CA1158305A - Efficiently rechargeable totally inorganic non- aqueous li/so.sub.2 cell with ligacl.sub.4 electrolyte salt - Google Patents
Efficiently rechargeable totally inorganic non- aqueous li/so.sub.2 cell with ligacl.sub.4 electrolyte saltInfo
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- CA1158305A CA1158305A CA000385027A CA385027A CA1158305A CA 1158305 A CA1158305 A CA 1158305A CA 000385027 A CA000385027 A CA 000385027A CA 385027 A CA385027 A CA 385027A CA 1158305 A CA1158305 A CA 1158305A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
M-3531 EFFICIENTLY RECHARGEABLE TOTALLY INORGANIC NONAQUEOUS Li/SO2 CELL WITH LiGaCl, ELECTROLYTE SALT A totally inorganic efficiently rechargeable nonaqueous cell having an active anode of metals, such as lithium or alloys of lithium, a sulfur dioxide electrolyte solvent/cathode depolarizer and a gallium containing electrolyte salt with anode metal cation such as LiGaCl4.
Description
~ ~5~305 This invention relate~ to room temperature rechargeable nonaqueous cells having active metal anodes such as lithium and more particularly to such cells having sulfur dioxide electrolyte svlvent/cathode depolarizers.
In the past a considerable amount of effort has been expended in the development of a viable, practical and commercially acceptable room temperature operable rechargeable lithium cell which would have the advantages over the co~mon rechargeable lead-acid and nickel-cadmium batteries of higher efficiency, lower weight and greater primary lifetimes thereby allowing for more time between charging cycles. Such efforts have met with varying degrees of success. However, such cells have rarely achieved greatex than 80% recycling efficiencies over extended charge and discharge cycles. These cy~ling efficiencie~ are to be differentiated from the very high lithium plating efficiencies since lithium plates out of electrolyte solutions, commonly used in lithium cells, with close to 10~ efficiency (the exchange current of the reaction Li~,Lit + e is very high-on the order of 1 x 10 3A/cm2).
The recycling efficiencies are instead related to subse~uent anodic oxidation of the plated lithium wherein generally the effectiveness of the plated lithium as an anode material decreases rapidly upon cycling despite the high plating efficiencies.
1 ~5~5 Several reasons have been postu]ated ~or the inefficlency of plated lithium for repeated anodlc oxidation and of cells containing such anodes. One reason given is that lithium is dendritically deFosited and becomes coated,particularly at the narrow point of contact with the anode substrate with an insulating film which electrically insulates it from the anode substrate despite its physical presence on the anode.
The plated lithium dendrites as they become electrically insulated become unavailable for efficient anodic oxidation during discharge.
Furthermore, the plated lithium dendrites are fragi~e and may be easily mechanically dislodged from the anode substrate. The dislodged lithium, because it is insoluble in the electrolyte is thereafter lost from discharge and further replating. Efficiency is therefore reduced by depletion of available lithium for repeated cycling.
The electrically insulated lithium generally results from the interaction of the lithium with the organic solvent or solvents utilized in the cells. As the cell is recycled, the lithium metal is deposited in the form cf dendrites having high surface areas which therefore react to an increasingly greater e~tent ~ith the electrolyte solvent particularly at the Flating site to form the insulating surface films of increasingly greater area whereby such plated ]ithium becomes increasingly electrically isolated from the anode. These films, when extensively formed, also tend to reduce the rate a~ which lithium cations enter solution and thereEore may also reduce cell capability. Furth~rmore, reaction products of lithium with commonly used electrolyte solvents are irreversible (particularly with respect to the solvent) in nature. Accordingly, during repeated cycling the electrolyte solvent itself becomes depleted with loss of conductivity and cell performance. The reaction products generated from the solvents also tend to act as detrimertal impurities further destroying cellcapability. Additionally, even lithium contained in such reaction products may also be lost thereby causing increasing reduction of available lithium for recycling.
~ 2 --1 ~ 5~3~ 3531 As an example, propylene carbonate will react with lithium to form an insulating film of lithium carbona~e and propylene gas which cannot be reversed to obtain the original solvent. Though recovery of some of the lithium is possible under charging, the lithium carbonate is however not efficiently reversible into its component elements. Some lithium is therefore lost from further cycling. Similarly other solvents such as tetrabydrofur~n and acetonitrile form complex reactior. products with lithium which are also irreversible. In fact the organic solvents by their very nature must react with the lithium anode. In order to dissolve the electrolyte salts needed for conductivity, the organic electrolytes must be somewhat polar, and it is this very chcracteristic which causes such solvents to react with the lithium in the formation of ; the irreversible reaction products.
` In order to attain a highly efficient rechargeable cell in accordance with the present invention, plated lithium should have reduced dendrite character and should not be coated with a non-reversib]e insulative film. It is also essential that there must be a complete cycling of substantially all of the active cell components without the introduction or formation of additional reaction by-products which are irreversible in nature. Accordingly, free organic solvents or co-solvents are excluded from the cells of the present invention. Furthermore, though the problem of recharging efficiency has been described as being inherent in organic solvent lithium cells, cells having only inorganic components such as a lithium cell with an inorganic thionyl chloride solvent/cathode depolarizer may have s:imilar problems of inefficient recycling. Reaction of the thionyl chloride with the lithium produces reaction products of lithium chloride and an unstable 'S~' species which cannot be effectively recombined to the original starting materials. Thus the electrolyte solvent and cathode depolarizer, even if inorganic, must only react with the anode metal only to the extent of formation of totally reversible reaction products.
~s~3a~
Cathode depolarizing materials have recently been discovered which are in themselves highly rechargeable. Examples of such materials include the layered metal chalcogenide compounds described by Whittingham in the ~.S. Patent No. 4,009,052 which intercalate lithium ions within the spacing between the layers without undergoing full reactions. This property makes them effectively reversible and rechargeable. However, such materials ~re rtilized in ambient temperature lithium cells with organic electrolytes whereby the cell as a whole remains inefficiently rechargeable.
