Feed-through

Abstract

A feed-through, for example a battery feed-through for a lithium-ion battery or a lithium ion accumulator, has at least one base body which has at least one opening through which at least one conductor, for example a pin-shaped conductor, embedded in a glass material is guided. The base body contains a low melting material, for example a light metal, such as aluminum, magnesium, AlSiC, an aluminum alloy, a magnesium alloy, titanium, titanium alloy or steel, in particular special steel, stainless steel or tool steel. The glass material consists of the following in mole percent: 35-50% P.sub.2O.sub.5; 0-14% Al.sub.2O.sub.3; 2-10% B.sub.2O.sub.3; 0-30% Na.sub.2O; 0-20% M.sub.2O, with M being K, Cs or Rb; 0-35% Li.sub.2O; 0-20% BaO; and 0-10% Bi.sub.2O.sub.3, the glass material being free of lead except for contaminants.

Claims

1. A feed-through, comprising: at least one base body having at least one opening; a conductor; and a glass material, said conductor being embedded in said glass material and inserted into said at least one opening of said at least one base body, said glass material including the following in mole percent (mol-%): TABLE-US-00007 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 K, Cs and Rb; Li.sub.2O 0-35 mol-%; BaO 0-20 mol-%; and Bi.sub.2O.sub.3 0-10 mol-%, wherein said glass material is free of lead except for contaminants.

2. The feed-through according to claim 1, wherein said glass material includes: TABLE-US-00008 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 12-20 mol-%; Li.sub.2O 0-35 mol-%; BaO 0-20 mol-%; and Bi.sub.2O.sub.3 1-5 mol-%.

3. The feed-through according to claim 2, wherein said glass material includes: TABLE-US-00009 Li.sub.2O 17-35 mol-%; BaO 5-20 mol-%; and Bi.sub.2O.sub.3 2-5 mol-%.

4. The feed-through according to claim 1, wherein said feed-through is a battery feed-through.

5. The feed-through according to claim 4, wherein said battery feed-through is for a lithium-ion battery.

6. The feed-through according to claim 4, wherein said battery feed-through is for a lithium ion accumulator.

7. The feed-through according to claim 1, wherein said conductor is a substantially pin-shaped conductor.

8. The feed-through according to claim 7, wherein said conductor includes one metal.

9. The feed-through according to claim 8, wherein said one metal is one of copper, copper silicon carbide (CuSiC), aluminum, aluminum silicon carbide (AlSiC), magnesium, silver, gold, aluminum alloys, silver alloys, gold alloys and nickel-iron (NiFe) alloys.

10. The feed-through according to claim 1, wherein said base body is formed from a material having a low melting temperature.

11. The feed-through according to claim 10, wherein said material having a low melting temperature is a light metal.

12. The feed-through according to claim 11, wherein said light metal is one of aluminum, magnesium, aluminum silicon carbide (AlSiC), an aluminum alloy, a magnesium alloy, titanium, a titanium alloy and steel.

13. The feed-through according to claim 12, wherein said steel is one of a high-grade steel, stainless steel and tool steel.

14. The feed-through according to claim 1, wherein said glass material includes: TABLE-US-00010 P.sub.2O.sub.5 38-50 mol-%; Al.sub.2O.sub.3 3-14 mol-%; B.sub.2O.sub.3 4-10 mol-%; Na.sub.2O 10-30 mol-%; and K.sub.2O 10-20 mol-%.

15. The feed-through according to claim 14, wherein said glass material includes: TABLE-US-00011 P.sub.2O.sub.5 39-48 mol-%; Al.sub.2O.sub.3 4-12 mol-%; B.sub.2O.sub.3 4-8 mol-%; Na.sub.2O 14-20 mol-%; and K.sub.2O 12-19 mol-%.

16. The feed-through according to claim 1, wherein said glass material has a coefficient of expansion in a range of between approximately 20 C. and 300 C. of >1410.sup.6/K.

17. The feed-through according to claim 16, wherein said coefficient of expansion in a range of between approximately 20 C. and 300 C. is in a range of between approximately 1510.sup.6/K and 2510.sup.6/K.

