 27±1.0 mol%, and a temperature of 20±1.0. % of boron oxide and 5 ± 1.0 mole % of alumina, and the glass template has more than 1 mol% of calcium oxide, cerium oxide, zirconium oxide, titanium oxide, magnesium oxide, rare earth oxide or oxidation yttrium.

Of course, the second glass sheet of the connector may have an upper "Γ" shaped flow path, the third glass sheet having a lower "Γ" shaped flow path, and the upper "Γ" shaped flow path and the lower " The Γ"-shaped flow channel synthesizes a "Γ"-shaped flow channel, and the glass template is a second type glass, and the second type glass has a yttrium oxide content of 32±1 mol%, 45±1.0 mol% The cerium oxide content, the boron oxide content of 22±1.0 mol%, and the alumina content of 1.5±1.0 mol%.

Preferably, the conductive line of the connector is a printed conductive circuit, the solid oxide fuel cell is a first battery component, and the first battery component is a cerium oxide or zirconia-based solid electrolyte fuel cell. And a first gap between the first battery component and a second battery component, the glass template further encapsulating the first gap by using a glass paste or cutting a glass foil, and the material of the glass paste comprises oxidation Antimony, boron oxide, antimony oxide, aluminum oxide, and process chemical additives. The glass paste has a cerium oxide content of 46±1 mol%, a cerium oxide content of 27±1.0 mol%, and an oxidation of 20±1.0 mol%. The boron content has an alumina content of 5 ± 1.0 mol%, and the glass paste has calcium oxide, cerium oxide, zirconium oxide, titanium oxide, magnesium oxide, rare earth oxide or cerium oxide.

Preferably, the first glass sheet of the connector is made by mixing a process aid with a glass frit, and using a ceramic forming method, the conveying pipe is a tiny gas pipe, the first, the second, the The third and the fourth glass flakes are further subjected to an intermediate temperature binder burning and a high temperature heat treatment to sinter the uniform dense template, the ceramic forming method comprising a doctor forming method, a dry pressing forming method and an extrusion forming method. The conveying pipe is located on the surface of one of the second glass sheets, and the ceramic forming method is used to form a flat sheet or to make the conveying pipe.

Of course, the connector may further comprise: modulating a glass frit into a glass paste, forming the glass paste into a glass sheet for packaging, and then cutting the glass sheet for packaging to form a package sheet. Between the power generating component and the glass template, there is a bonding surface or a second gap, and the glass template uses a coating or a screen printing method to evenly distribute a glass paste on the bonding surface, and in the second gap. Filling the glass paste or bonding the package sheet, and sintering the glass paste for a long time at a high temperature melting temperature, or burning off the polymer of the package sheet, and then melting the package sheet above the high temperature softening temperature, and then melting the package sheet. Wetting the second gap, controlling the cooling rate of the package sheet, to complete encapsulation of the power generating component, the material of the glass powder comprises cerium oxide, boron oxide, cerium oxide and aluminum oxide, and the average particle diameter of the glass powder is 0.5~ Between 3.0 microns, the high temperature melting temperature is between 900 and 1050 ° C, sufficient to produce a wetting effect, and the package sheet has a wetting angle of less than 20°.

Still in accordance with a primary technical point of view, the present invention can encompass a solid oxide fuel cell stack comprising a power generating component, a gas distributor having a curved flow path for delivering a fuel and the gas The dispenser is a glass template, and a current collector is mounted on the gas distributor for collecting a current generated by the oxidation of the fuel for output.

If viewed from another possible point of view, the present invention is an internal connector that includes a gas distributor having a plurality of sets of curved flow passages for conveying a fuel and air or oxidizing Gas, and the gas distributor is a glass template.

The invention is illustrated by the above concept, that is, the connector of the solid oxide fuel cell used can be seen, and the glass template can be used to fabricate the connector, and the fuel is transported in the designed curved flow channel and has the application. The left flow path of the second glass sheet is in communication with the backward flow path of the third glass sheet. The invention will be more apparent from the following detailed description and drawings.

