巴西专利BR102013022970A2 BOLDING ALLOY COMPOSITION, ELECTROCHEMICAL CELL, ENERGY STORAGE DEVICE AND METHOD FOR JOINING COMPON

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专利摘要:
a brazing alloy composition comprising nickel, from about 5% to about 40% of at least one refractory metal selected from niobium, tantalum or molybdenum; about 2% to about 32% chromium; and about 0.5% to about 10% of at least one active metal element. An electrochemical cell including two components joined together by such brazing composition is also described. A method for joining components, such as those within an electrochemical cell, is also described. The method includes the step of introducing a brazing alloy composition between a first component and a second component to be joined to form a brazing structure. In many instances, one component is formed of a ceramic while the other is formed of a metal or alloy.
公开号:BR102013022970A2
申请号:R102013022970-9
申请日:2013-09-09
公开日:2018-03-20
发明作者:Kumar Sundeep；Rahmane Mohamed；Rao Adharapurapu Raghavendra
申请人:General Electric Company；
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专利说明:

(54) Title: COMPOSITION OF BRAZIL ALLOY, ELECTROCHEMICAL CELL, ENERGY STORAGE DEVICE AND METHOD FOR UNITING COMPONENTS.
(51) Int. Cl .: C22C 19/05; B23K 35/00; H01M 4/139; H01M 8/02 (30) Unionist Priority: 27/09/2012 US 13 / 628,548 (73) Holder (s): GENERAL ELECTRIC COMPANY (72) Inventor (s): MOHAMED RAHMANE; SUNDEEP KUMAR; RAGHAVENDRA RAO ADHARAPURAPU (74) Attorney (s): GUSTAVO SARTORI GUIMARÃES (57) Abstract: This is a brazing alloy composition containing nickel, about 5% to about 40% of at least one refractory metal selected from niobium, tantalum or molybdenum; about 2% to about 32% chromium; and about 0.5% to about 10% of at least one active metallic element. An electrochemical cell that includes two components joined together by such a brazing composition is also described. A method for joining components, such as those within an electrochemical cell, is also described. The method includes the step of introducing a brazing alloy composition between a first component and a second component to be joined to form a brazing structure. In many instances, one component is formed from a ceramic, while the other is formed from a metal or metal alloy.
1/22 “COMPOSITION OF BRAZIL ALLOY, ELECTROCHEMICAL CELL, ENERGY STORAGE DEVICE AND METHOD FOR UNITING COMPONENTS”
Field of the Invention [001] This invention generally relates to a brazing composition. In some specific embodiments, the invention relates to a brazing composition that provides corrosion resistant sealing and other benefits for components used at high temperatures, for example, thermal rechargeable batteries.
Background of the Invention [002] A variety of electrochemical devices require processes and compositions to provide seals on or within the devices. The seals can be used to encapsulate the entire device or they can separate multiple chambers within the device. As an example, many types of sealing materials have been considered for use in high temperature rechargeable cells / batteries to join different components.
[003] Sodium / sulfur or sodium / metal halide are good examples of high temperature batteries that can include a variety of ceramic and metal components. Ceramic components generally include an electrically insulating alpha-alumina collar and an ion-conducting electrolyte beta-alumina tube and are usually joined or bonded by means of a sealing glass. Metal components generally include a metal coating, current-collecting components and other metal components that are generally joined by welding or welding under thermocompression (TCB). Although mechanisms for sealing these components are currently available, their use can sometimes present some difficulty. For example, metal-ceramic bonding
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2/22 can be challenging due to the thermal stress caused by an uneven thermal expansion coefficient for ceramic and metal components.
[004] The bonding of metal to ceramic is most critical for the reliability and safety of high temperature cells. Many types of sealing materials and sealing processes have been considered to join metal to ceramic components, including ceramic adhesives, brazing and sintering. However, most seals may not be able to withstand high temperatures and corrosive environments.
[005] A common connection technology for joining ceramic and metal components involves multiple stages of metallization of the ceramic component, followed by the connection of the metallized ceramic component to the metal component using a thermal compression connection (TCB). The bonding strength of such metal-ceramic joints is controlled by a wide range of variables. Some of the variables include the microstructure of the ceramic component, the metallization of the ceramic component and various TCB process parameters. In order to guarantee a good bonding strength, the process requires close control of several parameters involved in several stages of the process. In short, the method is relatively expensive and complicated, given the multiple processing steps and the difficulty in controlling the processing steps.
