Sodium-resistant joining glass and the use thereof
Abstract
The invention relates to a SiO-based2-B2O3-Na2O-Al2O3Sodium-resistant sealing glass (1) of the system, which is suitable for preparing sealing parts with metal and/or ceramics, and the sealing glass basically does not contain ZrO2; And a sealing piece of metal or ceramic and other sealing parts (2, 3, 4), which uses sealing glass (1), and a feedthrough that uses sealing glass (1) as a fixing material Device (20).

Term
8.2 yearsto projected expiry
Projected expiry 25 November 2034, counted from filing; an application has no term until it is granted.
- Priority
- Filed
- Published
- Today
- Projected expiry
14 claims: 10 independent, 4 dependent
- 1L 一种用于生产至少陶瓷或金属之间的封接件的封接玻璃(1),除了最多为杂质以 外,其不包含Zr()2,并包含(以基于氧化物的重量%计): SiO 2 40-50 BoO? 25-30 Na 2 O 5-15 A1 2 O 3 17-25 Σ MO 0 - 2, MO表示单独的或以任意组合的CaO和/或SrO和/或BaO。
- 2根据权利要求1所述的封接玻璃(1),其还包含单独的或以任意组合的(以基于氧 化物的重量%计): ZnO 0-5 TiO 2 0-5 SnO 2 0-5 MgO 0 - 15 ο
- 3根据前述权利要求中的任一项所述的封接玻璃(1),其在20-300C的温度范围内的 线性热膨胀系数α 20 - 30CTC为5. 5Χ 10一6晓至g 5・10一6晓,优选 5 . 5X 10邛-1至 8 . 5X ΙΟ小τ, 更优选6. 0Χ 10由-1至8. 0X10 -6晓。
- 4根据前述权利要求中的任一项所述的封接玻璃(1),其还包含高达30体积%的氧化 性填充剂、优选用于设定热膨胀行为和/或耐腐蚀性和/或流动行为,所述填充剂优选以颗 粒和/或纤维的形式存在。
- 5一种第一封接部件(2)和第二封接部件(3.4.41)之间的封接件,其使用了根据前 述权利要求中的任一项所述的封接玻璃(1),其中,所述封接玻璃(1)使所述第一封接部件 (2)的封接区域和所述第二封接部件(3.4.41)的封接区域相接合。
- 6根据权利要求5所述的封接件,其中,所述第一封接部件⑵至少在其封接区域包括 陶瓷,以及所述第二封接部件(3.4.41)至少在其封接区域包括金属和/或陶瓷。
- 7根据权利要求5-6中任一项所述的封接件,其中,所述第一封接部件⑵和/或所述 第二封接部件(3.4.41)的封接区域的陶瓷选自由氧化铝和/或α-氧化铝和/或8-氧 化铝和/或8 氧化铝和/或NASICON所组成的组中。
- 8根据权利要求5-7中任一项所述的封接件,其中,所述第二封接部件(41)的金属在 同样的温度范围内的线性热膨胀系数大于或等于陶瓷的线性热膨胀系数Ο 20-300ΓΟ
- 9根据权利要求5所述的封接件,其中,所述第一封接部件⑵至少在其封接区域包括 金属,以及所述第二封接部件(3.4.41)至少在其封接区域包括金属。
- 10根据权利要求5-9中任一项所述的封接件,其中,所述第二封接部件的金属(41)的 a 2 o-3oor 8X10- 6 r o 1L 一种电化学能量存储和/或能量产生单元,优选为钠硫电池或钠-金属氯化物电 池,其包括根据权利要求5-10中任一项所述的至少一个封接件。
- 1112 . 一种馈通装置(20),优选为电馈通装置(20),其包括根据权利要求5-10中任一项 所述的至少一个封接件。
- 1213 . 一种电馈通装置(20),其包括: 具有至少一个馈通开口的金属载体元件(30), 金属功能元件(31), 借助于根据权利要求1-4中任一项所述的封接玻璃(1),以此方式,所述金属功能元件 (31)固定在所述馈通开口内并与所述载体元件(30)电绝缘,并且封闭所述馈通开口。
- 1314 .根据权利要求1-4中任一项所述的封接玻璃(1)在制备钠硫电池或钠-金属氯化 物电池中的用途,优选用于气密密封其外壳(4)和/或用于封闭膜部件(2)。
- 1415 .根据权利要求12-13中任一项所述的馈通装置(20)在处置废弃物的装置或装置的 安全壳中的和/或核反应堆、优选核增殖反应堆中的用途,优选作为安全壳中的电馈通装 置(20)和/或作为用于冷却回路的电馈通装置(20)。
Independent claims14
100 paragraphs, as filed
Sodium-resistant sealing glass and its application technical field
[0001] The present invention relates to a sodium-resistant sealing glass, which can be used to prepare a combination with ceramics, such as alumina (also known as AI2O3, alumina ceramics or Aka ceramics) and/or with metals and/or bothThe seal. The sealing piece. The invention also relates to the use of the sodium-resistant sealing glass. Sodium-resistant sealing glass is a sealing material that can withstand especially liquid sodium and/or sodium vapor, and is therefore suitable for preparing exposed to, for example, liquid sodium and/or sodium vapor and/or other aggressive sodium compounds and/or containing Sealing element for sodium media.
