CA1151725A - Cathode collectors for nonaqueous cell having a metal oxide catalyst - Google Patents
Cathode collectors for nonaqueous cell having a metal oxide catalystInfo
- Publication number
- CA1151725A CA1151725A CA000354570A CA354570A CA1151725A CA 1151725 A CA1151725 A CA 1151725A CA 000354570 A CA000354570 A CA 000354570A CA 354570 A CA354570 A CA 354570A CA 1151725 A CA1151725 A CA 1151725A
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- cathode
- cell
- nonaqueous cell
- metal oxide
- nonaqueous
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/664—Ceramic materials
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- External Artificial Organs (AREA)
Abstract
12,296 CATHODE COLLECTORS FOR NONAQUEOUS CELL
HAVING A METAL OXIDE CATALYST
ABSTRACT
A nonaqueous cell comprising a metal anode, a cathode-electrolyte comprising a solute dissolved in a liquid active cathode, such as an oxyhalide, and a carbonaceous cathode collector containing a metal oxide catalyst.
SPECIFICATION
1.
HAVING A METAL OXIDE CATALYST
ABSTRACT
A nonaqueous cell comprising a metal anode, a cathode-electrolyte comprising a solute dissolved in a liquid active cathode, such as an oxyhalide, and a carbonaceous cathode collector containing a metal oxide catalyst.
SPECIFICATION
1.
Description
~L51725 , Fielt of the Invention The ~nvention relates to nonaqueous cells emplo~ing a liquld acti~e cathode, a metal anode and a carbonaceous csthode collector contain$ng a metal oxide catal~st.
~ Back~round of the Invention The development of high energy battery systems requires, among other things, the compatibility of an : electrolyte possessing desirable electrochemical proper-ties with highly reactive anode materials, such as lithlum or the like. The use of aqueous electrolytes is precluded in these systems since the anode materials are sufficiently active to react with water chemically. It has, therefore, been necessary in order to realize the h~gh energy density obtainable through use of these highly react~ve anodes to turn to the investigation of nonaqueous electrolyte systems.
$he term "nonaqueous electrolyte" as used herein ; refers to an electrolyte which is composed of a solute, such as, for example, a metal galt or a complex salt of Group IA, Group IIA, Group IIIA or Group VA elements of the Periodic Table, dissolved in an appropriate nonaqueous solvent. The term "Periodic Table" as used herein refers to the Periodic Table of Elements as set forth on the ; inside back cover of the Handbook of Chemistry and Physics, 48th Edition, The Chemical Rubber Co., Cleveland, Ohio, 1967-1968.
A multitude of solutesis known and many hsve been suggested ~or use but the selection of a suitable solvent has been ~articularly troublesome. The ideal battery electrolyte would comprlse a solvent-solute pair which has a long liquit range, high lonic contuctivity and stability. A long liquid range, i.e., hlgh bolllng point and low freezing polnt, iB e66ential if the battery is to operate at other than normal ambient ~em~eratures.
High ionic conductivity is necessary if the battery is to have high rate capability. Stability is necessary with the electrode materials, the materials of cell con-struction, and the products of the cell reaction to provide long shel~ l~fe when used in a primary or secondary battery system.
It has recently been disclosed in the literature that certain materials are capable of acting both as an electrolyte carrier, i.e., as solvent for the electrolyte salt, and as the active cathode for a nonaqueous electro-chemical cell. U. S. Patent Nos. 3,475,226, 3,567,515 ant 3,578,500 each disclose that liquid sulfur dioxide or solutions of sulfur tioxide and a co-solvent will perform th~s dual function in nonaqueous electrochemical cells. While these solutions perform their dual function, they are not without several disadvantages in use. Sulfur tioxide is always present and being a gas at ordinary temperature, it must be contained in the cell as a liquid under pressure or dissolved in a liquid solvent. Handling . and packaging problems are created if the sulfur dioxide - is used alone, and an additional component and assembly step ~ necessary if sulfur dioxide is to be dissolved in a liquid solvent. As stated above, a long liquid range encompassing normal ambient temperatures is a desirable characteristic in an electrolyte solvent. Obviously, ~ 51 7 Z 5 aulfur dioxide is ~eficient ln thi6 respect t tmospheric pressure Canadlan Patent Number 9~2,216 discloses nonaqueous electrochemical cell comprising n node, cathode collector nd a cathote-electrolyte,--sid c~thode-electrolyte comprising solut$on of n lonically conductive solute dissolved in an active cathode depolsriter wherein said ctive cathode depolarizer consists of a liquid oxyhalide of an clement of Group V or Group VI of the Periodic T-ble Although oxyh-lides can be used effectively s a component part of - cathode-electrolyte ln con~unction with n ~ctive metsl anode, it hss been found that t h~gh current drains, for ex~mple or sbove 10 mA/c~2, the system'~ efficiency gre~tly decresses Wlth the Jdvent of new battery-powered devices requiriag high-r~te disch-rge power supplies, cells utilizing llqu~t ctive cathodes, such s oxyhalites, will not effectively nd efficiency operste these devices It i6 n ob~ect of the present invention to provide nonsqueous li~uid csthode cell thst can operate at high current density Another object of the present invention ls to provide a nonaqueous oxyhalide cell employing a porous carbonJceous c-thode collector contsining a metal oxide c~talyst ~nothcr ob~ect of the prcsent lnvehtion 16 to provide a l~thium/oxyhslide cell employing -porous carbonaceous cathode collector containing a metal oxide a~ch as aluminum oxide (A1203) ._ - i2296 ~ S~ ~ Z 5 .
SummarY of the Invention The invention relates to a high energy density nonaqueous cell cDmprising an active metal snode, an ionically conductive cathode-electrolyte Rolution contsining 8 solute dissolved in a liquid sctive csthode with or without a reactive or non-reactive co~olvent, and a porous carbonaceous cathode collector containing at least one metal oxide to ensble the cell to effectively function at high current density discharge rates.
The metal oxide should be sdded in an amount between about 1 percent to about 30 percent by weight based on the weight of the csrbonaceous material in the cathode collector. Preferably, the amount should be between about 5 percent snd about 20 percent by weight. An amount of the metsl oxide below 1 percent would be ineffective in improving the high drain perform2nce of the cell.
An amount of the metsl oxide above 30 percent msy be effective; however, it would replace csrbon and thereby limit the flvsilsble reaction sites for the liquid csthode.
Metal oxide for use in this invention can be seclected from the group consisting of aluminum oxide (A1203), kaolin (A1203 2SiO2), snd nickel oxide (NiO). The more p~eferable metsl oxide is aluminum o~ide.
~ 2 5 12296 Although applicane does not want to be bound by theory of invention it i6 believed th~t intercalation of the carbonaceous cathode collector with the discharge product of the anode and cathode. which occurs during cell dischsrge, i5 facilitated in the presence of the metal oxide. Thus the metal oxide acts as a c~atalyst - for the cathode reaction. The intercalation process appears to be defusion-limited, which would account for the poor performance of liquid cathodes~ such as oxyhslides, w~h uncatalyred cathode collectors at high discharge rates.