The present invention relates to a pipeline and a circuit for a SOFC power generation component operating at a normal temperature or higher, a fuel required for a power generation component, an oxygen-containing gas, and an output component current, etc., using a high-temperature glass template having appropriate properties, Designed conduits (also known as tunnels or runners) and current lines that connect more than one component to connect a series of templates for the transfer (transmission) of fuel, gas, and current between a single cell.

The present invention discloses a glass template for gas, fuel and current communication flow for a medium temperature (500-650 ° C) power generation component, with a gas pipeline (road) design, and a circuit design feature with a current collecting function. The present invention also discloses the process of the template, which is formed by thin layer forming method, and the gas pipeline can be composed of multiple layers of glass sheets, each of which has designed holes, runners and inlets and exits; or glass sheets and dry pressed glass. The components of the stencil are joined to form a multi-layered pipe structure; the metal wires are fabricated in the stencil or on the stencil surface, so that the stencil has a current line design. The stencil material is made of glass or glass ceramic with a gas passage as small as ten microns.

Referring to the first figure, a solid oxide fuel cell connector 10 is shown comprising a gas distributor 11 having a curved flow path 12 for delivering a fuel and the gas distributor 11 being a glass. The template 11 and a current collector (not shown) are mounted on the gas distributor 11 for collecting a current generated by the oxidation of the fuel for output. The glass template 11 includes a first glass sheet 131, and the glass template 11 further includes a second, a third and a fourth glass sheet 132, 133, 134, and the first, second, third and fourth glass sheets 131, 132, 133, 134 are stacked.

Further, the second glass sheet 132 has a left flow path 14 having a rearward flow path 15 and a left end portion 16 of the left flow path 14 communicating with a rear end portion 17 of the rear flow path 15. The curved flow passage 12 is a conveying pipe 12, which is also a flow passage which is staggered by 90°. The conveying pipe 12 is for conveying a gas and deriving one of the exhaust gas after the reaction of the fuel, the gas is used for burning the fuel, and the connection is made. The device 10 further has an interface (not shown) for connecting a power generating component (not shown), and the material of the glass template 11 includes components such as yttrium oxide, boron oxide, yttrium oxide and aluminum oxide, and a small amount of other components. The composition of the oxide, the glass template 11 is used for external connection of a medium temperature solid oxide fuel cell, the current collector has a conductive line (ie, current line, not shown), the material of the conductive line is silver, a material of copper, nickel or aluminum, or an alloy thereof, which uses a screen printing method or an inkjet printing method to produce an image with a specific line connection, directs current, and enters and exits the power generating element, and the screen printing method uses silver. , copper, nickel or aluminum a specific metal paste, which is printed on a glass template, co-firing, or separately sintered, or other suitable heat treatment, such as infrared heating, to fix the metal circuit to the template. The ink jet printing method uses a dispersion of silver, copper, nickel or aluminum.

The glass template 11 has a cerium oxide content of 26 to 46 mol%, a boron oxide content of 19 to 23 mol%, a cerium oxide content of 30 to 47 mol%, and an alumina content of 0.5 to 6 mol%, and the others. The oxide content is below 1 mol%. Referring to the second figure, the second glass sheet 22 under the first glass sheet 21 has an upper semicircular flow path 25, and the third glass sheet 23 above the fourth glass sheet 24 has a lower semicircular flow path 26. The upper semicircular flow passage 25 and the lower semicircular flow passage 26 are combined into a semicircular flow passage 27, which is also a 180° turning flow passage, and the glass template can be a first type glass (Glass 1). The first type glass has a cerium oxide content of 46±1 mol%, a cerium oxide content of 27±1.0 mol%, a boron oxide content of 20±1.0 mol%, and an alumina content of 5±1.0 mol%, and the The glass template has 1 mol% or less of calcium oxide, cerium oxide, zirconium oxide, titanium oxide, magnesium oxide, rare earth oxide or cerium oxide, or a mixture thereof.