Background technique
[0002] For example, for the preparation of energy storage and energy generation units in which liquid sodium and/or sodium compounds are used as electrolytes or cooling media, this type of sodium-resistant sealing glass is of interest. Examples of such energy generating units are electrochemical cells, such as batteries and nuclear reactors, preferably the following types of nuclear reactors: fast breeder reactors, fast neutron reactors, sodium cooled fast reactors and/or liquid metal fast breeder reactors. The sealing glass that can be used in these reactors can be conveniently applied to technical components in and/or connected to these reactors and in contact with the sodium and/or sodium compounds. An example of such a technical component is preferably a feedthrough device, which is used to supply electric power and/or manipulation signals to sensors and/or actuators and/or motors, for example in electric pumps. Another application field of the sodium-resistant sealing glass to which the present invention belongs is equipment for the disposal of toxic materials, in which sodium compounds and/or sodium vapor and/or liquid sodium may be generated during the processing.
[0003] In recent years, especially electrochemical storage and energy generation technologies have gained considerable interest. In this regard, it can be used in the following areas of electric mobility: used as an emergency power system in local power supply, and used to stabilize network systems mainly due to the increased share of renewable energy.
[0004] Various battery technologies are discussed here, and lithium ion batteries (LIB) are among the most discussed. High-temperature sodium batteries (sodium 8-battery, SBB) represent another type of battery. Its advantages over LIB are higher energy density and high energy efficiency. At high temperatures generally greater than 250C, SBB uses liquid sodium as the negative electrode. In general, the difference between these two variants is: one is a sodium-sulfur battery (Na/S), which uses sulfur as the positive electrode. The other is a sodium-metal chloride battery, also known as a ZEBRA battery, which uses a metal chloride, such as magnesium chloride or ferric chloride, as the positive electrode and sodium tetrachloroaluminate (NaAlCL) as the liquid electrolyte. The common feature of both types is that they use a sodium ion conductive membrane composed of 8- or 8"-AI2O3 and a housing part composed of α-Al203, and the latter can be additionally connected with a metal cover if appropriate. The term "alumina", or the synonymous alumina ceramic or the synonymous ΑΙ2Ο3 or the same synonymous ΑΙ203 ceramic as used herein, preferably includes the following specific forms: α-and/or 8-and/or 8 -oxidation aluminum. The use of the term "alumina" does not imply any restriction on the purity and thus the content of Al 2 O 3 and/or the component under consideration in the Al 2 O 3 ceramic.
[0005] A component made of ceramic, preferably alumina, or a seal between another metal component represents a key component in an electrochemical cell, because it determines the useful life. If a leak occurs in this area, the liquid sodium can come into contact with the air and start to burn. The purpose of the sealing glass as the sealing material here is to achieve continuous hermetic sealing throughout the life of the battery. This can preferably be achieved by good compliance with the thermal expansion coefficients of all materials involved, which enables the sealing member to withstand operating conditions, and enables the glass to still have a very good resistance to all without impairing its function.
Chemical resistance of active ingredients.
[0006] There are two basic types of sealing glass used in batteries: silicate-based glass and borate-based glass, which are different. The borate-based glass has the advantage that it generally has very good resistance to molten sodium, but its performance in terms of chemical resistance to metal chlorides is worse. In addition, the frequently used aluminum borates generally only have low stability to crystallization, which limits them from the point of view of process control. A specific form is detailed in, for example, US 8,334,053 B2, which describes insulating glass that relies on corrosion resistance to the anode and cathode of SBB. According to the document, Si with a content of more than 40% by weight is used on the metal salt side. 2 and less than 25% by weight of B2O3 glass with high silicon content, and use of less than 20% by weight of Si on the sodium side. 2 and more than 35% by weight of B2O3 very low silicon content borate glass.
[0007] GB 2207545 A describes the use of borate glass 8245 from Schott AG as a sealing glass for Na/S batteries. The glass has very good chemical stability to the medium of Na/S battery, but due to its linear thermal expansion coefficient a 2<sub>cH</sub>3wc as low as 5.2X10-T<sup>1</sup>, So it can only be hermetically sealed with alumina to a limited extent for a long time.