[006] Brazing is another potential technology for making ceramic and metal joints. A brazing material is heated above its melting point and distributed between two or more parts by capillary action. However, most brazing materials (or brazing materials) have limitations that prevent them from meeting all the necessary high temperature battery requirements. In addition, some of the commercial brazing materials can be quite expensive; and their effective use in various processes can also be expensive. However, technologies
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3/22 brazing continues to be of considerable interest for joining ceramic and metal parts in various high temperature devices.
[007] In view of some of these challenge concerns, it may be desirable to develop new brazing alloy compositions that have properties and characteristics that satisfy performance requirements for high temperature rechargeable batteries and are less complicated and less expensive to process compared to existing sealing methods.
Description of the Invention [008] One embodiment of this invention is directed to a brazing alloy composition comprising:
a) nickel;
b) about 5% to about 40% of a refractory metal selected from niobium, tantalum, molybdenum or combinations thereof;
c) about 2% to about 32% chromium; and
d) about 0.5% to about 10% (total) of at least one active metallic element, based on the total weight of the composition.
[009] Another embodiment of the invention is directed to an electrochemical cell comprising a first component and a second component joined to each other by a brazing alloy composition as described above.
[010] A method for joining components forms the basis for another embodiment of this invention. The method comprises the step of introducing a brazing alloy composition between a first component and a second component to be joined, to form a brazing structure. The brazing alloy composition is as described above and further described in the remainder of this disclosure. In this method, the structure of
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4/22 braze that is put in place is heated to form an active brazing seal (joint) between the first component and the second component.
Brief Description of the Drawings [011] Figure 1 is a schematic view showing a cross section of an electrochemical cell according to some embodiments of this invention.
[012] Figure 2 is a representation of a scanning electron micrograph of a cross-section of a brazing joint between a ceramic component and a metal component.
Description of Embodiments of the Invention [013] The invention includes embodiments that relate to a brazing alloy composition to provide various types of seals. Non-limiting examples include the seals that are required in various electrochemical cells, for example, those in a sodium metal halide battery or a sodium / sulfur battery. The invention also includes embodiments that refer to devices made using the brazing composition. As discussed in detail below, some of the embodiments of the present invention provide a brazing alloy for sealing a ceramic component in a metal component, for example, in an electrochemical cell; along with the metal halide battery formed therefrom. These achievements advantageously provide an improved seal and method for sealing. Although the present discussion provides examples in the context of a metal halide battery, these processes can be applied to any other application, including joining ceramic to metal or ceramic to ceramic.
[014] During the introduction of elements of various embodiments of the present invention, the articles "one", "one", "o", "a", "said" and "said" are
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5/22 intended to mean that there is one or more of the elements, unless otherwise stated. The terms "comprises", "includes" and "has" are intended to be inclusive and mean that there may be additional elements other than those listed. As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items. Unless otherwise stated in this document, the terms "placed in", "deposited in" or "placed between" refer to either direct contact between layers, objects and the like or indirect contact, for example, which have layers intervention between them.
[015] The approximate language, as used in this document throughout the specification and claims, can be applied to modify any quantitative representation that may vary in a permissible manner without resulting in a change in the basic function to which it may be related. Consequently, a value modified by a term such as "about" is not limited to the precise value specified. In some instances, the approximate language may correspond to the accuracy of an instrument to measure the value.
[016] As used herein, the term "liquid temperature" generally refers to a temperature at which an alloy is transformed from a solid to a viscous or molten state. The liquid temperature specifies the maximum temperature at which crystals can coexist with melting in thermodynamic equilibrium. Above the liquid temperature, the alloy is homogeneous and below the liquid temperature, an increasing number of crystals begins to form in fusion over time, depending on the particular alloy. Generally, an alloy, at its liquid temperature, melts and forms a seal between two components to be joined.
[017] The liquid temperature can be contrasted with a "solid temperature". The solid temperature quantifies the point at which a
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6/22 material solidifies completely (crystallizes). Liquid and solid temperatures do not necessarily align or overlap. If there is a gap between liquid and solid temperatures, then within that range, the material consists of both solid and liquid phases simultaneously (like a slurry).
[018] “Sealing” is a function performed by a structure that joins other structures to reduce or prevent leakage through the articulation between the other structures. The sealing structure can also be referred to as a “seal” or “joint” in this document, for the sake of simplicity.
[019] Typically, “brazing” uses a brazing material (usually an alloy) that has a lower liquid temperature than the melting points of the components (ie, their materials) to be joined. The brazing material is brought slightly to its melting temperature (or liquid) while being protected by a suitable atmosphere. The brazing material then flows through the components (known as wetting) and is then cooled to join the components together. As used herein, "brazing alloy composition" or "brazing alloy", "brazing material" or "brazing alloy" refer to a composition that has the ability to wet the components to be joined and to seal the themselves. A brazing alloy, for a particular application, must withstand the required service conditions and must melt at a lower temperature than these base materials; or it must melt at a very specific temperature. Conventional brazing alloys generally do not wet ceramic surfaces sufficiently to form a strong bond at the interface of a joint. In addition, alloys may be at risk for corrosion of sodium and halide.
