JPS6318838B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention uses an active metal anode, a cathode collector, a separator disposed intermediate the cathode collector and anode to separate the cathode collector from the anode, and an active liquid cathode electrolyte, with the separator facing the anode. This invention relates to a non-aqueous battery whose surface is covered with a vinyl polymer film. The development of high-energy battery systems requires
Compatibility of electrolytes with desirable electrochemical properties and highly reactive anode materials such as lithium or the like is particularly required. In this type of system, the use of aqueous electrolytes is not allowed because the anode material is active enough to chemically react with water. Therefore, to achieve the high energy densities obtainable through the use of these highly reactive anodes, it was necessary to return to research into non-aqueous electrolyte systems. As used herein, the term "non-aqueous electrolyte" refers to, for example, a metal salt or complex salt of an element of Group A, Group A, Group A or Group A of the Periodic Table dissolved in a suitable non-aqueous solvent. Refers to the electrolyte that consists of
The term "periodic table" as used herein refers to the Chemical Rubber Company, Cleveland, Ohio.
1967-1968, 48th edition, “Handbook of
Refers to the Periodic Table of Elements as shown in the leaflet of ``Chemistry and Physics.'' Many solutes are known and the use of many of them has been proposed, but selecting an appropriate solvent is particularly troublesome. An ideal battery electrolyte would contain a solvent/solute pair with a long liquid range, high ionic conductivity, and stability.The long liquid range, i.e., high boiling point and low freezing point, would result if the battery It is essential if the battery is to operate at temperatures other than ambient temperature. High ionic conductivity is essential if the battery is to have high rate performance. When used in a primary or secondary battery system. In order to provide a long life,
Stability is required for electrode materials, battery construction materials, and products of battery reactions. Recently, it has been described in the literature that a few substances can act as carriers, i.e., solvents for electrolyte salts, in the electrolyte of non-aqueous electrochemical cells, and at the same time as active cathodes in non-aqueous electrochemical cells. . U.S. Patent Nos. 3,475,226, 3,567,515, and
No. 3,578,500 respectively describe liquid sulfur dioxide or a solution of sulfur dioxide and a cosolvent to perform this dual function in a non-aqueous electrochemical cell. Although each of these solutions performs a dual function, their use is not without a few disadvantages. Sulfur dioxide always exists as a gas at room temperature, but in a battery it must be contained as a liquid under pressure or dissolved in a liquid solvent. If sulfur dioxide is used alone, handling and packaging problems arise, and if sulfur dioxide is dissolved in a liquid solvent, other components and combination steps are required. As mentioned above, a long liquid range extending over the room temperature range is a desirable characteristic for electrolyte solvents. Clearly, sulfur dioxide is a failure in this regard at atmospheric pressure. U.S. Pat. No. 4,395,21 includes an anode, a cathode collector, and a cathode/electrolyte consisting of a solution of an ionically conductive solute in an active cathode (depolarizer). A non-aqueous electrochemical cell is disclosed comprising a liquid oxyhalide of an element from group or groups of the periodic table. Oxyhalides can be used as a component of the cathode/electrolyte with active metal anodes, such as lithium anodes, to form excellent high energy density batteries, but if the batteries are stored for long periods of time, about three days or more, Passivation of the anode then appears to result in undesirable voltage lag and high cell impedance during early discharge. U.S. Pat. No. 3,993,501 minimizes undesirable voltage lag during early discharge in non-aqueous cells using oxyhalide-containing cathodes/electrolytes by providing a vinyl polymer film on the anode surface in contact with the cathode/electrolyte. Discloses methods for preventing or preventing This disclosure is included as a reference. U.S. Pat. No. 015938 includes an active metal anode, such as lithium, and a liquid cathode/electrolyte consisting of a solute dissolved in a solvent of an oxyhalide of an element from group or groups of the periodic table; A non-aqueous battery is disclosed in which elemental sulfur or sulfur compounds are included in the cathode/electrolyte to substantially eliminate the initial voltage lag of the battery. This disclosure is incorporated herein by reference. One of the objects of the present invention is to substantially prevent passivation of active metal anodes in liquid cathode/electrolyte cells. Another object of the invention is to provide a liquid cathode/cathode with the separator surface facing the anode coated with a vinyl polymer film so as to substantially prevent passivation of the active metal anode during cell storage and use.