[0008] US 4,268,313 A describes a borosilicate glass for use in Na/S batteries. However, the glass contains a total of at least 6% by weight of alkaline earth metal oxides CaO, SrO and BaO. These components are beneficial for glass formation and can improve the flow behavior, but through ion migration with the electrolyte, preferably the electrolyte in the SBB, they can reduce the performance of the active component.
[0009] US 8, 034, 457 B2 describes a sealing glass for energy storage devices containing up to 25% by weight of B2O3. The limitation of the upper limit of the content of B2O3 is explained by the fact that otherwise, the sealing glass will suffer excessive erosion by the adsorbed water.
1T0Wt%ZrO [0010] US 8, 043, 986 B2 includes a sealing glass for SBB, which contains at least 0.1T0Wt%ZrO<sub>2</sub>The use of zirconium oxide in this document improves the chemical resistance. However, this also leads to a higher tendency for phase separation and crystallization, and also reduces the throughput of the glass manufacturing process due to the high cost of raw materials.
Summary of the invention
[0011] Contrary to the background art, an object of the present invention is to provide a sealing glass suitable for preparing a sealing member with metal and/or ceramics, which has very good resistance to molten metal salt and sodium melting. Resistance to body, liquid sodium and/or sodium vapor and/or aggressive sodium compounds. Preferably, the suitable ceramic to be sealed is alumina and/or sodium superion conductor (NASICON), and preferably, the suitable metal is steel and/or alloy. Another object of the present invention is to use the sealing glass to provide a ceramic, preferably alumina and/or sodium superionic conductor sealing member, and also to provide an electrochemical energy storage and /Or an energy generating unit, and an electrical feedthrough device including the sealing glass as an electrical insulating fixing material, which benefits from the performance of the sealing glass and therefore has improved performance.
[0012] The object is achieved by the sealing glass, the sealing member, the electrochemical energy storage and/or energy generation unit, and the feedthrough device and use according to the claims. Preferred embodiments are obvious from the claims dependent on the independent claims.
[0013] In the following, unless expressly specified otherwise, all data related to components and/or contents are provided based on the weight% of the oxide.
[0014] The sealing glass according to the present invention contains 40%-50% Si. 2 And more than 25% up to U 30% of B2O3. This combination affects especially the coefficient of thermal expansion and at the same time controls the flow behavior. According to the present invention, the sealing glass further covers
Contains 5% -15% Na2. And 17% -25% AI2O3. In particular, these components can be used to make the sealing glass have good chemical resistance.
[0015] The sealing glass according to the present invention contains, optionally, a total of less than 2% of alkaline earth metal oxide MO. M0 represents CaO, SrO and/or BaO, which can exist alone in the sealing glass or exist in any feasible combination up to the total content defined above. Alkaline earth metal oxides can have a positive effect on the flow behavior of the glass. Since it can reduce the performance of an active component through the diffusion or ion migration of sodium ions with the electrolyte, its content is reduced to the lowest value according to the present invention.
[0016] In addition, the sealing glass according to the present invention does not contain Zr() 2 except for the presence of impurities at most. Impurities can be added to the glass through contamination of the raw materials used in glass manufacturing and/or through contamination and/or corrosion of the melting unit used. Impurities of this type generally do not exceed a ratio of 0.2% by weight, preferably 0.1% by weight. This of course also includes the complete absence of Zr. (V Contrary to the teachings in the cited prior art, it has been found that even if the use of Zr() 2 is rejected to improve chemical resistance}, the sealing according to the present invention Glass also has very good chemical resistance. Moreover, it has been found that Zr() 2 can act as a seed crystal, which promotes crystallization during processing. The crystallization (including partial crystallization) of the sealing glass according to the present invention Is undesirable, because the crystalline area causes difficulties in the preparation of the sealing member and/or can even cause leakage of the sealing member. Therefore, the sealing glass according to the present invention is particularly preferably an amorphous glass, especially without Amorphous glass in the crystalline region.
[0017] Tests performed on the sealing glass have shown that, contrary to the cited prior art, if the content of B2O3 is increased to more than 25%, it is impossible to establish hydrolytic aging. In contrast, the inventors found that higher boron content of greater than 25% to 30% even unexpectedly improved resistance to sodium melt. Due to the above-mentioned composition, the sealing glass according to the present invention can be conveniently melted in a non-crystallization and non-melting manner.
