GLASS, IN PARTICULAR SOLDER GLASS OR FUSIBLE GLASS

Abstract

A glass, for example a glass solder, includes the following components in mole percent (mol-%): P.sub.2O.sub.5 37-50 mol-%, for example 39-48 mol-%; Al.sub.2O.sub.3 0-14 mol-%, for example 2-12 mol-%; B.sub.2O.sub.3 2-10 mol-%, for example 4-8 mol-%; Na.sub.2O 0-30 mol-%, for example 0-20 mol-%; M.sub.2O 0-20 mol-%, for example 12-20 mol-%, wherein M is, for example, K, Cs or Rb; Li.sub.2O 0-42 mol-%, for example 0-40 mol-% or 17-40 mol-%; BaO 0-20 mol-%, for example 0-20 mol-% or 5-20 mol-%; and Bi.sub.2O.sub.3 0-10 mol-%, for example 1-5 mol-% or 2-5 mol-%.

Claims

1. A feed-through, comprising: a glass having a composition including in mole percent (mol-%): P.sub.2O.sub.5 35-50 mol-%; Al.sub.2O.sub.3 0-14 mol-%; B.sub.2O.sub.3 2-10 mol-%; Na.sub.2O 0-30 mol-%; M.sub.2O 0-20 mol-%, wherein M is one of potassium, cesium and rubidium; Li.sub.2O 0-42 mol-%; BaO 0-20 mol-%; and Bi.sub.2O.sub.3 1-10 mol-%.

2. The feed-through according to claim 1, the glass having a composition including: P.sub.2O.sub.5 39-48 mol-%; Al.sub.2O.sub.3 2-12 mol-%; B.sub.2O.sub.3 4-8 mol-%; Na.sub.2O 0-20 mol-%; M.sub.2O 12-19 mol-%; Li.sub.2O 0-40 mol-%; BaO 5-20 mol-%; and Bi.sub.2O.sub.3 1-5 mol-%.

3. The feed-through according to claim 2, the glass composition including: Li.sub.2O 17-40 mol-%; and Bi.sub.2O.sub.3 2-5 mol-%.

4. The feed-through according to claim 1, wherein the glass is a solder glass.

5. The feed-through according to claim 1, the glass including at most 35 mol-% Li.sub.2O.

6. The feed-through according to claim 1, the glass including at least 17 mol-% Li.sub.2O.

7. The feed-through according to claim 1, the glass including 4-8 mol-% Bi.sub.2O.sub.3.

8. The feed-through according to claim 1, the glass being lead free except for contaminants.

9. The feed-through according to claim 1, the glass including at most 20 mol-% Na.sub.2O.

10. The feed-through according to claim 1, the glass including at least 2 mol-% Bi.sub.2O.sub.3.

11. The feed-through according to claim 1, the glass having a coefficient of expansion at a temperature in a range of between 20 C. and 300 C. of >1410.sup.6 per degree Kelvin (K).

12. The feed-through according to claim 11, the glass having a coefficient of expansion at a temperature in a range of between 20 C. and 200 C. being in a range of between 1310.sup.6/K and 2010.sup.6/K.

13. The feed-through according to claim 11, said coefficient of expansion at said temperature in said range of between 20 C. and 300 C. being in a range of between 1510.sup.6/K and 2510.sup.6/K.

14. The feed-through according to claim 1, the glass having a melting temperature of <600 C.

15. The feed-through according to claim 1, the glass having a hemispherical temperature in a range of between 500 C. and 650 C.

16. The feed-through according to claim 1, the glass having a composition such that the glass can be soldered at normal atmosphere with at least one of aluminum and copper.

17. The feed-through according to claim 1, the glass having a high chemical resistance to electrolytes, the electrolytes being at least one selected from the group consisting of non-aqueous electrolytes, carbonates, carbonate mixtures and LiPF.sub.6.

18. The feed-through according to claim 1, the feed-through being for a device.

19. The feed-through according to claim 18, wherein said device is a storage device.

20. The feed-through according to claim 19, wherein said storage device is a lithium-ion accumulator.

21. The feed-through according to claim 20, wherein said lithium-ion accumulator is a lithium-ion battery.

22. A device, the device comprising: a feed-through including a glass having a composition including in mole percent (mol-%): P.sub.2O.sub.5 35-50 mol-%; Al.sub.2O.sub.3 0-14 mol-%; B.sub.2O.sub.3 2-10 mol-%; Na.sub.2O 0-30 mol-%; M.sub.2O 0-20 mol-%, wherein M is one of potassium, cesium and rubidium; Li.sub.2O 0-42 mol-%; BaO 0-20 mol-%; and Bi.sub.2O.sub.3 1-10 mol-%.