18. The feed-through according to claim 1, said glass material further comprises a plurality of additives within a range of an emission maximum of infrared radiation.

19. The feed-through according to claim 18, wherein said plurality of additives include iron (Fe), Chromium (Cr), Cobalt (Co) and Vanadium (V).

20. The feed-through according to claim 1, wherein said glass material is sealed with at least one of said base body and said conductor under a normal atmosphere.

21. The feed-through according to claim 20, wherein said base body is an aluminum base body soldered with an aluminum conductor under said normal atmosphere.

22. The feed-through according to claim 1, wherein said glass material has a high chemical resistance to non-aqueous battery electrolytes.

23. The feed-through according to claim 22, wherein said glass material has a high chemical resistance to carbonates.

24. The feed-through according to claim 23, wherein said carbonates are carbonate mixtures with a conducing salt.

25. The feed-through according to claim 24, wherein said carbonate mixtures with a conducing salt include lithium hexafluorophosphate (LiPF.sub.6).

26. A storage device, comprising: a feed-through including: at least one base body having at least one opening; a conductor; and a glass material, said conductor being embedded in said glass material and inserted into said at least one opening of said at least one base body, said glass material including the following in mole percent (mol-%): TABLE-US-00012 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 K, Cs and Rb; Li.sub.2O 0-35 mol-%; BaO 0-20 mol-%; and Bi.sub.2O.sub.3 0-10 mol-%, wherein said glass material is free of lead except for contaminants.

27. The storage device according to claim 26, wherein the storage device is a battery.

28. The storage device according to claim 27, wherein said battery is a lithium-ion battery.

29. The storage device according to claim 28, wherein the storage device is a lithium-ion accumulator.

30. The storage device according to claim 29, wherein said battery includes a non-aqueous electrolyte.

31. The storage device according to claim 30, wherein said non-aqueous electrolyte is a carbonate.

32. The storage device according to claim 31, wherein said carbonate is a carbonate mixture with a conducting salt.

33. The storage device according to claim 32, wherein said carbonate mixture includes ethylene-carbonate and dimethyl-carbonate.

34. The storage device according to claim 33, wherein said carbonate mixture with said conducting salt is LiPF.sub.6.

35. The storage device according to claim 34, further comprising a housing accommodating said feed-through.

36. The storage device according to claim 35, wherein said housing is a battery housing.

37. The storage device according to claim 35, wherein said base body is one of a metal, a high-grade steel, stainless steel and a light metal.

38. The storage device according to claim 37, wherein said base body is one of aluminum, aluminum silicon carbide (AlSiC), an aluminum alloy, magnesium, a magnesium alloy, titanium and a titanium alloy.

39. The storage device according to claim 35, wherein said housing includes one of a metal, a high-grade steel, stainless steel and a light metal.

40. The storage device according to claim 39, wherein said housing includes one of aluminum, AlSiC, an aluminum alloy, magnesium, a magnesium alloy, titanium and a titanium alloy.

41. A method of utilizing a glass composition, the method comprising: providing a battery including a non-aqueous electrolyte; and using said glass composition to insert a conductor into a housing of a battery, said glass composition including: TABLE-US-00013 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 K, Cs and Rb; PbO 0-10 mol-%; Li.sub.2O 0-35 mol-%; BaO 0-20 mol-%; and Bi.sub.2O.sub.3 0-10 mol-%, wherein said glass composition is free of lead except for contaminants.

42. The method according to claim 41, wherein said glass composition includes: TABLE-US-00014 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 12-20 mol-%; PbO 0-9 mol-%; Li.sub.2O 0-35 mol-%; BaO 0-20 mol-%; and Bi.sub.2O.sub.3 1-5 mol-%.

43. The method according to claim 42, wherein said glass composition includes: TABLE-US-00015 Li.sub.2O 17-35 mol-%; BaO 0-20 mol-%; and Bi.sub.2O.sub.3 2-5 mol-%.