Referring to the third figure, the second glass sheet 32 under the first glass sheet 31 has an upper "Γ"-shaped flow path 35, and the third glass sheet 33 above the fourth glass sheet 34 has a "Γ"-shaped flow. The track 36 is also a 90° turning flow path, and the upper “Γ” shaped flow channel 35 and the lower “Γ” shaped flow channel 36 are combined into a “Γ” shaped flow channel 37, and the glass template can be changed to a second Glass (Glass 2), which has a cerium oxide content of 32 ± 1 mol%, a cerium oxide content of 45 ± 1.0 mol%, a boron oxide content of 22 ± 1.0 mol%, and a 1.5 ± 1.0 Mohr% alumina content.

The conductive circuit is a printed conductive circuit, the solid oxide fuel cell is a first battery component, and the first battery component is a cerium oxide or zirconia-based solid electrolyte fuel cell assembly, and the first battery There is a first gap (not shown) between the component and a second battery component to prevent gas leakage, and even if the temperature is maintained for a long time under high temperature, the function of sealing the airtight can be obtained, and the glass template utilizes a glass. Pasting or cutting a glass sheet to encapsulate the first gap, the material of the glass paste comprises cerium oxide, boron oxide, cerium oxide, aluminum oxide, a small amount of other oxide components and a process chemical auxiliary, the glass paste has 46± 1 Mohr% cerium oxide content, 27±1.0 mol% cerium oxide content, 20±1.0 mol% boron oxide content, and 5±1.0 mol% alumina content, the small amount of other oxide components are 1 Mohr% or less, which is selected from the group consisting of calcium oxide, cerium oxide, zirconium oxide, titanium oxide, magnesium oxide, rare earth oxide or cerium oxide, or a mixture thereof.

The first glass sheet 131 is produced by mixing a process aid with a glass frit, and using a ceramic forming method, the conveying pipe 12 is a small gas pipe, and the first, second, third and fourth glass sheets 131, 132, 133, 134 are stacked. After a medium temperature binder burnout and a high temperature heat treatment to sinter a uniform template, the ceramic forming method includes an industrial blade forming method, a dry pressing method and an extrusion forming method, or the like. With appropriate forming techniques, the delivery conduit 12 is located on one surface 18 of the second glass sheet 132 by which the planar forming sheet (e.g., the first and fourth glass sheets 131, 134) or a micro gas delivery conduit is fabricated. 12 (for example: conveying conduits 14, 15 of the second and third glass sheets 132, 133). After the green sheet 132 is sintered or sintered, a contact and a pipe 12 are formed by a cutting technique.

The bonding power generating component on the template 11 uses a sealing bonding material, and the packaging step includes selecting a glass material similar to a thermal expansion coefficient of the power generating component and the metal casing or the supporting component, and preparing a paste by using a compound such as a solvent or a binder. Forming, by coating, or screen printing, evenly distributing the glass paste on the bonding surface; or mixing a glass powder with a solvent and a polymer material to prepare a glass paste, and forming a thin film by a doctor blade method or a sheet forming method. Shape, then cut the sheet into the desired shape and fit it on the surface of the component.

The glass paste is also subjected to doctor blade forming to form a glass sheet for packaging, and then the glass sheet for packaging is formed to form a package sheet, wherein the power generating element and the glass template 11 have a joint surface or a A gap (not shown) adheres the power generation component to the template of the present case. When the present invention does not use the glass paste to prepare the glass powder into a paste (ie, a glass paste), the glass template 11 utilizes a coating or a screen printing method to evenly distribute the glass paste on the bonding surface. Filling in the glass paste or bonding the package sheet in the second gap, and sintering (or baking) the glass paste at a high temperature for a long time, or burning off the polymer of the package sheet (ie, passing through The polymer is fired, and then the package sheet is melted at the high temperature melting temperature, the second gap is wetted, and then the step of controlling the cooling rate of the package sheet is performed to complete the package of the power generating element and the gas line. Bonding, the power generating element is fixed, and the material type of the glass frit is selected from the group consisting of cerium oxide, boron oxide, cerium oxide and aluminum oxide, and a small amount of other oxides, and the power generating component can be fixed thereto by heat treatment. On the template having the inner tube, the average particle diameter of the glass powder is between 0.5 and 3.0 micrometers, and the high temperature melting temperature is 900 to 1050 ° C, which is sufficient to produce a wetting effect, and the package sheet has a thickness of less than 20°. Wet corner.