[020] As used in this document, the term “brazing temperature” refers to a temperature at which a structure
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7/22 of brazing is heated to allow a brazing alloy to wet the components to be joined and to form a brazing joint or seal. The brazing temperature is generally higher than or equal to the liquid temperature of the brazing alloy. In addition, the brazing temperature must be lower than the temperature at which the components to be joined can become chemically, compositionally and mechanically unstable. There may be several other factors that influence the selection of the brazing temperature, as those skilled in the art understand.
[021] The embodiments of the present invention provide a brazing alloy composition with the ability to form a joint by "active brazing" (described below). In some specific embodiments, the composition also has a high resistance to corrosion of sodium and halide. The brazing alloy composition includes nickel, at least one selected refractory metal, chromium and at least one active metallic element, as described in this document. Each of the alloy elements generally contributes and optimizes at least one property of the overall brazing composition. These properties can include liquid temperature, thermal expansion coefficient, fluidity or wettability of the brazing alloy with a ceramic; corrosion resistance and ease of processing. Some of the properties are described below.
[022] According to most embodiments of the invention, the brazing alloy composition is a nickel based alloy. In other words, the alloy generally contains a relatively high amount of nickel compared to the amount of other elements in the alloy. Nickel is relatively inert in a corrosive environment compared to other known base metals, for example, copper, iron, chromium, cobalt, etc. Additionally, it is observed that nickel can improve other properties of
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8/22 brazing alloy, such as thermal expansion coefficient and phase stability.
[023] In some embodiments of this invention, a suitable level for the amount of nickel can be at least about 30%, based on the total weight of the brazing alloy. Very often, nickel is present in an amount of at least about 45%. In some embodiments that are preferred for selective end-use applications, nickel is present from about 50% to about 70%, based on the total weight of the brazing alloy and, more often, from about 50% to about 65%.
[024] As described above, the concept of “active brazing” is important for the realizations of this invention. Active brazing is a technology often used to join a ceramic to a metal or a ceramic to a ceramic. Active brazing uses an active metallic element that promotes wetting of a ceramic surface, improving the ability to provide an airtight seal. An “active metallic element”, as used in this document, refers to a reactive metal that has a high affinity for oxygen within the ceramic and thereby reacts with the ceramic. A brazing alloy that contains an active metallic element can also be referred to as an "active brazing alloy." The active metallic element undergoes a reaction with the ceramic when the brazing alloy is in a molten state and leads to the formation of a thin reaction layer at the interface of the ceramic and the brazing alloy. The thin reaction layer allows the brazing alloy to wet the ceramic surface, resulting in the formation of a ceramic-ceramic connection / joint or a ceramic-metal connection, which can be referred to as an “active brazing seal”.
[025] Thus, an active metallic element is an essential constituent of a brazing alloy to employ active brazing. A variety of suitable active metal elements can be used to
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9/22 form the active brazing alloy. The selection of a suitable active metal element depends primarily on the chemical reaction with the ceramic (eg, alumina) to form a uniform and continuous reaction layer and the ability of the active metal element (for example, as measured by free-forming energy Gibbs) form an alloy with a base alloy. (In this instance, the base alloy is nickel with chromium and selected refractory elements, as discussed above).
[026] In terms of cost, availability and performance, the active metallic element for the achievements in this document is often titanium. However, for other embodiments, zirconium is preferred; and in some cases, hafnium is preferred. Under certain conditions and for different types of "matching" surfaces, each of these elements may be especially suitable for diffusing and reacting with a ceramic surface during brazing. A continuous transitional layer (ie, the “reaction layer”) provides a wettable surface that has a semi-metallic character. In this way, a coherent brazing joint is formed between the components. In other embodiments, it may sometimes be advantageous to include vanadium as the active metal.
[027] The presence and quantity of the active metal can influence the thickness and quality of the thin reaction layer, which contributes to the wetting or fluidity of the brazing alloy and, therefore, to the bond strength of the resulting joint. In some embodiments, the active metal is present in an amount that is not greater than about 10% by weight, based on the total weight of the brazing alloy. A suitable range is often from about 0.5% by weight to about 5% by weight. In some specific embodiments (although not all), the active metal is present in an amount ranging from about 1% by weight to about 3% by weight, based on the total weight of the brazing alloy. O
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10/22 active metallic element is usually present in smaller amounts suitable for improving the wetting of the ceramic surface and forming the thin reaction layer, for example, less than 10 microns. A high amount of the active metal layer can cause or accelerate the corrosion of halide.