Various attempts have been made to improve the efficiency and the rechargeability of the lithium anodes in nonaqueous cells. Such expedients generally attempted to minimize the dendri~ic plating of the lithium with the use of various means such as additives, alloying of the lithium anode, utilization of specific electrolyte salts and solvents etc. U.S. Patents Nos. 3,953,302 and 4,091,152 describe the use of metal salt additives comprised of metals which are reducible by lithium and which coplate with the lithium on charging to form lithium-rich metallics or alloys. The use of polyalkylene glycol ethers in ~.S.
Patent No. 3,928,067 was described as improving the recycling characteristics of lithium ce]ls by improving the morphology of the plated lithium.
Though such expedients improve rechargeabiligy, such cells still contain organic elements which preclude truly efficient rechargeable cells as described. Dendritic plating of lithium in secondary cells is described in U.S. Patent No. 4,139,fi80 as being effectively prevented ~ith the use of clovoborate electrolyte salts. ~lowever, such electrolyte salts are difficult to synthesize and are accordingly very expensive. U.S. Patent No. 3,580,828 describes specific electrolyte salt concentra~ions and current density limlts which, if observed, improve lithium deposition characteristics. Other methods for improving rechargeability of plated lithium include the initial utilization of lithium allo;~ anodes particu]arly with aluminum as described in U.S. Patent No. 4,002,492.
~ 15~3~5 General improvements in rechargeable lithium cells include the use of complexed inorganlc lithium salts as charge transfer agents (U.S.
Patent No. 3,7~,6,385~ and the judicious use of organic cosolvents with S2 in order to improve solubility of the electrolyte salts (U.S. Patent No. 3,953,234). The use of solvents which are relatively stable with respect to the lithium anode was in fact recognized in patents such as U.S. Patent No. 3,540,988 as being required in order to provide enhanced rechargeability of the cells.
Various systems requiring external mechanical components include molten lithium cells (not inherently sub~ect to dendritic plating) which require extensive heating and shielding components but which are the most feasible efficient rechargeable lithium cells since there are no dendrites or films on molten lithiumO Other systems include cycling electrolytes such as in ~.S. Patent No, 4,154,902 which require complex circulating mechanisms.
Electrolytic processes for lithium deposition, however, generally require organic solvent carriers of the electrolyte salt for high conductivity and efficient plating out of the lithium metal. Exemplary of such lithium deposition procedures are ~.S. Patents Nos. 3,791,945 and 3,580,828.
Similarly, cells as described above (e~cept for those containing clovoborate electrolyte salts) require organic solvents for high conductivity and efficient lithium plating.
Electrodeposition of lithium in an electrolyte comprised of lithium and sodium tetrachloroaluminate or lithium and sodium tetrabromoaluminate dissolved in pure sulfur dioxlde (without organic cosolvents) is described in ~.S. Patent No. 3,493,433. However discharge performance of such cells is severely llmited with a discharge capacity substantially ]ess than theoretical capacity. Since such enumerated salts are described therein as being the only salts having sufficient solubility and conductivity in pure liquid S02 for plating efficiency, cells having other salts in ~ ~5~3~
liquid SO 2 have as a rule re~uired the further utilization of organic cosolvents as described in U.S. Patent No. 3,953,234 and as discussed above.
It is an object of the present invention to provide a highly efficient roorn temperature rechargeable inorganic lithium or other alkali or alkaline earth metal cell having substantially only reversible reaction products which is both efficiently dischargeable and substantially completely rechargeable over extended periods of cycling.
This and other objects, features and advantages of the present invention will become more evident from the following discussion and drawing.
The sole figure of the drawing is a voltage profile of charge and discharge cycles of a cell of the present invention.
Generally the present invention comprises a totally inorganic non-aqueous efficiently rechargeable cell having a lithium or other active metal (generally alkali or alkaline earth metal or alloys thereof) anode, a totally inorganic electrolyte solvent consisting essentially of sulfur dioxide which may also function as cathode depolarizer (with an inert generally carbon cathode) and an inorganic gallium salt such as gallium halides having anode metal cations and LiGaCl4 (with a lithium cation and a GaC1 4 anion in a lithium anode cell) in particular, dissolved in said sulfur dioxide electrolyte solvent~ Other gallium salts include Li 2 O(GaC13 ) 2 and Li2 S(GaC13 )2 (with lithium cations and O(GaCl3 )2 and S(GaC1 3 )2 anions respectively) described in co-pending application (M-31l65).
A completely reversible solid cathode depolarizer such as an intercalation compound may optionally be utilized with the S02 electrolyte solvent. Examples of such solid cathode depolarizers include chromium oxide (SELOXCETTE, a trade mark of Ventron Division of Thiokol Corp. - Alfa Products.), titanium disulfide, manganese dioxide, etc. ~he cell is efficiently rechargeable since all reactions therein including internal reactions between cell compounds such as between the lithium anode and the S02 solvent and the electrochemical cell reactions produce substantially :~ ~$~3~3~
~1-3531 /
only reversible products of, for example, lithium dithionite which is 100% reversible on recharge or intercalated or similarly reacted lithium which is also cc,mpletely reversible. Additionally, use of the gallium salts appreciably reduces dendritic plating as well~
Generally, a]l of the organic co-solvents commonly used in non-aqueous lithium cells/S02 cells such as propylene carbonate, acetonitrile, tetrahydrofuran, dioxolane, gamma-butrolactone and the like are detrimental as co-solvents in the present invention since they tend to form complex non-reversible reaction products with the active metal anodes such as lithium. Thus it is a re~uirement of the present invention that the electrolyte solvent be entirely inorganic. It is, however, not sufficient that the electrolyte solvent be entirely inorganic since the most common inorganic solvent ~sed in completely inorganic cells, thionyl chloride, as described above, also forms irreversible reaction products with an active metal anode such as lithium. Accordingly, the inor~anic solvent of the present invention is specifically S02 which reacts with lithium in the formation of the completely reversible lithium dithionite.
However, sulfur dioxide is a relatively poor solvent for lithium salts since it is an acceptor solvent which interacts primarily with the electrolyte salt anion rather than cation. Accordingly, in order to promote solubility and conductivity, organic solvents (normally donor solvents) have been invariably coupled therewith in order to complete solvation, with the organic solvents solvating the electrolyte salt cations as fully described in U.S. Patent ~o. 3,953,234. The only salts generally described as being sufficiently soluble in the S02 alone are the aforementioned lithium and sodlum tetrachloroaluminates and borates, and clovoborates. However, while a salt may be soluble in S02 it must also provide a cationically conductive solution (greater than 1 x 10 3 ~1 --1 ohm cm ) for it to be considered as providinL an acceptible electrolvte.
