3,764,385 United States Patent Office Patented Oct. 9, 1973 2 3,764,385 a high energy density electric battery by utilizing Li or ELECTREC BATTERY USENG COMPLEXED N. Al anodes with a charge transfer agent comprising Li salts ORGANIC LITHUM SALTS AS CHARGE in either their molten or solid state. These batteries have TRANSFERAGENT been described in U.S. Pats. 3,445,288; 3,506,490; and Arthur W. Langer, Jr., Watchung, and Thomas A. 5 3,506,492. All the batteries so described must be oper Whitney, Linden, N.J., assignors to Esso Research and ated at temperatures in excess of 250 C. Engineering Company A new approach to designing a high energy density bat No Drawing. Continuation-in-part of application Ser. No. 808,328, Mar. 18, 1969. This application Dec. 22, 1970, tery has been described in U.S. Pat. No. 3,404,042. The Ser. No. 100,813 batteries described therein represent an improvement over Int, C. H01m 29/00, 43/00 10 the prior art. U.S. C. 136-6R 6 Claims SUMMARY OF THE INVENTION Novel batteries are described herein which are not sub ABSTRACT OF THE DISCLOSURE ject to the problems encountered in the prior art, More An electric battery which is characterized by use there 5 specifically, the electric batteries of the instant invention in of a complexed inorganic lithium salt as the charge achieve high energy densities by utilizing as a charge trans transfer agent between the electrodes. The electric bat fer agent a complex of an inorganic lithium salt and a tery can be a primary or a secondary electrical energy monomeric or polymeric polyfunctional Lewis base. The first component of the charge transfer agent of this storage device, and in a preferred embodiment the com invention is an inorganic lithium salt having a lattice plexed lithium salt is dissolved in an aromatic solvent. 20 energy no greater than about that of lithium hydride, pref erably no greater than about 210 kilocalories per mole CROSS REFERENCE TO RELATED APPLICATIONS (measured at about 18 C.). The lattice energies of var This case is a continuation-in-part of U.S. application ious inorganic lithium salts may be found in the "Hand Ser. No. 808,328, filed on Mar. 18, 1969, in the names of 25 book of Electrochemical Constants' by Roger Parsons Arthur W. Langer, Jr. and Thomas A. Whitney. (Academic Press, 1959). The lithium salts useful for this invention must have BACKGROUND OF THE INVENTION less than the requisite maximum lattice energy and must (1) Field of the invention also be inorganic in nature; they will normally have melt 30 ing points less than about 650 C. The term "inorganic,” This invention relates to an electric battery which is for the purposes of this invention, means that (1) there characterized by use therein of a complexed inorganic is no hydrocarbon radical bonded directly to the lithium lithium Salt as the charge transfer agent between the elec atom and (2) any hydrocarbon radical present in the trodes. The electric battery can be a primary or a second anion moiety must be indirectly bonded to the lithium. ary electrical energy storage device, and in a preferred 35 through a third atom which cannot be nitrogen, oxygen, embodiment the complexed lithium salt is dissolved in an phosphorus or sulfur. Thus, lithium compounds such as aromatic solvent. n-butyllithium and phenyllithium do not meet criteria (1) (2) Prior art and are outside the scope of this invention. Similarly, It is desirable to achieve maximum energy density (watt compounds of the type LiOR, LiNHR or LiNR2, LiSR, hrs./lb.) and maximum current density (watts./lb.) in 40 LiPR2 LiOOCR do not meet criteria (2) and are there an electric battery. Since one of the large contributors to fore outside the scope of this invention. On the other hand, the Weight of a battery is the charge transfer agent, it compounds of the type LiNH2, LiCN, LiSCN, LiSH, has been deemed desirable to substitute lower density or LiCOs, LiHCO3, LiAlR2Cl2, LiAlH(OR)3, LiBH(OR3), ganic solutions for the aqueous solutions primarily used. LiAIRaH, etc. are within the scope of this invention. Another advantage of using organic solutions as