To provide electrolyte batteries. Another object of the present invention is that the separator side facing the active metal anode is coated with a thin adhesive vinyl polymer film, so as to effectively prevent passivation of the active metal anode during cell storage and use. It is an object of the present invention to provide an oxyhalide cathode/electrolyte cell system using elemental sulfur or sulfur compounds in the cathode/electrolyte in accordance with the disclosure of US Pat. No. 0,159,38. The above objects and other objects will be explained in further detail below. The present invention comprises an active metal anode, a cathode collector, a separator interposed between said anode and cathode collector, and an active liquid cathode (depolarized) with or without reactive or non-reactive co-solvents. The separator surface facing the anode is coated with a vinyl polymer film to reduce the initial voltage lag time during battery discharge. The present invention relates to high energy density non-aqueous batteries. Preferably, the vinyl coating on the separator is used in a range of about 0.7 to about 3.5 grams per square meter of raised area, preferably in a range of about 1.5 to about 1.8 grams per square meter. Amounts less than about 0.7 g per square meter appear to be ineffective in significantly shortening the voltage lag time during the initial discharge, whereas amounts greater than about 3.5 g per square meter may cause cracks in the separator. It appears to interfere with the flow of electrolytes. Vinyl polymer materials suitable for use in accordance with the present invention include vinyl chloride or vinylidene chloride homopolymers copolymerized therein, consisting of vinyl esters, dibasic acids, diesters of dibasic acids, and monoesters of dibasic acids. Usually solid vinyl polymers such as vinyl chloride or vinylidene chloride-containing copolymers having at least one monomer selected from the group consisting of: The term copolymer is used herein to mean mixed polymers or polymer blends and heteropolymers formed from two or more dissimilar monomers polymerized together (see Concise Chemical Co., Ltd.). - End Technical Dictionary, 3rd edition, edited by H. Bennett, Chemical Publishing Company, 1974). Common examples of suitable copolymers include vinyl chloride copolymerized with a vinyl ester such as vinyl acetate: vinyl chloride copolymerized with a diester of a dibasic acid such as dibutyl maleate; Included are combinations of vinyl esters such as maleic acid or vinyl chloride copolymerized with dibasic acids, monoesters or diesters of dibasic acids, such as dibutyl maleate or monobutyl maleate. A special example is 97% vinyl chloride −
Vinyl chloride-vinyl acetate copolymer containing 3% vinyl acetate: 86% vinyl chloride-vinyl acetate copolymer containing 14% vinyl acetate; 86% vinyl chloride-13% vinyl acetate-1%
Vinyl chloride containing maleic acid - vinyl acetate -
It is a dibasic acid copolymer. Suitable vinyl polymer materials for use in the present invention are also disclosed in US Pat. No. 4,141,870, which is incorporated herein by reference. Also herein referred to as “Journal of
Chemical Education”, Volume 49, 587~
As described in the paper entitled "Electrochemical Reactions in Batteries" by Akiya Kozawa and RA Powers, published on page 291, September 1972, the cathode depolarizer is a cathode reactant, so the electrochemical reaction at the cathode is It is a substance that is reduced to The cathode collector is not an active reducing substance, but acts as a current collector + electron conductor to the positive terminal (cathode terminal) of the battery. In other words, the cathode collector is the site of the electrochemical reduction reaction of the active cathode material and the conductor of electrons to the cathode terminal of the cell. The active liquid reducing cathode material (depolarizer) can be mixed with a non-reactive material, but with a conductive solute that is added to improve the electrical conductivity of the liquid active reducing cathode material, or It can be mixed with reactive solutes as well as reactive or non-reactive co-solvent materials. A reactive co-solvent material is a material that is electrochemically active and therefore acts as an active cathode material, whereas a non-reactive co-solvent material is a material that is electrochemically inert and therefore acts as an active cathode material. A substance that cannot act as an active cathode material. The separator used in the present invention must be chemically inert and insoluble in the liquid cathode/electrolyte, and must be permeable to the liquid electrolyte and brought into contact with the cell anode to separate the anode and cathode. It must be porous to form an ion transmission path between the layers. Separators suitable for use in the present invention are nonwoven or woven glass fiber mats. Any compatible substantially electrically conductive solid may be used as the cathode collector in the cell of the invention. It is desirable to have as much surface contact as possible between the cathode/electrolyte and the collector. Therefore,