A9 used herein and as described in an article titled "Electrochemical Reactions In Batteries" by Akiya Kozawa snd R. A. Powers in the Journal of Chemical Education - Vol. 49, pages 587 to 591, September 1972 issue, a cathode depolarizer is the cathode resctant and, thereore, is the material electrochemically reduced at the csthode. The cathode collector i9 not an active reducible material and unctions as a current collector plu5 electronic conductor to the positive (cathode) terminal of a cell. In other words, the cathode collector is a situs for the electrochemical reduction reaction of the active cathode material and the electronic conductor to the cathode terminal of a cell.
~151725 12296 In accord~nce with thls invention, in a cell employlng a l~quid ctive cathode and a cathode collector, the cathode collector in addition to functioning as the current collector must also serve as extended area reaction 6ites for the cathodic electrochemicsl process of the cell. Thus the cathode collector shou~d be ~ at least 50Z porous 80 as to provide increased access ; to reaction sites and be of a material cspable of cstalyzing or sustaining the cathodic electrochemical process. Materials suitable for use as a cathode collector are carbon materisls with scetylene black and graphite being preferable. In addition to the above characteristics, the cathode col~ector in some applicatio~ must be capable of being molded directly within a container or capable of being molded into various size discrete bodies thst can be handled without cracking or bresking. To impart J cohesive characteristic to carbonacebus cathote collectors, a suitable binder material, with or without plasticizers and with or without stab~lizers, can be atted to the cathode collector materials.
Suitable binder materia1s for this purpose may include vinyi polymers, polyethylene, polypropylene, polyacrylic, polystyrene and the like. ~or example, polytetrafluoro-ethylene would be the preferred binder for cathode col-lectors for use with liquid oxyhalide cathodes. The binder, lf required,may be added in an amount between 1% and about 40% by weight of the molded cathode collector since an amount less than 1% would not provide sufficient ~trength , ~151~25 to the molded body while an amount larger thsn 40%
would mask the surfsce of the c~rbon and/or reduce the avfiilable surf~ce of the csrbon, thereby unacceptably reducing the activstion site aress required for the ca~hodic electrochemicsl process of the cell. Preferably, the binder should be between about 5% and about-15~ by 7 weight of the cathode collector. Of importance in T selecting the m~terisls for the csthode collector is to select msterials thst will be chemically stable in the cell system in which they are to be used.
In some spplicstions,the metal oxide, such as kaolin, while being employed as a catalyst could slso function as a binder for the carbonaceous cathode collector thereby elim$nating the addition of a separate binder material to the csthode collector. The use of the metal oxide in this dual function will provide ma~imum volume for the active components of t;he cell iQ a given cell size. 1~ other applications, it may be preferable to employ a binder as tescribed sbove in the cathode collector slong with the metsl oxide catslyst.
The metal oxide catalyst can be mixed with the carbonaceous msterial in a number of ~ays. For example, the metal oxide could be blended with the carbonaceous material in the wet or dry form. The specific ~mount of the metal oxide catalyst to be added to the carbonaceous material will depend on such factors as the mode of blending the ingredients;
whether or not a binder is to be employed; the intended rate of discharge for the cell; and the ;. 1~51~25 12296 desi~ed cell capacity. As stated above the preferred range o~ the metal oxide catalyst is between about 5 wt.
percent and 20 wt. percent based on the weight of the carbonaceous material.
Alternatively,a carbonaceous cathode collector - containing aluminum oxide uniformly dispersed between the layers of a microcystalline macroaromatic molecule, e.g., graphite or carbon Cacetylene) black, can be prepared as follows. A lamellar compound can be made by intercalating alu~inum chloride (AlC13) from an oxyhalide solution. After the intercalation compound i8 made with carbon and AlC13 within the larger planes, it can be reacted with water to produce A12O3 and HCl.
This reaction may or may not go to completion. However, following this chemical reaction, the carbon could be "defoliated" by heating in a conventional manner.
The end product will be a material made up of a high surface area carbon substrate partially covered with A12O3 dispersed uniformly within the particles of carbon. This material could then be used as cathode collectors for liquid cathode cell systems.
In accordance with this invention, an active liquid reducible cathode material (depolarizer) can either be mixed with a conductive solute which is a nonreactive material but is added to improve conductivity ~ of the liquid active reducible cathode materials, or it can be mixed with both a conductive solute and a react~ve or nonreactive co-solvent material. A reactive co-solvent material is one that is electrochemically active and, therefore, functions as an active cathode material ~hile a nonreactive co-solvent materlal is one that is eIectroche~lcall~ inacti~e and, there~o~e, cannot ~unction as an acti~e cathode material.
The solute may be a simple or double ~alt whlcn will produce an ionicslly conductive ~olution-when tie-~olvet in the ~olvent. Preferred ~olutes ~rc complexes ; of inorganic or organic Lewi8 acids and inorganic ionlzable sslts. The main requirement6 for ut~lity re that the ~alt, whether ~imple or comple~, be compa~ible with the solvent being employed and that it yield a solution which is ionically conductive. ~ccorting to the Lewi6 or electronic concept of acids and base~, many ~ubstance6 which do not contain active hydrogen can act as acids or scceptor6 of electron doublets. The basic concept i8 Bet forth in the chemical literature (Journal of the Frankl~n Institute, Vol. 226 - July/December, 1938, page6 293-313 by G. N. Lewi6).
A ~uggested reaction mechanism for the manner in whlch these complexes function in a solvent i8 described ~n detail in U. S. ~atent 3,542,602 whereln lt i6 sugge6ted that the complex or double salt formRd be~ween the Lewi6 acit and the ionizable salt yields an entity which is ~ore ~table than either of the components alone.
Typical Lew$6 acids suitable for u~e in the ; present ln~entlon include aluminum fluorlte, aluminum bromlte, aluminum chlorite, antimony pentachloride, zirconium tetrachlorlde, phosphoru6 pentnchlcritc, boron fluoride, boron chloride and boron brom$de.
Ionizable salt6 useful ln co~bination with the Lewls acids lnclude lithium fluoride, llthium chloride, lithium brcmide, lithlum sulfide, ~odium fluoride, sodium 10.
; ~L517ZS
chlor~de, sodium bromide, potass$um fluorid~, potessium chloride and potsssium bromide.
It will be obvious to those skilled in the art that the double salts formed by a Lewis acid and an inorganic ionizeble salt may be used as such or the individual components may be added to the solvent separately to form the salt or the resulting ions in situ. One such double salt, for example, is that formed by the combination of alumlnum chloride nd lithium chloride to yield lithium al~m~m tetrachloride.