23. The device according to claim 22, the device being a storage device.

24. The device according to claim 23, wherein said storage device is an accumulator.

25. The device according to claim 24, wherein said storage device is a lithium-ion accumulator.

26. The device according to claim 25, wherein said lithium-ion accumulator is a lithium-ion battery.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0076] The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become more apparent and the invention will be better understood by reference to the following description of an embodiment of the invention taken in conjunction with the accompanying drawing, wherein:

[0077] FIG. 1 illustrates an inventive feed-through.

[0078] The exemplification set out herein illustrates one embodiment of the invention and such exemplification is not to be construed as limiting the scope of the invention in any manner.

DETAILED DESCRIPTION OF THE INVENTION

[0079] Referring now to the drawing, and more particularly to FIG. 1, there is shown a feed-through 1 according to the present invention. Feed-through 1 includes a metal pin 3 as a conductor, in particular as a pin shaped conductor which consists for example of a material, such as aluminum or copper. It further includes a base body 5 in the embodiment of a metal part consisting according to the present invention of a metal which has a low melting point, that is a light metal such as aluminum. Metal pin 3 is guided through an opening 7 which leads through metal part 5. Even though only the insertion of a single metal pin through the opening is illustrated, several metal pins could be inserted through the opening, without deviating from the present invention.

[0080] The outer contour of opening 7 can be round, but also oval. Opening 7 penetrates through the entire thickness D of base body 5, or respectively metal part 5. Metal pin 3 is sealed into a glass material 10 and is inserted inside glass material 10 through opening 7 through base body 5. Opening 7 is introduced into base body 5 through a separation process, for example stamping. In order to provide a hermetic feed-through of metal pin 3 through opening 7, metal pin 3 is sealed into a glass plug consisting of the inventive glass material. A substantial advantage of this production method consists in that even under increased pressure upon the glass plug, for example a compression load, expulsion of the glass plug with metal pin from opening 7 is avoided. The sealing temperature of inventive glass material 10 with the base body 5 is 20K to 100K below the melting temperature of the material of base body 5 and/or of the conductor 3, for example the pin shaped conductor 3.

TABLE-US-00001 TABLE 1 Examples (AB1-AB8): Mol-% AB1 AB2 AB3 AB4 AB5 AB6 AB7 AB8 P.sub.2O.sub.5 47.6 43.3 43.3 43.3 37.1 40.0 42.0 46.5 Al.sub.2O.sub.3 4.2 8.6 8.7 2.0 2 12.0 12.0 4.2 B.sub.2O.sub.3 7.6 4.8 4.7 4.8 4.9 6.0 6.0 7.6 Na.sub.2O 28.3 17.3 15.0 16.0 28.3 K.sub.2O 12.4 17.3 17.3 18.0 19.0 12.4 PbO 9.0 0 0 BaO 8.7 8.7 15.4 14 Li.sub.2O 17.3 34.6 42.1 Bi.sub.2O.sub.3 5 1 Hemispherical 513 554 564 540 625 553 502 Temperature ( C.) (20-300 C.) 19 17.2 15.1 13.7 14.8 16.7 16.0 19.8 (10.sup.6/K) Tg ( C.) 325 375 354 369 359 392 425 347 Density 2.56 3 3 [g/cm.sup.3] Leaching in 18.7 3.7 3.7 Mass % Weight 10.7 0.37 0.1 0.13 0.13 n.b. 0.006/0.001 0.45/0.66 Loss (%) after 70 hours in 70 C.- water

[0081] Besides leaching, the hydrolytic resistances of the individual glasses were also determined.

[0082] The hydrolytic resistance tests were conducted so that melted down glass samples were produced (22 centimeters (cm), height: 0.5 cm) which were stored in 200 milliliters (ml) water at 25 C. and 70 C. for 70 hours. Subsequently the material loss in weight-% was determined and listed in the table.

[0083] Example 1 (AB1) in Table 1 is suitable, for example, for aluminum/aluminum sealing, that is sealing an aluminum pin as conductor into a surrounding aluminum base body.

[0084] Even though some of the examples indicate a coefficient of expansion which is too low for bonding with copper (Cu) it becomes clear that a high lithium component can be dissolved in the molten mass without the glass becoming unstable with a glass composition of this type.

[0085] Examples AB7 and AB8 distinguish themselves in that they contain Bi.sub.2O.sub.3, in place of PbO, as is the case in example 6 (AB6).

[0086] Surprisingly it has been shown that the hydrolytic resistance can be clearly increased by including Bi.sub.2O.sub.3. For example, by introducing 1 mol-% Bi.sub.2O.sub.3, a 10-times higher hydrolytic resistance can be achieved compared to example AB1. Bi.sub.2O.sub.3, can in particular also be used in place of PbO according to example 6. Exemplary glass compositions according to the present invention which distinguish themselves as being environmentally friendly are lead free, in other words free of PbO, except for contaminants. These are for example examples AB1, AB2, AB3, AB4, AB5, AB7 and AB8.