[028] The brazing alloy composition of this invention further comprises a refractory element selected from niobium, tantalum and combinations thereof. The refractory element is especially useful for providing strength and resistance to high temperature in brazing. A refractory element such as niobium can also provide good corrosion resistance in a sodium-containing environment. In addition, the refractory element, along with selected nickel and chromium qualities (discussed below), effectively forms a ternary alloy that provides the general brazing composition with a liquid temperature below about 1,350 ° C. (In most embodiments, the brazing alloy has a lower liquid temperature than the melting temperatures of the components that will be joined by brazing.) [029] The liquid temperature is an important resource for the brazing alloy, in terms of flow properties and wetting capabilities. As described below, these properties are especially critical when sealing ceramic-metal components (for example, ring-collar sealing) in a high temperature battery. In some preferred embodiments, the refractory element (s), nickel and chromium are present in ratios that provide the general brazing composition with a liquid temperature less than about 1,250 ° C.
[030] In many specific embodiments, the refractory element is niobium (alone) or a refractory composition that contains at least about 50% niobium, by weight, for example, in which the balance comprises tantalum. When niobium is the refractory element, it is usually present
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11/22 at a level in the range of about 5% to about 20%, based on the total weight of the brazing composition. In some preferred embodiments, the level is in the range of about 10% to about 15%. (Specific levels also depend on the relative levels of the active metal and chromium as well). However, in other instances, the level of niobium can extend up to about 30% by weight and in some instances, up to about 40% by weight. It should be noted, however, that the presence of relatively high levels of niobium can, in some cases, result in the formation of brittle intermetallic phases, so very often the lowest levels of niobium are preferred, within the ranges shown above.
[031] In other embodiments, the refractory element is tantalum. In brazing compositions for various embodiments, tantalum is generally present at a level in the range of about 5% to about 25%, based on the total weight of the brazing composition. As in the case of niobium, there may be applications in which the tantalum level can extend up to about 30% by weight and, in some instances, up to about 40% by weight. However, the relatively high levels of tantalum can result in an alloy with a liquid temperature beyond about 1,350 ° C to 1,400 ° C, thus making many brazing applications (although not all applications) impractical. In some specific embodiments, the tantalum level is in the range of about 5% to about 20% and, preferably, in the range of about 10% to about 20%.
[032] As previously mentioned, a combination of niobium-tantalum is also possible. The ratio (Nb to Ta) of the two elements can be in the range of about 3: 1 to about 1: 3. (The specific proportions of each element will also depend on the desired liquid temperature, as described above).
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12/22 [033] In some end-use applications, the refractory element can be molybdenum, alone or in combination with other refractory elements. The use of molybdenum can result in a relatively high liquid temperature for the brazing composition. However, if a component that is brazed is formed from molybdenum, higher brazing temperatures may be required compared to nickel brazing. For example, the metal rings used in battery sealing systems, described below, may possibly be formed from molybdenum or a molybdenum alloy. In those instances, a braze containing molybdenum may be very appropriate. The level of molybdenum will vary based on the general factors discussed in this document (such as melting temperature). Generally, the various ranges described above for tantalum would also be suitable for molybdenum.
[034] Chromium is another important constituent for the brazing alloy composition. Chromium plays a key role in resistance to the environment, for example, resistance to “hot corrosion”, mixed gas attack and mechanical damage, such as erosion. Chromium can also be important for improving the high temperature resistance of the braze and its resistance to inherent oxidation.
[035] The level of chromium present is based on a number of factors, including the environment in which the brazing material will be employed, as well as the relative amounts of nickel and the refractory element (s) that are gifts. Generally, the chromium level is about 2% to about 32%, based on the weight of the brazing composition. In some specific achievements, the level is in the range of about 10% to about 30%. In some especially preferred embodiments - especially when joining components from within a sodium metal halide thermal battery, the chromium level is in the range of about 25% to about 30%.
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13/22 [036] In some embodiments (although not all), the brazing alloys described in this document may also include cobalt. The addition of cobalt can further improve the corrosion resistance of the general composition. Cobalt is generally present in relatively small amounts, for example. about 0.5% to about 20% by weight. In some preferred embodiments, the level is about 5% to about 10%.
[037] Another optional constituent is palladium. In the case of sodium metal halide electrochemical cells, the presence of palladium can further improve the corrosion resistance in the sodium-containing environment. In other end-use applications, palladium can function as a melting point depressant. The melting point depressant can decrease the viscosity of the molten alloy and, in turn, increase its “fluidity” or wettability. In some embodiments, the brazing alloy includes up to about 10% by weight of palladium (for example, about 0.5% by weight to about 10% by weight), based on the total weight of the alloy.