In accordance with the present invention, there i8 provided a nonaqueous electrochemical system comprising an active metal anode, a porous carbonaceous cathode collector containing at least one metal oxide catslyst, ant a cathode-electrolyte, said cathode-electrolyte comprising, for example, a solute dissolved in an active reducible cathode ~olvent such as at least one oxyhalide of a Group V or Group VI element of the Periodic Table and/
or a li~uid halide of a Group IV , V, or VI element of the Periodic Table, with or without a co-solvent. The active reducible electrolyte solvent performs the dual function of scting as solvent for the electrolyte salt and as an active cathode depolarizer of the cell. The term "cathode-electrolyte" is used herein to describe electrolytes containing ~olvents that csn perfonm this dusl function.
The use of A single component of the cell as both an electrolyte solvent and active eathode (depolarizer) is a relatively recent development since previously it ' was generally considered that the two functions were necessarily independent and could not be served by the same material. For an electrolyte solvent to function in ' 122a6 ' cell, ~t is necessary that it contact both the anode ~nd the ca~hode(depolari2æ~ ~o s to form ~ continuous ~onic path therebetween. Th~s ~t haB generally been ~8sumed that the ac~ive cathode material must never directly contact the anode and, therefore, it ~ppeared ~ that the two functions were mutu~lly exclusi~e. However, ~- it has recently been discovered that certain ~ctive cathode materials, ~uch as the llquid oxyhslldes, do not appreciably react chemically with an ~ctive anode metsl at the inter-face between the metal and the cathode msterial, therebyallowing the cathode material to contact the anode tirectly and act B8 the electrolyte carrier. While the theory behind the cause of the inhibition of direct chemical reaction is not fully understood at the present time and the applicant does not desire to be lim$ted to any theory of ~nvention, it appear8 that direct chemlcal reaction is inhibited either by an inherently high activa-tion energy of reaction or the formation of a thin, pro-tective film on the anode surface. ~Any protective film on the anode ~urface mu6t not be formed to such an excess th~t a large increase ~n ~node polarization results.
Suitable oxyhalides for use in this invention include sulfuryl chloride, thionyl chloride, phosphorus oxychloride, thionyl bromide, chsomyl chloride, vanadyl tribromide and selenium oxychloride.
Useful organic co-solvents for use in this - in~ention inclute the following classes of compounds:
12.
~lS17Z5 Trialkyl borates: e.g., trimethyl borate, (CH30)3B
(liquid range --29.3 to 67C.) Tetraalkyl silicates: e.g., tetramethyl silicate, ~CH30)4Si (boiling point 121C.) Nitroalkanes: e.g., nitromethane, CH3N02 (liquid range -17 to 100.8C.) Alkylnitriles: e.g., acetonitrile, CH3CN
(liquid range -45 to 81.6C.) Dialkylamides: e.g., dimethylformamide, HCON(CH3)2 (liquid range -60.48 to 149C.) Lactams: e.g., N-methylpyrrolidone, CH2-CH2-CH3-CO-N-CH3 (liquid range -16 to 202C.) Tetraalkylureas: e.g., tetramethylurea, (CH3)2N-CO-N(CH3)2 (liquid range -1.2 to 166C.) Monocarboxylic acid esters: e.g., ethyl acetate (liquid range -83.6 to 77.06C.) Orthoesters: e.g., trimethylorthoformate, HC(OCH3)3 (boiling point 103C.) Lactones: e.g.,~-(gamma)butyrolactone, CH2-CH2-CH2-0-CO
(liquid range -42 to 206C.) Dialkyl carbonates: e.g., dimethyl carbonate, ; OC(OCH3)2 (liquid range 2 to 90C.) Alkylene carbonates: e.g., propylene carbonate, CH(CH3)CH2-0-CO-0 (liquid range -48 to 242C.) Monoethers: e.g., diethyl ether (liquid range -116 to 34.5C.) h~ r .
~' - ~S1725 Polyethers: e.g., 1,1- and 1,2-dimethoxyethane (liquid ranges -113.2 to 65.5C. and -58 to 83C., respectively) Cyclic ethers: e.g., tetrahydrofuran (liquid range -65 to 67C.); 1,3-dioxolane (liquid range -95 to 78C.) Nitroaromatics: e.g., nitrobenzene (liquid range 5.7 to 210.8C.) Aromatic carboxylic acid halides: e.g., benzoyl chloride (liquid range 0 to 197C.); benzoyl bromide (liquid range -24 to 218C.) Aromatic sulfonic acid halides: e.g., benzene sulfonyl chloride (liquid range 14.5 to 251C.) Aromatic phosphonic acid dihalides: e.g., benzene phosphonyl dichloride (boiling point 258C.) Aromatic thiphosphonic acid dihalides: e.g., benzene thiophosphonyl dichloride (boiling point 124C. at 5 mm.) Cyclic sulfones: e.g., sulfolane, CH2-cH2-cH2-cH2-so2 (melting poin~ 22 C.)i 3-methylsulfolane (melting point -1C.) Alkyl sulfonic acid halides: e.g., methanesulfonyl chloride (boiling point 161C.) Alkyl carboxylic acid halides: e.g., acetyl chloride (liquid range -112 to 50.9C.); acetyl bromide (liquid range -96 to 76.C.); propionyl chloride (liquid range -94 to 80C.) 14 .
~517Z5 Saturated heterocyclics: e.g., tetrahydrothiophane (liquid range -96 to 121C.); 3-methyl-2-oxa-zolidone (melting point 15.9C.) Dialkyl sulfamic acid halides: e.g., dimethyl sulfamyl chloride (boiling point 8~C., 16 mm.) Alkyl halosulfona~es: e.g., ethyl chlorosulfonate (boiling point 151C.) Unsaturated heterocyclic carboxylic acid halides:
e g., 2-furoylchloride (liquid range -2 to 173C.) 0 Five-membered unsaturated heterocyclics: e.g., 3,5-dimethylisoxazole (boiling point 140C.);
l-methylpyrrole (boiling point 114C.);
~ Back~round of the Invention The development of high energy battery systems requires, among other things, the compatibility of an : electrolyte possessing desirable electrochemical proper-ties with highly reactive anode materials, such as lithlum or the like. The use of aqueous electrolytes is precluded in these systems since the anode materials are sufficiently active to react with water chemically. It has, therefore, been necessary in order to realize the h~gh energy density obtainable through use of these highly react~ve anodes to turn to the investigation of nonaqueous electrolyte systems.
$he term "nonaqueous electrolyte" as used herein ; refers to an electrolyte which is composed of a solute, such as, for example, a metal galt or a complex salt of Group IA, Group IIA, Group IIIA or Group VA elements of the Periodic Table, dissolved in an appropriate nonaqueous solvent. The term "Periodic Table" as used herein refers to the Periodic Table of Elements as set forth on the ; inside back cover of the Handbook of Chemistry and Physics, 48th Edition, The Chemical Rubber Co., Cleveland, Ohio, 1967-1968.