[0087] An especially crystallization stable glass composition which displays no, or almost no substantial crystallization is achieved when the lithium content is less than 35 mol-%, for example less than 20 mol-%. These are for example examples AB1, AB2, AB3, AB4, AB6, AB7 and AB8.

[0088] A special resistance in regard to electrolytes is achieved if the sodium content is less than 20 mol-%. This is especially true of sodium free glasses, in other words glasses which are free of sodium except for contaminants. These are for example the examples AB2, AB3, AB4, AB5, AB6 and AB7.

[0089] An especially high hydrolytic water resistance is achieved, if at least 1 mol-% Bi.sub.2O.sub.3, for example at least 2 mol-% Bi.sub.2O.sub.3 is present in the glass composition. This is the case for example in examples AB7 and AB8.

[0090] Table 2 below lists conventional glass compositions (VB1-VB9) which were examined in comparison to the aforementioned inventive examples AB1-AB8.

[0091] Tables 1 and 2 show the composition in mol-%, the transformation temperature Tg as defined for example in Schott Guide to Glass, second edition, 1996, Chapman & Hall, pages 18-21, the total leaching in mass percentage (Ma-%), the coefficient of expansion at in 10.sup.6/K in the range of 20 C.-300 C., as well as the density in grams per cubic centimeter (g/cm.sup.3). The total leaching is determined as described in the introductory section, meaning that the glass compositions were ground to glass powder having a d50=10 micrometers (m) granularity, and were exposed for one week to the electrolyte consisting of ethylene-carbonate/dimethyl-carbonate at a ratio 1:1, with 1 Molar LiPF.sub.6 in the form of conducting salt dissolved therein and after this time were examined for glass components which were leached from the glass. n.b. in Table 1 denotes unknown properties.

TABLE-US-00002 TABLE 2 Comparison examples VB 1 VB 2 VB 3 VB 4 VB 5 VB 6 VB 7 VB 8 VB 9 Composition System [mol-%] SiO.sub.2 SiO.sub.2 SiO.sub.2 SiO.sub.2 P.sub.2O.sub.5 P.sub.2O.sub.5 P.sub.2O.sub.5 P.sub.2O.sub.5 P.sub.2O.sub.5 SiO.sub.2 66.5 66.6 63.3 77.8 55.4 2.6 ZrO.sub.2 2.4 11.8 Al.sub.2O.sub.3 9.3 10.4 1.0 3.3 8.4 5.5 12.8 4.0 7.4 B.sub.2O.sub.3 4.0 7.3 4.1 9.4 31.2 1.7 MgO 4.0 4.4 3.3 4.3 20.5 2.9 BaO 3.8 1.5 2.5 0.2 7.0 7.8 La.sub.2O.sub.3 1.3 Li.sub.2O 0.6 K.sub.2O 7.9 2.0 2.4 P.sub.2O.sub.5 5.3 6.8 29.3 59.7 50.5 CaO 12.3 9.6 4.7 1.6 7.9 8.1 Na.sub.2O 9.1 7.0 0.5 SrO 11.3 F 1.0 0.6 54.7 PbO SnO 27.0 42.2 ZnO 8.9 Tg 720 716 508 562 464 680 n.b. 462 n.b. Total leaching in Mass % 43.5 52.4 167.0 64.4 2.1 127.6 50.2 18.8 1.9 (20 C.-300 C.) 4.6 3.8 10.4 4.9 14.8 5.5 n.b. n.b. n.b. Density [g/cm.sup.3] 2.6 2.5 n.b. 2.3 3.7 2.8 n.b. 2.8 n.b.
The comparison examples VB1, VB2 and VB6 cited in table 2 show a transformation temperature Tg which is too high and a thermal coefficient of expansion which is too low compared to the inventive compositions (AB1-AB8) in table 1. Comparison example VB3 does have a sufficiently low Tg, a better, however not sufficient coefficient of expansion (20 C. to 300 C.), however a high instability in respect to electrolytes. Comparison example VB4 shows a favorable Tg, however the resistance and the coefficient of expansion are not sufficient. Comparison example shows VB5 an excellent resistance, the Tg is satisfactory, however the coefficient of expansion is not sufficient.

[0092] Surprisingly, inventive examples AB1 to AB8 of the inventive glass compositions according to table 1 show a high a, (20 C.-300 C.) according to the present invention, low Tg and high chemical resistance. The inventive glass compositions thereby provide sealing glasses for use in battery feed-throughs, having a low process temperature, a sealing temperature which is lower than the melting point of aluminum, a high coefficient of expansion and an excellent resistance to battery electrolytes. Even though the glass compositions are described for use in feed-throughs, in particular battery feed-throughs they are not restricted thereto. Other fields of application are, for example, sealing of housings, of sensors and/or actuators. In principle the feed-throughs are suitable for all applications in lightweight construction, in particular as feed-throughs in electrical components which must be light and temperature resistant. Such components are found for example in aircraft construction and in astronautics.

[0093] While this invention has been described with respect to at least one embodiment, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.