the 45 Specific nonlimiting examples of useful inorganic lith charge transfer agent is that certain desirable electrode ium salts are those in which the anion is: amide, azide, materials can be utilized. For example, Li, which is the chlorate, cyanide, fluosulfonate, chloride, bromide or oretically capable of the highest energy density of all the iodide, hydrogen sulfate, hydrosulfide, iodate, nitrate, hy anodic materials, cannot be used with an aqueous charge pochlorite, nitrite, sulfate, thiocyanate, perchlorate, Brs, transfer agent because of its inherent instability in water 13, CIBr2, IBr2, ICl4, BrF4, IFs, etc. and other aprotic media. The organic solutions which 50 Also useful are those inorganic lithium salts in which have been used fall into two categories, each with its own the anion is a complex metal anion which may be repre disadvantages. sented by the formula R'MXm wherein n is an integer In Electrochemical Technology, vol. 6, No. 1-2, Jan of 0 to 6 inclusive depending on the valence of M, m is uary-February 1968, pp. 28-35, a series of electric bat an integer and (n--in-1) equals the valence of M, X teries are described which are capable of yielding high 55 is a halogen, R' is a C1-Cao alkyl, aryl or aralkyl radical energy densities. These batteries utilize a lithium anode, and M is a metal selected from the group consisting of a charge transfer medium comprising LiClO4 or LiAlCl4 beryllium, magnesium, Group I-B elements, Group II-B dissolved in a solvent selected from the group consisting elements, Group III elements, Group IV-A elements other of acetonitrile, dimethyl formamide, propionitrile, di 60 than carbon and silicon, Group V-A elements other than methyl sulfoxide, methylacetate, 4-butyrolactone, nitro nitrogen; and the transition metals, i.e. subgroup B of methane, 2-pentanone, propylene carbonate and dimethyl Groups IV through VIII. The Periodic Table employed in carbonate, and a AgCl, cathode. Various problems with describing this invention is that which appears on the back these systems are encountered due to the tendency of the cover of "Handbook of Chemistry and Physics' (Chemi solvent to undergo oxidation and reduction reactions dur cal Rubber Co., 49th Edition). ing battery use. Further, the more effective solvents of 65 Nonlimiting examples of useful complex metal anions this series, i.e., propylene carbonate, dimethylformamide, include the hydridoaluminates, the hydridoborates, the dimethyl sulfoxide, and similar solvents such as hexa chloroaluminates (tetra-, hepta-, etc.), the aluminum al methylphosphoramide are expensive. Batteries which also kyl halides AuBra, BF4, BeCl4, SnCls, PF6, TiCl, FeCl utilize these solvents are described in U.S. Pat. No. 3,514 Cr(CO)5I, MnOls, Ni(CN)4, VFs, HgCl, BH, UF 337. These batteries suffer from the same disadvantages. 70 AsF6, etc. It is also known in the art that it is possible to achieve Preferably, the inorganic lithium salt is one of the 3,764,385 3 4 following: lithium chloride, lithium bromide, lithium iodide, lithium aluminum hydride, lithium borohydride, (IV) (R)b (O) lithium nitrate, lithium nitrite, lithium hexafluorophos phate, lithium tetrafluoborate, lithium tetraphenylborate,

lithium perchlorate, lithium azide, LiAsF6, and LiBeF. wherein a is 1 or 2, depending on the valence of Y or Y'; The most preferred inorganic lithium saits are LiBr, b is 0 or 1, depending on the valence of Y or Y'; c is LiI, LiBH, LiAlH4 LiBF4, and combinations thereof. 0 an integer of 0 to 10,000, inclusive; d is 0, 1 or 2, de The complexing agent contains at least two function pending on the valence of Y or Y'; e is an integer of 0 alities; at least one functionality is a secondary amine to 3, inclusive; R is the same or different C1-C alkyl group, a tertiary amine group, an amine oxide group, a radical; R' is hydrogen when d is 0 or is the same or secondary phosphine group, a thioether group, a sulfone different C1-C4 alkyl radical or C-C aryl or aralkyl group or a sulfoxide group; at least one other functionality 5 radical when d is 0, 1 or 2; Y is a nitrogen, sulfur or is a secondary