A multitude of solutesis known and many hsve been suggested ~or use but the selection of a suitable solvent has been ~articularly troublesome. The ideal battery electrolyte would comprlse a solvent-solute pair which has a long liquit range, high lonic contuctivity and stability. A long liquid range, i.e., hlgh bolllng point and low freezing polnt, iB e66ential if the battery is to operate at other than normal ambient ~em~eratures.
High ionic conductivity is necessary if the battery is to have high rate capability. Stability is necessary with the electrode materials, the materials of cell con-struction, and the products of the cell reaction to provide long shel~ l~fe when used in a primary or secondary battery system.
It has recently been disclosed in the literature that certain materials are capable of acting both as an electrolyte carrier, i.e., as solvent for the electrolyte salt, and as the active cathode for a nonaqueous electro-chemical cell. U. S. Patent Nos. 3,475,226, 3,567,515 ant 3,578,500 each disclose that liquid sulfur dioxide or solutions of sulfur tioxide and a co-solvent will perform th~s dual function in nonaqueous electrochemical cells. While these solutions perform their dual function, they are not without several disadvantages in use. Sulfur tioxide is always present and being a gas at ordinary temperature, it must be contained in the cell as a liquid under pressure or dissolved in a liquid solvent. Handling . and packaging problems are created if the sulfur dioxide - is used alone, and an additional component and assembly step ~ necessary if sulfur dioxide is to be dissolved in a liquid solvent. As stated above, a long liquid range encompassing normal ambient temperatures is a desirable characteristic in an electrolyte solvent. Obviously, ~ 51 7 Z 5 aulfur dioxide is ~eficient ln thi6 respect t tmospheric pressure Canadlan Patent Number 9~2,216 discloses nonaqueous electrochemical cell comprising n node, cathode collector nd a cathote-electrolyte,--sid c~thode-electrolyte comprising solut$on of n lonically conductive solute dissolved in an active cathode depolsriter wherein said ctive cathode depolarizer consists of a liquid oxyhalide of an clement of Group V or Group VI of the Periodic T-ble Although oxyh-lides can be used effectively s a component part of - cathode-electrolyte ln con~unction with n ~ctive metsl anode, it hss been found that t h~gh current drains, for ex~mple or sbove 10 mA/c~2, the system'~ efficiency gre~tly decresses Wlth the Jdvent of new battery-powered devices requiriag high-r~te disch-rge power supplies, cells utilizing llqu~t ctive cathodes, such s oxyhalites, will not effectively nd efficiency operste these devices It i6 n ob~ect of the present invention to provide nonsqueous li~uid csthode cell thst can operate at high current density Another object of the present invention ls to provide a nonaqueous oxyhalide cell employing a porous carbonJceous c-thode collector contsining a metal oxide c~talyst ~nothcr ob~ect of the prcsent lnvehtion 16 to provide a l~thium/oxyhslide cell employing -porous carbonaceous cathode collector containing a metal oxide a~ch as aluminum oxide (A1203) ._ - i2296 ~ S~ ~ Z 5 .
SummarY of the Invention The invention relates to a high energy density nonaqueous cell cDmprising an active metal snode, an ionically conductive cathode-electrolyte Rolution contsining 8 solute dissolved in a liquid sctive csthode with or without a reactive or non-reactive co~olvent, and a porous carbonaceous cathode collector containing at least one metal oxide to ensble the cell to effectively function at high current density discharge rates.
The metal oxide should be sdded in an amount between about 1 percent to about 30 percent by weight based on the weight of the csrbonaceous material in the cathode collector. Preferably, the amount should be between about 5 percent snd about 20 percent by weight. An amount of the metsl oxide below 1 percent would be ineffective in improving the high drain perform2nce of the cell.
An amount of the metsl oxide above 30 percent msy be effective; however, it would replace csrbon and thereby limit the flvsilsble reaction sites for the liquid csthode.
Metal oxide for use in this invention can be seclected from the group consisting of aluminum oxide (A1203), kaolin (A1203 2SiO2), snd nickel oxide (NiO). The more p~eferable metsl oxide is aluminum o~ide.
~ 2 5 12296 Although applicane does not want to be bound by theory of invention it i6 believed th~t intercalation of the carbonaceous cathode collector with the discharge product of the anode and cathode. which occurs during cell dischsrge, i5 facilitated in the presence of the metal oxide. Thus the metal oxide acts as a c~atalyst - for the cathode reaction. The intercalation process appears to be defusion-limited, which would account for the poor performance of liquid cathodes~ such as oxyhslides, w~h uncatalyred cathode collectors at high discharge rates.
A9 used herein and as described in an article titled "Electrochemical Reactions In Batteries" by Akiya Kozawa snd R. A. Powers in the Journal of Chemical Education - Vol. 49, pages 587 to 591, September 1972 issue, a cathode depolarizer is the cathode resctant and, thereore, is the material electrochemically reduced at the csthode. The cathode collector i9 not an active reducible material and unctions as a current collector plu5 electronic conductor to the positive (cathode) terminal of a cell. In other words, the cathode collector is a situs for the electrochemical reduction reaction of the active cathode material and the electronic conductor to the cathode terminal of a cell.
~151725 12296 In accord~nce with thls invention, in a cell employlng a l~quid ctive cathode and a cathode collector, the cathode collector in addition to functioning as the current collector must also serve as extended area reaction 6ites for the cathodic electrochemicsl process of the cell. Thus the cathode collector shou~d be ~ at least 50Z porous 80 as to provide increased access ; to reaction sites and be of a material cspable of cstalyzing or sustaining the cathodic electrochemical process. Materials suitable for use as a cathode collector are carbon materisls with scetylene black and graphite being preferable. In addition to the above characteristics, the cathode col~ector in some applicatio~ must be capable of being molded directly within a container or capable of being molded into various size discrete bodies thst can be handled without cracking or bresking. To impart J cohesive characteristic to carbonacebus cathote collectors, a suitable binder material, with or without plasticizers and with or without stab~lizers, can be atted to the cathode collector materials.
Suitable binder materia1s for this purpose may include vinyi polymers, polyethylene, polypropylene, polyacrylic, polystyrene and the like. ~or example, polytetrafluoro-ethylene would be the preferred binder for cathode col-lectors for use with liquid oxyhalide cathodes. The binder, lf required,may be added in an amount between 1% and about 40% by weight of the molded cathode collector since an amount less than 1% would not provide sufficient ~trength , ~151~25 to the molded body while an amount larger thsn 40%
would mask the surfsce of the c~rbon and/or reduce the avfiilable surf~ce of the csrbon, thereby unacceptably reducing the activstion site aress required for the ca~hodic electrochemicsl process of the cell. Preferably, the binder should be between about 5% and about-15~ by 7 weight of the cathode collector. Of importance in T selecting the m~terisls for the csthode collector is to select msterials thst will be chemically stable in the cell system in which they are to be used.