Preferably, a porous collector is used. This type of collector provides a large area interface to the liquid cathode/electrolyte. The collector can be metal and can have any shape such as a metal film, screen or pressed powder. Preferably, however, the pressed powder collector should consist at least partially of carbonaceous or other large-area material. A solute is a single or double salt that produces an ionically conductive solution when dissolved in a solvent. Preferred solutes are complexes of inorganic or organic Lewis acids and inorganic ionizable salts. The main requirement is that the salt, whether single or double, be compatible with the solvent used and yield an ionically conductive solution. According to the Lewis or electronic concept of acids and bases, many substances that do not contain active hydrogen can act as acid or electron doublet acceptors. The basic concept is described in the chemical literature (Journal of the Franklin Institute, Volume 226 - July/December 1938,
pp. 293-313, by GN Lewis). The reaction mechanism for the functioning of these complexes in solvents is described in detail in U.S. Pat. It is said to produce a more stable entity than either component alone. Representative Lewis acids suitable for use in the present invention include aluminum fluoride, aluminum bromide, aluminum chloride, and antimony pentachloride, zirconium tetrachloride, phosphorous pentachloride, boron fluoride, boron chloride, and boron bromide. including. Ionizable salts suitable for use with Lewis acids include lithium fluoride, lithium chloride, lithium bromide, lithium sulfide, sodium fluoride, sodium chloride, sodium bromide, potassium fluoride, potassium chloride, and potassium bromide. include. As is clear to those skilled in the art, the double salt formed by a Lewis acid and an inorganic ionizable salt can be used as such or each of these components can be added separately to a solvent. salts or resulting ions can be formed in situ. An example of such a double salt is one formed by combining aluminum chloride and lithium chloride to yield lithium aluminum tetrachloride. According to the invention, the present invention comprises an active metal anode, a cathode collector, a separator disposed intermediate the anode and the cathode collector and coated with a vinyl polymer film on the side facing the anode, and a cathode/electrolyte, The cathode/electrolyte is in an active reducing electrolyte solvent such as at least one oxyhalide of an element of Group 1 or Groups of the Periodic Table and/or a halide of an element of Group 1, Group 3 or Group of the Periodic Table. , non-aqueous electrochemistry, etc., in which solutes are dissolved with or without co-solvents. The active reducing electrolyte solvent serves the dual function of acting as a solvent for the electrolyte salt and as an active cathode for the cell. The term "cathode/electrolyte" is used herein to refer to a solvent-containing electrolyte that can perform this dual function. The use of a single component in a battery as the electrolyte solvent as well as the active cathode is a relatively new development.
This is because in the past, it was generally believed that these two functions were naturally mutually independent and could not be performed by the same substance. For an electrolyte solvent to function in a battery, it must contact both the anode and cathode to form a continuous ionic path between the two. It was also generally believed that the active cathode material should never be in direct contact with the anode. Therefore, the above two functions were considered to be mutually contradictory. However, recently some active cathode materials, such as liquid oxyhalides, do not react significantly chemically with the active anode metal at the interface with this anode metal, allowing the cathode material to directly contact the anode and the electrolyte. It was discovered that it can act as a carrier.