[0018] In a preferred embodiment, the sealing glass according to the present invention contains up to 5% ZnO and/or up to 5% Tit)? and/or up to 5% SnO2 and/or up to 15% MgO. The optional additional components can be present in the sealing glass alone or in any desired combination. These components particularly improve the chemical resistance in the alkaline range. MgO is an optional component and can be included in the sealing glass to adapt the thermal expansion of the sealing glass to the joining partner. Generally, an increase in the content of MgO leads to an increase in the thermal expansion coefficient. The present invention also foresees an increase in the thermal expansion coefficient. It can advantageously contain 0Y2% MgO in the sealing glass.
[0019] Particularly preferably, the components of the sealing glass are selected within the above-mentioned limits, so that the linear thermal expansion coefficient α 20-3ocrc value of the sealing glass in the temperature range of 20 °C -300 °C is 5. 5Χ 10 ^^ to g δΧΙΟ^Γ<sup>1</sup>, Or more preferably 5.5X 10-6h to<sub>8</sub>. 5X10 is very particularly preferred 6. OXIO-VM 8. 0X10 One, Xiao. In particular, this can realize the adaptation of the sealing glass to the thermal expansion behavior of alumina.
[0020] It is also preferred that the sealing glass additionally contains up to 30% by volume of oxide fillers, especially inorganic oxide fillers. These fillers can be used in particular to set the thermal expansion behavior and/or corrosion resistance and/or flow behavior. The fillers are preferably present in the form of particles and/or fibers. Examples of such fillers are MgO, A12()3 and/or stable ZrO<sub>2</sub>These can be preferably applied in order to adapt the thermal expansion of the sealing glass and filler mixture to the thermal expansion of the metal mating seal. The filler material is usually not part of the glass matrix, but is usually embedded in it as a separate component.
[0021] The present invention also includes a sealing member between the first sealing member and the second sealing member, which uses the above-mentioned sealing glass. The sealing part should be understood as any part connected with the sealing glass. In this case, the sealing glass in particular forms a complete joint with each sealing member. The complete joint is distinguished by the following facts: mating joints, here each
Whether the sealing part and the sealing glass are held together by atomic force or molecular force. This leads to an inseparable joint, which can only be separated by breaking the joint method, here the sealing glass. It is particularly advantageous that the sealing glass can be used as a mating sealing element to provide an airtight joint between the sealing parts.
[0022] The sealing member between the sealing parts is prepared by sealing glass, and correspondingly exists in the sealing area of each sealing part joined with the sealing glass. Therefore, the sealing area is an area located on the surface of each sealing member in contact with the sealing glass. The sealing member can be joined to the sealing glass over its entire surface area or in any desired area, and it can be joined to other sealing members through the latter. As mentioned above, the sealing glass according to the present invention is particularly suitable for sealing ceramics and/or metals. Correspondingly, the sealing member according to the present invention provides a first sealing member, which includes a ceramic or metal component at least in the sealing area. The second sealing member also contains ceramic or metal at least in the sealing area. Combinations of metals or ceramics are of course equally feasible and are included in the present invention. In combination, this also means that the second sealing part can be a mixed part made of metal and ceramic in the area of the sealing part. In other words and possibly simplified, the sealing glass according to the present invention provides a connection between metal and metal, or ceramic and metal, or ceramic and ceramic, or metal or ceramic and a mixed component containing metal and ceramic.
[0023] As described above, the sealing glass according to the present invention is particularly suitable for sealing alumina, and thus a sealing member according to the present invention is provided, wherein the first sealing member includes at least in the sealing area Alumina, especially composed of alumina. The second sealing member includes one or a combination of metal and aluminum oxide at least in the sealing area. In the combination, a sealing part is obtained in particular in the form of a mixed part composed of metal and alumina in the sealing area.
[0024] It is preferable if the alumina of the first sealing member contains α- or 8- or β-alumina, especially if it consists of it. It is particularly preferred that the alumina of the second sealing member is also α-alumina, 8-alumina, or 8"-alumina, if it is composed of or contains alumina at least in the sealing area. However, this does not mean that the embodiment of the alumina of the first sealing part must be the same as the embodiment of the alumina of the second sealing part; on the contrary, if the alumina of the first and second sealing parts is implemented The examples are different, for example if the first sealing member contains α-alumina and the second sealing member contains 8-alumina or 8-alumina, it may be preferable. This configuration is used in SBB in particular, and it is therefore of interest.
[0025] From the types of NASICON (sodium super ionic conductor) ceramics, typical ones having alkali metal ions A (such as Na) and polyvalent metal ions B (such as Fe, Cr, Ti) (PO/3 type) Among the types, it is also feasible and preferable to choose ceramics instead of alumina. All the above embodiments have these types of ceramics, and it is also feasible.
[0026] Equally feasible are sealing parts in the housing of the sensor and/or actuator, which are exposed to aggressive media, in particular liquid sodium or sodium salt. Possible applications in which these can be found are, for example, in the electrolysis of liquid sodium through salt melts, and also in the field of cooling breeder reactors with liquid sodium.