Still in accordance with a primary technical point of view, the present invention can encompass a solid oxide fuel cell stack including a power generating component, a gas distributor 11 having a curved flow path 12 for delivering a fuel, and The gas distributor 11 is a glass template 11, and a current collector is disposed on the gas distributor 11 for collecting a current generated by the oxidation of the fuel for output.

If viewed from another possible perspective, the present invention is an inner connector 10 that includes a gas distributor 11 having a curved flow passage 12 for delivering a fuel and a gas distributor. 11 is a glass template.

According to oxide glass, it is most commonly used for sealing high-temperature solid fuel cells. The composition and content range are summarized in Table 1 [Wei, 2008]. The main components are glass ceramics, although there are other materials or design choices. For example, mica is used [Chou et al., US 7,258,942 B2 (2007); US 7,222,406 (2007); Yang et al., US 6,843,406 B2 (2005); Meinhardt et al., US 6,532,769 B1 (2003) and US 6,430,966 B1 ( 2002)], or in a tight manner [US 7,217,300], can achieve the purpose of airtightness, but in the past patent literature, no glass material was used as a template for gas and current pipes (not used for glass molds). group). Such as:

1. Battelle Memorial Inst. US application for G18 glassware formulation uses a zirconia electrolyte fuel cell at a temperature of 800 ° C, which is different from the application temperature range of the present invention, and uses an electrolyte material.

1. Battelle Memorial Inst. US6, 532, 769, the scope of the glass ceramics includes mica mixed glass powder, packaged, the best component of the G18 (code) formula application temperature of 800 ° C zirconia electrolyte fuel cell, and the present invention The application temperature and material range are different.

2. The Corning patent contains an alkali metal oxide and is mixed with refractory zirconia powder or white garnet powder without the use of a bismuth-containing formulation. The formulation of this patent contains no alkali metal oxide components except for impurities.

3. The Hybrid power generation system patent uses Corning 4063 or 3130 glass powder mixed titanate ceramic powder, which is different from pure glass in this formulation.

4. The Allied signal patent is similar to the Corning patent, but is mixed with metal powder (Ni, Fe, etc), which is different from the conductive layer used in this patent.

5. The patent range of Ford Global Tech. LLC does not contain boron oxide, which is different from this patent.

6. The University of Chicago patent range contains 1-45% bismuth oxide. This program does not contain hydrazine or its compounds.

7. Alstom's patented range formulation does not contain boron oxide, which is different from this patent.

8. Sarnoff's patented formula contains 10-21% boron oxide and contains zinc oxide and calcium carbide, which is different from this patent.

Glass and glass ceramics have been used in many electronic components, and the technologies required for construction and manufacturing are being developed one after another, and the technology is relatively mature. The properties of glass in the amorphous phase show many manufacturing advantages. After high-temperature plastic forming, or after sintering, the glass ceramics can be partially crystallized by appropriate heat treatment, and the strength is usually increased, and the corrosion resistance is also greatly increased. The airtightness and partial glass properties of the material are still retained, and its glass transition temperature ( _Tg ), coefficient of thermal expansion (CTE), and electrical resistivity can be adjusted by changing the ratio of a small amount of oxide. Therefore, it has its advantages for various packaging applications.

If yttrium-doped zirconia (Y-CSZ) is used as the electrolyte material of the generator set, the properties required for the glass material used for the template are as follows: T _g temperature is lower than the temperature-holding operation temperature, and the medium temperature operation is low. At 650 ° C; CTE is equivalent to solid electrolyte, taking zirconia as an example, 10.5-11.5 x ^{10 6} ppm / ° C; in the operating temperature range, the resistivity is higher than 10 ⁵ ohm / cm.

