United States Patent to 4,009,052 Whittingham 45 Feb. 22, 1977 54 CHALCOGENIDE BATTERY the anode-active material a metal selected from the group consisting of Group la metals, Group Ib metals, (75. Inventor: M. Stanley Whittingham, Fanwood, Group IIa metals, Group IIb metals, Group IIIa metals N.J. and Group IVa metals (lithium is preferred), the cath 73) Assignee: Exxon Research and Engineering ode contains as the cathode-active material a chalco Company, Linden, N.J. genide of the formula MZ wherein M is an element selected from the group consisting of titanium, zirco 22 Filed: Apr. 5, 1976 nium, hafnium, niobium, tantalum and vanadium (tita nium is preferred); Z is an element selected from the (21 Appl. No.: 673,696 group consisting of sulfur, selenium and tellurium, and x is a numerical value between about 1.8 and about 2. 1, Related U.S. Application Data and the electrolyte is one which does not chemically 63 Continuation-in-part of Ser. No. 552,599, Feb. 24, react with the anode or the cathode and which will 1975, abandoned, which is a continuation-in-part of permit the migration of ions from said anode-active Ser. No. 396,051, Sept. 10, 1973, abandoned. material to intercalate the cathode-active material. A highly useful battery may be prepared utilizing lithium (52) U.S. Cl. ............................... 429/191; 429/193; as the anode-active material, titanium disulfide as the 429/194; 429/199; 429/218; 429/229 cathode-active material and lithium perchlorate dis (51) Int. Cl’........................................ H01M 35/02 solved in tetrahydrofuran (70%) plus dimethoxyethane. 58 Field of Search ................. 136/6 R, 6 LN, 6 L, (30%) solvent as the electrolyte. 136/6 F, 6 FS, 20,83 R, 100 R, 137, 154-155 Alternatively, the battery may be constructed in the 56) References Cited discharged state of a cathode containing as the cath UNITED STATES PATENTS ode-active material an intercalated chalcogenide in 3,681,144 8/1972 Dey et al. ........................ 136183 R which the intercalating species is derived from the 3,791,867 21 1974 Broadhead et al. ............... 13616 R same materials previously mentioned as being useful 3,864, 167 21 1975 Broadhead et al. ............. 136/6 LN for the anode-active material and the chalcogenide would be the same as that previously described. In this Primary Examiner-Anthony Skapars alternate type of battery, the anode may merely be a Attorney, Agent, or Firm-Jack Matalon; M. A. substrate (e.g., a metal grid) capable of receiving the Ciomek intercalating species deposited thereon. (57) ABSTRACT A battery is provided in which the anode contains as 24 Claims, No Drawings 4,009,052 2 The cathode-active material is a good clectronic con CHALCOGENDE BATTERY ductor and may thus serve as its own current collector. The cathode-active material should not be admixed or REFERENCE TO RELATED APPLICATIONS diluted with any other electrochemically active mate This application is a continuation-in-part of U.S. Ser. 5 rial except that alloys (i.e. solid solutions) of the indi No. 552,599, filed Feb. 24, 1975, which in turn is a vidual dichalcogenides may be used as well as the indi continuation-in-part of U.S. Ser. No. 396,051, filed vidual dichalcogenides. The cathode may be readily Sept. 10, 1973, both now abandoned. fabricated from the individual or alloyed dichalcoge nides using materials and methods well known in the BACKGROUND OF THE INVENTION O prior art, e.g., polytetrafluoroethylene bonding agents This invention relates to batteries. In the past, batter or support structures such as nickel or copper mesh. ies utilizing intercalation compounds of graphite and The dichalcogenides to be utilized as the sole cath fluorine as the cathode-active material and lithium ode-active material may be any compounds within the metal as the anode have been found to be useful as scope of the formula set forth above. Either the individ primary batteries, e.g., see U.S. Pat. No. 3,514,337. 15 ual chalcogenides or alloys of the chalcogenides with However, such batteries, although of relatively high one another may be used. Vanadium disulfide is not energy density, suffer serious deficiencies in that they known to exist but theoretically it should possess the are primary batteries, i.e. they are not capable of being layered structure of the other disclosed dichalcoge recharged. In contrast thereto, the present invention nides and should be similarly electrochemically active. provides for batteries which in many cases have not 20 Disulfides of vanadium and other transition metals, only high energy densities but are also capable of being such as VosTiorsS, display the requisite electrochemi discharged and recharged over many cycles. cal activity. Vanadium diselenide and vanadium ditel It is also well known (U.S. Pat. No. 3,711,334) to