amine group, a tertiary amine group, a sec phosphorus atom; Y is a nitrogen, oxygen, sulfur or ondary phosphine group, a tertiary phosphine group, a phosphorus atom; and Z is a nonreactive radical selected thioether group, or an ether group. from the group consisting of (1) Ca-Cio cycloaliphatic The terms "amine oxide group' and "phosphine oxide or aromatic radicals and their lower alkyl derivatives group,” for the purposes of this invention mean that the 20 wherein said radicals are attached to the Y and Y atoms underlying amine and phosphine must be tertiary (rather in Formula I and the nitrogen atoms in Formula II at than primary or secondary) in nature. Thus, the desired 1,2-positions on the aromatic rings or 1,2- or 1,3-posi "amine oxide group' and "phosphine oxide group” have tions on the cycloaliphatic rings; and (2) 1 to 4 meth the formulas: ylenic radicals, wherein each methylenic radical contains 25 0 to 2 monovalent hydrocarbon radicals of 1 to 6 carbon 9 atoms. R-N-R and R-N-R Preferably, the chelating Lewis base has (a) at least R R one Y being nitrogen and at least one Y being oxygen (i.e. an aminoether) or (b) all the Y and Y atoms being The oxides of primary or secondary amines or phosphines 30 the same atom (i.e. polyamines, polyamine oxides, poly either do not exist or are unstable and undergo rearrange phosphines, polyphosphine oxides, polythioethers, poly ment, e.g. sulfones and polysulfoxides). It should be understood that the prefix "poly-' employed in describing the non-chelat 9 pH ing and chelating Lewis bases means that the Lewis base 35 is a monomer or a polymer in the classical sense and R-NH ma- R that such monomer or polymer has two or more of the R R same functionalities. The complexing agent may be non-chelating or chelat Suitable nonlimiting examples of chelating Lewis bases ing in nature; the chelating types (preferred herein) have falling within the scope of the above formulas are: one required functionality in a spatial relationship with 40 Formula I (where all heteroatoms are nitrogen atoms). the other required functionality(ies) in the molecule such N,N',N',N'-tetramethyl-1,2-cyclopentanediamine, that coordinate bonds are established between the func N,N',N',N'-tetramethyl-1,2-cyclohexanediamine (cis, tionalities and the lithium cation of the inorganic lithium salt. N,N',N',N'-tetramethyl-o-phenylenediamine,trans or mixtures), Suitable, nonlimiting examples of nonchelating com 45 4-ethyl-N,N',N',N'-tetramethyl-o-phenylenediamine, plexing agents are: N,N',N',N'-tetramethyl-N'-phenyl diethylenetiriamine, amines such as triethylenediamine, tetramethyl-1,6-hex N,N,N',N'-tetramethyl-1,2-ethanediamine, anediamine, N,N'-dimethylpiperazine, tetramethyl-1,5- N,N,N',N'-tetramethyl-1,3-propanediamine, pentanediamine, tetramethyl-1,10-decanediamine, etc.; N,N,N',N',N'-pentamethyl-diethylenetriamine, aminoethers such as N-methyl morpholine, 6-(dimethyl 50 N,N',N',N'-tetramethyl-1,2-propanediamine, amino)-hexyl methyl ether, etc.; and N,N'-dimethyl-N,N'-diethyl-1,2-ethanediamine, amine oxides such as N,N,N',N'-tetramethyl-1,6-hexane N,N',N',N'-tetramethyl-1-cyclohexyl-1,2-ethanediamine, N,N,N',N'-tetramethyl-2,3-butanediamine, diamine dioxide, triethylenediamine dioxide, etc. N,N',N',N'-tetramethyl-1,4-butanediamine, The chelating type of complexing agent may be spar 55 N,N,N',N',N',N'-hexamethyltriethylenetetramine, teine, an N,N'-di-(C-C alkyl) bispidin, tris-2 (dimeth poly-(N-ethyl-ethyleneimine), ylaminoethyl)-amine as well as those compounds falling poly-(N-methyl ethyleneimine), within the scope of the following general formulas: N,N',N',N'-1,8-naphthylenediamine, (I) (O)d (O)d (O)d beta-(dimethylamino)-ethyl methyl ether, 60 beta-diethylaminoethyl ethyl ether, ce.'" TY". Ya. bis-3-(dimethylaminoethyl) ether, (H)b Ld), e (H) b beta-(dimethylamino)-ethyl ethyl ether, gamma-(dimethylamino)-propyl methyl ether, (II) / CHN vey ortho-dimethylamino anisole, (CEH) N-Z-N CE) 1-dimethylamino-2-dimethylphosphino ethane, s' yvils bis-(beta-dimethylaminoethyl) methyl phosphine, beta-(dimethylaminoethyl) methyl sulfide, (III) (O)d 