In some spplicstions,the metal oxide, such as kaolin, while being employed as a catalyst could slso function as a binder for the carbonaceous cathode collector thereby elim$nating the addition of a separate binder material to the csthode collector. The use of the metal oxide in this dual function will provide ma~imum volume for the active components of t;he cell iQ a given cell size. 1~ other applications, it may be preferable to employ a binder as tescribed sbove in the cathode collector slong with the metsl oxide catslyst.
The metal oxide catalyst can be mixed with the carbonaceous msterial in a number of ~ays. For example, the metal oxide could be blended with the carbonaceous material in the wet or dry form. The specific ~mount of the metal oxide catalyst to be added to the carbonaceous material will depend on such factors as the mode of blending the ingredients;
whether or not a binder is to be employed; the intended rate of discharge for the cell; and the ;. 1~51~25 12296 desi~ed cell capacity. As stated above the preferred range o~ the metal oxide catalyst is between about 5 wt.
percent and 20 wt. percent based on the weight of the carbonaceous material.
Alternatively,a carbonaceous cathode collector - containing aluminum oxide uniformly dispersed between the layers of a microcystalline macroaromatic molecule, e.g., graphite or carbon Cacetylene) black, can be prepared as follows. A lamellar compound can be made by intercalating alu~inum chloride (AlC13) from an oxyhalide solution. After the intercalation compound i8 made with carbon and AlC13 within the larger planes, it can be reacted with water to produce A12O3 and HCl.
This reaction may or may not go to completion. However, following this chemical reaction, the carbon could be "defoliated" by heating in a conventional manner.
The end product will be a material made up of a high surface area carbon substrate partially covered with A12O3 dispersed uniformly within the particles of carbon. This material could then be used as cathode collectors for liquid cathode cell systems.
In accordance with this invention, an active liquid reducible cathode material (depolarizer) can either be mixed with a conductive solute which is a nonreactive material but is added to improve conductivity ~ of the liquid active reducible cathode materials, or it can be mixed with both a conductive solute and a react~ve or nonreactive co-solvent material. A reactive co-solvent material is one that is electrochemically active and, therefore, functions as an active cathode material ~hile a nonreactive co-solvent materlal is one that is eIectroche~lcall~ inacti~e and, there~o~e, cannot ~unction as an acti~e cathode material.
The solute may be a simple or double ~alt whlcn will produce an ionicslly conductive ~olution-when tie-~olvet in the ~olvent. Preferred ~olutes ~rc complexes ; of inorganic or organic Lewi8 acids and inorganic ionlzable sslts. The main requirement6 for ut~lity re that the ~alt, whether ~imple or comple~, be compa~ible with the solvent being employed and that it yield a solution which is ionically conductive. ~ccorting to the Lewi6 or electronic concept of acids and base~, many ~ubstance6 which do not contain active hydrogen can act as acids or scceptor6 of electron doublets. The basic concept i8 Bet forth in the chemical literature (Journal of the Frankl~n Institute, Vol. 226 - July/December, 1938, page6 293-313 by G. N. Lewi6).
A ~uggested reaction mechanism for the manner in whlch these complexes function in a solvent i8 described ~n detail in U. S. ~atent 3,542,602 whereln lt i6 sugge6ted that the complex or double salt formRd be~ween the Lewi6 acit and the ionizable salt yields an entity which is ~ore ~table than either of the components alone.
Typical Lew$6 acids suitable for u~e in the ; present ln~entlon include aluminum fluorlte, aluminum bromlte, aluminum chlorite, antimony pentachloride, zirconium tetrachlorlde, phosphoru6 pentnchlcritc, boron fluoride, boron chloride and boron brom$de.
Ionizable salt6 useful ln co~bination with the Lewls acids lnclude lithium fluoride, llthium chloride, lithium brcmide, lithlum sulfide, ~odium fluoride, sodium 10.
; ~L517ZS
chlor~de, sodium bromide, potass$um fluorid~, potessium chloride and potsssium bromide.
It will be obvious to those skilled in the art that the double salts formed by a Lewis acid and an inorganic ionizeble salt may be used as such or the individual components may be added to the solvent separately to form the salt or the resulting ions in situ. One such double salt, for example, is that formed by the combination of alumlnum chloride nd lithium chloride to yield lithium al~m~m tetrachloride.
In accordance with the present invention, there i8 provided a nonaqueous electrochemical system comprising an active metal anode, a porous carbonaceous cathode collector containing at least one metal oxide catslyst, ant a cathode-electrolyte, said cathode-electrolyte comprising, for example, a solute dissolved in an active reducible cathode ~olvent such as at least one oxyhalide of a Group V or Group VI element of the Periodic Table and/
or a li~uid halide of a Group IV , V, or VI element of the Periodic Table, with or without a co-solvent. The active reducible electrolyte solvent performs the dual function of scting as solvent for the electrolyte salt and as an active cathode depolarizer of the cell. The term "cathode-electrolyte" is used herein to describe electrolytes containing ~olvents that csn perfonm this dusl function.
The use of A single component of the cell as both an electrolyte solvent and active eathode (depolarizer) is a relatively recent development since previously it ' was generally considered that the two functions were necessarily independent and could not be served by the same material. For an electrolyte solvent to function in ' 122a6 ' cell, ~t is necessary that it contact both the anode ~nd the ca~hode(depolari2æ~ ~o s to form ~ continuous ~onic path therebetween. Th~s ~t haB generally been ~8sumed that the ac~ive cathode material must never directly contact the anode and, therefore, it ~ppeared ~ that the two functions were mutu~lly exclusi~e. However, ~- it has recently been discovered that certain ~ctive cathode materials, ~uch as the llquid oxyhslldes, do not appreciably react chemically with an ~ctive anode metsl at the inter-face between the metal and the cathode msterial, therebyallowing the cathode material to contact the anode tirectly and act B8 the electrolyte carrier. While the theory behind the cause of the inhibition of direct chemical reaction is not fully understood at the present time and the applicant does not desire to be lim$ted to any theory of ~nvention, it appear8 that direct chemlcal reaction is inhibited either by an inherently high activa-tion energy of reaction or the formation of a thin, pro-tective film on the anode surface. ~Any protective film on the anode ~urface mu6t not be formed to such an excess th~t a large increase ~n ~node polarization results.
Suitable oxyhalides for use in this invention include sulfuryl chloride, thionyl chloride, phosphorus oxychloride, thionyl bromide, chsomyl chloride, vanadyl tribromide and selenium oxychloride.
Useful organic co-solvents for use in this - in~ention inclute the following classes of compounds:
12.
