USOO630654.4B1 (12) United States Patent (10) Patent No.: US 6,306,544 B1 Frysz et al. (45) Date of Patent: Oct. 23, 2001 (54) COBALT-BASED ALLOYS AS POSITIVE 5,051,233 9/1991 Horn et al. ............................. 420/50 ELECTRODE CURRENT COLLECTORS IN 5,053,297 10/1991 Yamahira et al. ................... 429/194 NONAQUEOUSELECTROCHEMICAL 5,114,810 * 5/1992 Frysz et al. ...... 429/194 CELLS 5,147,739 9/1992 Beard ....... ... 429/194 5,187,033 2/1993 Koshiba ....... ... 429/194 (75) Inventors: Christine A. Frysz, East Amherst; 2. : E. Tateishi et al. ...................... 428/548 2 : Y-2 /1995 Idota .................................... 429/194 Sally Ann Smesko, North Tonawanda; 5,578,396 * 11/1996 Fauteux et al. .. 429/209 Peter A. Kreidler, Oakfield; W. 5,643,690 * 7/1997 Tateishi et al. .. ... 429/34 Richard Brown, Clarence Center; 5,733,680 * 3/1998 Hong ............ ... 429/101 Esther S. Takeuchi, East Amherst, all 5,783,333 * 7/1998 Mayer .............. ... 429/223 of NY (US) 5,795,679 * 8/1998 Kawakami et al. 429/218 5.962,160 * 5/1999 Oyama et al. ....................... 429/104 (73) Assignee: Wilson Greatbatch Ltd., Clarence, NY 6,136,477 10/1998 Gan et al. ............................ 429/307 (US) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this WO9833224 7/1998 (WO). patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS Standard Specification for Wrought Cobalt-Nickel-Chromi (21) Appl. No.: 09/257,795 um-Molybdenum-Tungsten-Iron Alloy For Surgical Implant Applications; pp. 102-104; Designation F563-88. (22) Filed: Feb. 25, 1999 Standard Specification for Wrought Cobalt-Nickel-Chromi (51) Int. Cl." .............................. H01M 4/64; H01 M 4/72 um-Molybdenum-Tungsten-Iron Alloy For Surgical (52) U.S. Cl. ....................... 429,233. 429,21s. 429,218.1. Implant Applications; pp. 99-101; Designation F562–92. 420/38; 420/900 (List continued on next page.) (58) Field of Search ..................................... 429/233, 218, 429/218.1 420/38, 585, 900 Primary Examiner Tom Dunn / s /38, s ASSistant Examiner L. Edmondson (56) References Cited (74) Attorney, Agent, or Firm-Hodgson Russ LLP U.S. PATENT DOCUMENTS (57) ABSTRACT 3,904,402 * 9/1975 Smashey ................................ 75/170 Cobalt-based alloys are provided for use as a positive 4.012,564 3/1977 Auborn .......... ... 429/194 electrode current collector in a Solid cathode, nonaqueous 4,154,906 5/1979 Bubnick et al. ....................... 429/94 liquid electrolyte, alkali metal anode active electrochemical 4,167,468 * 9/1979 Juckniess et al. ... 204/247 cell. The cobalt-based alloys are characterized by chemical 4,216.275 : 8/1980 Hartmann et al. ................... 429/104 compatibility with aggressive cell environments, high cor 4,255.247 3/1981. Oda et al. ............................ 22 rosion resistance and resistance to fluorination and passiva 4,400.211 * 8/1983 Kudo et al. ... 420/443 tion at elevated temperatures, thus improving the longevity 4,520,0834,508,608 5/19854/1985 PalmerPrater et ...........al. ...... 204/192429/101 andd periormanceperf off the electrochemicalelectrocnemical cell. TheIne cell can bbe 4.585,715 4/1986 Marple ................................. 429,194 of either a primary or a secondary configuration. 4,830.940 5/1989 Keister et al. ....................... 429/194 5,037,712 8/1991 Shackle et al. ...................... 429/129 41 Claims, 11 Drawing Sheets 4000 800 4000 800 3000 800 3000 600 S. g e 5 2000 400 2OOO 400 li C e 9 ? > O s E Lif O 1OOO 2005 1000 200 ? 2 O Er s sm H O O Hora 3HA. O 0 500 1000 1500 2000 2500 O 500 1000 1500 2000 2500 CAPACITY, mAh CAPACITY, mAh US 6,306,544 B1 Page 2 OTHER PUBLICATIONS Implant Applications; pp. 102-104; Designation F563-88 Standard Specification for Wrought Cobalt-Nickel-Chromi (no date available). um-Molybdenum-Tungsten-Iron Alloy For Surgical Standard Specification for Wrought Cobalt-Nickel-Chromi Implant Applications; pp. 11-13; Designation F90-92. um-Molybdenum-Tungsten-Iron Alloy For Surgical Corrosion of Current Collectors in Li/CF-Elements; S.A. Implant Application; pp. 99-101; Designation F562–92 (no Fateev, O.O. Denisova, I.P. Monakhova, E.H. Lubnin and date available). T.R. Agladze; pp. 219–220. Standard Specification for Wrought Cobalt-Nickel-Chromi Chemical Abstracts, vol. 96, No. 4, Jan. 25, 1982 Columbus, um-Molybdenum-Tungsten-Iron Alloy For Surgical Ohio, US; abstract No. 25832, Skaggs, Lester S. et al: “Experience with thin Havar foils for cyclotron target win Implant Applications; pp. 11-13; Designation F90-92 (no dows XP002140171 *abstract & Prep. Nucl. Targets Part. date available). Accel., Proc. World Conf. Int. Nucl. Target Dev. Soc. Corrosion of Current Collectors in Li/CF-Elements; S.A. (1981) Meeting date 1979, 