[038] In the case of some of the thermal battery applications, the particular nature of the electrode and electrolyte compositions and their chemical reactions can influence the inclusion or exclusion of elements in the brazing composition that can sometimes interact with the chemistry of the battery . An example is provided in the case of sodium metal halide electrochemical cells. Aluminum is believed to be chemically stable in the secondary electrolyte of the cell, typically NaAlCÇ, and can sometimes be included in active brazing compositions, usually at a level of less than about 5% by weight (eg 0.5 % by weight to about 5% by weight). However, in other situations for these cell types, aluminum can react adversely with additives that can be used at the cathode and must therefore be omitted entirely.
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14/22 [039] Another example refers to iron, which can also be an important constituent in sodium metal halide chemistry, that is, in the cell's electrode activity. In general, iron is chemically stable in both the cathodic and anode environments of the cell. However, iron can be electrochemically active at the operating voltages of the cell and this can be problematic, especially when cells need to be filled almost entirely with electrochemical components for a higher energy density. Although brazing sealing mechanisms for joining ceramic-metal components in the cell do not participate in an electrochemical way, the presence of iron in the brazing can result in the brazing itself becoming electrically active and this can lead to a decrease in the brazing integrity. Thus, in some preferred embodiments, the brazing composition must be free of any iron.
[040] Gold and silver are ductile precious metals that can also reduce the liquid temperature and thus lower the brazing temperature. However, their presence can sometimes be problematic in the case of sodium metal halide electrochemical cells. These metals tend to form various intermetallics with sodium at the operating temperature of the cells and this can promote corrosion when the cell is in operation. Therefore, it is often preferred that the other and silver, if present, are each at a level no greater than about 10% by weight. In some specific embodiments, the brazing composition must be free of each of these metals.
[041] As previously mentioned, other embodiments of this invention are directed to an electrochemical cell comprising a first component and a second component joined to each other by a brazing alloy composition. The cell can be a sodium sulfur cell or a sodium metal halide cell, for example. The composition of
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15/22 brazing alloy is as described above and comprises nickel, at least one refractory element, chromium and at least one active metal. The respective amounts of the constituents of the alloy are described above. In some embodiments, the brazing alloy composition consists essentially of nickel, the refractory metal (s), chromium and at least one active metallic element. In other embodiments, the brazing alloy composition additionally and essentially consists of at least one of palladium or cobalt. (Those skilled in the art understand that trace amounts of various elements, for example, in impurity levels, can be introduced into an alloy from various sources, during preparation and use. These trace amounts can generally be considered insignificant).
[042] As described above as well, the first component of the electrochemical cell often comprises a metal or metal alloy and the second component often comprises a ceramic. The metal component can be a ring formed from a variety of materials, such as nickel, niobium, molybdenum, ferrous nickel-cobalt alloys (e.g., Kovar ^TM alloys) and the like. The ceramic component can be a necklace that includes an electrically insulating material, such as alumina. A specific illustration of such a cell, which contains metal-to-ceramic joints, is provided in Figure 1.
[043] Figure 1 is a schematic diagram representing an exemplary embodiment of a sodium metal halide battery cell 10. Cell 10 has an ion-conducting separator tube 20 placed in a cell box 30. Separator tube 20 is usually made of β-alumina or β '' - alumina. Tube 20 defines an anodic chamber 40 between cell box 30 and tube 20 and a cathodic chamber 50, within tube 30. Anodic chamber 40 is generally filled with anodic material 45, for example,
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16/22 sodium. The cathodic chamber 50 contains cathode material 55 (e.g. sodium chloride and nickel) and a molten electrolyte, usually sodium chloroaluminate (NaAlCU).
[044] An electrically insulating ceramic necklace 60, which can be made of alpha-alumina, is located at the top end 70 of tube 20. A cathode current collector assembly 80 is placed in cathode chamber 50, with a structure cover 90 in the top region of the cell. The ceramic collar 60 is fitted to the top end 70 of the separator tube 20 and is sealed by a glass seal 100. In one embodiment, the collar 60 includes an upper portion 62 and a lower inner portion 64 that is confined to an inner wall of tube 20, as shown in Figure 1.
[045] In order to seal cell 10 at the top end (that is, its upper region), a metal ring 110 is sometimes placed. The metal ring 110 has two portions; an outer metal ring 120 and an inner metal ring 130, which are joined, respectively, with the upper portion 62 and the lower portion 64 of the ceramic collar 60, by means of the active brazing seals 140 and 150. The sealing by active brazing 140, seal 150 or both can be formed using a suitable brazing alloy composition described above. The collar 60 and the metal ring 110 can be temporarily held together with a set (for example, a fastener) or by other technologies, until the sealing is completed.