1,2-dipiperidylethane, (H) --(R) A. tris-(1,3,5-dimethylamino) cyclohexane, 70 N,N',N'-trimethyl-1,3,5-hexahydrotriazine, tetrabutylethylenediamine dioxide, tetramethylmethanediamine monoxide, (p)a S co). tetramethylethylenediphosphine dioxide, (H)-y- Y-(H) b 2,5-dithiahexane-2,5-disulfone, and (R) (R) a 75 2.5-dithiahexane-2,5-disulfoxide, etc. 3,764,385 5 6 The chelating type of complexing agent is preferred over Regardless of the method employed the preparation of the non-chelating type of chelating agent since the former the complex is preferably carried out under anhydrous results in more stable complexed inorganic lithium salts. conditions. Particularly preferred, since they generally give rise to The complex may be readily prepared at temperatures hydrocarbon-soluble complexes, are those chelating Lewis of about -50° C. to about 200° C.; preferably 0 to 100° bases which are (1) tertiary polyamines (i.e. all of the C.; the latter temperature range is preferred because of heteroatoms are tertiary nitrogen atoms) containing at convenience and also since higher temperatures favor dis least 5 carbon atoms and at least 2 tertiary nitrogen atoms sociation of the less stable complexes. In general, from and (2) tertiary aminoethers (i.e. all nitrogen atoms 0.25 to 50, preferably 0.5 to 10, moles of complexing present are tertiary nitrogen atoms) containing at least 5 O agent per mole of inorganic lithium salt is employed; the carbon atoms and at least 1 tertiary nitrogen atom and at complexing agent may also be employed as a solvent least one ether group. Particularly preferred species of However, it should be understood that the amount the chelating tertiary polyamines are of complexing agent employed may influence the struc ture of the resultant complex. Thus, it has been found N,N,N',N'-tetramethyl-1,2-ethanediamine, 5 possible to prepare complexes of the following types: N,N,N',N'-tetramethyl-1,3-propanediamine, (1) Two moles of inorganic lithium salt to one mole N,N',N',N'-tetramethyl-1,2-cyclohexanediamine (cis, trans of complexing agent such as (LiBr)26 hexamethyltriethyl or mixtures), enetetramine. N,N,N',N',N'-pentamethyldiethylenetriamine, (2) One mole of inorganic lithium salt to one mole N,N,N',N',N',N'-hexamethyltriethylenetetramine, 20 of complexing agent, such as LiBrepentamethyldiethylene poly-(N-methyl ethyleneimine), etc. triamine, Lietetramethylenethanediamine. (3) One mole of inorganic lithium salt to two moles Particularly preferred species of the tertiary aminoethers of complexing agent, such as LiAlH4O2(tetramethyl is beta-(dimethylamino)-ethyl methyl ether. ethanediamine), LiAlH4O2(tetramethyl methanediamine), The most particularly preferred species are pentamethyl 25 LiBro2(tetramethylethanediamine). diethylenetriamine and hexamethyltriethylenetetramine, Of course, the minimum amount of complexing agent tris - (B - dimethylaminoethyl)amine and combinations should be that stoichiometric amount required to produce thereof. the desired type of complex (where more than one type of The complex of the inorganic lithium salt (with the complex is possible from a particular inorganic lithium non-chelating or chelating complexing agent) may be 30 salt and a particular complexing agent). Where only one readily prepared by mixing the selected inorganic lithium type of complex can be formed or where one is not con salt (having the requisite maximum lattice energy) with cerned with the particular type of complex to be formed the selected complexing agent in the absence of solvent. (assuming more than one type is possible), it is desirable Such mixing may also be accomplished in the presence to employ amounts of complexing agent in excess of the of inert hydrocarbons, e.g. CA-Cao alkanes (e.g. pentane, 35 stoichiometric amount. heptane, hexadecane); Co-Cao aromatics (e.g. benzene, Although we do not wish to be bound by the following toluene, xylene, dibutylnaphthalene); halogenated aro theoretical structure, it is believed that the 1:1 complex matics (e.g. chlorobenzene, dichlorobenzene, hexa made using a tridentate chelating agent