Thus, materials such as LiAlC14 which are soluble and electrically conductive in ~2 are nevertheless generally unsuitable for the cells 1 ~ 5~3~ 3531 of the present invention because of the low caticnic conductivity of the electrolyte. The clovoborate salts which are soluble and cationically conductive are, however, very expensive. The electrolyte salts of the present invention which are specifically gallium salts such as halides with anode metal cations have been discovered to be soluble and highly cationically conductive in pure S02. Furthermore, when compared to clovoborate salts such salts are relatively inexpensive.
It is preferred that the anode metal be supported on a metal foil substrate. A preferred substrate for a lit~ium anode is a copper foil with the lithium being applied to both sides of the copper in tbe form of a sen~ cll.
With an S02 cathode depolarizer, the cathode is an inert material such as carbon supported on a usually metallic substrate such as an expanded metal, for example aluminum.
The most preferred gallium halide salt having the requisite conductivity in S02 without the need for orgaric cosolvents is one having a gallium tetrachloride anion such as a LiGaC14 salt for use in a lithium anode cell as described in ~.S. Patent ~o. 4,177,329. In said patent the gallium salts are, however, specificE~lly described as being utili~ed in an inorganic SOC12 contEining cell which is not rechargeable in accordance with the present invention. lt has been discovered that such salt~ may be formed in situ in a pure S02 solvert by reaction between, for examrle~ LiCl and GaCl~ to form LiGaCl~. This is in acldition to such in situ salt formation in an SOCl2 solvent as described in said patent.
The LiGaCl4 salt may also be prepared by direct fusion of LiCl and GaC13 by melting such materials tcgether in stoichiometric amounts and allowing the melt to crystalli7e.
As shown in Table I, LiGaC14 electrolyte salt provides a high cationic conductivity over a wide range of temperature even when dissolved 1~5~3~5 in a relatively poor electrolyte solvent of pure S02:
TABLE I
TE~ERATURE CONDUCTIV~TY (lM LiGaC14-S02) (ohm cm) ~0C 5.32 x 10 30C 5.27 x 10 2 20C 5.17 x 10 2 10C 5.05 x 10 2 0C 4.76 x 10 2 -10C 4.45 x 10 -16.8C ' 4.19 x 10-2 It has also been discovered that the aforementiGned LiGaCl4 salt reduces dendritic plating of anode materials such as lithium since the electrolyte solutions remain clear of li~hium particles and limited in~
soluble precipitates even under repeated cycling. It is also postulated that because the electrolyte solution remains clear of such particles, the LiGaC14 also forms scavenging species during charging which scavenge disconnected lithium dendrites, and lithium from lithium reaction products both at the anode and the cathode. As a result, cell reaction generated products even if isolated from the anc,de or cathode substrates are returned to solution to reform both anode metal and electrolyte solven~:.
In order to illustrate the efficacy of the present invention in providing an efficiently rechargeable cell, the following examples and comparative data (relative to other materials in t'he prior art) are presented. It is understood that such examples are for comparative purposes and that any enumeration of detail should not be construed as a limitation on the present invention. Unless otherwise indicated all parts are parts by weight.
A 'D' siæe c,ell is constructed with convolute wound lithium foil (20"(50.8cm) x 18 (4.13cm) x 0.012"(0.03cm)) and porous carbon _ 9 _ 3 ~ 5 (an aluminum expanded metal substrate) (20'(50.8cm) x 4 (4.4cm) x 0.025" ~0.063cm)) electrodes with a polypropylene separator therebetween.
The cell is filled with a so]ution of 1~ LiGaC14 in pure S02 (about 40 grams). The theoretical capacity of the lithium anode is about 13 Ahr and the capacity of the S02 is about 14 Ahr. The cell is cycled at 0.5A
OD 2 hour discharge followed by 2 hour charge~ The voltage profiles of the second and sixty ninth cycles (the cell failed abruptly after the 69th cycle) are shown in the figure. There is almost a negligible change in the discharge and charging voltages thereby indicating an almost 100% cycling efficiency.
Rechargeability alone is not~ however, a sufficient criterion of cell utility. The cell must also have good primary cell characteristics.
The following examples 2-4 illustrate such capabili~y of the cells of the present invention.
A 'D' cell is constructed as in Example 1 and is polarized at room temperature (25C) and-30C with the results shown in Table II:
TABI.E II
i (Am ) Volts at 25~Volts at-30 P
open circuit 2.91 2.97 .026 2.o9 2.85 .050 2.89 2.80 0.10 2.87 2.7S
0.25 2.84 ----0 35 ---- 2.58 0.5G 2.79 2.53 1.0 2.63 ----1.5 2.58 2.32
In the past a considerable amount of effort has been expended in the development of a viable, practical and commercially acceptable room temperature operable rechargeable lithium cell which would have the advantages over the co~mon rechargeable lead-acid and nickel-cadmium batteries of higher efficiency, lower weight and greater primary lifetimes thereby allowing for more time between charging cycles. Such efforts have met with varying degrees of success. However, such cells have rarely achieved greatex than 80% recycling efficiencies over extended charge and discharge cycles. These cy~ling efficiencie~ are to be differentiated from the very high lithium plating efficiencies since lithium plates out of electrolyte solutions, commonly used in lithium cells, with close to 10~ efficiency (the exchange current of the reaction Li~,Lit + e is very high-on the order of 1 x 10 3A/cm2).
The recycling efficiencies are instead related to subse~uent anodic oxidation of the plated lithium wherein generally the effectiveness of the plated lithium as an anode material decreases rapidly upon cycling despite the high plating efficiencies.
1 ~5~5 Several reasons have been postu]ated ~or the inefficlency of plated lithium for repeated anodlc oxidation and of cells containing such anodes. One reason given is that lithium is dendritically deFosited and becomes coated,particularly at the narrow point of contact with the anode substrate with an insulating film which electrically insulates it from the anode substrate despite its physical presence on the anode.