luride exist and display electrochemical activity. Pref utilize molybdates (e.g. MoO) rather than the layered erably, M in the formula MZ is titanium, Z is prefer chalcogenides (e.g. TiS) employed in the instant in 25 ably sulfur and x preferably has a numerical value be vention. In this prior art reference, the cell is not re tween about 1.95 and about 2.02. An especially useful chargeable and the lithium of the anode is converted to cathode-active material is titanium disulfide. lithium oxide during discharge. In the instant invention, the lithium ions intercalate into the chalcogenide and The Anode upon recharging are readily redeposited on the anode 30 The anode contains as the anode-active material a in the form of lithium metal. metal selected from the group consisting of Group a Broadhead et al (U.S. Pat. No. 3,791,867) makes use metals, Group Ib metals, Group Ila metals, Group IIh of an intercalatable transition metal chalcogenide and a metals, Group IIIa metals, Group IVa metals, and mix material such as lithium. However, this patent utilizes tures of the aforesaid metals with one another or with iodine, bromine, sulfur, selenium or tellurium as the 35 other substances such that the aforesaid metals can be cathode-active material and the transition metal chal electrochemically released from the mixture to interca cogenide merely serves as the host structure for the late, during discharge, the cathode-active material. cathode-active material. Examples of such suitable substances are ammonia and amines. Preferably the anode-active material is se SUMMARY OF THE INVENTION 40 lected from the group consisting of Group la metals, The present invention provides for batteries which magnesium, calcium and zinc. Especially useful anode may be fabricated either in a charged or discharged active materials are lithium (most preferred), potas state. The components of the two types of batteries sium and sodium. For the purpose of this invention, (denoted herein as the Charged Battery and the Dis boron, carbon, silicon and germanium are not to be charged Battery) will now be described herein in 45 regarded as "metals' useful for the anode-active mate greater detail. rial. As in the case of the cathode, the anode may be I. CHARGED BATTERY fabricated entirely from the above described metals or The Cathode it may consist of an underlying structure (fabricated of 50 a material such as aluminum, nickel, etc.) upon which The cathode contains as the sole cathode-active ma the anode-active material is deposited. terial (1) an intercalatable dichalcogenide of the for mula MZ, wherein M is an element selected from the The Electrolyte group consisting of titanium, zirconium, hafnium, nio The electrolyte useful for preparing the charged bat bium, tantalum and vanadium; Z is an element selected 55 tery is one which does not chemically react with the from the group consisting of sulfur, selenium and tellu anode or with the cathode and must be the type which rium, and x is a numerical value between about 1.8 and will permit the migration of ions to intercalate the cath about 2.1, or (2) alloys of the aforesaid dichalcoge ode-active material and vice-versa (during the dis nides with one another. For the purpose of this inven charge and charging cycles, respectively). tion, no other electrochemically active material should 60 The electrolyte may be present in a pure state (in the be utilized as a cathode-active material. It should be form of a solid, fused solid or liquid) or it may be con noted that in the charged state, the intercalatable di veniently dissolved in a suitable solvent. chalcogenide contains no intercalated species. As a general rule, the electrolyte material should The cathode structure itself need not necessarily consist of a compound of the same species as that consist of the cathode-active material but may be a 65 which is selected for the anode-active material. Thus, structure such as carbon, nickel, zinc, etc. upon which useful electrolytes may be conveniently represented by the dichalcogenide is deposited. Preferably, the cath the general formula LY wherein L is a cationic moiety ode structure consists entirely of the dichalcogenide. selected from the same materials useful as the anode 4,009,052 3 4 active material and Y is an anionic moiety or moieties The Anode such as halides, sulfates, nitrates, beta-aluminas, phos phofluorides, perchlorates and rubidium halide. In the case of the Discharged Battery, the anode may Especially useful electrolyte materials include LiPFs, consist simply of a current-collecting structure (e.g., a LiCIO, sodium beta-alumina, KCNS, LiCNS, etc. The wire, grid, or foil) which is capable of receiving the electrolyte may be present in a pure state in the form of intercalating species of elemental form deposited a solid, fused solid (i.e.