[0027] As described above, the second sealing member also preferably contains metal at least in the sealing area. It is particularly preferred that the linear thermal expansion coefficient ά such as 3wc (within the same temperature range) of the metal is greater than or equal to the linear thermal expansion coefficient of ceramics, especially alumina
Q 20-300Ό °
[0028] Particularly preferably, the linear thermal expansion coefficient a 20.3WC of the metal has a value greater than 8×10%7. Examples of such preferred metals are high-grade steel, low-carbon steel and/or magnesium alloy.
[0029] The sealing member according to the present invention makes it possible to prepare an electrochemical energy storage and/or energy generation unit with increased service life and/or increased efficiency. Therefore, these are also included in the present invention. An example of an electrochemical energy storage device is a battery in a charging mode, and an example of an electrochemical energy generating unit is a battery or a battery in the discharge mode. Reactors for chemical and/or biochemical reactions are equally feasible, in which the energy state is determined by the reactants
And the respective oxidation and reduction states of the product. It is particularly preferred that the energy storage and/or energy generation unit according to the present invention is a sodium-sulfur battery or a sodium-metal chloride battery including the sealing member according to the present invention.
[0030] The sealing member according to the present invention also facilitates the preparation of feedthrough devices, especially electrical feedthrough devices.
[0031] A preferred electrical feedthrough device includes a metal carrier element provided with a feedthrough opening and a metal functional element. The functional element is fixed in the feedthrough opening with the sealing glass, and the carrier element is electrically insulated from the functional element. As a result, the feedthrough opening is sealed, in particular hermetically sealed.
[0032] It is very particularly preferred to use the sealing glass according to the present invention to prepare a sodium-sulfur battery or a sodium-metal chloride battery, in particular for hermetically sealing its casing and/or for sealing and/or joining in its electrolyte unit Membrane parts. It can also be joined to a suitable carrier element or the like.
[0033] Most advantageously, the feedthrough device according to the present invention can be applied to a device for the disposal of toxic waste and/or a nuclear reactor, in particular a fast breeder reactor. Among them, the application as an electrical feedthrough device for the containment of the reactor and/or as an electrical feedthrough device for the cooling circuit mainly benefits from the sealing glass and/or the sealing joint as described herein. The cooling circuit may include primary and/or secondary cooling circuits that use liquid sodium as the cooling medium, especially in fast breeder reactors. The feedthrough can be exposed to liquid sodium and/or sodium vapor, and must be able to withstand such permanent exposure or exposure due to emergency situations. The feedthrough device can be used to provide, for example, an electric pump and/or sensor with an electric circuit in the cooling circuit, and/or to derive the signal of the sensor applied in or at the cooling circuit. Another preferred application of the feedthrough device is in the containment of a reactor, so as to connect the inside of the containment with the outside without the passage of harmful media. In this type of application, the feedthrough device can be exposed to liquid sodium and/or sodium vapor, especially in emergency situations, so the most important thing is that the feedthrough device reliably seals the hermetic device.
[0034] Another useful application field of the feedthrough device is equipment for the disposal of toxic wastes, for example, where the waste is burned or chemically destroyed, which may produce corrosive sodium compounds and/or liquid sodium and / Or such equipment for sodium vapor.
Description of the drawings
[0035] The present invention will be explained in more detail on the basis of the drawings. All drawings are completely schematic, and the size of the actual object can deviate from the size and/or performance in the drawings, where:
[0036] FIG. 1a: shows a cross-sectional view of the first sealing member with sealing glass in certain areas.
[0037] FIG. 1b: shows a cross-sectional view of another first sealing component with sealing glass in certain areas.
[0038] FIG. 2a: shows a cross-sectional view of a component assembly device including a sealing member.
[0039] FIG. 2b: shows a cross-sectional view of another component assembly device including a sealing member.
[0040] FIG. 3: shows a cross-sectional view of the ZEBRA battery.
[0041] FIG. 4: shows a cross-sectional view of another ZEBRA battery.
[0042] FIG. 5a: shows a cross-sectional view of the feedthrough device.
[0043] FIG. 5b: shows a top view of the feedthrough device according to FIG. 5a.
[0044] FIG. 6: shows a cross-sectional view of an alternative feedthrough device.
[0045] FIG. 7: shows a cross-sectional view of the containment vessel of the reactor.
[0046] FIG. 8: shows a cross-sectional view of the containment vessel of the reactor and the reactor itself.