The plated lithium dendrites as they become electrically insulated become unavailable for efficient anodic oxidation during discharge.
Furthermore, the plated lithium dendrites are fragi~e and may be easily mechanically dislodged from the anode substrate. The dislodged lithium, because it is insoluble in the electrolyte is thereafter lost from discharge and further replating. Efficiency is therefore reduced by depletion of available lithium for repeated cycling.
The electrically insulated lithium generally results from the interaction of the lithium with the organic solvent or solvents utilized in the cells. As the cell is recycled, the lithium metal is deposited in the form cf dendrites having high surface areas which therefore react to an increasingly greater e~tent ~ith the electrolyte solvent particularly at the Flating site to form the insulating surface films of increasingly greater area whereby such plated ]ithium becomes increasingly electrically isolated from the anode. These films, when extensively formed, also tend to reduce the rate a~ which lithium cations enter solution and thereEore may also reduce cell capability. Furth~rmore, reaction products of lithium with commonly used electrolyte solvents are irreversible (particularly with respect to the solvent) in nature. Accordingly, during repeated cycling the electrolyte solvent itself becomes depleted with loss of conductivity and cell performance. The reaction products generated from the solvents also tend to act as detrimertal impurities further destroying cellcapability. Additionally, even lithium contained in such reaction products may also be lost thereby causing increasing reduction of available lithium for recycling.
~ 2 --1 ~ 5~3~ 3531 As an example, propylene carbonate will react with lithium to form an insulating film of lithium carbona~e and propylene gas which cannot be reversed to obtain the original solvent. Though recovery of some of the lithium is possible under charging, the lithium carbonate is however not efficiently reversible into its component elements. Some lithium is therefore lost from further cycling. Similarly other solvents such as tetrabydrofur~n and acetonitrile form complex reactior. products with lithium which are also irreversible. In fact the organic solvents by their very nature must react with the lithium anode. In order to dissolve the electrolyte salts needed for conductivity, the organic electrolytes must be somewhat polar, and it is this very chcracteristic which causes such solvents to react with the lithium in the formation of ; the irreversible reaction products.
` In order to attain a highly efficient rechargeable cell in accordance with the present invention, plated lithium should have reduced dendrite character and should not be coated with a non-reversib]e insulative film. It is also essential that there must be a complete cycling of substantially all of the active cell components without the introduction or formation of additional reaction by-products which are irreversible in nature. Accordingly, free organic solvents or co-solvents are excluded from the cells of the present invention. Furthermore, though the problem of recharging efficiency has been described as being inherent in organic solvent lithium cells, cells having only inorganic components such as a lithium cell with an inorganic thionyl chloride solvent/cathode depolarizer may have s:imilar problems of inefficient recycling. Reaction of the thionyl chloride with the lithium produces reaction products of lithium chloride and an unstable 'S~' species which cannot be effectively recombined to the original starting materials. Thus the electrolyte solvent and cathode depolarizer, even if inorganic, must only react with the anode metal only to the extent of formation of totally reversible reaction products.
~s~3a~
Cathode depolarizing materials have recently been discovered which are in themselves highly rechargeable. Examples of such materials include the layered metal chalcogenide compounds described by Whittingham in the ~.S. Patent No. 4,009,052 which intercalate lithium ions within the spacing between the layers without undergoing full reactions. This property makes them effectively reversible and rechargeable. However, such materials ~re rtilized in ambient temperature lithium cells with organic electrolytes whereby the cell as a whole remains inefficiently rechargeable.
Various attempts have been made to improve the efficiency and the rechargeability of the lithium anodes in nonaqueous cells. Such expedients generally attempted to minimize the dendri~ic plating of the lithium with the use of various means such as additives, alloying of the lithium anode, utilization of specific electrolyte salts and solvents etc. U.S. Patents Nos. 3,953,302 and 4,091,152 describe the use of metal salt additives comprised of metals which are reducible by lithium and which coplate with the lithium on charging to form lithium-rich metallics or alloys. The use of polyalkylene glycol ethers in ~.S.
Patent No. 3,928,067 was described as improving the recycling characteristics of lithium ce]ls by improving the morphology of the plated lithium.
Though such expedients improve rechargeabiligy, such cells still contain organic elements which preclude truly efficient rechargeable cells as described. Dendritic plating of lithium in secondary cells is described in U.S. Patent No. 4,139,fi80 as being effectively prevented ~ith the use of clovoborate electrolyte salts. ~lowever, such electrolyte salts are difficult to synthesize and are accordingly very expensive. U.S. Patent No. 3,580,828 describes specific electrolyte salt concentra~ions and current density limlts which, if observed, improve lithium deposition characteristics. Other methods for improving rechargeability of plated lithium include the initial utilization of lithium allo;~ anodes particu]arly with aluminum as described in U.S. Patent No. 4,002,492.
~ 15~3~5 General improvements in rechargeable lithium cells include the use of complexed inorganlc lithium salts as charge transfer agents (U.S.
Patent No. 3,7~,6,385~ and the judicious use of organic cosolvents with S2 in order to improve solubility of the electrolyte salts (U.S. Patent No. 3,953,234). The use of solvents which are relatively stable with respect to the lithium anode was in fact recognized in patents such as U.S. Patent No. 3,540,988 as being required in order to provide enhanced rechargeability of the cells.
Various systems requiring external mechanical components include molten lithium cells (not inherently sub~ect to dendritic plating) which require extensive heating and shielding components but which are the most feasible efficient rechargeable lithium cells since there are no dendrites or films on molten lithiumO Other systems include cycling electrolytes such as in ~.S. Patent No, 4,154,902 which require complex circulating mechanisms.
Electrolytic processes for lithium deposition, however, generally require organic solvent carriers of the electrolyte salt for high conductivity and efficient plating out of the lithium metal. Exemplary of such lithium deposition procedures are ~.S. Patents Nos. 3,791,945 and 3,580,828.
Similarly, cells as described above (e~cept for those containing clovoborate electrolyte salts) require organic solvents for high conductivity and efficient lithium plating.
