US006225009B1 (12) United States Patent (10) Patent N0.: US 6,225,009 B1 Fleischer et al. (45) Date of Patent: *May 1, 2001 (54) ELECTROCHEMICAL CELL WITH A NON- (51) Int. Cl.7 ........................... .. H01M 4/52; H01M 4/60; LIQUID ELECTROLYTE H01M 10/40 52 US. Cl. ........................ .. 429/306; 429/213; 429/220; (75) Inventors: Niles A Fleischer; J00st Manassen, ( ) 429/221; 429/224 lgiithRzfsllfech?ggzs?ogig?lgigméylm; (58) Field Of Search ............................ ..442299//23236 320261, 221234; Marvin S. Antelman, Rehovot, all of ’ ’ (IL) (56) References Cited (73) Assignee: E.C.R. -Electr0-Chemical Research US. PATENT DOCUMENTS Ltd” Rehovot (IL) 4,366,216 * 12/1982 McGinness ........................ .. 429/213 ( * ) Notice: PawntSubject is to mendedany disclaimer, or adjusted the term under of this 35 4,847,174 * 7/1989 §$1I1l:r:1_etj1_'_Palmer et a1. ....... .. 429/112 U-S-C- 154(b) by 0 days- 5,731,105 * 3/1998 Fleischer et al. .............. .. 429/213 X This patent is subject to a terminal dis- * Cited by examiner Clalmer' Primary Examiner—Stephen Kalafut (21) APPL NO; 09/068,864 (74) Attorney, Agent, or Firm—Mark M. Friedman (22) PCT Filed: Sep. 23, 1997 (57) ABSTRACT (86) PCT NO; PCT/US97/16901 A non-liquid electrolyte containing electrochemical cell which operates ef?ciently at room temperature. The cell § 371 Datei May 19, 1998 includes (a) a non-liquid electrolyte in which protons are _ mobile, (b) an anode active material based on an organic § 102(6) Date' May 19’ 1998 com P ound which is a source of P rotons durin g cell (87) PCT Pub. N0.: WO98/13887 discharge, or an anode active material including a metal _ whose cation can assume at least two different non-Zero PCT Pub‘ Date'Apr‘ 2’ 1998 oxidation numbers and (c) a solid cathode including a . compound which forms an electrochemical couple with the Related U'S' Apphcatlon Data anode. Anode and cathode active materials can be chosen so (63) Continuation of application NO‘ 08/718,833’ ?led on SeP' that the cell has the feature that the electrochemlcal reactlons 24, 1996, now Pat. No. 5,731,105, which is a continuation at the anode and cathode are at least partially reversible. An in-part of application No. 08/399,017, ?led on Mar. 6, 1995, important feature of the cell is that no thermal activation is now Pat. No. 5,580,681, which is a continuation-in-part of required for its operation, therefore, the cell ef?ciently application No. 08/208,326, ?led on May 2, 1994, now Pat. operates under ambient temperatures. No. 5,512,391, which is a continuation-in-part of application No. 08/128,497, ?led on Sep. 7, 1993, now Pat. No. 5,382, 481. 32 Claims, 1 Drawing Sheet 10 14 12 18 U.S. Patent May 1, 2001 US 6,225,009 B1 10 14 12 y 18 US 6,225,009 B1 1 2 ELECTROCHEMICAL CELL WITH A NON advantages such as a high form factor, thin, ?at, ?exible LIQUID ELECTROLYTE shapes and avoidance of ?uid leakage or drying out. HoWever, some of these batteries employ electrodes com This is a national phase Application claiming priority posed of metals, such as palladium (see for example US. from PCT application Ser. No. US97/16901, ?led Sep. 23, Pat. No. 4,894,301), Which are expensive, or materials 1997, Which is a continuation US. patent application Ser. Which may be dangerous to health and dif?cult to manufac No. 08/718,833. ?led Sep. 24, 1996, now US. Pat. No. ture. Other batteries release hydrogen ions from a metal 5,731,105, issued Mar. 24, 1998, Which is a continuation alloy or metal hydride anode material in a liquid electrolyte in-part of US. patent application Ser. No. 08/399,017, ?led battery such as a nickel-metal hydride cell. Other batteries require thermal activation in order to release hydrogen ions Mar. 6, 1995, now US. Pat. No. 5,580,681, issued Dec. 3, 10 1996, Which is a continuation-in-part of US. patent appli from the anode via deintercalation of protons from the anode cation Ser. No. 08,208,326, ?led May 2, 1994, now US. Pat. (see for example US. Pat. No. 4,847,174). No. 5,512,391, issued 30 Apr. 1996, Which is a continuation In the past, aromatic nitro compounds Were considered for in-part of US. patent application Ser. No. 08/128,497, ?led active battery cathode materials in non-rechargeable batter ies and only for liquid aqueous electrolytes (see for instance 7 Sep. 1993, now US Pat. No. 5,382,481, issued 17 Jan. 15 1995. US. Pat. No. 2,306,927, Dec. 29, 1942, US. Pat. No. 3,025,336, Mar. 13, 1962, R. Glicksman and C. K. FIELD AND BACKGROUND OF THE Morehouse, J. Electrochem. Soc., 105 (1958) 299 and R. INVENTION Udhayan and D. P. Bhatt, J. Electrochem. Soc., 140 (1993) This invention relates to electrochemical cells Which can L58). Since these compounds are reduced irreversibly under be used as poWer sources for storage and release of electrical these conditions, they are not suitable for rechargeable energy. In