has a structure of fluorobenzene); heterocyclic compounds (e.g. pyridine, the type represented by lithium chloride and N,N,N',N', pyrrole, furan, thiophene, sulfolane, borazole); polar 40 N'-pentamethyl diethylenetriamine: solvents (e.g. alcohols, ketones, dimethylsulfoxide, acetonitrile dimethylformamide, liquid ammonia, triethyl amine, propylene carbonate, ethers, etc.); or mixtures C1G thereof. lip The amount of the diluent is not critical and amounts 45 in the range of 0 to 99.9 wt. percent, based on the chelated CHs --- : ss CH lithium salt may be conveniently employed. Thus, the NCH-CH-N-CH-CHN complex can be prepared in the absence of solvents, in the cí. ch, CH form of pastes and in solutions. In those situations where the inorganic lithium salt 50 Regardless of the number of functional groups in the of choice is not solubilized by the admixture of the com chelating complexing agent, the number of functional plexing agent and solvent, the complex may be formed groups solvating the lithium at one time will rarely exceed by mixing the inorganic lithium salt (which is preferably four and will usually be three. Of course, the bidentate in finely divided form) with the complexing agent of chelating agents can have only two functional groups sol choice in stoichiometric amounts, or preferably, with ex 55 vating the lithium. cess complexing agent. The complexes of this invention can be utilized either in Another method for preparing the complex involves their molten state or dissolved in a solvent. Preferably, anion exchange. In this method, the complexing agent of because of temperature requirements, the complexes are choice is mixed with an inorganic lithium salt (in which dissolved in a solvent. The preferred solvents are aromatic the anion is not the desired anion) by one of the methods 60 in nature and include benzene, alkylbenzenes, haloben described above. Thereafter the resultant complex is sub Zenes, pyridine, alkyl substituted pyridines, pyrrole, naph jected to anion exchange in the presence of a metal salt thalene, alkyl naphthalenes, indenes, and combinations (or other well known techniques such as anion exchange thereof. Of this group single ring aromatic solvents are resins) containing the anion of choice; alternatively, all preferred. components may be mixed simultaneously and both com 65 The most preferred solvents for use in this invention plexation and metathesis occurs in situ. are benzene and toluene. Another method for preparing the complex is analogous Specific, nonlimiting examples of the solvents which to the preceding method except that here the anion is may be utilized are benzene, toluene, xylene, chloroben one of choice, but the complexing agent is not one of Zene, nitrobenzene, ethylbenzene, pyridine, pyrrole, quino choice. After preparing the non-preferred complex by 70 line, hexafluorobenzene, fluorobenzene, styrene. one of the above methods, the non-preferred complexing The electric batteries of this invention can be utilized agent moiety is exchanged for the preferred complexing as either primary or secondary electrical energy storage agent moiety by mixing the complex (utilizing one of the devices. When a primary battery is desired, the cathodes former methods) with the desired complexing agent and are preferably selected from the group consisting of H2, thereafter recovering the desired complex. 75 O2, Cl2, Ag-AgI, Ag-AgCl and Ag-AgBr, The most pre 3,764,385 7 8 ferred material for use as the anodic electrode is lithium was found feasible and the conductivity remained un due to its high energy density. changed at 6.8x104 (ohm-cm.)". In a secondary battery, the electrodes are preferably selected from the group consisting of Li, Fe, Co, Ni, Cu, EXAMPLE 4 Zn, Cd, Bi, Pb, Hg, Al, Mg, Ag, Au, Pt, Pd, Rh, Sn, Sb, In the same system as described above, a 1.5 molar carbon, and alloys of the aforesaid metals. solution of PMDTeLi in indene was examined. The As stated previously, the charge transfer agent of the open voltage was 2.2 volts. After several discharging and instant invention can be effectively utilized in a