The present invention is generally directed to forming glass-to-metal seals that are of particular use when hermeticity is required for very long exposures to harsh environments. These seals can be used for the glass-to-metal seals in components exposed to severe chemical environments, e.g., in headers for ambient temperature lithium-ion batteries.
Hermetic seals are often used for harsh environmental applications. They are used to present a barrier that protects sensitive electronic components from outside environmental conditions, which would otherwise destroy the hardware components. In the case of medical devices, hermetic seals can also protect living tissue from electronic components. The challenge is to manufacture the hermetic seal as ruggedly as possible for applications where hermeticity will be required for extended exposures to harsh environments.
Ambient temperature lithium batteries provide high energy densities and high rate capabilities at low temperatures; however, a major problem associated with these cells is presented by the highly corrosive nature of lithium chemistry. Standard glass insulators, used to separate the header of a battery from the center pin, while providing a hermetic seal for the battery, experience extensive corrosion over relatively short periods of time, thus severely limiting the shelf life of the cells.
An additional problem associated with conventional lithium batteries is encountered when uncoated molybdenum is used as the pin material for center pins in lithium battery headers. Molybdenum pins are subject to rapid corrosion when the polarity is reversed from a negative terminal to a positive and hence are not usable for lithium battery designs. Uncoated molybdenum is difficult to work with, being difficult to weld, difficult to machine as it is very brittle, and is susceptible to aqueous corrosion. It is desirable to use alternative pin materials, instead of uncoated molybdenum. Replacement of uncoated molybdenum with weldable, machinable, and chemically resistant alloys improves both the ability to manufacture lithium batteries and their ultimate performance.
In order to form an acceptable glass-to-metal seal in a lithium battery at ambient temperature the glass must meet three criteria. First, it must have a high resistance to lithium corrosion; second, it must be able to make a hermetic seal between the metal header and the metal center pin, which requires a thermal expansion match between the glass and the pin; and, third, it must be an electrical insulator, so that the header and the center pin are electrically isolated.
Also, where feedthroughs are utilized in connection with implanted devices, where the electrical terminals may come into contact with body fluids, it is necessary to choose terminals or pins made of bio-stable materials since there is the possibility of hydrogen embrittlement occurring, especially at the negative terminal in a lithium-ion battery.
One glass used in the glass-to-metal seal in headers for ambient temperature lithium batteries is TA-23, which has a finite corrosion rate when in contact with lithium metal that limits the lifetime of the battery.
Glasses based on the CaO—Al2O3—B2O3 and CaO—MgO—Al2O3—B2O3 systems have been developed to improve the corrosion resistance and extend the battery lifetime. Cabal-12 is a promising glass which exhibits corrosion resistance. Although this glass has desirable corrosion resistance and resistance to cracking, many metals do not wet Cabal-12 so as to create strong, hermetic seals, nor do the metals exhibit weldability or desired thermal expansion characteristics. Like TA-23, Cabal-12 has a CTE that approximates that of the molybdenum pin, which is about 6.0×10−6/° C. Cabal-12 has superior corrosion resistance over TA-23. The alkaline earth alumino-borate glasses, such as CaO—Al2O3—B2O3 and CaO—MgO—Al2O3—B2O3 have a CTE range, on the order of 6.0-9.0×10−6/° C., making them unsuitable for sealing to high CTE metal pins.
U.S. Pat. No. 5,015,530 describes glass-to-metal seals for use in lithium electrolyte environments, using glass compositions that seal hermetically with higher expansion, metal pin materials. Alkaline earth-aluminoborate glasses, based on the (CaO, SrO, BaO)—B2O3—Al2O3 systems and high thermal expansion metal pins are discussed. The glasses are boroaluminate glasses with SrO and BaO substituted for the CaO and MgO used in Cabal-12, and a CaO—B2O3—Al2O3 glass, having CTEs that match the CTE of the pin materials, while resisting attack by lithium. The composition of these glasses is adjusted to achieve a CTE between 9.0 and 12×10−6/° C., allowing hermetic seals to high CTE pin materials, such as 446 stainless steel (CTE of 11.4×10−6/° C.) and Alloy-52 (CTE of 9.8×10−6/° C.).