Electrodeposition of lithium in an electrolyte comprised of lithium and sodium tetrachloroaluminate or lithium and sodium tetrabromoaluminate dissolved in pure sulfur dioxlde (without organic cosolvents) is described in ~.S. Patent No. 3,493,433. However discharge performance of such cells is severely llmited with a discharge capacity substantially ]ess than theoretical capacity. Since such enumerated salts are described therein as being the only salts having sufficient solubility and conductivity in pure liquid S02 for plating efficiency, cells having other salts in ~ ~5~3~
liquid SO 2 have as a rule re~uired the further utilization of organic cosolvents as described in U.S. Patent No. 3,953,234 and as discussed above.
It is an object of the present invention to provide a highly efficient roorn temperature rechargeable inorganic lithium or other alkali or alkaline earth metal cell having substantially only reversible reaction products which is both efficiently dischargeable and substantially completely rechargeable over extended periods of cycling.
This and other objects, features and advantages of the present invention will become more evident from the following discussion and drawing.
The sole figure of the drawing is a voltage profile of charge and discharge cycles of a cell of the present invention.
Generally the present invention comprises a totally inorganic non-aqueous efficiently rechargeable cell having a lithium or other active metal (generally alkali or alkaline earth metal or alloys thereof) anode, a totally inorganic electrolyte solvent consisting essentially of sulfur dioxide which may also function as cathode depolarizer (with an inert generally carbon cathode) and an inorganic gallium salt such as gallium halides having anode metal cations and LiGaCl4 (with a lithium cation and a GaC1 4 anion in a lithium anode cell) in particular, dissolved in said sulfur dioxide electrolyte solvent~ Other gallium salts include Li 2 O(GaC13 ) 2 and Li2 S(GaC13 )2 (with lithium cations and O(GaCl3 )2 and S(GaC1 3 )2 anions respectively) described in co-pending application (M-31l65).
A completely reversible solid cathode depolarizer such as an intercalation compound may optionally be utilized with the S02 electrolyte solvent. Examples of such solid cathode depolarizers include chromium oxide (SELOXCETTE, a trade mark of Ventron Division of Thiokol Corp. - Alfa Products.), titanium disulfide, manganese dioxide, etc. ~he cell is efficiently rechargeable since all reactions therein including internal reactions between cell compounds such as between the lithium anode and the S02 solvent and the electrochemical cell reactions produce substantially :~ ~$~3~3~
~1-3531 /
only reversible products of, for example, lithium dithionite which is 100% reversible on recharge or intercalated or similarly reacted lithium which is also cc,mpletely reversible. Additionally, use of the gallium salts appreciably reduces dendritic plating as well~
Generally, a]l of the organic co-solvents commonly used in non-aqueous lithium cells/S02 cells such as propylene carbonate, acetonitrile, tetrahydrofuran, dioxolane, gamma-butrolactone and the like are detrimental as co-solvents in the present invention since they tend to form complex non-reversible reaction products with the active metal anodes such as lithium. Thus it is a re~uirement of the present invention that the electrolyte solvent be entirely inorganic. It is, however, not sufficient that the electrolyte solvent be entirely inorganic since the most common inorganic solvent ~sed in completely inorganic cells, thionyl chloride, as described above, also forms irreversible reaction products with an active metal anode such as lithium. Accordingly, the inor~anic solvent of the present invention is specifically S02 which reacts with lithium in the formation of the completely reversible lithium dithionite.
However, sulfur dioxide is a relatively poor solvent for lithium salts since it is an acceptor solvent which interacts primarily with the electrolyte salt anion rather than cation. Accordingly, in order to promote solubility and conductivity, organic solvents (normally donor solvents) have been invariably coupled therewith in order to complete solvation, with the organic solvents solvating the electrolyte salt cations as fully described in U.S. Patent ~o. 3,953,234. The only salts generally described as being sufficiently soluble in the S02 alone are the aforementioned lithium and sodlum tetrachloroaluminates and borates, and clovoborates. However, while a salt may be soluble in S02 it must also provide a cationically conductive solution (greater than 1 x 10 3 ~1 --1 ohm cm ) for it to be considered as providinL an acceptible electrolvte.
Thus, materials such as LiAlC14 which are soluble and electrically conductive in ~2 are nevertheless generally unsuitable for the cells 1 ~ 5~3~ 3531 of the present invention because of the low caticnic conductivity of the electrolyte. The clovoborate salts which are soluble and cationically conductive are, however, very expensive. The electrolyte salts of the present invention which are specifically gallium salts such as halides with anode metal cations have been discovered to be soluble and highly cationically conductive in pure S02. Furthermore, when compared to clovoborate salts such salts are relatively inexpensive.
It is preferred that the anode metal be supported on a metal foil substrate. A preferred substrate for a lit~ium anode is a copper foil with the lithium being applied to both sides of the copper in tbe form of a sen~ cll.
With an S02 cathode depolarizer, the cathode is an inert material such as carbon supported on a usually metallic substrate such as an expanded metal, for example aluminum.
The most preferred gallium halide salt having the requisite conductivity in S02 without the need for orgaric cosolvents is one having a gallium tetrachloride anion such as a LiGaC14 salt for use in a lithium anode cell as described in ~.S. Patent ~o. 4,177,329. In said patent the gallium salts are, however, specificE~lly described as being utili~ed in an inorganic SOC12 contEining cell which is not rechargeable in accordance with the present invention. lt has been discovered that such salt~ may be formed in situ in a pure S02 solvert by reaction between, for examrle~ LiCl and GaCl~ to form LiGaCl~. This is in acldition to such in situ salt formation in an SOCl2 solvent as described in said patent.
The LiGaCl4 salt may also be prepared by direct fusion of LiCl and GaC13 by melting such materials tcgether in stoichiometric amounts and allowing the melt to crystalli7e.