249–68. Editor(s): Jaklovsky, Fateev, O.O. Denisova, I.P. Monakhova, E.H. Lubnin and Jozef. Publisher: Plenum, New York, N.Y. 1981. T.R. Agladze; pp. 219–220 (no date available). Standard Specification for Wrought Cobalt-Nickel-Chromi um-Molybdenum-Tungsten-Iron Alloy For Surgical * cited by examiner U.S. Patent Oct. 23, 2001 Sheet 1 of 11 US 6,306,544 B1 U.S. Patent Oct. 23, 2001 Sheet 2 of 11 US 6,306,544 B1 4000 800 3000 600 2000 400 gO d5 S Lif 9 1000 200 s 2 O O O 500 1000 1500 2000 2500 CAPACITY, mAh - EIG. 3 U.S. Patent Oct. 23, 2001 Sheet 3 of 11 US 6,306,544 B1 4000 800 3000 600 2 DE 5 2000 400 li O Z CC O n 2 1000 200 O 500 1000 1500 2000 2500 CAPACITY, mAh - EIG. 4 U.S. Patent Oct. 23, 2001 Sheet 4 of 11 US 6,306,544 B1 U.S. Patent Oct. 23, 2001 Sheet S of 11 US 6,306,544 B1 U.S. Patent Oct. 23, 2001 Sheet 6 of 11 US 6,306,544 B1 U.S. Patent Oct. 23, 2001 Sheet 7 of 11 US 6,306,544 B1 U.S. Patent 23, 2001 Sheet 8 U.S. Patent Oct. 23, 2001 Sheet 9 of 11 US 6,306,544 B1 U.S. Patent Oct. 23, 2001 Sheet 10 of 11 US 6,306,544 B1 & U.S. Patent Oct. 23, 2001 Sheet 11 of 11 US 6,306,544 B1 US 6,306,544 B1 1 2 COBALT-BASED ALLOYS AS POSITIVE nium can react with Species present within the internal cell ELECTRODE CURRENT COLLECTORS IN environment to undesirably increase cell impedance by NONAQUEOUSELECTROCHEMICAL fluorination and excessive passivation of the current collec CELLS tor interface (Fateev, S. A., Denisova, O. O., I. P. Mona khova et al., Zashchita Metallov, Vol. 24, No. 2, pp. BACKGROUND OF THE INVENTION 284-287, 1988, transl.). The kinetics of this process are temperature dependent. At elevated temperatures, excessive 1. Field of the Invention passivation may occur quite rapidly (for example, at 100 C., The present invention generally relates to a positive the reaction requires less than 10 days). electrode current collector for an alkali metal, Solid cathode, Other current collector alloys used to fabricate positive nonaqueous liquid electrolyte electrochemical cell, and electrode current collectors have been described in the art. more specifically to cobalt-based alloys as positive electrode Highly alloyed chromium-containing Stainless Steel materi current collector materials. als are described in Japanese patent publications Nos. 18647 2. Prior Art and 15067. However, the ferritic stainless steel material Solid cathode, liquid organic electrolyte, alkali metal 15 disclosed in publication No. 15067 requires costly melting anode electrochemical cells or batteries are used in appli procedures, Such as Vacuum melting, to limit the alloy to the cations ranging from power Sources for implantable medical cited carbon and nitrogen levels. Highly alloyed nickel devices to down-hole instrumentation in oil/gas well drill containing ferritic Stainless Steel materials, which provide ing. Typically, the battery is comprised of a casing housing Superior corrosion resistance, particularly where elevated a positive electrode comprised of cathode active material, temperature Storage and performance is required, are dis material to enhance conductivity, a binder material, and a closed in U.S. Pat. No. 5,114,810 to Frysz, et al., which current collector material; a negative electrode comprised of patent is assigned to the assignee of the present invention active material Such as an alkali metal and a current collector and incorporated herein by reference. However, use of Such material; a nonaqueous electrolyte Solution which includes alloyed ferritic Stainless Steels is limited in Several respects. an alkali metal Salt and an organic Solvent System; and a 25 Chief among them is the alloy is not readily available in Separator material encapsulating either or both of the elec thicknesses typically required for use as a current collector, trodes. Such a battery is described in greater detail in U.S. and developing a commercial Source has proven difficult. Pat. No. 4,830,940 to Keister et al., which is assigned to the Current collectors are preferably thin to permit increased assignee of the present invention and incorporated herein by Volumetric and gravimetric energy density, as well as to reference. permit increased Surface area per Volume for rapid discharge The positive electrode current collector Serves Several at high current densities. functions. First, the positive electrode current collector acts Therefore, the present invention is directed to providing a as a Support matrix for the cathode material utilized in the positive electrode current collector material which exhibits cell. Secondly, the positive electrode current collector Serves chemical compatibility with aggressive cell environments, to conduct the flow of electrons between the active material 35 provides high corrosion resistance but does not develop and the positive cell terminal.