solvent recharging cycles the system had the same conductivity as less, molten state. It is well known that molten alkali at the start: 9X106 (ohm-cm.), metal salts, such as lithium iodide in the molten state, are O EXAMPLE 5 useful as electrical conductors. However, the use of such molten salts entails special equipment and procedures In the same physical set-up as described in Example 1, since they have high melting points, e.g. Lil melts at 450 a 1 molar solution of LiAlH4e hexamethyltriethylene C. and LiBr melts at 547 C. However, this disadvantage tetramine (HMTT) in benzene was charged and the open can be readily overcome by complexing the lithium 5 voltage was 0.45 volt. After repeated charging and dis salt with a complexing agent such as N,N',N',N',N'- charging the conductivity of the system was 1.1 x 103 pentamethyldiethylenetriamine (PMDT). Crystalline (ohm-cm.), the same as at the start of the experiment. Lie PMDT EXAMPLE 6 complex starts to melt at about 84 C. and is completely 20 Instead of chel0LiAlH4, 2 molar HMTTeLiBH in molten at about 110° C. At 110° C., PMDTeLiBr is benzene was used. The open voltage was 1.1 volts and the molten and has a conductivity of 5.2X10 (ohm-cm.). conductivity after repeated charging and discharging was Some lithium salts, such as lithium aluminum hydride, still 4.4x 104 (ohm-cm.) - as at the start of the experi decompose below their melting points but complexation Inent. can extend their utility. For example, LiAlH4 decomposes 25 EXAMPLE 7 at 110-125 C., whereas PMDTeLiAlH4 melts without Conductivity of LiBr and LiBF chelates in dipolar decomposition at 150-155 C. and can be sublimed with aprotic solvents out decomposition at 125 C./0.5 mm. When complexed by HMTT, LiAlH4 is stable to over 200 C. Conductivity measurements were made of the follow The following examples are for illustration and not ing systems, utilizing the apparatus and procedure of Ex 30 ample 1. It was noted that the complex salts of this inven intended to limit the scope of the instant invention. tion yield conductivities similar to the uncomplexed salt EXAMPLE in propylene carbonate and dimethylformamide indicating A secondary battery was formed by containing in a that the use of the complex salts of the instant invention closed glass vessel two parallel electrodes each having an 35 with solvents of this class yields no advantage. This phe effecitve area of about cm. and separated from each nomenon can be compared with the behavior of the com other by 0.1 cm. The vessel contained about 25 ml. of a plex salts in benzene wherein the uncomplexed salts yield 2 molar solution of pentamethyldiethylenetriamine conductivities on the order of from 1010 to 10-18 (ohm cm.). (PMDT) eLiBr 40 chelate in benzene. The AC conductivity of this system was 2.9x10-4 (ohm-cm.). This assembly was subjected to a polarizing voltage of 3.5 volts for one hour. During this time a current of about 1.5x108 amps passed ABLE through the system which charged or polarized the elec Conductivity trodes. When the applied voltage was removed and the 45 Chelate a, b Solvent (ohm-cm.)C1 TMED9L.Br. Propylene carbonate------1.8x10-3 open circuit potential of the cell was read by connecting PMDTLiBr------. do------2.5X10-3 an electronic voltmeter to the two electrodes, an EMF of HMT Libr. 2.8x10-3 PMOT9LibF. 2.9x10-3 2.6 volts was observed. The cell was then allowed to dis MTTPiRF 3.3X10-3 charge across a 10,000 ohm resistor for six hours. During LiBr------8XO-3 LiBF4---- 2, 6x103 this time the current delivered by the cell dropped from TMEDEBr. ... 6x10-3 2X 104 to 6x10-6 amperes and the open voltage PMDT'Libr------'O------3.3X10-3 HMTT9LiBr (s). 8.5X104 dropped to 0.06 volt. The charging process was repeated TMEDoLiBF- 5X10-3 and the cell reached an open voltage of 2.3 volts. The PMDTOLiBF- 5X10-8 iso-MTTeLiBF 5X10-3 same discharge pattern was followed with quite repro 5 5 TMEDeLiBr (s). 