Although the theory behind the inhibition of such direct chemical reactions is not currently well understood and the inventors do not wish to be limited to the theory of the invention, it is important to note that the inherent high activation energy of the reaction Alternatively, direct chemical reactions may be inhibited by the formation of a thin protective film on the anode surface. This protective film on the anode surface must not be formed so excessively as to significantly increase the anodic polarization effect. Activated reducing liquid cathodes, such as oxyhalides, inhibit direct reaction with active metal anode surfaces sufficiently to act as cathode materials and electrolyte carriers in non-aqueous cells, especially at high temperatures. During cell storage, this liquid cathode forms a surface film on the active metal anode. This surface film consists of a relatively thick layer of crystalline material. This layer of crystalline material causes passivation of the anode, with voltage lag in the initial discharge of the crystalline cell, as well as high cell impedance values in the range of 11 ohms to 15 ohms for standard C-size cells. It seems to be a monster. The degree of anode passivation can be measured by measuring the time required for the closed circuit voltage of the storage cell to reach its desired voltage level after discharge has begun. If this delay is 20
Above seconds, this anode passivation would be considered excessive for most applications.
For example, what is observed in lithium/oxyhalide battery systems is that after a constant load is applied across the terminals of the battery, the battery voltage immediately drops below the desired discharge and then changes with temperature, layer thickness, and load. It grows at a dependent rate. The exact composition of this crystalline layer is unknown. The thickness and density of the crystal layer as well as the size and shape of the crystals are
It was observed that it varied with the length of storage period and the temperature during storage. For example, in low-temperature storage, compared to the large growth of the crystal layer in high-temperature storage at about 70℃,
Relatively small growth is observed. Also, oxyhalides such as thionyl chloride or sulfuryl chloride are SO ₂
When placed in a lithium anode cell after being saturated with , a crystalline layer was observed to passivate the lithium by rapidly forming on the lithium surface. In accordance with the present invention, it has been discovered that anode passivation can be largely prevented by adhering a vinyl polymer film to the side of the battery separator facing the anode. The vinyl polymer film must adhere to the separator during battery storage and discharge, remain stable in the liquid cathode/electrolyte, and not unduly reduce battery capacity. In most cases, the presence of a polymer film can even increase battery capacity at high rate discharges. Although the inventors do not wish to be bound by the theory of the invention, it is clear that vinyl polymers, such as vinyl chloride polymers, are stable in oxyhalide cathode/electrolyte battery systems, such as in lithium/oxyhalide battery systems. The reason may be explained as follows. One of the accepted mechanisms for vinyl chloride polymer degradation is dehydrochlorination. That is, the mechanism is that one Cl atom and one H atom split to form HCl. This process continues until the electron negativity of the remaining Cl atoms on the polymer is compensated by conjugation energy (ie, double bond formation). The subsequent degradation is claimed to occur via a free radical mechanism as described below. Most of the compounds observed to interact or interfere with polymer degradation are R●, RO●,
It is explained by the formation of a ROO● type free radical and a chlorine atom. The reaction mechanism in which SO ₂ Cl ₂ decomposes is explained in Zeit.fu¨r Physikalische Chemie Neue
Folge 12:168-195 (1952), ZGSzabo and T.
“Thermal decomposition mechanism of sulfuryl chloride” by Be´rcez
As described in the paper titled, free radicals i.e. Cl●
It is thought that this process proceeds through the formation of SO 2 Cl● and SO ₂ Cl●. In this way, according to Leciatelier's principle (chemical equilibrium theory), the stability of vinyl chloride polymers can be enhanced in the environment prevailing in the oxyhalide system. In other words, if the concentration of any of the degradation products increases;