As shown in Table I, LiGaC14 electrolyte salt provides a high cationic conductivity over a wide range of temperature even when dissolved 1~5~3~5 in a relatively poor electrolyte solvent of pure S02:
TABLE I
TE~ERATURE CONDUCTIV~TY (lM LiGaC14-S02) (ohm cm) ~0C 5.32 x 10 30C 5.27 x 10 2 20C 5.17 x 10 2 10C 5.05 x 10 2 0C 4.76 x 10 2 -10C 4.45 x 10 -16.8C ' 4.19 x 10-2 It has also been discovered that the aforementiGned LiGaCl4 salt reduces dendritic plating of anode materials such as lithium since the electrolyte solutions remain clear of li~hium particles and limited in~
soluble precipitates even under repeated cycling. It is also postulated that because the electrolyte solution remains clear of such particles, the LiGaC14 also forms scavenging species during charging which scavenge disconnected lithium dendrites, and lithium from lithium reaction products both at the anode and the cathode. As a result, cell reaction generated products even if isolated from the anc,de or cathode substrates are returned to solution to reform both anode metal and electrolyte solven~:.
In order to illustrate the efficacy of the present invention in providing an efficiently rechargeable cell, the following examples and comparative data (relative to other materials in t'he prior art) are presented. It is understood that such examples are for comparative purposes and that any enumeration of detail should not be construed as a limitation on the present invention. Unless otherwise indicated all parts are parts by weight.
A 'D' siæe c,ell is constructed with convolute wound lithium foil (20"(50.8cm) x 18 (4.13cm) x 0.012"(0.03cm)) and porous carbon _ 9 _ 3 ~ 5 (an aluminum expanded metal substrate) (20'(50.8cm) x 4 (4.4cm) x 0.025" ~0.063cm)) electrodes with a polypropylene separator therebetween.
The cell is filled with a so]ution of 1~ LiGaC14 in pure S02 (about 40 grams). The theoretical capacity of the lithium anode is about 13 Ahr and the capacity of the S02 is about 14 Ahr. The cell is cycled at 0.5A
OD 2 hour discharge followed by 2 hour charge~ The voltage profiles of the second and sixty ninth cycles (the cell failed abruptly after the 69th cycle) are shown in the figure. There is almost a negligible change in the discharge and charging voltages thereby indicating an almost 100% cycling efficiency.
Rechargeability alone is not~ however, a sufficient criterion of cell utility. The cell must also have good primary cell characteristics.
The following examples 2-4 illustrate such capabili~y of the cells of the present invention.
A 'D' cell is constructed as in Example 1 and is polarized at room temperature (25C) and-30C with the results shown in Table II:
TABI.E II
i (Am ) Volts at 25~Volts at-30 P
open circuit 2.91 2.97 .026 2.o9 2.85 .050 2.89 2.80 0.10 2.87 2.7S
0.25 2.84 ----0 35 ---- 2.58 0.5G 2.79 2.53 1.0 2.63 ----1.5 2.58 2.32
2.0 2.53 2.27
3.0 2.47 2.15 1.85 1~583~5 M-3531 The relatively high voltages obtained at currents over l ampere show the high conductivity of the electrolyte salt and the good rate capability of the cell at both amhient and low temperatures.
Two 'D' cells are constructed as in Example 1 and are discharged at various rates and temperatures with the ~onditions and results given in Table III:
TABKE III
Ex.#Temperature Discharge rate or load Capacity to 2v 3 -30C 4.4 ohm 3.5 Ahr
Two 'D' cells are constructed as in Example 1 and are discharged at various rates and temperatures with the ~onditions and results given in Table III:
TABKE III
Ex.#Temperature Discharge rate or load Capacity to 2v 3 -30C 4.4 ohm 3.5 Ahr
4 25C 0.25 A 9.0 Ahr Since the cell has a theoretical capacity of 10 Ahr ( C limited) the room temperature capacity obtained (90%) at a rate of 0.25 A indicates very good primary cell performance. The 3.5 Ahr obtained at -30C is also excellent for low temperature performance.
A cell made in accordance with Example 1 but with an anode of two 0.010" (0.025cm) foils of lithium sandwiching a copper foil substrate, is cycled at 0.10 A for 10 hours discharge and charge. The cell pro~ides about 104 Ahrs about S times original lithium capacity.
EXA~IPLE 6 A glass cell is made using a 2 cm x 0.5 cm Li anode and a 2.0 cm x 0.5 cm catalytic carbon cathode with about 20 cc of lM LiGaC14 in pure S02 electrolyte. The cell is discharged at 1 ma/cm for 5 hours then recharged at 1 ma/cm2 for 5 hours. AEter 15 cycles the lithium surface is clean and dendrite free and the e]ectrolyte remains clear.
EXA~IPLE 7 Two cells are made in accordance w th Example 1 but with one having an electrolyte of lM LiAlC14 in pure S02 as in ~.S. Patent ~o.
3,493,433. The cells are discharged with the results given in Table IV:
~L ~583~5 TABLE IV
_ectrolyte OCV Cap (0.25A discharge rate) 1 M LiGaCl4 2.94V 9.0 A.hr 1 M LiAlC14(PRIOR ART) 3.26 0.38 It is evident from the above comparison that the LiAlC14 electrolyte slat described in the prior art provides only a minimal primary cell capability in pure SO2 and is certainly unsuitable for the secondary or rechargeable cells of the present invention. It may also be noted that LiAlCl4 is the electrolyte salt of choice in totally inorganic cells having lithium anodes and thionyl chloride electrolyte solvent/cathode depolarizers.
The following examples are presented as further illustrating the rechargeable efficacy of the cells of the present invention under varying cycling conditions.
Three cells are made in accordance with Example 5 and are cycled under conditions and with results shown in Table V:
TA~LE V
l)tili7ation Ex. # Test cond. (disch. ~ ch.) Capacity (Ahr) Li S02 8 0.5 A x 2 hrs D/C 73 360% 57n%
9 0.25A x 4 hrs 66 330~O 500%
0.5A (discharge to 2.5v 80 400% 600 charge at 3.5v) The above examples are for illustrative purposes only with changes in cell structure and components being within the scope of th~
present invent;on as defined by the following claims.
A cell made in accordance with Example 1 but with an anode of two 0.010" (0.025cm) foils of lithium sandwiching a copper foil substrate, is cycled at 0.10 A for 10 hours discharge and charge. The cell pro~ides about 104 Ahrs about S times original lithium capacity.
EXA~IPLE 6 A glass cell is made using a 2 cm x 0.5 cm Li anode and a 2.0 cm x 0.5 cm catalytic carbon cathode with about 20 cc of lM LiGaC14 in pure S02 electrolyte. The cell is discharged at 1 ma/cm for 5 hours then recharged at 1 ma/cm2 for 5 hours. AEter 15 cycles the lithium surface is clean and dendrite free and the e]ectrolyte remains clear.
