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(12) Patent Application Publication (10) Pub. No.: US 2015/0207145 A1 Palazzo Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2015/0207145 A1 Palazzo Et Al US 20150207145A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2015/0207145 A1 Palazzo et al. (43) Pub. Date: Jul. 23, 2015 (54) HIGH CAPACITY CATHODE MATERIAL HIM I/0568 (2006.01) WITH IMPROVED RATE CAPABILITY HIM I/0563 (2006.01) PERFORMANCE HOLM 4/485 (2006.01) HOLM 4/62 (2006.01) (71) Applicant: Greatbatch Ltd., Clarence, NY (US) (52) U.S. Cl. CPC .............. H01 M 4/521 (2013.01); H0IM 4/485 (72) Inventors: Marcus J. Palazzo, Wheatfield, NY (2013.01); H01 M 4/622 (2013.01); H0IM (US); Ashish Shah, East Amherst, NY 4/625 (2013.01); H01 M 4/523 (2013.01); (US) H0IM 10/0568 (2013.01); H0IM 10/0563 (21) Appl. No.: 14/599,915 ( 2013.01);) H0IM(2013.01); 4/62 E.(2013.01); 2): H01 (2013.01) M 4/049 (22) Filed: Jan. 19, 2015 (57) ABSTRACT Related U.S. Application Data (60) Provisional application No. 61/928,768, filed on Jan. The present invention related to an electrochemical cell com 17, 2014. prising an anode of a Group IA metal and a cathode of a s composite material prepared from an aqueous mixture of iron Publication Classification sulfate, cobalt sulfate and sulfur. The cathode material of the present invention provides an increased rate pulse perfor (51) Int. Cl. mance compared to iron disulfide cathode material. This HOLM 4/52 (2006.01) makes the cathode material of the present invention particu HOLM 4/04 (2006.01) larly useful for implantable medical applications. Patent Application Publication Jul. 23, 2015 Sheet 1 of 6 US 2015/02071.45 A1 xx CD t -- & Patent Application Publication Jul. 23, 2015 Sheet 2 of 6 US 2015/02071.45 A1 x : (N is . CD H 8 R 8. s Patent Application Publication Jul. 23, 2015 Sheet 3 of 6 US 2015/02071.45 A1 . 3k 3. s co CD Assei Patent Application Publication Jul. 23, 2015 Sheet 4 of 6 US 2015/02071.45 A1 BE'9'I, {}{}{} Patent Application Publication Jul. 23, 2015 Sheet 5 of 6 US 2015/02071.45 A1 Patent Application Publication Jul. 23, 2015 Sheet 6 of 6 US 2015/02071.45 A1 ques s w to eases . c 2. & E o w o (N s g 8 8 a. f ty sm a. von 'gar w wa (ALL) efield? US 2015/02071.45 A1 Jul. 23, 2015 HIGH CAPACITY CATHODE MATERAL as an implantable cardiac defibrillator. However, lithium cells WITH IMPROVED RATE CAPABILITY constructed with cathodes comprising SVO typically have a PERFORMANCE lower discharge capacity as compared to those having cath odes comprising CFX. Silver Vanadium oxide cathode mate CROSS-REFERENCE TO RELATED rial is generally known to have a discharge capacity of about APPLICATION 315 mAh/g, which is significantly less than the discharge 0001. This application claims priority from U.S. Provi capacity of 875 mAh/g for CFX as previously discussed. Therefore, what is desired is a cathode material and electro sional Application Ser. No. 61/928,768, filed Jan. 17, 2014. chemical cell thereof that comprises a “high discharge TECHNICAL FIELD capacity in addition to an increased rate capability. Such an electrochemical cell would be well suited for powering addi 0002. This invention relates to the art of electrochemical tional electronic devices that require an increased charge cells, and more particularly, to a new and improved electro capacity with an increased discharge rate. chemical cell, and a cathode therefore. The cell comprises a Group IA anode and a new composite metal cathode material. 0007. The applicants, therefore, have developed a new Still more particularly, the present invention is directed to the iron cobalt disulfide cathode material formulation and cath preparation of iron-cobalt-disulfidehaving the stoichiometric ode thereof that provides a lithium electrochemical cell with a discharge capacity of between about 700 mAh/g to about formula of Fe-CoS. 850 mAh/g and an increased rate capability of between about BACKGROUND OF THE INVENTION 15 mA/cm to about 20 mA/cm. Thus, a cathode composed of the iron cobalt disulfide material of the present invention 0003 Electrochemical cells provide electrical energy that when constructed within an electrochemical cell having a powers a host of electronic devices such as external and lithium anode is well suited for powering a variety of electri implantable medical devices. Among these many medical cal devices that require a “high discharge capacity with an devices powered by electrochemical cells are external medi increased rate capability. cal drills and implantable cardiac defibrillators. Such medical devices generally require the delivery of a significant amount 0008. The use of iron disulfide as a cathode material is of current in a relatively short duration of time. Thus, these generally known. In particular, Awano et al. in “Li/Fe. devices typically require the use of electrochemical cells that aCoS System. Thermal Battery Performance” Power comprise an increased delivery capacity and an increased rate Sources Symposium 1992, p. 219-222 disclose an iron cobalt of charge delivery. As defined herein, “delivery capacity' is disulfide cathode material having a