In addition, other more detailed power-generating component encapsulation properties, such as gas leakage rates, can be seen in Fergus's recent review [Fergus, 2005], with a gas leak rate of approximately 10 ^-4 sccm cm ^-1 at an operating pressure of 20 kPa . [Chou et al., J. Power Sources, 170 395-400 (2007)]. If it is in a clamped package [Chou and Stevenson, J. Power Sources, 191 384-9 (2009)], test it at 800 ° C. The leak rate is best only 10 ² sccm cm ^-1 .

In the past reports in the literature and the glass systems found in academic journals, the commonly used raw materials are multi-component medium temperature glass systems formed by alkaline earth oxides (BaO, SrO, etc.) and boron oxide, which have appropriate adiabatic and electrical properties. Used in packaging applications for electronic components. The oxides covered by the patent are mainly cerium oxide, or low-temperature boron oxide or cerium oxide [Dyamant et al., 2005]; [Chen Duru, 2006 ], adding zinc oxide and alkaline earth oxides [Bloom and Ley, US 5, 453, 331 (1995); Tompson et al., US 6, 656, 625 B1 (2003); Lara et al., 2004]. If phosphoric acid is added to form a phosphate glass [Larsen, and James, 1998; Larsen et al., 1999; Bingham et al., 2006], the CTE value is much lower than that of zirconia, which is not appropriate. Other components of low temperature glass, such as boron oxide, sodium oxide and potassium oxide, contain a small portion.

In the past, the patented glass-ceramic materials used for encapsulating glass were mainly matched with zirconia-based electrolytes, and the temperatures used were as high as 800-1000 ° C. For other solid electrolyte materials, such as cerium oxide groups, cerium oxide groups, it has not been seen. In addition, various glass ceramic materials (Table 1) that are found in the patents are used for packaging and are not part of the battery structure.

The glass synthesized by the template material has a thermal expansion coefficient similar to that of zirconia-based or cerium oxide-based, and the long-term temperature holding at 650 ° C does not react with the solid electrolyte and the outer shell metal, and the glass phase is maintained for a long time. The characteristics of the amorphous phase are such that the thermal expansion coefficient is not changed by the formation of the crystal phase (crystallization), and the glass material is bonded between the template and the electrolyte using a package similar to the template.

The template has a current line inside, the section is as small as tens of micrometers wide, and the thickness is 0.3 micrometer. It is co-fired with the glass template to form a current line, and has an appropriate external outlet to output the current generated by the power generating element. There is no interface reaction between the metal circuit and the glass template for long-term use.

Example 1

The composition of the glass material is shown in Table 2, referred to as Glass 1 glass, and other material properties are listed in the table. The formulation of the scraper formula is shown in Table 3. The procedure for preparing the tempered glass flakes is as follows. Using pure water as a carrier, a CMC dispersant (Carboxymethyl cellulose sodium salt, Sigma-Aldrich Inc., USA), PVP (Poly-vinylpyrrolidone, Sigma-Aldrich Inc., USA) is first added. 5wt% of the binder, after mixing and dissolving, the powder (33 vol%) and the plasticizer glycerin were added, placed in a zirconia grinding ball, and ball-milled for 24 hours, and the prepared slurry was used for blade forming, and the forming speed was 2.0 cm/sec. By tap-casting, a sheet having a thickness of 10 μm to 250 μm can be produced. After drying, after 490 ° C, sintering for four hours, a flat, dense glass flake can be obtained.

Example 2

Another glass powder of higher temperature is used, referred to as Glass 2, and its properties are as shown in Table 3. According to the same process conditions as in the first embodiment, the scraped strip is dried, and cracks are generated, and the process conditions are modified (lifting binder) The content of PVP is up to 10% by weight while reducing the solid content of Glass 2 glass to 27 vol%), and a glass piece having a thickness of 80 μm can be obtained, and the blade is dried without cracking, and at the same time, has appropriate strength and flexibility. It is conducive to the subsequent processing application, that is, the glass ribbon after the blade is dried can withstand the shear stress received during cutting.