EXA~IPLE 7 Two cells are made in accordance w th Example 1 but with one having an electrolyte of lM LiAlC14 in pure S02 as in ~.S. Patent ~o.
3,493,433. The cells are discharged with the results given in Table IV:
~L ~583~5 TABLE IV
_ectrolyte OCV Cap (0.25A discharge rate) 1 M LiGaCl4 2.94V 9.0 A.hr 1 M LiAlC14(PRIOR ART) 3.26 0.38 It is evident from the above comparison that the LiAlC14 electrolyte slat described in the prior art provides only a minimal primary cell capability in pure SO2 and is certainly unsuitable for the secondary or rechargeable cells of the present invention. It may also be noted that LiAlCl4 is the electrolyte salt of choice in totally inorganic cells having lithium anodes and thionyl chloride electrolyte solvent/cathode depolarizers.
The following examples are presented as further illustrating the rechargeable efficacy of the cells of the present invention under varying cycling conditions.
Three cells are made in accordance with Example 5 and are cycled under conditions and with results shown in Table V:
TA~LE V
l)tili7ation Ex. # Test cond. (disch. ~ ch.) Capacity (Ahr) Li S02 8 0.5 A x 2 hrs D/C 73 360% 57n%
9 0.25A x 4 hrs 66 330~O 500%
0.5A (discharge to 2.5v 80 400% 600 charge at 3.5v) The above examples are for illustrative purposes only with changes in cell structure and components being within the scope of th~
present invent;on as defined by the following claims.
Claims (16)
1. A rechargeable totally inorganic non-aqueous electrochemical cell comprising an anode comprised of an alkali or alkaline earth metal or alloys thereof and a gallium and halogen containing electrolyte salt having an anode metal cation, said electrolyte salt being dissolved solely in a solvent consisting essentially of sulfur dioxide whereby said cell is efficiently rechargeable.
2. The cell of claim 1 wherein said anode is comprised of lithium or alloys thereof.
3. The cell of claim 2 wherein said lithium or alloys thereof are supported on a metal substrate.
4. The cell of claim 3 wherein said metal substrate comprises a metal foil sandwiched by said lithium or alloys thereof.
5. The cell of claim 4 wherein said metal substrate is comprised of copper.
6. The cell of claim 1 wherein said sulfur dioxide also comprises the cathode depolarizer of said cell.
7. The cell of claim 6 wherein said cell further includes an inert carbon cathode.
8. The cell of claim 7 wherein said carbon is supported on an expanded aluminum substrate.
9. The cell of claim 1 wherein said cell includes a solid cathode depolarizer which when reacted with cations of said active metal anode during cell discharge forms a completely reversible product on cell charging.
10. The cell of claim 9 wherein said solid cathode depolarizer is an intercalation compound.
11. The cell of claim 10 wherein said cathode depolarizer is selected from the group consisting of TiS2, MnO2 and chromium oxide.
12. The cell of claim 1 wherein said electrolyte salt is an anode metal gallium chloride salt.
13. The cell of claim 12 wherein said salt has anions selected from the group consisting of GaCl?, O(GaCl3)?-2, and S(GaCl3)?-2 .
14. The cell of claim 13 wherein said anion is GaCl?.
15. A rechargeable totally inorganic non-aqueous electrochemical cell comprising an anode of lithium or alloys thereof and a LiGaCl4 electrolyte salt dissolved in an electrolyte solvent consisting essentially of SO2.
16. The cell of claim 15 wherein said SO2 also comprises the cathode depolarizer of said cell.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18686880A | 1980-09-12 | 1980-09-12 | |
| US186,868 | 1980-09-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1158305A true CA1158305A (en) | 1983-12-06 |
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ID=22686596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000385027A Expired CA1158305A (en) | 1980-09-12 | 1981-09-02 | Efficiently rechargeable totally inorganic non- aqueous li/so.sub.2 cell with ligacl.sub.4 electrolyte salt |
Country Status (23)
| Country | Link |
|---|---|
| JP (1) | JPS57107576A (en) |
| KR (1) | KR830008419A (en) |
| AU (1) | AU543584B2 (en) |
| BE (1) | BE890101A (en) |
| BR (1) | BR8105538A (en) |
| CA (1) | CA1158305A (en) |
| DD (1) | DD202081A5 (en) |
| DE (1) | DE3133211A1 (en) |
| DK (1) | DK404081A (en) |
| ES (1) | ES8206919A1 (en) |
| FR (1) | FR2490407A1 (en) |
| GB (1) | GB2083942B (en) |
| GR (1) | GR74676B (en) |
| HK (1) | HK57989A (en) |
| IE (1) | IE52180B1 (en) |
| IL (1) | IL63515A (en) |
| IN (1) | IN157369B (en) |
| IT (1) | IT1138588B (en) |
| NL (1) | NL8104075A (en) |
| NO (1) | NO813104L (en) |
| PL (1) | PL232993A1 (en) |
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| ZA (1) | ZA815453B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4513067A (en) * | 1983-06-30 | 1985-04-23 | Duracell Inc. | Inorganic non-aqueous cell |
| EP0269855A3 (en) * | 1986-12-01 | 1988-09-07 | Whittaker Technical Products, Inc. | Rechargeable electrochemical cell |
| DE3826812A1 (en) * | 1988-08-06 | 1990-02-08 | Heitbaum Joachim | NONWATER, RECHARGEABLE GALVANIC LITHIUM ELEMENT WITH INORGANIC ELECTROLYTE SOLUTION |