5X10-3 ducible results. The discharged cells conductivity was HMTTLiBr------do------4, 8x103 iso-HMTTLi Br (s) 4.3x103 measured three days after the end of the discharge and PMOTPLB 4.2x10-3 found to be still 2.9X104 (ohm-cm.). This charging LiBr------5.3X10s and discharging process could be repeated several times a All solutions were 1 molar in chelate unless followed by (s) in which without adverse effects. case they were saturated and the concentrations were less than 1 Imolar. 60 b TMED=MegNCHCHNMe2, PMDT = Me2NCH2CH2N (Me) CH CHNMe2, HMTT's Me2NCH2CH2-N (Me) CH2CH2NMe2, iso EAXMPLE 2 HMTT = N (CECHNMe2)3. In the same system described in the preceding example PMDTOLiI was used as a 1.7 molar solution in benzene and the open voltage of the cell was found to be 1.9 volts. Again several charging and discharging cycles were made. At the end of these cycles, the AC conductivity of the EXAMPLE 8 system was, within experimental error, the same as at the Conductivity of LiBrand LiBF chelates in substituted start: 8x104 (ohm-cm.). and heterocyclic aromatic solvents 70 EXAMPLE 3 Table II records conductivity measurements made In the same system described in Example 2, the sol utilizing the apparatus and procedure of Example 1 for went was ortho-dichlorobenzene instead of benzene, the the complex salts in chlorobenzene, fluorobenzene, m PMDTOLi was 2 molar and the open voltage was 2.9 dichlorobenzene and pyridine. These data demonstrate volts. Charging and discharging of the system repeatedly 75 that aromatic solvents of these types may be used with 3,764,385 10 the complex salts of the instant invention as a charge sisting of benzene, indene, dichlorobenzenes, monochloro transfer medium to prepare an electric battery cell. benzene, fluorobenzene, pyridine, toluene, Xylene and hexafluorobenzene. TABLE II 11. In an electric battery cell as defined by claim 9, Conductivity 5 the inorganic lithium salt being selected from the group Chelate/ Solvent (ohm-cm.) consisting of LiBr, Li, LiBH4, LiAlH4, LiBF4 and com binations thereof. HMTTOLiBF (s). -- Chlorobenzene.------4x10 HMTTLiBr (S)------do------5X10-4 12. In an electric battery cell as defined by claim 9, PMOTOLiBr.------do------19x10-4 the polyfunctional chelating tertiary amine being selected PMDTLiBF (s).------do---- 5.3X105 TMEDOLiBF (s). ----do---- 1s10.6 O from the group consisting of pentamethyldiethylenetri TMED9LiBr (s). ----do------7.4x108 iso-MTTLiBr. Fluorobenze 6.5x104 amine, hexamethyltriethylenetetramine and tris-(6-di PMDTOLiBr. ----do------2, 6x104 methylaminoethyl)amine and combinations thereof. TMEDLiBr------do------7x10-8 iso-HMTTOLiBr (s). m-Dichlorobenzene. 4.3X104 13. In an electric battery cell as defined by claim 9, PMDTOLiBr (s)------do---- 1.5X10-4 the ratio of complexing agent to inorganic lithium salt TMEDOLiBr(s) 1.4X10-7 HMTTOLiBF- 3.1X103 5 varying from about 0.5 to about 2.5. PMDTOLiBF- 35&S 14. In an electric battery as defined in claim 9, wherein TMED9LiBF--- 2.3X10 HMTTOLiBI. 1. & said inorganic lithium salt is selected from the group con iso-MTTPLiBr- 1. 2&S sisting of LiBr, Li, LiBH4, LiAlH4, LiBF and com PMDTOLIBr (S)----- 1.0X10 binations thereof, and said polyfunctional chelating ter a All solutions were 1 molar in chelate unless followed by (s) in which 20 tiary amine is selected from the group consisting of penta case they were saturated and the concentrations were less than 1 molar methyldiethylenetriamine, hexamethyltriethylenetetra mine, tris(f-dimethylaminoethyl)amine and combinations EXAMPLE 9 thereof. Using the apparatus and procedures of Example 1, the 15. In an electric battery as defined in claim 1 a conductivity of a 0.9 molar solution of pentamethyldi 25 chelating tertiary amine being selected from the group ethylenetriamineoLiBr in hexafluorobenzene Was meas. consisting of compounds represented by the following ured. The conductivity in ohm-cm.) was 2.62X 10-5 at general formulas: 25 C., 3.7x10-5 at 50° C. and 4.05X10 at 75° C. using a frequency of 60 Hz. I What is claimed is: 30 1. In an electric battery cell, the combination of elec (I) co-tra. trodes with a charge transfer agent comprising an inor ganic lithium salt having a lattice energy of not more than (II) CR els about 210 kilocalories per mole at 18 C. complexed 35 (oN-Z-N sch). with a monomeric or polymeric polyfunctional chelating C CH tertiary amine containing at least two nitrogen atoms. 