U.S. Pat. No. 5,821,011 addresses a similar issue for implants of bio-stable materials. The glass insulator is a Cabal-12 glass. The terminal is comprised of a metal that has CTEs compatible with the glass seal. For glass seals having a CTE in the range of 6.8-8.0×10−6/° C. the terminal is a thin layer of titanium clad over niobium or tantalum. For glass seals having a thermal expansion in the range of 8.0-9.0×10−6/° C. the terminal is platinum, platinum-iridium, their alloys, or pure titanium.
U.S. Pat. No. 5,851,222 discusses centerless grinding of pins for lithium batteries for implantable medical devices where the pin may be platinum, stainless steel, aluminum, tantalum, niobium, or titanium. TA-23 and Cabal-12 sealing glasses are also discussed.
This conventional sealing scenario is fundamentally flawed in two regards. First, the design of glass-to-metal seals generally requires that the sealing glass 7 have a higher coefficient of thermal expansion (CTE) than the pin 1,
Another shortcoming is based upon the desire for the sealing glass 7 to flow and wet to the platinum pin 1. The alkaline earth alumino-borate sealing glass 7 candidates do not wet certain metals, such as platinum. Since they do not wet platinum or platinum alloys, they do not exhibit chemical bonding.
In a typical lithium-ion bonded assembly 10, titanium, titanium alloy or a lithium-ion resistant metal will form the header 5 (see
A need exists for an improved lithium-ion battery header.
The present invention is directed to the formation of seals that are of particular use when hermeticity must be retained for long exposures to harsh environments.
Lithium-ion batteries, for example, contain a very corrosive electrolyte. A lithium-ion battery in a conventional application may not require true hermeticity because the battery will “wear out” before the seal does. However, the use of these batteries for rechargeable applications demands that the battery remain hermetically sealed and that the battery keep the electrolyte from escaping the battery package for longer terms. Due to the potential for hydrogen embrittlement or chemical attack by the electrolyte, lithium-ion battery seals occasionally require the use of platinum pin materials. Platinum pins in a glass-to-metal seal, normally, are fabricated as a compression seal. When a Cabal glass is used with a platinum pin, it is not a compression seal because the Cabal glass has a lower coefficient of thermal expansion (CTE) than the platinum. This leads to tensile stresses developing at the glass to pin interface that, in turn, lead to leaking seals. The second problem with lithium-ion battery hermetic seals of glass to platinum pins is the lack of any chemical bonding of the glass to the pin. Platinum is known to be chemically inert. It has been demonstrated that it is possible to push on the end of a pin in a sealed assembly and slide the pin out of the seal with little or no damage to the sealing glass.
In other hermetic applications, such as seawater, saline, in vivo and/or implantable devices and the like, a different set of materials may be used to facilitate the hermetic seal. However, the same essential problem remains. First, it is difficult to find good lithium-ion chemically resistant glasses or glass-ceramics that have higher CTE values than platinum or platinum alloys. Second, even though many metallophillic glasses will readily wet most metals, the exception is platinum. Platinum has long been used for glass melting as an inert container or a lining of the ceramic crucible used in the melting of glasses. Platinum prevents the glass from reacting with the crucible walls and the platinum does not react with the glass. Therefore, even though a much wider glass selection is available for seals exposed to seawater, saline, in vivo and/or in vitro type medical devices, the same problem remains of non-wetting of the platinum pin.
Therefore, if platinum is to be successfully used, it must be used in conjunction with a low expansion core in order to for the glass to effectively put the pin in compression and not rely on any chemical bonding. An appropriate example would be platinum coated Molybdenum or Alloy 42.
This invention addresses the problem in several ways. The first method for consideration is to reduce the coefficient of expansion (CTE) of the pin in the seal, yet maintain the electrochemical protection. This is to be done by using platinum, platinum alloy or platinum family metals that are metallurgically bonded with a lower expansion metal at the core of the pin, such that the lower CTE of the core will yield a seal of proper CTE design considerations. The ratio of platinum metal to low expansion core material may vary as desired, provided that the lower expansion member in the core is the dominant member for expansion characteristics. The low expansion core materials can be molybdenum, tungsten, Invar, Kovar, alloy 36, alloy 42 or any material that will yield a lower expansion CTE than the Cabal 12 or any formulation in the Cabal family of glasses. The platinum may be applied to the low expansion pin material by cladding, electroplating, sputtering, evaporation, CVD or modified CVD, PVD or modified PVD, explosion welding or any such method that will form a metallurgically bonded platinum to low expansion metal core.