The reaction equilibrium will be shifted in favor of undegraded raw polymer. The polymers used in the present invention must not degrade or degrade in the presence of solvents used in the coating process or in the presence of liquid cathodes/electrolytes used in cells. It must also be able to form a thin coating that can be adhered to the separator. Although not all materials in the group have the aforementioned properties, those that do are conveniently selected by testing as a coating on the surface of a separator immersed in a liquid cathode/electrolyte. I can do things. For example, polyethylene and polypropylene are not suitable because they decompose in liquid oxyhalides. Vinyl polymer films can be prepared by spraying, painting or similar methods with or without the use of suitable liquid suspending media such as 3-pentanone, methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK) and 2-pentanone. It can be applied to the surface of the separator by conventional techniques. Suitable liquid suspension media can be oxyhalide solvents used in batteries, such as thionyl chloride (SOCl ₂ ) or sulfuryl chloride (SO ₂ Cl ₂ ). That is, vinyl chloride-vinyl acetate (molecular weight ~40,000, 86% vinyl chloride/
A vinyl polymer such as 14% vinyl acetate) is dissolved in thionyl chloride and applied to the separator surface by dipping the separator in this solution or by painting or spraying this solution onto the separator surface. Can be done. When the oxyhalide solvent evaporates, a thin film remains adhered on the separator surface. For example, coating can be conveniently done by dipping the separator in a 1% vinyl acetate/vinyl chloride copolymer solution in 3-pentanone and then drying the separator at about 200°C for 1 minute. can. This treatment not only allows the desired vinyl polymer layer to be deposited on the separator surface, but also improves the mechanical handling properties of the separator material. Also, if desired, a thin layer of vinyl polymer film can be laminated to the separator as long as intimate contact and adhesion to the separator is obtained. In the industrial production of batteries, it is much easier to coat the surface of the separator than the anode, and the mechanical handling properties of the separator are enhanced, thereby facilitating its assembly into the battery. As long as the vinyl polymer is deposited on the separator as described above, the vinyl polymer concentration in the liquid medium can be varied within a wide range. about 50
When using a separator with a porosity of %,
A suitable concentration of vinyl polymer has been observed to be in the range of about 0.5-3.0% by weight based on the weight of the liquid suspending medium. Concentrations below 0.5% by weight will probably not be sufficient to form an effective film on the separator, and concentrations above 3.0% by weight will not provide the metal anode with much greater protection against passivation. This may cause damage to the separator during operation. Effective ranges of vinyl polymer concentrations can vary from about 0.7 to about 3.5 grams per square meter of apparent surface area, preferably from about 1.5 to about 1.8 grams per square meter of apparent area. Concentrations below about 0.7 g per square meter are insufficient to provide substantial protection against passivation of active metal anodes such as lithium, whereas concentrations above about 3.5 g per square meter are This would undesirably increase the internal resistance. Oxyhalides suitable for use in the present invention are sulfuryl chloride, thionyl chloride, phosphorus oxychloride, thionyl bromide, chromyl chloride, vanadyl tribromide and selenium oxychloride. Organic cosolvents suitable for use in the present invention include the following classes of compounds. Trialkyl borate: e.g., trimethyl borate,
( _CH3O ) _3B (Liquid range -29.3~67℃) Trialkyl silicate: e.g., tetramethyl silicate,
(CH ₃ O) ₄ Si (boiling point 121 °C) Nitroalkanes: e.g., nitromethane, CH ₃ NO ₂ (liquid range -17 to 100.8 °C) Alkylnitrile: e.g., acetonitrile,
CH ₃ ON (liquid range -45~81.6℃) Dialkylamide: e.g. dimethylformamide,
HCON( _CH3 ) ₂ (liquid range -60.48~149℃) Lactams: e.g., N-methylpyrrolidone, Liquid range -16~202℃) Tetraalkylurea: e.g., tetramethylurea,
(CH ₃ ) ₂ N-CO-N (CH ₃ ) ₂ (liquid range -1.2 to 166°C) Monocarboxylic acid ester: e.g., ethyl acetate (liquid range -83.6 to 77.06°C) Orthoester: e.g., trimethyl orthoform Mart, HC (OCH ₃ ) ₃ (boiling point 103°C) Lactones: e.g. γ-(gamma)butyllactone, (Liquid range -42~206℃) Dialkyl carbonate: e.g. dimethyl carbonate, OC
(OCH ₃ ) ₂ (liquid range 2-90℃) Alkylene carbonate: e.g. propylene carbonate (liquid range -48 to 242°C) Monoethers: e.g. diethyl ether (liquid range -116 to 34.5°C) Polyethers: e.g. 1,1- and 1,2-dimethoxyethane (liquid range -113.2 to 64.5°C, respectively) and −58
~83°C) Cyclic ethers: e.g., tetrahydrofuran (liquid range -65 to 67°C); 1,3-dioxolane (liquid range -95 to 78°C) Nitroaromatics: e.g., nitrobenzene (liquid range
5.7 to 210.8℃) Aromatic carboxylic acid halide: e.g., benzoyl chloride (liquid range 0 to 197℃); benzoyl bromide (liquid range -24 to 218℃) Aromatic sulfonic acid halide: e.g., benzenesulfonyl chloride (liquid range 14.5-251°C) Aromatic phosphonic acid dihalide: e.g., benzenephosphonyl dichloride (boiling point 258°C) Aromatic thiophosphonic acid dihalide: e.g., benzenethiophosphonyl chloride (boiling point 124°C, 5 mm) Cyclic sulfone: e.g., sulfolane