Example 3 Test Results of Matching Properties of Glass Material and Electrolyte, Anode, and Metal Alloy (Crofer 22)

G6 glass has a thermal expansion coefficient of 11.9x10 ^-6 /K, and is used as a SOFC electrolyte material for YSZ (Y ₂ O ₃ -doped ZrO ₂ ), SDC (Sm ₂ O ₃ -doped CeO ₂ ), and as a metal bipolar. Interface bonding test of Crofer 22 of sheet material. The experimental results show that at a package temperature higher than 970 ° C, the wettability of Glass 2 on the surface of either the electrolyte, the Crofer or the anode material (YSZ/NiO) is quite good. Even after 2000 hours of long-term testing at 650 ° C, the Glass 2 glass and any of the above materials did not show any significant interfacial reaction or elemental diffusion.

Example 4 multiple layers of glass and co-firing test

The glass sheet stacking and co-firing test methods are as follows: after drying, the glass ribbon can be cut and then placed in a "double-sided alignment hot press forming machine" (VC-10 tons, Lin Cheng Machinery Co., Taiwan) Stacking and forming a single glass structure; taking into account the integrity of the internal flow path, the temperature, pressure, and time of hot pressing must be adjusted to an appropriate value, such as 2 MPa at 50 ° C for 2 minutes. The hot-pressed glass template shall be sintered at 650~690 °C; the experimental results show that when the flow channel width is smaller, the sintering temperature is lower, and the holding time is shorter, the channel integrity will be better, otherwise the flow channel will be better. The top of the top will easily produce a small amount of creep and collapse due to its own weight.

In addition to blade forming in combination with high temperature sintering, other suitable methods of glass forming are listed below, and these forming techniques can be used to make the gas flow path required for the power generating component.

a. Hot extrusion forming: glass in the melting stage, using high-temperature extrusion die, graphite or tantalum carbide (SiC) material, to make a glass template with a cross-sectional shape from complex to simple shape;

b. inkjet film forming;

Sintering dimensional changes are quite large and control is difficult. Since the layered structure is slumped due to the weight of the self during the sintering, the sintering temperature and the sintering time should be minimized, so that the sintering deformation can be effectively prevented and the size of the channel can be maintained. For example, the second and third layers of the four layers have straight gas channels. The second layer has a straight channel, and the temperature is maintained at about 700 ° C for ten hours to maintain the channel straightness.

Example 5 Electrode coating and baking

The conductive electrode is coated with an inkjet printer (Mimatix, Materials Printer, DMP-2800 FUJIFILM, USA), using nano silver ink, the resolution of the best printing point is 41μm, the line resolution is 56μm, once The print thickness is approximately 0.30 μm. The nano silver wire is co-fired with glass, the sintering temperature is 700 ° C, and sintering can be sintered for one hour.

The two glass sheets of the previous examples were coated with silver glue (Ted Pella, Inc., CA, USA), dried, and co-fired at 690 ° C (Glass 1) or 700 ° C (Glass 2) for four hours. A two-point electrical measurement method is used to test the conductivity of a glass sheet or a glass template containing a silver layer. It can be seen from the data that the effect of silver conduction is maintained. Other metal materials that can be used, including copper, nickel, and aluminum, can be used as a conductive current for the exchange of silver.

In summary, the present invention can indeed deliver the fuel in a curved flow path of the design by using a glass template to fabricate the connector in a novel design, and the second glass sheet to be used is left. The flow path can achieve the effect of communicating with the backward flow path of the third glass sheet. Therefore, anyone who is familiar with this skill can be modified by all kinds of ideas, but they are not protected by the scope of the patent application.