~lS17Z5 Trialkyl borates: e.g., trimethyl borate, (CH30)3B
(liquid range --29.3 to 67C.) Tetraalkyl silicates: e.g., tetramethyl silicate, ~CH30)4Si (boiling point 121C.) Nitroalkanes: e.g., nitromethane, CH3N02 (liquid range -17 to 100.8C.) Alkylnitriles: e.g., acetonitrile, CH3CN
(liquid range -45 to 81.6C.) Dialkylamides: e.g., dimethylformamide, HCON(CH3)2 (liquid range -60.48 to 149C.) Lactams: e.g., N-methylpyrrolidone, CH2-CH2-CH3-CO-N-CH3 (liquid range -16 to 202C.) Tetraalkylureas: e.g., tetramethylurea, (CH3)2N-CO-N(CH3)2 (liquid range -1.2 to 166C.) Monocarboxylic acid esters: e.g., ethyl acetate (liquid range -83.6 to 77.06C.) Orthoesters: e.g., trimethylorthoformate, HC(OCH3)3 (boiling point 103C.) Lactones: e.g.,~-(gamma)butyrolactone, CH2-CH2-CH2-0-CO
(liquid range -42 to 206C.) Dialkyl carbonates: e.g., dimethyl carbonate, ; OC(OCH3)2 (liquid range 2 to 90C.) Alkylene carbonates: e.g., propylene carbonate, CH(CH3)CH2-0-CO-0 (liquid range -48 to 242C.) Monoethers: e.g., diethyl ether (liquid range -116 to 34.5C.) h~ r .
~' - ~S1725 Polyethers: e.g., 1,1- and 1,2-dimethoxyethane (liquid ranges -113.2 to 65.5C. and -58 to 83C., respectively) Cyclic ethers: e.g., tetrahydrofuran (liquid range -65 to 67C.); 1,3-dioxolane (liquid range -95 to 78C.) Nitroaromatics: e.g., nitrobenzene (liquid range 5.7 to 210.8C.) Aromatic carboxylic acid halides: e.g., benzoyl chloride (liquid range 0 to 197C.); benzoyl bromide (liquid range -24 to 218C.) Aromatic sulfonic acid halides: e.g., benzene sulfonyl chloride (liquid range 14.5 to 251C.) Aromatic phosphonic acid dihalides: e.g., benzene phosphonyl dichloride (boiling point 258C.) Aromatic thiphosphonic acid dihalides: e.g., benzene thiophosphonyl dichloride (boiling point 124C. at 5 mm.) Cyclic sulfones: e.g., sulfolane, CH2-cH2-cH2-cH2-so2 (melting poin~ 22 C.)i 3-methylsulfolane (melting point -1C.) Alkyl sulfonic acid halides: e.g., methanesulfonyl chloride (boiling point 161C.) Alkyl carboxylic acid halides: e.g., acetyl chloride (liquid range -112 to 50.9C.); acetyl bromide (liquid range -96 to 76.C.); propionyl chloride (liquid range -94 to 80C.) 14 .
~517Z5 Saturated heterocyclics: e.g., tetrahydrothiophane (liquid range -96 to 121C.); 3-methyl-2-oxa-zolidone (melting point 15.9C.) Dialkyl sulfamic acid halides: e.g., dimethyl sulfamyl chloride (boiling point 8~C., 16 mm.) Alkyl halosulfona~es: e.g., ethyl chlorosulfonate (boiling point 151C.) Unsaturated heterocyclic carboxylic acid halides:
e g., 2-furoylchloride (liquid range -2 to 173C.) 0 Five-membered unsaturated heterocyclics: e.g., 3,5-dimethylisoxazole (boiling point 140C.);
l-methylpyrrole (boiling point 114C.);
2,4-dimethylthiazole (boiling point 144C.);
furan (liquid range -85.65 to 31.36C.) Esters and/or halides of dibasic caroxylic acids:
e.g., ethyl oxalyl chloride (boiling point 135C.) Mixed alkyl sulfonic acid halides and carboxylic ac~d halides: e.g., chlorosulfonyl acetyl chloride (boiling point 98C. at 10 mm.) 0 Dialkyl sulfoxides: e.g., dimethyl sulfoxide (liquid range 18.4 to 189C.) Dialkyl sulfates: e.g., dimethylsulfate (liquid range -31.75 to 188.5C.) Dialkyl sulfites: e.g., dimethylsulfite (boiling point 126C.) Alkylene sulfites: e.g., ethylene gylcol sulfite (liquid range -11 to 173C.) ~ ~51~25 12296 ~alogenatet Alkanes: e.g., methylene chloride (liq~d range -95 to 40C.); 1,3-dichloro-propane (liquid r~nge -99.5 to 120.4C.).
Of the above, the preferred cosolvent~ are nitrobenzene; tetrahydrofuran; 1,3-dioxolane;
furan (liquid range -85.65 to 31.36C.) Esters and/or halides of dibasic caroxylic acids:
e.g., ethyl oxalyl chloride (boiling point 135C.) Mixed alkyl sulfonic acid halides and carboxylic ac~d halides: e.g., chlorosulfonyl acetyl chloride (boiling point 98C. at 10 mm.) 0 Dialkyl sulfoxides: e.g., dimethyl sulfoxide (liquid range 18.4 to 189C.) Dialkyl sulfates: e.g., dimethylsulfate (liquid range -31.75 to 188.5C.) Dialkyl sulfites: e.g., dimethylsulfite (boiling point 126C.) Alkylene sulfites: e.g., ethylene gylcol sulfite (liquid range -11 to 173C.) ~ ~51~25 12296 ~alogenatet Alkanes: e.g., methylene chloride (liq~d range -95 to 40C.); 1,3-dichloro-propane (liquid r~nge -99.5 to 120.4C.).
Of the above, the preferred cosolvent~ are nitrobenzene; tetrahydrofuran; 1,3-dioxolane;
3-methyl-2-oxazolidone; propylene carbonate; ~-butyro-lactone; sulfolane; ethylene glycol sulfite; dimethyl r~ sulfite and benzoyl chloride. Of the preferred r cosolvents, the best are nitro~enzene; 3-methyl-2-oxazolidone; benzoyl chloride; dimethyl sulfite and ethylene glycol sulfite becsuse they are more chemically inert to battery components and have long liquid ranges, and especially beceuse they permi~ highly effic~ent utilizatiGn of the cathode materials.
It i8 8190 within this inve~ ion to employ ~norg~nic solvents such as liquid inorganic halides of Group IV, V or VI elements of the Periodic Table,e.g., ~elenium tetrafluoride (SeF4), selenium monobromide (Se2Br2~, thiophosphoryl chloride (PSC13), thiophos-phoryl brom~de (PSBr3), vanadium pentafluoride (VF5), leat tetrachloride (PbC14), tit~nium tetr~chloride (TiC14), disulfur decafluoride (S2Flo~, tim bromide tr~chloride (SnBr2C13) tin dibromide dlchloride (SnBr2C12), tin tribromide chloride (SnBr3Cl), sulfur monchloride (S2C12) and ~ulfur dichloride (SC12).
These hslides, in addition to functioning as an elec-trolyte ~olvent in nonaqueous cells, will also function - as an active reducible cathode thereby contri~ut~ng to the overall active reducible material in such cells.
16.