Detailed ways
[0047] FIG. 1a schematically shows a cross-sectional view of the first sealing member. The sealing part (2) represents the so-called substrate for the sealing glass (1). The sealing glass (1) is located on the surface of the sealing part (2) in certain areas, and forms and seals in these areas. Complete joining of parts (2). The area where the sealing glass (1) is present may be a sealing area, and is defined as a sealing area hereinafter, in which a sealing member with other sealing components is prepared. The sealing part (2) shown with the sealing glass (1) can be used to prepare the sealing part, in particular by joining with another sealing part. In this example, the sealing member (2) is composed of 8-alumina or 8"-alumina or NASICON. As mentioned above, the aluminum oxide (2) of the sealing component is only present in those sealing areas where the sealing glass (1) is used for bonding, and other areas of the sealing component are composed of different materials, which is also feasible.
[0048] FIG. 1b shows a sealing member with sealing glass substantially the same as FIG. 1a, except that in this example the sealing member (3) is composed of α-alumina, or at least in the presence of the sealing glass (1 ) These sealing areas include the latter. All further statements related to Fig. 1b can also be applied to Fig. 1b.
[0049] FIG. 2a shows a cross-sectional view of a sealing member formed by a component assembly device, which is joined by a sealing glass (1), and is composed of a first sealing member (2) and a second sealing member (3). It can be seen that with regard to Figure 2a, the object shown is basically a combination of Figures la and 1b. In this figure, the material of the first sealing member (2) is also 8-alumina or 8"-alumina, and the material of the second sealing member (3) is α-alumina. The sealing glass (1) is completely bonded to the surface of the sealing parts (2, 3) in the sealing area, and thus an airtight and durable joint can be produced between the sealing parts (2.3).
[0050] Figure 2b shows a cross-sectional view of an embodiment similar to Figure 2a, except that the first sealing member is composed of 8-alumina or 8"-alumina (2) and α-alumina (3). In this exemplary embodiment, the second sealing member (4) is composed of metal. It is obvious to a person skilled in the art that a variety of different entire parts can be prepared through appropriate combinations of the sealing members shown, which can be adapted to the needs related to their use.
[0051] FIG. 3 shows a schematic cross-sectional view of a ZEBRA battery. The battery is closed by a can-shaped casing (4) and a cover (3). The shell (4) and the cover (3) are joined to each other through the sealing glass (1). The cover (3) represents the so-called first sealing member, and the housing (4) represents the so-called second sealing member of the above-mentioned sealing member. In ZEBRA batteries, the casing (4) is usually composed of metal, such as high-grade steel, silver alloy or low carbon steel, and the cover (3) is composed of alumina, especially α-alumina. The sealing glass (1) according to the present invention produces a reliable and permanent tight joint between the two sealing parts, the cover (3) and the casing (4), so the contents of the ZEBRA battery are safely enclosed in the casing in.
[0052] A hollow cylindrical semipermeable membrane (2), usually made of β-alumina or β -alumina, is located inside the housing. The intermediate space between the inner wall of the casing (4) and the outer wall of the membrane (2) is filled with liquid sodium (11), which forms the anode. By contacting the conductive housing (4), the latter also functions as an anode. The inner space of the hollow cylindrical membrane (2) is filled with, for example, sodium tetrachloroaluminate as the electrolyte (10) and functions as a cathode. The semi-permeable membrane composed of 8-alumina or β-alumina (2) is only permeable to sodium ions. It is joined with the cover through the sealing glass (1). The film (2) here represents the so-called first sealing member, and the cover (3) represents the second sealing member in the general principle of the above-mentioned sealing member. In the sealing member in this area of the ZEBRA battery, it is important that the sealing glass is not permeable to the electrolyte (10) and liquid sodium (11), because otherwise the electrolyte (10) and/or liquid sodium (11) It may be contaminated by other substances, and accordingly the battery may be destroyed or at least its capacitance may be reduced.
[0053] In this example, the cover (3) itself is an electrical insulator, so an electrode (52) is required in order to make the battery contact the anode and cathode to form a circuit. In the example shown in Figure 3, the metal rod (52) passes through the cover (3) through the sleeve (51). In this regard, it is also conceivable to guide a metal rod (52) or generally an electrode through the cover (2) in the glass-metal guide containing the sealing glass according to the present invention.
[0054] FIG. 4 shows another embodiment of the ZEBRA battery as shown in FIG. 3. Since the sealing glass (1) produces an electrically insulating seal between the two sealing parts at the junction between the housing (4) and the cover (41), the cover as shown in Figure 4 is made of metal or at least a conductive material (41), and it is also possible to have a geometric shape in such a way that it does not contact the electrolyte (10) so that it is possible to omit the guide electrode (52) and then the cover itself functions as a cathode. After that, the sealing glass is in a single area, here in the form of a ring, and especially the three sealing parts-the shell (4), the cover (3) and the film (2) are joined.