particular, this invention relates to electrochemi batteries. In addition, these compounds suffer from one or cal cells such as, but not limited to, batteries, capacitors and more of the folloWing de?ciencies: loW cell voltages, hybrid electrochemical cells termed batcaps. The latter toxicity, signi?cant solubility in the electrolyte, instability exhibit characteristics of both a battery and a capacitor. With regards to the electrolyte, poor shelf-life, high self More particularly, this invention relates to electrochemical 25 discharge, and loW poWer density. cells Which accomplish the conversion of chemical energy to Further prior art considered the halogenated organic com electrical energy at ambient temperature by using a non pounds for active battery cathode materials because of their liquid electrolyte in Which protons are mobile, Which cells generally higher voltage but only in non-rechargeable bat require no thermal activation for their operation. teries and only for liquid aqueous electrolytes (US. Pat. No. Electrochemical cells including batteries, capacitors and 30 2,874,079, Feb. 17, 1959 and R. Udhayan and D. P. Bhatt, batcaps are useful for storage and/or release of electrical J. Electrochem. Soc., 140 (1993) L58). Besides the disad energy and use similar electrolytes and electrodes. They vantages mentioned above for the aromatic nitro differ, hoWever, in the mechanisms used for energy storage compounds, the halogenated compounds also suffer from and their discharge characteristics. being corrosive, producing chlorine odors and are dif?cult to 35 In rechargeable batteries, stored chemical energy is con handle. In still more recent prior art, some quinone com verted into electrical energy almost entirely via reversible pounds have been used as anodes in liquid aqueous electro charge transfer reactions of active materials occurring lyte batteries (see for instance H. Alt, et. al., Electrochim. mainly in the electrode bulk. The double layer that exists at Acta, 17 (1972) 873 and F. Beck, et. al., The Electrochemical the surface of the electrodes contributes only a minor Society Abstracts, No. 152, October 1994 Meeting). HoW 40 ever inherent de?ciencies limit their applicability in practi amount to the total energy. cal batteries. These electrode materials are not stable With In conventional capacitors the electrodes are made of respect to the liquid electrolyte and so they degrade. In materials Which essentially do not participate in charge addition, these electrode materials are soluble in liquid transfer reactions and so almost all the energy is stored in the electrolytes and so the integrity of the electrodes is signi? double layer at the surface of the electrodes. HoWever, in 45 cantly diminished and there is high self-discharge and poor electrochemical capacitors, electrodes are made of materials shelf life. Furthermore, they are not useful in practical Which can participate in reversible charge transfer reactions, batteries because their voltages are generally too loW. and so a large portion of energy is also contributed by these reversible charge transfer reactions, occurring mostly at the SUMMARY OF THE INVENTION surface of the electrodes. The present invention serves to provide an ambient (i.e., Regarding discharge characteristics, electrochemical room) temperature operateable electrochemical cell contain capacitors, as compared to rechargeable batteries, are typi ing a non-liquid proton conductor electrolyte, in Which there cally characteriZed by loWer energy density, higher poWer is employed an anode free of elemental metals and/or alloys density, shorter capacity retention time, and greater cycle thereof and Which contains a solid organic compound Which life. 55 is a source of protons during discharge, thus achieving the A batcap has discharge properties Which can be charac advantages of non-liquid electrolytes and avoiding the dis teriZed as intermediate betWeen those of batteries and those advantages of proton-donating elemental metals and/or of electrochemical capacitors. Reducing the thickness of a metal alloy anodes. rechargeable battery results in very thin electrodes. Such an Thus, in accordance With the invention, there is provided ultra-thin battery can be considered a batcap since the ratio 60 an electrochemical cell comprising an anode, a cathode and of electrode bulk to electrode area is diminished and its a non-liquid electrolyte betWeen, and in contact With, the poWer density increases. When high currents are used in the anode and cathode, Wherein (a) the anode includes an operation of such a thin electrochemical cell the charge organic compound Which is a source of protons during transfer reactions occur mainly at the surface of the elec discharge; (b) the cathode includes a compound Which forms trodes and the cell can be considered to be a batcap.