~LlS1725 Useful anode materials are generally consumable metals and include aluminum, the alkali metals, alkaline earth metals and alloys of alkali metals or alkaline earth metals with each other and other metals. The term "alloy" as used herein and in the appended claims is intended to include mixtures, solid solutions such as lithium-magnesium, and intermetallic compounds such as lithium monoaluminide. The preferrred anode materials are the alkali metals such as lithium, sodium and potassium, and alakline earth metals such as calcium.
In the preferred embodiment, in selecting the particular oxyhalide for a particular cell in accordance with this invention one should also consider the stability of the particular oxyhalide in the presence of the other cell components and operating temperatures at whi~h the cell 1B expected to perform. Thus an oxyhalide should be selected that will be stable in the presence of the other cell components.
In addition, if it is desiret to render the electrolyte solution more viscous or convert it into a gel, a ~elling agent such as colloidal silica may be added.
The following examples are illustrative of the present invention and are not intended in any manner to be limitative thereof.
Drawin~s Figure 1 is a plot of voltage vs. time for the four cells described in Example 1.
17.
~5~725 Four nonaqueous cells were constructed employing about 2 grams of a lithium anode; a c~rbonaceous cathode c~llector made of the ingredients shown in Table 1; 8 non~oven glass fiber mat separator disposed between the anode and the cathode collector;
and 12cc of a liquid cathode-electrolyte solution of LiAlC14 (1.63 molar Al) in S02C12 or SOC12. Each cell was discharged across a 20-ohm load and the plot of voltage versus time for each cell is shown in Figure l.
As evident from the data shown in Figure 1, the cells employing the cathode collectors with the metal oxide kaolin (A1203 ' 2SiO2~ performed significsntly better than the cells employing the c~thode collectors without the metal oxide kaolin.
~ TABLE 1 Cell SamPle Cathode Collector Liquid Cathode 1 85% Carbon black + S2C12 15% A1203 2SiO2 2 ~5% C~rbon black I
15% A1203 ' 2SiO2 SOC12 3 85% Carbon black + S2C12 15% Teflon*
It i8 8190 within this inve~ ion to employ ~norg~nic solvents such as liquid inorganic halides of Group IV, V or VI elements of the Periodic Table,e.g., ~elenium tetrafluoride (SeF4), selenium monobromide (Se2Br2~, thiophosphoryl chloride (PSC13), thiophos-phoryl brom~de (PSBr3), vanadium pentafluoride (VF5), leat tetrachloride (PbC14), tit~nium tetr~chloride (TiC14), disulfur decafluoride (S2Flo~, tim bromide tr~chloride (SnBr2C13) tin dibromide dlchloride (SnBr2C12), tin tribromide chloride (SnBr3Cl), sulfur monchloride (S2C12) and ~ulfur dichloride (SC12).
These hslides, in addition to functioning as an elec-trolyte ~olvent in nonaqueous cells, will also function - as an active reducible cathode thereby contri~ut~ng to the overall active reducible material in such cells.
16.
~LlS1725 Useful anode materials are generally consumable metals and include aluminum, the alkali metals, alkaline earth metals and alloys of alkali metals or alkaline earth metals with each other and other metals. The term "alloy" as used herein and in the appended claims is intended to include mixtures, solid solutions such as lithium-magnesium, and intermetallic compounds such as lithium monoaluminide. The preferrred anode materials are the alkali metals such as lithium, sodium and potassium, and alakline earth metals such as calcium.
In the preferred embodiment, in selecting the particular oxyhalide for a particular cell in accordance with this invention one should also consider the stability of the particular oxyhalide in the presence of the other cell components and operating temperatures at whi~h the cell 1B expected to perform. Thus an oxyhalide should be selected that will be stable in the presence of the other cell components.
In addition, if it is desiret to render the electrolyte solution more viscous or convert it into a gel, a ~elling agent such as colloidal silica may be added.
The following examples are illustrative of the present invention and are not intended in any manner to be limitative thereof.
Drawin~s Figure 1 is a plot of voltage vs. time for the four cells described in Example 1.
17.
~5~725 Four nonaqueous cells were constructed employing about 2 grams of a lithium anode; a c~rbonaceous cathode c~llector made of the ingredients shown in Table 1; 8 non~oven glass fiber mat separator disposed between the anode and the cathode collector;
and 12cc of a liquid cathode-electrolyte solution of LiAlC14 (1.63 molar Al) in S02C12 or SOC12. Each cell was discharged across a 20-ohm load and the plot of voltage versus time for each cell is shown in Figure l.
As evident from the data shown in Figure 1, the cells employing the cathode collectors with the metal oxide kaolin (A1203 ' 2SiO2~ performed significsntly better than the cells employing the c~thode collectors without the metal oxide kaolin.
~ TABLE 1 Cell SamPle Cathode Collector Liquid Cathode 1 85% Carbon black + S2C12 15% A1203 2SiO2 2 ~5% C~rbon black I
15% A1203 ' 2SiO2 SOC12 3 85% Carbon black + S2C12 15% Teflon*
4 85V/o Carbon black +
15% Teflon SOC12 * Trademark for polytetrafluoroethylene ~5172S
EXAM~LE 2 Each of four button cells were constructed employing 0.0279 gram of lithium anode; a cathode ; collector as shown in Table 2; a nonwoven glass fiber mat separator in contact with the lithium anode; and a cathode-electrolyte of lM LiAlC14 in SO2C12. The lithium anode of each cell was coated with a vinyl polymer film as disclosed in U. S. Patent 3,993,501.
Cell -------Cathode Collec~r----- Cathode-Electrolyte Sample Carbon Black Teflon A12 3 cc 1 55% 15% 30% 0.150 cc 2 65% 15% 20% 0. 160 cc 3 75% 15% 10% 0. 160 cc 4 85% 15% --- 0.150 cc Each cell was tested across a continous 150-kilohm background load with 300-ohm loat pulses at intervals of 2 seconds per day for 5 days a week. The pulse voltage readings taken at various time periods for each cell are shown in Table 3. The control cell (sample 4) that did not contain any A12O3 in the cathode collector dropped to zero volt when tested with the 300-ohm load pulses while the A12O3-containing cathode collector cells operated above 2.5 volts for several days.
19 .
~ ~5~725 12296 TA~LE 3.
Cell Samples l 2 - 3 Time ~oltage Voltage ~ol~agP
CdaYs~ C~olts) (volts~ (volts) 1 2.9 2.9 2.8 2 2.85 2.8 2.~
2.6 2.5 ` 2.3 7 2.~5 2.2 2.25 9 2.1 2.0 2.0 13 1.9 2.0 1.8 1.6 1.6 1.4 19 1.2 1./l 1.1 21 1.0 1.3 1.1 26 0.8 1.2 0.9 - 28 0.9 1.2 0.8 0.6 0.9 0.5 37 0.7 1.0 0.5 20.