[0055] FIG. 5a schematically shows a cross-sectional view of the feedthrough device (20). The feedthrough (20) comprises a carrier element (30), which in this example is represented by a metal cylinder. The carrier element (30) usually has the function of an outer conductor. In the application area, it is usually made of steel. The preferred embodiment is made of carbon steel, austenitic steel and/or ferritic steel. For specific application areas, the carrier element (30) can be made of Kovar alloy or ceramic. The carrier element (30) also includes a feed-through opening that connects one side of the carrier element (30) to the other side. The functional element (31) is arranged inside the feedthrough opening. In this example, the functional element (31) is represented by a rod acting as an electrical conductor, also called an inner conductor. The functional element (31) may be composed of different suitable materials, such as Kovar and/or copper and/or alloys, for example, silver-iron alloys and/or silver-ming alloys. The sealing glass (1) fixes the functional element (31) in the feedthrough opening in an electrically insulating manner and simultaneously seals the feedthrough opening. According to the sealing glass (1) of the present invention, the feedthrough device (20) has the advantage that the feedthrough opening can be hermetically sealed. For the preparation of the feedthrough device (20), the sealing glass (1) is usually welded with the carrier element (30) and the functional element (31), so that the carrier element (30), the sealing glass (1) and A sealing connection is established between the functional elements (31).
[0056] FIG. 5b shows a top view of the feedthrough device (20) according to FIG. 5a. It can be seen that the functional element (31) is centered in the feed-through opening. This geometry is usually used in compression seals where the thermal expansion of the carrier element (30) is greater than the thermal expansion of the sealing glass (1). As an effect, during the period when the sealing glass is melted within the feed-through opening, the cooling carrier element (30) then shrinks on the sealing glass, and thus a compressive stress on the sealing glass (1) is generated. This compressive stress enhances the mechanical force required to push the sealing glass out of the feed-through opening, and thereby increases the mechanical stability of the entire feed-through device (20).
[0057] The feedthrough device (20) as shown in FIGS. 5a and 5b represents a typical device of the so-called large feedthrough device category. [0058] FIG. 6 shows a cross-sectional view of another embodiment of the feedthrough device (20), which has a plurality of contact openings in the carrier element (30). This so-called planar element has a dimension whose width is greater than its height. The feedthrough opening can be provided in the matrix. The substrate itself is variable, which means that the location of the feedthrough opening can be selected according to the desired application. This embodiment can be used, for example, to provide a plurality of electrical and/or electronic components with circuits that drive them, for example, and/or to guide signals generated by those components passing through the carrier element (30). The carrier element (30) may or may not seal the housing of the device. The carrier element (30) can be made of metal and/or alloy, or ceramic, especially the aforementioned materials.
[0059] In FIG. 7 is shown a containment (80) of an energy generating device, such as a containment of a reactor, in particular a nuclear reactor, or equipment for disposing of toxic waste. These must be safely enclosed in a containment (80), also in emergency and fault conditions. In order to provide contact with the generator and/or device in the containment, preferably a feedthrough device (20) according to the present disclosure can be used. Such equipment is, for example, a device that monitors the operating conditions of a generator and/or a device that manipulates a reactor or other devices.
[0060] An energy generating device (81) such as a reactor is shown in FIG. 8. This illustrative example also includes the cooling circuit of the reactor, in the case of a fast breeder reactor, in particular its primary and/or secondary cooling circuit operating with liquid sodium as the cooling medium. The feedthrough device (20) can be used to supply manipulators and/or sensors and/or actuation devices and/or motors with current, especially those in electric pumps. In addition, the containment (80) can have the upper and lower sides as shown in Fig. 7
The feedthrough device (20) described in the text.
[0061] The sealing glass (1) according to the present invention can be prepared by a conventional glass melting method. The details of glass melting are known to those skilled in the art and will not be repeated here.
[0062] The following Table 1 summarizes the composition and physical properties of four exemplary sealing glasses (1) 1-4 according to the present invention
[0063]
<td>Components:</td><td>1</td><td>2</td><td>3</td><td>4</td>
<td>Si0<sub>2</sub></td><td>49</td><td>44</td><td>40</td><td>42</td>
<td>b<sub>2</sub>o<sub>3</sub></td><td>26</td><td>26</td><td>30</td><td>26</td>
<td>Na<sub>2</sub>0</td><td>8</td><td>10</td><td>6</td><td>15</td>
<td>AI2Q3</td><td>17</td><td>20</td><td>24</td><td>17</td>
<td>performance:</td><td></td><td></td><td></td><td></td>
<td>T<sub>g</sub>[℃ ]</td><td>546</td><td>488</td><td>548</td><td>533</td>
<td>Density [g/cm<sup>3</sup>]</td><td>2. 35</td><td>2. 26</td><td>2. 43</td><td>2.40</td>
<td>Q 20-300Γ [1. 6K Η</td><td>5. 80*</td><td>6. 61</td><td>5. 62</td><td>8. 34</td>
[0064]
[0065] Table 1: An example of the sealing glass according to the present invention, the data is based on the weight% of the oxide.