[046] The outer metal ring 120 and the inner metal ring 130 are generally closed by welding to seal the cell after the union with the ceramic collar 60 is completed. The outer metal ring 120 can be welded to the cell box 30; and the inner metal ring 130 can be welded to the current collector assembly 80.
[047] The shape and size of the various components discussed above with reference to Figure 1 are only illustrative for understanding
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17/22 of the cell structure and are not intended to limit the scope of the invention. The exact position of the seals and joined components can vary to some degree. In addition, each of the terms "necklace" and "ring" is intended to comprise parts of metal or ceramic of circular or polygonal shape and, in general, all shapes that are compatible with a particular cell design. An additional description of electrochemical cells of this type is provided in the Application Application pending 13 / 600.333 (R. Adharapurapu et al), deposited on August 31, 2012, and all content is incorporated into this document as a reference.
[048] Brazing alloys and active brazing seals formed from them generally have good stability and chemical resistance within certain parameters at a given temperature. It is desirable (and, in some cases, critical) that the brazing seal retains its integrity and properties during various processing steps during the manufacture and use of the cell, for example, during a glassy sealing process for a ceramic joint with ceramics and during cell operation. In some instances, the optimum performance of the cell is usually achieved at a temperature greater than about 300 ° C. In one embodiment, the operating temperature can be in the range of about 270 ° C to about 450 ° C. In one embodiment, the glass sealing process is carried out at a temperature of at least about 1,000 ° C. In some other embodiments, the glass sealing process is carried out in a range of about 1,000 ° C to about 1,200 ° C and in some situations, at even higher temperatures. In addition, the bond strength and tightness of the seal can depend on several parameters, such as the composition of the brazing alloy, the thickness of the thin reaction layer, the composition of the ceramic and the surface properties of the ceramic.
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18/22 [049] Other embodiments of the invention are directed to an energy storage device that includes a plurality of electrochemical cells as disclosed in previous embodiments. The cells are, directly or indirectly, in thermal and / or electrical communication with each other. Those of ordinary skill in the art are familiar with the general principles of such devices. For example, U.S. Patent 8,110,301 is illustrative and incorporated by reference into this document. However, there are many other references that generally describe various types of energy storage devices and their construction.
[050] Some embodiments provide a method for joining a first component to a second component using a brazing alloy composition. The method includes the steps of introducing the brazing alloy between the first component and the second component to form a brazing structure. (The alloy can be deposited on one or both of the interlocking surfaces, for example, as also described above). The brazing structure can then be heated to form an active brazing seal between the first component and the second component. In one embodiment, the first component includes a ceramic; and the second component includes a metal. (The brazing alloy composition is as previously described).
[051] In the general preparation of the brazing alloy, a desired alloy powder mixture can be obtained by combining (for example, mixing and / or grinding) commercial metal powders of the constituents in their respective amounts. In some embodiments, the brazing alloy can be used as a foil, blade, ribbon, preconformation or wire or it can be formulated into a paste that contains water and / or organic fluids. In some embodiments, precursor metals or metal alloys can be fused to form homogeneous fusions before they are formed and
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19/22 shaped into particles. In some cases, the molten material can be directly formed into sheets, preconditions or threads. The formation of the particulate materials may initially comprise spraying the alloy melt in a vacuum or inert gas to obtain a pre-alloy powder from the brazing alloy. In other cases, the pellets of the materials can be milled into a desirable shape and particle size.
[052] In one embodiment, a layer of the brazing alloy is arranged on at least one surface of the first component or the second component to be joined by brazing. The brazing alloy layer, in a specific embodiment, is placed on a surface of the ceramic component. The thickness of the alloy layer can be in the range of about 5 microns to about 300 microns. In some specific embodiments, the thickness of the layer is in the range of about 10 microns to about 100 microns. The layer can be deposited or applied to one or both surfaces to be joined by any suitable technology, for example, by a printing process or another dispersion process. In some instances, the sheet, wire or preconformation can be properly positioned to connect the surfaces to be joined. In some embodiments, a paste or dispersion of the active metal can be applied initially to a surface of a ceramic component that is joined. For example, a layer of titanium paste can be applied in this way, functioning as a type of main layer, as described in PCT Application WO 99/65642, incorporated by reference in this document.