2. In an electric battery cell defined in claim 1, the wherein Z is a nonreactive radical selected from the group charge transfer agent being dissolved in an aromatic Sol consisting of (1) C4 to C10 cycloaliphatic or aromatic vent. 40 radicals and their lower alkyl derivatives, wherein said 3. In an electric battery cell defined in claim 2, the radicals are attached to the nitrogen atoms at 1, 2 posi inorganic lithium salt being selected from the group con tions on the aromatic ring or 12 positions or 1,3 positions sisting of LiBr, LiI, LiBH, LiAlH4, LiBF4 and com on cycloaliphatic rings, and (2) 1 to 4 methylenic radicals, binations thereof. wherein each methylenic radical contains 0 to 2 mono 4. In an electric battery cell defined in claim 2, the 45 valent hydrocarbon radicals of 1 to 6 carbon atoms; R polyfunctional chelating tertiary amine being selected is a C1 to CA alkyl radical; a is 2, c is an integer of from the group consisting of pentamethyldiethylene tri from 0 to 10,000, e is an integer of from 0 to 3, sparteine, amine, hexamethyltriethylenetetramine and tris-(3-di and N,N'-di-(C1-C4 alkyl) bispidin, and tris-2-(dimethyl methylaminomethyl) amine and combinations thereof. aminoethyl)amine. 5. In an electric battery cell defined in claim 2, the 50 16. In an electric battery as defined in claim 15 the ratio of complexing agent to inorganic lithium Salt vary lithium salt being selected from the group consisting of ing from about 0.5 to about 2.5. lithium chloride, lithium bromide, lithium iodide, lithium 6. In an electric battery cell defined in claim 2, the aluminum hydride, lithium borohydride, lithium nitrate, aromatic solvent being selected from the group consist lithium nitrite, lithium hexafluorophosphate, lithium tetra ing of benzene, alkylbenzene, halobenzenes, pyridine, pyr 55 fluoroborate, lithium tetraphenylborate, LiAl(CH5)Hs, role, naphthalene, alkyl naphthalenes, halonaphthalenes, LiAl(CH5)2Pd2, LiAl(CH5)3H, LiAl(C2H5)4, lithium indene and combinations thereof. perchlorate, lithium azide, LiAsF6, and LizBeF. 7. In an electric battery cell as defined by claim 2, the electrodes being selected from the group consisting of Li, References Cited H, O, Cl, Ag-AgI, Ag-AgCl and Ag-AgBr electrodes. 8. An electric battery cell as defined by claim 1, in 60 UNITED STATES PATENTS which one of the electrodes serving as a cathode on dis 3,073,884 1/1963 Pinkerton ------136-137 charge being unreactive solid material, said cell being 3,110,630 11/1963 Wolfe ------136-154 polarized by application of polarizing voltage which re 3,404,042 10/1968 Forster et al. ------136-6 verses discharge reactions in the cell. 65 3,542,602 11/1970 Gabano ------136-155 9. In an electric battery cell as defined by claim 8, 3,578,500 5/1971 Maricle et al. ------136-154 the electrodes being selected from the group consisting of Li, Fe, Co, Ni, Cu, Zn, Cd, Bi, Pb, Hg, Al, Mg, Ag, Au, DONALD L. WALTON, Primary Examiner Pt, Pd, Rh, Sn, Sb, C and alloys thereof. 10. In an electric battery cell as defined by claim 9, 70 U.S. C. X.R. the aromatic solvent being selected from the group con 136-83 R, 137, 154 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,764,385 Dated October 9, lS73 Inventor(s). Arthur W. Langer, Jr. and Thomas A. Whitney It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: Q Column 3, line 27, change "and R--R" tO -- and R-R-R m me Column (, line 36, after "about" insert -- lo -- ; line 6l, change "EAXMPLE" to -- EXAMPLE --. Column 8, Example 7, Table l, line 45, last column, change (9am-et-)gll" t (ohm-cm.). --; iine 62, change N(CH2CH2NMe2)3" to - N(CH2CH2NMe2) --. --;Column line 9, 49,line change 27, change"methylaminomethyi)" "in ohm-cm.)" to to-- --methylaminoethyl) in (ohm-cm.)l

Signed and sealed this 9th day of April 1974.

(SEAL) Atte St : EDWARD M.FLETCHER, JR. C. MARSHALL, DANIN Attesting Officer Commissioner of Patents

FORM PO-1 O50 (10-59) USCOMM-DC 80378-989 U.S. GOVERNMENT PRNTING OFFICE: 969 O-366-334,