<td>Components:</td><td>CE 1</td><td>CE 2</td>
<td>Si0<sub>2</sub></td><td>69. 8</td><td>68. 0</td>
<td>b<sub>2</sub>o<sub>3</sub></td><td>15. 6</td><td>13. 0</td>
<td>Na<sub>2</sub>0</td><td>7. 2</td><td>12. 0</td>
<td></td><td>5. 4</td><td>5. 0</td>
<td>ZnO</td><td>2. 0</td><td>1. 0</td>
<td>BaO</td><td>—</td><td>1. 0</td>
<td>performance:</td><td></td><td></td>
<td>T<sub>g</sub>[℃ ]</td><td>505</td><td>565</td>
<td>Density [g/cnfl</td><td>2. 31</td><td>2. 44</td>
<td>Q 20-300 °C [1. K]</td><td>5. 2</td><td>6. 7</td>
[0066] Table 2: Comparative examples of sealing glass, the data is based on the weight% of oxide.
[0067] Table 2 shows the composition and physical properties of the sealing glass that is not within the range of the glass composition according to the present invention, which will be referred to as CE 1 and CE 2 as comparative examples hereinafter.
[0068] The glass of the comparative example has a higher content of SiO2 and a lower content of B than the sealing glass according to the present invention <sub>2</sub>0<sub>3</sub> And Α1<sub>2</sub>Ο<sub>3</sub>0
[0069] The resistance of the sealing glass according to the present invention as shown in Table 1 was measured and compared with the glasses CE1 and CE2 of the comparative example as shown in Table 2. For this purpose, the side length of the glass block composed of the glass is placed in a molten sodium bath at 300°C for a specific period of time, and the appearance of the sample, the surface structure of the sample, and the mass loss are measured. It is proved that all the sealing glasses according to the present invention as shown in Table 1 are more resistant than the comparative example shown in Table 2, or show a higher coefficient of thermal expansion, which leads to the difference between the metal as a mating sealing member Improvements in the ability to perform sealing joints.
[0070] The advantages of the sealing glass according to the present invention over the prior art are that it can be used to prepare ceramic and/or metal sealing parts and can also improve its chemical resistance.
6 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6
Every citation, both ways
| Document | Relation | Office | Category | Cited during | Relevant claims |
|---|---|---|---|---|---|
| CN109748574A | Cited by | China | – | Search report | – |
| EP0482785A2 | Cites | European Patent Office (EPO) | X | Search report | 1-16 |
| CN101462828A | Cites | China | X | Search report | 1-15 |
| US5194337A | Cites | United States of America | X | Search report | 1-15 |
21 members in 8 offices
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| 102013224111 | Germany | A | |
| 102013224111 | Germany | A | |
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| 1020132241119 | – | – | – |
| DE201310224111 | – | – | – |
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| GB201420295D0 | United Kingdom | D0 | |
| US2015146840A1 | United States of America | A1 | |
| CH708728A2 | Switzerland | A2 | |
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| CN104671663AThis record | China | A | |
| KR20150060529A | Republic of Korea | A | |
| DE102013224111A1 | Germany | A1 | |
| JP2015110512A | Japan | A | |
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| KR20160030496A | Republic of Korea | A | |
| DE102013224111B4 | Germany | B4 | |
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| JP2017141145A | Japan | A | |
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| CN109180003A | China | A | |
| CH708728B1 | Switzerland | B1 | |
| FR3013703B1 | France | B1 | |
| CN109180003B | China | B |
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Numbers
- Publication
- 104671663
- Publication, DOCDB
- 104671663
- Publication, EPODOC
- CN104671663
- Application
- 10688273
- Application, DOCDB
- 201410688273
- Application, EPODOC
- CN201410688273
Titles2
- Chinese
- 抗钠封接玻璃及其用途
- English
- Sodium-resistant sealing glass and its use
Classification
- CPC, 20
- C03C8/24
- C03C3/091
- H01M50/186
- G21C1/02
- C03C3/093
- C03C8/02
- C03C8/04
- H01M10/39
- Y10T29/4911
- Y10T403/477
- G21C13/02
- Y02E30/30
- Y02E60/10
- C04B37/005
- C04B37/025
- H01M10/3909
- C03C2204/00
- C03C2205/00
- F16B11/00
- H02G3/22
- IPC, 2
- C03C8 24
- H01M50 186