[053] In some specific embodiments, a brazing alloy blade or sheet may be desirable. The thickness of the slides or sheets can generally vary between about 20 microns and about 200 microns. The alloys can be laminated into sheets or sheets by suitable technology, for example, melt spinning. In one embodiment, the league
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20/22 can be pulled by melting into a blade or sheet, along with rapid rapid cooling during spinning.
[054] In a typical embodiment, the method additionally includes the step of heating the brazing structure to the brazing temperature. When the brazing structure is heated to the brazing temperature, the brazing alloy melts and flows over the surfaces. Heating can be undertaken in a controlled atmosphere, such as highly ultra pure argon, hydrogen and argon, highly ultra pure helium; or in a vacuum. To achieve good flow and wetting of the brazing alloy, the brazing structure is kept at the brazing temperature for a few minutes after the brazing alloy has melted and this period can be referred to as the “brazing time”. During the brazing process, a load can also be applied to the samples.
[055] Brazing temperature and brazing time can influence the quality of the active brazing seal. The brazing temperature is generally lower than the melting temperatures of the components to be joined and higher than the liquid temperature of the brazing alloy. In one embodiment, the brazing temperature is in the range of about 900 ° C to about 1,500 ° C, for a period of about 1 minute to about 30 minutes. In a specific non-limiting embodiment, heating is carried out at the brazing temperature of about 1,000 ° C to about 1,300 ° C, for about 5 minutes to about 15 minutes.
[056] During brazing, the alloy melts and the active metallic element (or elements) present in the melting reacts with the ceramic and forms a thin reaction layer at the interface of the ceramic surface and the brazing alloy, as previously described. The thickness of the reaction layer can be in the range of about 0.1 micron to about 2 microns, depending on the amount of active metal element available to react with the
Petition 870160050284, of 09/09/2016, p. 33/36
21/22 ceramic and depending on the surface properties of the ceramic component. In a typical sequence, the brazing structure is then subsequently cooled to room temperature; resulting in active brazing sealing between the two components. In some instances, rapid cooling of the brazing structure is permitted.
[057] In some embodiments, an additional layer containing the active metallic element can first be applied to the ceramic component. The additional layer may have a high amount of the active metal element, for example, more than about 70% by weight. Suitable examples may include nanoparticles of the active metal element or a hydride of the active metal element, for example, titanium hydride.
[058] Some of the embodiments of the present invention advantageously provide brazing alloys, which are compositionally stable and chemically stable in the corrosive environment in relation to known brazing alloys and have the ability to form an active brazing seal for a joint ceramic with metal. These brazing alloys have high resistance to sodium corrosion and resistance to halide corrosion for many end uses. The formation of ceramic-to-metal seals for high temperature cells (as discussed above) by active brazing simplifies the overall cell assembly process and improves cell reliability and performance. The present invention provides advantages for leveraging a relatively inexpensive, simple and fast process for sealing the cell or battery compared to currently available methods.
Examples [059] The example provided in this document is for illustrative purposes only and should not be construed as limiting the scope of the claimed invention. Unless otherwise specified, all ingredients may be commercially available
Petition 870160050284, of 09/09/2016, p. 34/36
22/22 suppliers of common chemicals such as Alfa Aesar, Inc. (Ward Hill, Massachusetts), Sigma Aldrich (St. Louis, Missouri), Spectrum Chemical Mfg. Corp. (Gardena, California) and the like.
[060] A brazing alloy composition of nickel, chromium, niobium and titanium was prepared, whose nominal composition is Ni-27.2Cr-14.1Nb-4Ti (% by weight). In preparing the alloy, the individual elements were weighed according to the desired proportions and then fused to arc to provide an ingot of the material. In order to guarantee the homogeneity of the composition, the ingot was cast three times. The sample's liquid temperature was determined to be 1,203 ° C, using a Differential Calorimetry Scan (DSC).
[061] The ingot was formed in approximately a 75 micron thick slide and cooled. The sample slide was placed between the surfaces of an alpha alumina component and a nickel component to be joined. The set was then heated to about 1,250 ° C for about 10 minutes and then cooled to room temperature to form a joint.
[062] Figure 2 is a SEM image in cross section of the brazed components. The image represents the interface between the brazing alloy 200 and the alumina component 202, in the joint region. A reaction layer 204 was observed at the interface, indicating reaction between the brazing alloy and the ceramic and the formation of an active brazing seal.
[063] The present invention has been described in terms of some specific embodiments. They are intended for illustration only and should not be construed as limiting in any way. Thus, it should be understood that modifications can be made to them are within the scope of the invention and the attached claims. In addition, all patents, patent applications, articles and texts that are mentioned above are incorporated by reference into this document.