10. . . (inner) connector for solid oxide fuel cells

11. . . Gas distributor / glass template

12. . . Curved runner/conveyor

131. . . First glass flake

132. . . Second glass flake

133. . . Third glass flake

134. . . Fourth glass flake

14. . . Left flow channel

15. . . Backward runner

16. . . Left end

17. . . Back end

18. . . surface

twenty one. . . First glass flake

twenty two. . . Second glass flake

twenty three. . . Third glass flake

twenty four. . . Fourth glass flake

25. . . Upper semicircular flow path

26. . . Lower semicircular flow path

27. . . Semicircular runner

31. . . First glass flake

32. . . Second glass flake

33. . . Third glass flake

34. . . Fourth glass flake

35. . . Upper "Γ" shaped runner

36. . . Lower "Γ" shaped runner

37. . . "Γ" shaped flow channel

First: is a perspective view of a preferred embodiment of a connector for a solid oxide fuel cell of the present invention;

Second: is a perspective view of a preferred embodiment of a connector for yet another solid oxide fuel cell;

Third: is a perspective view of a preferred embodiment of a connector for another solid oxide fuel cell

10. . . Solid oxide fuel cell connector

11. . . Gas distributor / glass template

12. . . Curved runner/conveyor

131. . . First glass flake

132. . . Second glass flake

133. . . Third glass flake

134. . . Fourth glass flake

14. . . Left flow channel

15. . . Backward runner

16. . . Left end

17. . . Back end

18. . . surface

Claims (9)