general formula of Fe. the maximum amount of electrical current that can be drawn aCoS wherein XeO.4. The Awano cathode material is sig from a cell under a specific set of conditions. The terms, “rate nificantly distinct from the iron cobalt disulfide formulation of charge delivery” and “rate capability” are defined hereinas of the present invention. That is both in terms of its chemical the maximum continuous or pulsed output current a battery structure and electrical performance. can provide per unit of time. Thus, an increased rate of charge 0009. The Awano material is fabricated by mixing dry iron delivery occurs when a cell discharges an increased amount of powder, metal cobalt powder and sulfur together and then current per unit of time in comparison to a similarly built cell, Subjecting the powder mixture to a temperature of between but of a different anode and/or cathode chemistry. 350° C. to 550°C. in an argon gas environment. In contrast, 0004 Cathode chemistries such as carbon monofluoride the iron cobalt disulfide cathode material of the present inven (CFx) have been developed to provide increased discharge tion is fabricated using a hydrothermal process in which iron capacities that meet the power demands of external and Sulfate, cobalt Sulfate, Sulfur are mixed in an aqueous mixture implantable medical devices. CFX cathode material is gener at a temperature of about 200° C. ally known to have a discharge capacity of about 875 mAh/g, which is well suited for powering implantable medical 0010. In addition, the Awano cathode material comprises a devices over long periods of time. chemical structure that is different than the cathode material 0005. However, electrochemical cells constructed with of the present invention. Specifically, the iron cobalt disulfide cathodes comprised of carbon monofluoride are generally material of the present invention comprises an increased considered to exhibit a relatively “low” rate capability. For amount of cobalt as compared to Awano. Furthermore, the example, electrochemical cells constructed with lithium lattice structure of the iron cobalt disulfide material of the anodes and CFX cathodes typically exhibit rate capabilities present invention decreases in size with an increasing amount from about 0.5 mA/cm to about 3 mA/cm. As such, elec of cobalt. In contrast, the Awano iron cobalt disulfide material trochemical cells constructed with Li/CFX couples are gen comprises a lattice structure that increases in size with erally well suited for powering electrical devices, like an increasing amounts of cobalt. implantable cardiac pacemaker that are powered over long 0011. These chemical and structural differences between periods of time at a relatively low rate capability. the iron cobalt disulfide cathode materials of Awano and that 0006. In contrast, electrochemical cells constructed with of the present invention manifest themselves in electrical lithium anodes and cathodes comprising silver Vanadium performance differences when constructed within a lithium oxide (SVO) are generally considered to exhibit a relatively electrochemical cell. For example, lithium cells constructed “high' rate capability. Lithium cells constructed with SVO with the Awano cathode material exhibit an increased back cathodes, in contrast to CFX cathodes, generally exhibit rate ground Voltage as compared to lithium cells constructed with capabilities that range from about 25 mA/cm to about 35 the cathode material of the present invention. Thus, as will be mA/cm. As such, lithium electrochemical cells constructed discussed in more detail, the iron cobalt disulfide cathode with cathodes comprised of SVO are generally well suited to material of the present invention comprises a unique chemical power devices that require an increased rate capability, Such structure that provides a lithium electrochemical cell with US 2015/02071.45 A1 Jul. 23, 2015 electrical properties that are well suited to power a variety of current. The pulse is designed to deliver energy, power or electrical devices that require an increased discharge capacity current. If the pulse train consists of more than one pulse, they with increased rate capability. are delivered in relatively short succession with or without open circuit rest between the pulses. SUMMARY OF THE INVENTION 0021. In performing accelerated discharge testing of a cell, 0012. The present invention relates to an electrochemical an exemplary pulse train may consist of one to four 5- to cell comprising an anode of a Group IA metal and a cathode 20-second pulses (23.2 mA/cm) with about a 10 to 30 second of a composite material prepared from a combination of metal rest, preferably about 15 second rest, between each pulse. A salts. Specifically, the present invention is of an electrochemi typically used range of current densities for lithium cells cal cell having a lithium anode and iron cobalt disulfide powering implantable medical devices is from about 15 cathode material that comprises iron Sulfate, cobalt Sulfate mA/cm to about 50 mA/cm, and more preferably from and Sulfur.
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