Petition 870160050284, of 09/09/2016, p. 35/36
1/3

权利要求:
Claims (23)
[1]
Claims
1. COMPOSITION OF BRAZY ALLOY, characterized by comprising:
a) nickel;
b) from 5% to 40% of at least one refractory metal selected from niobium, tantalum or molybdenum;
c) from 2% to 32% chromium; and
d) 0.5% to 10% (total) of at least one active metallic element, based on the total weight of the composition.
[2]
2. COMPOSITION, according to claim 1, characterized by the fact that the refractory metal is niobium.
[3]
3. COMPOSITION, according to claim 1, characterized by the fact that the refractory metal is tantalum or a combination of tantalum and niobium.
[4]
4. COMPOSITION, according to claim 1, characterized by the fact that the chromium level is in the range of 10% to 30%.
[5]
5. COMPOSITION, according to claim 1, characterized by the fact that the active metallic element is selected from the group consisting of titanium, zirconium, hafnium and vanadium.
[6]
6. COMPOSITION, according to claim 1, characterized by the fact that the active metallic element is titanium.
[7]
7. COMPOSITION, according to claim 1, characterized by the fact that the active metallic element is zirconium.
[8]
8. COMPOSITION, according to claim 1, characterized by the fact that the active metallic element is hafnium.
[9]
9. COMPOSITION, according to claim 1, characterized by the fact that it comprises at least 30% nickel.
Petition 870160050284, of 09/09/2016, p. 11/36
2/3
[10]
10. COMPOSITION, according to claim 9, characterized by the fact that it comprises from 45% to 70% nickel.
[11]
11. COMPOSITION, according to claim 1, characterized by additionally comprising at least one among cobalt and palladium.
[12]
12. COMPOSITION, according to claim 1, characterized by the fact that it comprises from 0.5% to 20% cobalt.
[13]
13. COMPOSITION, according to claim 1, characterized by the fact that it comprises from 0.5% to 10% palladium.
[14]
14. COMPOSITION, according to claim 1, characterized by the fact that it has a net temperature of less than 1,250 ° C.
[15]
15. COMPOSITION, according to claim 1, characterized by the fact that it is iron-free.
[16]
16. COMPOSITION, according to claim 1, characterized by the fact that it additionally comprises aluminum, at a level of less than 5% by weight.
[17]
17. ELECTROCHEMICAL CELL (10), characterized by comprising a first component and a second component joined together by a brazing alloy composition comprising:
a) nickel;
b) 5% to 40% of at least one refractory metal selected from niobium, tantalum or molybdenum.
c) from 2% to 32% chromium; and
d) 0.5% to 10% (total) of at least one active metallic element, based on the total weight of the composition.
[18]
18. ELECTROCHEMICAL CELL (10), according to
Petition 870160050284, of 09/09/2016, p. 12/36
3/3 claim 17, characterized by the fact that the brazing alloy composition provides an active brazing seal that joins the first component to the second component.
[19]
19. CELL (10) according to claim 18, characterized in that the first component comprises a metal and the second component comprises a ceramic.
[20]
20. CELL (10), according to claim 19, characterized by the fact that the first component comprises nickel.
[21]
21. CELL (10) according to claim 19, characterized by the fact that the second component comprises alumina.
[22]
22. ENERGY STORAGE DEVICE, characterized by comprising a plurality of electrochemical cells (10), as defined in claim 17.
[23]
23. METHOD FOR JOINING COMPONENTS, characterized by comprising the step of introducing a brazing alloy composition between a first component and a second component to be joined to form a brazing structure, wherein the brazing alloy composition comprises
a) nickel;
b) from 5% to 40% of at least one refractory metal selected from niobium, tantalum or molybdenum;
c) from 2% to 32% chromium; and
d) 0.5% to 10% (total) of at least one active metallic element, based on the total weight of the composition; and then heat the brazing structure to form an active brazing seal (joint) between the first component and the second component.
Petition 870160050284, of 09/09/2016, p. 13/36
1/2

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法律状态:
2018-03-20| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|

2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2019-04-16| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

2019-08-13| B09B| Patent application refused [chapter 9.2 patent gazette]|

2019-10-29| B09B| Patent application refused [chapter 9.2 patent gazette]|Free format text: MANTIDO O INDEFERIMENTO UMA VEZ QUE NAO FOI APRESENTADO RECURSO DENTRO DO PRAZO LEGAL |

优先权:

申请号 | 申请日 | 专利标题

US201261651817P| true| 2012-05-25|2012-05-25|

US13/628,548|US20130315659A1|2012-05-25|2012-09-27|Metallic compositions useful for brazing, and related processes and devices|

US13/628,548|2012-09-27|

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