44. The method according to claim 41, wherein said battery is a lithium-ion battery.

45. The method according to claim 41, wherein said battery is a lithium-ion accumulator.

46. The method according to claim 42, wherein said non-aqueous electrolyte is a carbonate.

47. The method according to claim 46, wherein said carbonate is a carbonate mixture with a conducting salt.

48. The method according to claim 47, wherein said carbonate mixture with a conducting salt includes LiPF.sub.6.

49. The method according to claim 41, wherein said glass composition includes: TABLE-US-00016 P.sub.2O.sub.5 38-50 mol-%; Al.sub.2O.sub.3 3-14 mol-%; B.sub.2O.sub.3 4-10 mol-%; Na.sub.2O 10-30 mol-%; and K.sub.2O 10-20 mol-%.

50. The method according to claim 49, wherein said glass composition includes: TABLE-US-00017 P.sub.2O.sub.5 39-48 mol-%; Al.sub.2O.sub.3 4-12 mol-%; B.sub.2O.sub.3 5-8 mol-%; Na.sub.2O 14-20 mol-%; and K.sub.2O 12-19 mol-%.

51. The method according to claim 50, wherein the conductor includes one metal.

52. The method according to claim 51, wherein said one metal is one of aluminum, AlSiC, copper, CuSiC, magnesium, silver, gold, an aluminum alloy, a magnesium alloy, a copper alloy, a silver alloy, a gold alloy and a NiFe alloy.

53. The method according to claim 52, wherein said base body includes one of a light metal, a high-grade steel, steel and stainless steel.

54. The method according to claim 53, wherein said base body includes one of aluminum, AlSiC, an aluminum alloy, magnesium, a magnesium alloy, titanium, and a titanium alloy.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) 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:

(2) The FIGURE illustrates a feed-through according to the present invention.

(3) 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

(4) Referring now to the drawing, there is shown a feed-through 1 according to the present invention. Feed-through 1 includes a metal pin 3 as a conductor, for example a pin shaped conductor which consists of a material, for example aluminum, an aluminum alloy, a copper alloy or copper. Feed-through 1 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, an aluminum alloy, magnesium, a magnesium alloy, titanium or a titanium alloy. Metal pin 3 is inserted through an opening 7 which leads through base body or 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.

(5) The outer contour of opening 7 can be round, but also oval. Opening 7 penetrates through entire thickness D of base body 5, or respectively metal part 5. Metal pin 1 is sealed into 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 formed of the glass material according to the present. A substantial advantage of this production method is 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 the glass material according to the present invention with the base body is 20K to 100K below the melting temperature of the material of base body 5 and/or of the conductor, for example the pin shaped conductor.

(6) Table 1 below illustrates eight exemplary embodiments (AB1-AB8) for the inventive glass compositions which are compared in Table 2 with comparative glasses (VB1-VB9).

(7) TABLE-US-00005 TABLE 1 AB1 AB2 AB3 AB4 AB5 AB6 AB7 AB8 Mol-% P.sub.2O.sub.5 47.6 43.3 43.3 43.3 37.1 40.0 42.0 46.5 B.sub.2O.sub.3 7.6 4.8 4.7 4.8 4.9 6.0 6.0 7.6 Al.sub.2O.sub.3 4.2 8.6 8.7 2.0 2 12.0 12.0 4.2 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 BaO 8.7 8.7 15.4 14 Li.sub.2O 17.3 34.6 42.1 Bi.sub.2O.sub.3 5 1 Hemisphere 513 554 564 540 625 553 502 Temperapture ( C.) (20-300 C.) 19 16.5 14.9 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 3.02 2.63 [g/cm.sup.3] Leaching 18.7 14.11 7.66 12.63 1.47 3.7 29.01 8.43 In Ma-% Weight- 10.7 0.37 0.1 0.13 0.13 n.b. 0.006/0.001 0.45/0.66 Loss (%) after 70 h in 70 C.- Water

(8) In addition to leaching, the hydrolytic resistances of the individual glasses were also determined.

(9) 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 mililiters (mL) water at 25 C. (degrees Celsius) and 70 C. for 70 hours. Subsequently the material loss in weight-% was determined and listed in the table.