A solid oxide fuel cell (SOFC) connector comprising: a gas distributor having a curved flow path for delivering a fuel, and the gas distributor is a glass module; and a current collector disposed on the gas distributor for collecting a current generated by a connection of the battery at a medium temperature operation for outputting; wherein the curved flow path is a conveying pipe, and the conveying pipe is used for the conveying pipe Disposing a gas and deriving one of the exhaust gas after the reaction of the fuel, the gas is used to burn the fuel, and the connector further has a joint to connect a power generating component, and the material of the glass template comprises cerium oxide and boron oxide. The ruthenium oxide and the aluminum oxide are used for external connection of a medium temperature solid oxide fuel cell. The current collector has a conductive line, and the conductive line is made of silver, copper, nickel or aluminum. Using a screen printing method or an inkjet printing method to produce a line image using a paste of silver, copper, nickel or aluminum, the inkjet printing method using silver, copper, nickel a dispersion of aluminum, the glass template comprises a first glass sheet, and the glass template further comprises a second, a third and a fourth glass sheet, and stacking the first, the second, the third and the The fourth glass flake. The connector of claim 1, wherein the second glass sheet has a left flow channel, the third glass sheet has a rear flow channel, and the left end of the left flow channel communicates with The back end of the back flow channel, and the glass template has a cerium oxide content of 26 to 46 mol%, a boron oxide content of 19 to 23 mol%, a cerium oxide content of 30 to 47 mol%, and 0.5~ 6 Mohr% alumina content. The connector of claim 2, wherein the second glass sheet has an upper semicircular flow path, the third glass sheet having a lower semicircular flow path, and the upper semicircular flow The channel and the lower semicircular flow channel are combined into a semicircular flow channel, and the glass template is a first type glass having a cerium oxide content of 46±1 mol% and 27±1.0 mol%. a cerium oxide content, a boron oxide content of 20±1.0 mol%, and an alumina content of 5±1.0 mol%, and the glass template further has less than 1 mol% of calcium oxide, cerium oxide, zirconium oxide, titanium oxide, Magnesium oxide, rare earth oxide or cerium oxide. The connector of claim 2, wherein the second glass sheet has an upper "Γ" shaped flow channel, the third glass sheet having a lower "Γ" shaped flow path, and the upper "Γ" The shaped flow channel and the lower "Γ" shaped flow channel are combined into a "Γ" shaped flow channel, and the glass template is a second type glass, and the second type glass has a cerium oxide content of 32 ± 1 mol%. , a cerium oxide content of 45 ± 1.0 mol%, a boron oxide content of 22 ± 1.0 mol%, and an alumina content of 1.5 ± 1.0 mol%. The connector of claim 1, wherein the conductive line is a printed conductive line, the solid oxide fuel cell is a first battery component, and the first battery component is ruthenium oxide or oxidized. a zirconium-based solid electrolyte fuel cell assembly, and a first gap between the first battery component and a second battery component, the glass template further utilizing a glass paste or cutting a glass foil to encapsulate the first gap, The material of the glass paste comprises cerium oxide, boron oxide, cerium oxide, aluminum oxide and process chemical auxiliaries. The glass paste has a cerium oxide content of 46±1 mol%, a cerium oxide content of 27±1.0 mol%, 20 ±1.0 mole% boron oxide content and 5±1.0 mole% oxygen The aluminum paste content has calcium oxide, cerium oxide, zirconium oxide, titanium oxide, magnesium oxide, rare earth oxide or cerium oxide. The connector of claim 1, wherein the first glass sheet is produced by mixing a process aid with a glass frit, and using a ceramic forming method, the conveying pipe is a small gas pipe, the first 1. The second, the third and the fourth glass flakes are further subjected to an intermediate temperature binder burn-off and a high temperature heat treatment to sinter a uniform dense template comprising a doctor blade forming method and a dry pressing forming method. And an extrusion molding method, the conveying pipe is located on a surface of one of the second glass sheets, and the ceramic forming method is used to form a flat sheet or to manufacture the conveying pipe. The connector of claim 6, further comprising preparing a glass frit into a glass paste, forming the glass paste into a glass sheet for packaging, and then cutting the package. a glass sheet to form a package sheet, wherein the power generating element and the glass template have a bonding surface or a second gap, and the glass template uses a coating or a screen printing method to uniformly distribute a glass paste on the bonding surface And filling the glass paste or laminating the package sheet in the second gap, and sintering the glass paste for a long time at a high temperature melting temperature, or burning the polymer of the package sheet, followed by the high temperature softening temperature Melting the package sheet, rewet the second gap, and controlling the cooling rate of the package sheet to complete encapsulation of the power generating component. The material of the glass frit includes cerium oxide, boron oxide, cerium oxide and aluminum oxide. The average particle size is between 0.5 and 3.0 microns, and the high temperature melting temperature is between 900 and 1050 ° C, which is sufficient to produce a wetting effect. The package sheet has a wetting angle of less than 20°. A solid oxide fuel cell stack comprising: a power generating component; a gas distributor having a curved flow path for delivering a fuel, and the gas distributor is a glass template; and a current collector Disposed on the gas distributor for collecting a current generated by oxidation of the fuel for output; wherein the curved flow channel is a conveying pipe, and the conveying pipe is used for conveying a gas and deriving the fuel after the reaction An exhaust gas for burning the fuel, and the battery pack further has a joint for connecting a power generating component, and the material of the glass template comprises cerium oxide, boron oxide, cerium oxide and aluminum oxide, and the glass template That is, for external connection of a medium temperature solid oxide fuel cell, the current collector has a conductive line, the material of which is silver, copper, nickel or aluminum, and the conductive line uses a screen printing method or an inkjet printing a method for producing a line image using a paste of silver, copper, nickel or aluminum, the inkjet printing method using a dispersion of silver, copper, nickel or aluminum, the glass A template comprising a first glass sheet, and the glass template further comprises a second, a third and a fourth glass sheet, and stacking the first, the second, the third and the fourth glass sheet. An internal connector includes a gas distributor having a plurality of sets of curved flow passages for conveying a fuel and air or an oxidizing gas, and the gas distributor is a glass template; The curved flow channel is a conveying pipe for conveying a gas and deriving one of the exhaust gas after the reaction of the fuel, the gas is used for burning the fuel, and the connector further has a joint port for connecting a power generating element And the material of the glass template comprises cerium oxide, boron oxide, cerium oxide and aluminum oxide, and the glass template is used for external connection of a medium temperature solid oxide fuel cell, and the inner connector further comprises a current collector. The conductive circuit is made of silver, copper, nickel or aluminum. The conductive circuit uses a screen printing method or an inkjet printing method to produce a line image. The screen printing method uses silver, copper, a nickel or aluminum paste, the inkjet printing method uses a dispersion of silver, copper, nickel or aluminum, the glass template comprises a first glass sheet, and the glass template further comprises a second, a third and a a fourth glass sheet, and the first, second, third and fourth glass sheets are stacked.