[Formula] (melting point 22℃); 3-methylsulfolane (melting point -
1°C) Alkyl sulfonic acid halide: e.g., methanesulfonyl chloride (boiling point 161°C) Alkylcarboxylic acid halide: e.g., acetyl chloride (liquid range -112 to 50.9°C); acetyl bromide (liquid range -96 to 76°C); Propionyl chloride (liquid range -94~80°C) Saturated heterocyclic compounds: e.g., tetrahydrothiophene (liquid range -96~121°C); 3-methyl-2-oxazolidone (melting point 15.9°C) Dialkylsulfamic acid halides: e.g., dimethylsulfamyl chloride (boiling point 80°C, 16 mm) Alkylhalosulfonate: e.g., ethylchlorosulfonate (boiling point 151°C) Unsaturated heterocyclic carboxylic acid halide: e.g., 2-furoyl chloride (liquid range -2 ~173°C) Five-membered unsaturated heterocyclic compounds: Examples, 3,5-dimethylisoxazole (boiling point 140°C); 1-methylpyrrole (boiling point 114°C); 2,4-dimethylthiazole (boiling point 144°C); Furan (liquid range −85.65~
31.36°C) Esters and/or halides of dibasic carboxylic acids: e.g. ethyloxalyl chloride (boiling point 135°C)
) Mixed alkyl sulfonic acid halides and carboxylic acid halides: e.g., chlorosulfonylacetyl chloride (boiling point 98°C, 10 mm) Dialkyl sulfoxides: e.g., dimethyl sulfoxide (liquid range 18.4-189°C) Dialkyl sulfates: e.g., dimethyl sulfate (liquid range −
31.75-188.5℃) Dialkyl sulfite: e.g., dimethyl sulfite (boiling point
126℃) Alkylene sulfite: e.g., ethylene glycol sulfite (liquid range -11 to 173℃) Halogenated alkanes: e.g., methylene chloride (liquid range -95 to 40℃); 1,3-dichloropropane (liquid range - (99.5-120.4°C) Among the above, preferred cosolvents include nitrobenzene; tetrahydrofuran; 1,3-dioxolane; 3-methyl-2-oxazolidone; propylene carbonate; γ-butyrolactone; sulfolane; ethylene glycol sulfite; dimethyl sulfite and chloride. It's benzoyl. The most preferred of the preferred co-solvents are nitrobenzene; 3-methyl-2-oxazolidone; benzoyl chloride; dimethyl sulfite and ethylene glycol sulfite. This is because these compounds are more chemically inert towards battery components and have a long liquid range, and in particular they allow highly efficient utilization of the cathode material. Also within the scope of the present invention, inorganic solvents are used, such as liquid inorganic halides of elements of Groups, Groups, and Groups of the Periodic Table. For example, selenium tetrafluoride (SeF ₄ ), selenium monobromide (Se ₂ Br ₂ ), thiophosphoryl chloride (PSCl ₃ ), thiophosphoryl bromide (PSBr ₃ ), vanadium pentafluoride (VF ₅ ), tetrachloride Lead (PbCl ₄ ), titanium tetrachloride (TiCl ₄ ), disulfur decafluoride (S ₂ F ₁₀ ), tin trichloride bromide (SnBrCl ₃ ),
These are tin dichloride dibromide (SnBr ₂ Cl ₂ ), tin chloride tribromide (SnBr ₃ Cl), sulfur monochloride (S ₂ Cl ₂ ), and sulfur dichloride (SCl ₂ ). In addition to functioning as electrolyte solvents in non-aqueous batteries, these halides act as active reducing cathodes;
It contributes to the total active reducing substance in this type of battery. Useful anode materials are generally consumable metals and include aluminum, alkali metals, alkaline earth metals, and alloys of alkali or alkaline earth metals with one or more other metals. As used herein and in the claims, the term "alloy" is intended to include mixtures, solid solutions such as lithium-magnesium, and intermetallic compounds such as lithium, monoaluminides. Preferred anode materials are alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as calcium. In a preferred embodiment, when selecting a particular oxyhalide for a particular cell according to the invention, consideration is given to the stability of the particular oxyhalide in the presence of other cell components and the operating temperature at which the cell is expected to operate. Must. Therefore, oxyhalides must be selected that are stable in the presence of other battery components. Additionally, gelling agents such as colloidal silica can be added if it is desired to make the electrolyte solution more viscous or convert it into a gel. When a vinyl polymer film is provided on the separator as in the present invention, it is easier to manufacture than when it is provided on an active metal anode. Highly active metal anodes, such as lithium, must be stored and handled in dry boxes under an inert atmosphere. In addition, whereas it is necessary to use a specific solvent that does not affect lithium, in the present invention, there is no need to use a specific atmosphere for a non-reactive separator, and many solvents can be used. This is because it is rich in sexuality. Coated separators also have advantageous strength properties compared to separators without any coating. The present invention will be explained below with reference to a few examples.