(10) Exemplary embodiment 1 (AB1) in Table 1 is suitable in particular for aluminum/aluminum sealing, that is sealing an aluminum pin as conductor into a surrounding aluminum base body.

(11) Exemplary embodiment 6 in Table 1 is, for example, suitable for Cu/Al glazing, that is sealing a copper pin in the embodiment of a conductor into a surrounding aluminum base body.

(12) Even though some of the exemplary embodiments indicate a coefficient of expansion which is too low for bonding with Cu it becomes clear that a high Li component can be dissolved in the molten mass without the glass becoming unstable with a glass composition of this type.

(13) Exemplary embodiments 7 and 8 (AB7 and AB8) distinguish themselves in that they contain Bi.sub.2O.sub.3, in place of PbO, as is the case in exemplary embodiment 6 (AB6).

(14) Surprisingly it has been shown that the water resistance can be clearly increased by Bi.sub.2O.sub.3. For example, by introducing 1 mol-% Bi.sub.2O.sub.3 a 10-times higher hydrolytic resistance could be achieved in exemplary embodiment 8 (AB8) compared to exemplary embodiment 1 (AB1) with essentially the same alkali content. This is surprising to the expert.

(15) Bi.sub.2O.sub.3, can in particular also be used in place of PbO according to exemplary embodiment 6 (AB6). Since lead is environmentally harmful, glass compositions which, except for contaminants, are free of PbO, that is where PbO can be set to 0 mol-%are advantageous. In this application free of, except for contaminants means that less than 100 parts per million (ppm), for example less than 10 ppm, or less than 1 ppm of the respective components, for example lead, are contained in the glass.

(16) Table 2 below lists conventional glass compositions (VB1-VB9) which were examined in comparison to the aforementioned inventive exemplary embodiments AB1 through AB9.

(17) 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 in 10.sup.6/K in the range of 20 C.-300 C., as well as the density in 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 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.

(18) TABLE-US-00006 TABLE 2 Comparison examples VB 1 VB 2 VB 3 VB 4 VB 5 VB 6 VB 7 VB 8 VB 9 System 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 Composition [mol-%] 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 Ma.-% 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.

(19) 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 compositions according to exemplary embodiments AB1-AB8. Comparison example VB3 does have a sufficiently low Tg, a better, however not sufficient coefficient of expansion in the range of 20 C. to 300 C., and a high instability with respect to the battery electrolytes. Comparison example VB4 shows a favorable Tg, however the resistance and the coefficient of expansion are not sufficient. Comparison example VB5 shows an excellent resistance, the Tg is satisfactory, however the coefficient of expansion is not sufficient.

(20) Surprisingly, exemplary embodiments AB1-AB8 according to Table 1 show a high coefficient of expansion according to the present invention, low Tg and high chemical resistance in the inventive composition range. The inventive glass compositions thereby provide sealing glasses or respectively fusible glasses or respectively solder glasses for battery feed-throughs, having a low process temperature, a sealing temperature which is lower than the melting point of light metal, for example aluminum, a high coefficient of expansion and an excellent resistance to battery electrolytes.

(21) The current invention cites for the first time a feed-through for a housing, in particular for a battery housing, for example for a lithium-ion battery which can be integrated into housing components of battery cell housings consisting of a light metal, such as aluminum (Al), aluminum alloy, magnesium, magnesium alloy, titanium or titanium alloy. However, steel or high-grade steel, in particular stainless steel are also conceivable as materials for the battery cell housing. In such a case, the materials of, for example, a pin shaped conductor with head part and, if necessary, the base body are selected and adapted accordingly.

(22) With the feed-through component according to the present invention a battery housing can be provided which is hermetically sealed even when the battery housing is deformed, in contrast to plastic feed-throughs which have a tendency toward cracking. On batteries with battery housings which are equipped with an inventive feed-through an especially high fire resistance is provided in the event of a vehicle accident. This is particularly relevant in the use of batteries, for example Li-ion batteries in automobiles.

(23) 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.