Another method to be disclosed is to form a chemical bond at the pin to Cabal glass interface. This may be accomplished by coating either the platinum pin surface with metal(s) known to be wettable by Cabal type glass, such as titanium, niobium, chromium and tantalum, alone or in any combination. It is also known in the art that titanium will bond to platinum. Another preferred method is to selectively remove the platinum in the seal area only and coat the low expansion metal, which is then exposed, with a wettable. The coating may be titanium, tantalum, chromium or niobium, alone or in any combination. It may also be sufficient to only remove the platinum in the seal area and not coat the low expansion metal. Another method is to remove or diminish by abrasion, the platinum in the seal area of the pin. Then to further enhance the seal by coating the abraded area with the above-mentioned metals that are wettable by the Cabal type glass. The abrasion strengthens the seal by providing mechanical retention of the glass to the pin. Such seals have a chemical as well as mechanical sealing characteristic. The coatings of Ti, Nb, Cr and Ta, alone or in any combination may be applied by the above-mentioned methods for applying the platinum to the low expansion metals.
The object of this invention therefore, is to disclose methods of making optimum hermetic seals with platinum pins, platinum alloy pins, molybdenum pins, or any other metal pins used in glass-to-metal seals, using a Cabal glass or other suitable glass, glass-ceramic. Titanium, titanium alloy, stainless steel or any suitable header material that is resistant to lithium-ion chemistry, seawater, saline or bodily fluids, may be used for the header of the seal.
The invention will be best understood from the following description when read in conjunction with the accompanying drawings.
It is an object of the invention to bond a platinum pin in a glass-to-metal seal for corrosive environments.
It is an object of the invention to achieve a compression bond in a glass-to-metal seal for corrosive environments.
It is an object of the invention to provide a chemical bond in a glass-to-metal seal for corrosive environments.
It is an object of the invention to provide a mechanical bond in a glass-to-metal seal for corrosive environments.
It is an object of the invention to achieve a glass-to-metal seal in a lithium-ion battery.
Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawing.
The following description is of the best mode presently contemplated for carrying out the invention. This description is not to be taken in a limiting sense, but is made merely for the purpose of describing the general principles of the invention. The present invention is directed to improved techniques for generating a hermetic seal that is particularly rugged such that hermeticity can be maintained for extended periods in harsh environments, such as in implantable lithium-ion batteries.
Typical alkaline earth alumino-borates sealing glass compositions are listed in Table 1.
In the following discussion, reference to alkaline earth alumino-borates sealing glasses, such as Cabal-12, refer to sealing glasses as presented generally in Table 1.
A typical assembly is presented in
As shown in
A lithium-ion resistant metal, such as titanium or a titanium alloy comprises a header 25. Low CTE pin core 15 is comprised of a metal that yields a lower CTE than alkaline earth alumino-borate sealing glass candidates, such as molybdenum, tungsten, Invar, Kovar, Alloy 36, Alloy 42, Alloy 46, or Alloy 52. The coating 29 is applied to the pin core 15 by cladding, electroplating, sputtering, evaporation, CVD, modified CVD, PVD, modified PVD, explosion welding, or a known method that forms a metallurgically-bonded coating 29 to low CTE pin core 15.
Another embodiment of a bonded assembly 120, presented in
An alternative embodiment to form assembly 120 is presented in
Another method of achieving a bonded assembly 220 is with a compression bond (see
A further alternative embodiment to achieve a competent seal is presented in
The pin 415 may be comprised of a low CTE metal, as previously discussed. A further alternative embodiment is presented in
A glass-to-metal seal is further improved by increasing the compression within the sea, which is accomplished by adding a high CTE metal bushing 606 to the sealing area of the feedthrough (see
An alternative embodiment of a compression bond is presented in
Another embodiment (see
Accordingly, what has been shown are techniques for forming hermetic seals, suitable for a lithium-ion battery or the like, that are particularly rugged and thus can maintain hermeticity for extended periods in a harsh environment. While the invention has been described by means of specific embodiments and applications thereof, it is understood that numerous modifications and variations could be made thereto by those skilled in the art without departing from the spirit and scope of the invention.
This application is a continuation-in-part of U.S. patent application Ser. No. 10/290,140, filed Nov. 7, 2002; which claims the benefit of U.S. Provisional Application No. 60/346,031, filed Nov. 9, 2001.
Number | Date | Country | |
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60346031 | Nov 2001 | US |
Number | Date | Country | |
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Parent | 10290140 | Nov 2002 | US |
Child | 11152443 | Jun 2005 | US |