The present invention is not limited to these examples. Example 1 Three lots of 0.475 inch diameter batteries were made using the following components. 0.45 g of lithium; cathode collector made of 0.65 g of a mixture of 90% by weight carbon black and 10% by weight Teflon ^* binder, (*trademark of polytetrafluoroethylene) fused glass in contact with cathode collector Non-woven fabric separator (934S type manufactured by Mead),
and lithium sulfide was added to its saturation point,
2.4 cc of 1 molar LiAlCl ₄ liquid cathode-electrolyte solution in SOCl ₂ . These ingredients were assembled into a stainless steel container and sealed with a cover member in the conventional manner. The cells were stored under various conditions and then discharged into a 75 ohm load. The average discharge voltage after 1 second for the three batteries of each lot is shown in the table.

[Table] Three other lots of batteries were made as described above. However, before assembly in the cell, the separator must be immersed in a 1% by weight vinyl acetate/vinyl chloride solution in 3-pentanone and then for approximately 1 minute.
It was rapidly dried by heating at 200°C. This vinyl acetate/vinyl chloride consists of 86% by weight vinyl chloride and 14% by weight vinyl acetate.
It is commercially available from Union Carbide Corporation as VYHH. Separators with this vinyl polymer coating are mechanically easy to manipulate and easy to assemble into a battery. These three lots were stored under various conditions and then discharged into a 75 ohm load. The average voltage (V) observed after 1 second for the three cells of each lot is shown in the table below.

Table: As is evident from the data above, batteries with vinyl polymer coated separators had higher average voltage readings after 1 month and 3 months than batteries with uncoated separators. . The six lots of batteries described above were then stored under various conditions and then continuously discharged through 75 ohms to give an average ampere per hour (AH) for the three batteries in each lot.
The results are shown in the table.

[Table] Example 2 A number of batteries were separately manufactured in the same manner as in Example 1.
However, the solution used to coat the separator was vinyl acetate/vinyl chloride copolymer (VYHH) in 3-pentanone, as shown in the table.
was varied between 0.5 and 3% by weight. Three cells of each type, including three cells in which the separator was not coated, were stored under various conditions and then discharged into a 75 ohm load. The average voltage after 1 second and the average ampere/hour delivered are shown in the table.

Table: The amount of vinyl retained on the separator after coating with various vinyl solutions ranges from approximately 0.7 to 1.0 g/ ^m2 of separator material for a 0.5 wt.% vinyl/solvent solution to 3 wt.% vinyl/m2 of separator material. Up to about 3.5 g/m ² of separator material for the vinyl/solvent solution. Calculated on the separator weight (about 25 g/m ² ), about 2.8% by weight to about 14% by weight, respectively, for the range of coating solution concentrations used from 0.5 to 3%.