| TWI251951B (en) * | 2003-09-19 | 2006-03-21 | Lg Chemical Ltd | Nonaqueous lithium secondary battery with cyclability and/or high temperature safety improved |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6511298A (en) * | 1964-10-13 | 1966-04-14 | ||
| US3493433A (en) * | 1964-10-13 | 1970-02-03 | American Cyanamid Co | Electrodeposition of alkali metals from nonaqueous solvents |
| FR1556247A (en) * | 1967-11-15 | 1969-02-07 | ||
| GB1258498A (en) * | 1968-06-11 | 1971-12-30 | ||
| US3764385A (en) * | 1970-12-22 | 1973-10-09 | Exxon Research Engineering Co | Electric battery using complexed inorganic lithium salts as charge transfer agent |
| DE2263115C2 (en) * | 1971-12-27 | 1982-04-22 | Gte Laboratories Inc., Wilmington, Del. | Galvanic cell |
| US3953302A (en) * | 1973-08-16 | 1976-04-27 | P. R. Mallory & Co. Inc. | Prevention of dendritic plating of lithium |
| US4091152A (en) * | 1973-08-16 | 1978-05-23 | P.R. Mallory & Co. Inc. | Lithium SO2 cell |
| US3928067A (en) * | 1974-09-06 | 1975-12-23 | Bell Telephone Labor Inc | Polyalkylene glycol ethers in rechargeable lithium nonaqueous batteries |
| US4009052A (en) * | 1975-02-24 | 1977-02-22 | Exxon Research And Engineering Company | Chalcogenide battery |
| US4002492A (en) * | 1975-07-01 | 1977-01-11 | Exxon Research And Engineering Company | Rechargeable lithium-aluminum anode |
| JPS526446A (en) * | 1975-07-04 | 1977-01-18 | Mitsubishi Electric Corp | Unipole antenna |
| US4020240A (en) * | 1975-09-03 | 1977-04-26 | P. R. Mallory & Co., Inc. | Electrochemical cell with clovoborate salt in electrolyte and method of operation and composition of matter |
| US4154902A (en) * | 1976-09-13 | 1979-05-15 | American Energizer Corporation | Electric battery cell, system and method |
| US4075397A (en) * | 1977-03-01 | 1978-02-21 | Exxon Research & Engineering Co. | Cell having chalcogenide cathode and solvated alkali metal salt electrolyte |
| US4139681A (en) * | 1978-03-02 | 1979-02-13 | Exxon Research & Engineering Co. | Electrochemical cells having alkali metal anodes and electrolyte salt complex compositions including haloorganometallic alkali metal salt complexes |
| US4177329A (en) * | 1978-11-02 | 1979-12-04 | P. R. Mallory & Co. Inc. | Electrolyte salts for non aqueous electrochemical cells |
| US4238552A (en) * | 1979-07-03 | 1980-12-09 | P. R. Mallory & Co. Inc. | Electrolyte salt for non-aqueous electrochemical cells |
| IL60238A (en) * | 1980-06-05 | 1983-07-31 | Tadiran Israel Elect Ind Ltd | Cathode and electric cell containing same |
-
1981
- 1981-08-06 IL IL63515A patent/IL63515A/en not_active IP Right Cessation
- 1981-08-07 ZA ZA815453A patent/ZA815453B/en unknown
- 1981-08-07 AU AU73876/81A patent/AU543584B2/en not_active Ceased
- 1981-08-19 GR GR65822A patent/GR74676B/el unknown
- 1981-08-21 DE DE19813133211 patent/DE3133211A1/en active Granted
- 1981-08-25 GB GB8125832A patent/GB2083942B/en not_active Expired
- 1981-08-26 BE BE0/205779A patent/BE890101A/en not_active IP Right Cessation
- 1981-08-27 IE IE1958/81A patent/IE52180B1/en not_active IP Right Cessation
- 1981-08-31 BR BR8105538A patent/BR8105538A/en unknown
- 1981-09-01 ES ES505098A patent/ES8206919A1/en not_active Expired
- 1981-09-02 NL NL8104075A patent/NL8104075A/en not_active Application Discontinuation
- 1981-09-02 CA CA000385027A patent/CA1158305A/en not_active Expired
- 1981-09-03 FR FR8116765A patent/FR2490407A1/en active Granted
- 1981-09-09 KR KR1019810003362A patent/KR830008419A/en unknown
- 1981-09-09 IT IT23853/81A patent/IT1138588B/en active
- 1981-09-11 DK DK404081A patent/DK404081A/en not_active Application Discontinuation
- 1981-09-11 PL PL23299381A patent/PL232993A1/xx unknown
- 1981-09-11 DD DD81233230A patent/DD202081A5/en unknown
- 1981-09-11 SE SE8105426A patent/SE8105426L/en not_active Application Discontinuation
- 1981-09-11 NO NO813104A patent/NO813104L/en unknown
- 1981-09-11 JP JP56143713A patent/JPS57107576A/en active Granted
- 1981-10-12 IN IN654/DEL/81A patent/IN157369B/en unknown
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1989
- 1989-07-20 HK HK579/89A patent/HK57989A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB2083942A (en) | 1982-03-31 |
| IL63515A0 (en) | 1981-11-30 |
| DE3133211C2 (en) | 1990-09-13 |
| JPH0345507B2 (en) | 1991-07-11 |
| PL232993A1 (en) | 1982-06-21 |
| IE52180B1 (en) | 1987-08-05 |
| IT1138588B (en) | 1986-09-17 |
| IE811958L (en) | 1982-03-12 |
| JPS57107576A (en) | 1982-07-05 |
| DD202081A5 (en) | 1983-08-24 |
| IT8123853A0 (en) | 1981-09-09 |
| DE3133211A1 (en) | 1982-04-29 |
| FR2490407B1 (en) | 1985-03-22 |
| IL63515A (en) | 1984-05-31 |
| ES505098A0 (en) | 1982-08-16 |
| GB2083942B (en) | 1984-05-16 |
| ZA815453B (en) | 1982-07-28 |
| NL8104075A (en) | 1982-04-01 |
| IN157369B (en) | 1986-03-08 |
| GR74676B (en) | 1984-07-02 |
| BR8105538A (en) | 1982-05-18 |
| ES8206919A1 (en) | 1982-08-16 |
| KR830008419A (en) | 1983-11-18 |
| FR2490407A1 (en) | 1982-03-19 |
| AU543584B2 (en) | 1985-04-26 |
| SE8105426L (en) | 1982-03-13 |
| AU7387681A (en) | 1982-03-18 |
| NO813104L (en) | 1982-03-15 |
| HK57989A (en) | 1989-07-28 |
| DK404081A (en) | 1982-03-13 |
| BE890101A (en) | 1981-12-16 |
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