Becomes vinyl. Example 3 A number of separate batteries were made as in Example 1. The separators of some of the cells were coated with a 1% by weight vinyl acetate/vinyl chloride copolymer solution in 3-pentanone. Also, lithium/aluminum alloy electrodes were used in place of lithium electrodes in some batteries. This electrode weighs 0.52g, 85% by weight
of lithium and 15% aluminum by weight. Three batteries of each type were stored under various conditions and discharged into a 75 ohm load. The average voltage and average ampere/hour delivered after 1 second are shown in the table.

[Table] Example 4 Multiple batteries were made in the same manner as Example 1. However, in each cell, 0.479 g of lithium foil or 0.450 g of lithium extrudate was used as the anode. The cathode collector consists of 85% by weight carbon black and 15% by weight Teflon. Cathode/electrolyte solution is 1M in 2.4cc SO ₂ Cl ₂
It consisted of a LiAlCl ₄ solution, lithium sulfide was added to the saturation point of the solution, and the separator was coated with a vinyl solution as shown in the table. These cells were stored at various conditions and then discharged into a 75 ohm load. The average voltage and average ampere/hour delivered for the three cells observed after 1 second are shown in the table. In the eighth lot, the separators were dried for two hours at room temperature after soaking in the solution. In the ninth lot, the separators were dried at 175°C for one minute, and in the tenth lot, the separators were dried at 225°C for one minute.

[Table] The present invention is not limited to the above description, and can be modified and implemented as desired within the scope of the spirit thereof.

Claims (1)

[Scope of Claims] 1. An ionically conductive cathode-electrolyte solution comprising a solute dissolved in an active liquid cathode, an active metal anode, a cathode collector, and a separator disposed between the anode and the cathode collector. A non-aqueous battery comprising: a surface of the separator facing the anode is coated with a vinyl polymer film. 2 Vinyl polymer is a homopolymer of vinyl chloride or vinylidene chloride, vinyl ester,
A copolymer containing vinyl chloride or vinylidene chloride having at least one monomer selected from the group consisting of dibasic acids, diesters of dibasic acids, and monoesters of dibasic acids and copolymerized therein. The non-aqueous battery according to claim 1, which is selected from the group consisting of: 3. The nonaqueous battery according to claim 1, wherein the vinyl polymer is selected from the group consisting of vinyl chloride vinyl acetate copolymer, vinyl chloride-dibasic acid copolymer, and vinyl chloride homopolymer. 4. The amount of vinyl polymer film on the separator ranges from about .07 to about
The non-aqueous battery according to claim 1, 2 or 3, characterized in that the weight is in the range of 3.5g. 5. A non-aqueous battery according to claim 1, 2 or 3, wherein the amount of vinyl polymer film on the separator is in the range of about 1.5 to 1.8 g per square meter of the raised area. 6. The non-aqueous battery according to claim 1, 2 or 3, wherein the cathode electrolyte contains a material selected from the group consisting of lithium sulfide, sulfur monochloride and mixtures thereof. 7 Claim in which the cathode-electrolyte contains at least one liquid oxyhalide selected from the group consisting of thionyl chloride, sulfuryl chloride, phosphorous oxychloride, thionyl bromide, chromyl chloride, vanadyl tribromide, and selenium oxychloride. range 1st, 2nd
Or the non-aqueous battery according to item 3. 8. The nonaqueous battery of claim 7, wherein the at least one liquid oxyhalide is selected from the group consisting of thionyl chloride and sulfuryl chloride. 9. The non-aqueous battery according to claim 1, 2 or 3, wherein the anode is selected from the group consisting of lithium, sodium, calcium, potassium and aluminum. 10. The non-aqueous battery of claim 7, wherein the cathode-electrolyte is an inorganic co-solvent. 11. The non-aqueous battery of claim 7, wherein the cathode-electrolyte is an organic co-solvent. 12. The non-aqueous battery according to claim 7, wherein the anode is lithium and the liquid oxyhalide is thionyl chloride. 13 Claim 7: The anode is lithium and the liquid oxyhalide is sulfuryl chloride.
Non-aqueous batteries as described in section. 14. The non-aqueous battery according to claim 1, 2 or 3, wherein the solute is a complex salt of a Lewis acid and an inorganic ionizable salt.