Each cell in three additional cell lots was constructed as in Example 2 using 0.0279 gram of lithium anode; a cathode collector as shown in Table 4; a nonwoven glass fiber separator in contact with the lithium anode; and a 0.145 cc of a cathode electrolyte of lM LiAlC14 in SO2C12. Each cell lot consisted of three cells.
Cell Sample -------Cathode Collect~
Lot Carbon Black Teflon A12O~*
1 85% 15~
2 75% 15% 10%
3 70% 15% 15%
99~9% pure A12O3 Each cell ln the cell lots was continuously discharged across a 150-kilohm load background with either a 300-ohm, 60-ohm, or l-kilohm pulse load for two seconds per day for five days a week. The pulse voltage vs. time data obtained are shown on Table 5.
As evidenced from the data, the presence of the A12O3 increased the pulse-carrying capabilities of the cells, except for the unexplained performance of test sample lot 2 (10% A12O3) on the l-kilohm pulse test.
~ ~5~72S
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Six cells were constructed using 0.0279 gram of lithium, various concentrations of LiAlC14 in S02C12 along with the other components shown in Table 6. Each cell was continuously discharged across a 150-kilohm load background with a l-kilohm pulse load test for two seconds during various time periods. The data observed showed that the presence of the metal oxide A1203 improved the pulse voltages at the l.OM and 1.3M electrolyte levels that were previously below that observed with 1.5M concentrations.
Thus, greater variation in electrolyte concentrations can be permitted in the presence of the metal oxide catalyst without jeopardizing pulse performance.
------Cathode Mi~-------- Electrolyte Cell SampleCarbon Teflon M Al 03 Conc.tM) (g) (%) (~) 1 0.045 15% --- 1.0 2 0.045 15% --- 1.3 3 0.045 15% ___ 1.5 4 0.045 15~ 15% 1.0 0.047 15% 15% 1.3 6 0.047 15% 15% 1.5 ;
.
23.
~ 1 5~ 7 2 5 12296 xamPle 5 Scver-l lots of three cells were constructed u~ing lithium node, a cathote-electrolyte of lM LlAlC14 in S02C12 nd cathode collector of 0 65 g carbon nd 10 perce~t Teflon, Tn some ,ots, the cathote collector also containet 10 ~ A1203 Each cell was t~scharged Jcross varlous loads to a 2 7-volt cutoff The dat-ver ge~ ob~crved and calculated for e ch lot of 3 eell6 re ~hown ~n T ble 7.
Table 7 Lo~d Te~t Lot Without ~1203 Test Lot with A1203 kmpere Watt Hr~ per Ampere Watt Hrs per HoursCublc Inch ~ours Cubic Inch 35 ohms 0 68 7 1 1 15 11 8 75 ohms 1 31 14 1 1 31 14 8 2S0 ohm~ 1 24 15 0 1 23 14 6 S00 ohms 1 27 16 0 1 28 16 2 The ~-t- show that the catalyst adtition pro-duc-d c~ th-t had a cubstantially higher output on high dr-~n conditions Several cells were produced using a lithium anode, a c-thode-electrolyte of IM LiAlCl in S02C12 TM
nd c-thode collector o$ car~on and Te$10n Some of the cclls had 10% by weight nickel oxide added to the cathode collcctor The cells were d~scharged across various loads and the voltag~ observed re reportet in T~ble 8 ~6 evident from the data, the greatest i~proYe-ment was observed at the higher current drains 24.
~ o ~
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~1517Z5 12296 While the present invention has been described with reference to many particular details thereof, it is not intended that these details should be construed as limiting the scope of the invention.
26.
;,
15% Teflon SOC12 * Trademark for polytetrafluoroethylene ~5172S
EXAM~LE 2 Each of four button cells were constructed employing 0.0279 gram of lithium anode; a cathode ; collector as shown in Table 2; a nonwoven glass fiber mat separator in contact with the lithium anode; and a cathode-electrolyte of lM LiAlC14 in SO2C12. The lithium anode of each cell was coated with a vinyl polymer film as disclosed in U. S. Patent 3,993,501.
Cell -------Cathode Collec~r----- Cathode-Electrolyte Sample Carbon Black Teflon A12 3 cc 1 55% 15% 30% 0.150 cc 2 65% 15% 20% 0. 160 cc 3 75% 15% 10% 0. 160 cc 4 85% 15% --- 0.150 cc Each cell was tested across a continous 150-kilohm background load with 300-ohm loat pulses at intervals of 2 seconds per day for 5 days a week. The pulse voltage readings taken at various time periods for each cell are shown in Table 3. The control cell (sample 4) that did not contain any A12O3 in the cathode collector dropped to zero volt when tested with the 300-ohm load pulses while the A12O3-containing cathode collector cells operated above 2.5 volts for several days.
19 .
~ ~5~725 12296 TA~LE 3.
Cell Samples l 2 - 3 Time ~oltage Voltage ~ol~agP
CdaYs~ C~olts) (volts~ (volts) 1 2.9 2.9 2.8 2 2.85 2.8 2.~
2.6 2.5 ` 2.3 7 2.~5 2.2 2.25 9 2.1 2.0 2.0 13 1.9 2.0 1.8 1.6 1.6 1.4 19 1.2 1./l 1.1 21 1.0 1.3 1.1 26 0.8 1.2 0.9 - 28 0.9 1.2 0.8 0.6 0.9 0.5 37 0.7 1.0 0.5 20.
Each cell in three additional cell lots was constructed as in Example 2 using 0.0279 gram of lithium anode; a cathode collector as shown in Table 4; a nonwoven glass fiber separator in contact with the lithium anode; and a 0.145 cc of a cathode electrolyte of lM LiAlC14 in SO2C12. Each cell lot consisted of three cells.
Cell Sample -------Cathode Collect~
Lot Carbon Black Teflon A12O~*
1 85% 15~
2 75% 15% 10%
3 70% 15% 15%
99~9% pure A12O3 Each cell ln the cell lots was continuously discharged across a 150-kilohm load background with either a 300-ohm, 60-ohm, or l-kilohm pulse load for two seconds per day for five days a week. The pulse voltage vs. time data obtained are shown on Table 5.
As evidenced from the data, the presence of the A12O3 increased the pulse-carrying capabilities of the cells, except for the unexplained performance of test sample lot 2 (10% A12O3) on the l-kilohm pulse test.
~ ~5~72S
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~1 ~iIII~IIIIIII
_l ,...............
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~lSl'7ZS
Six cells were constructed using 0.0279 gram of lithium, various concentrations of LiAlC14 in S02C12 along with the other components shown in Table 6. Each cell was continuously discharged across a 150-kilohm load background with a l-kilohm pulse load test for two seconds during various time periods. The data observed showed that the presence of the metal oxide A1203 improved the pulse voltages at the l.OM and 1.3M electrolyte levels that were previously below that observed with 1.5M concentrations.
Thus, greater variation in electrolyte concentrations can be permitted in the presence of the metal oxide catalyst without jeopardizing pulse performance.
------Cathode Mi~-------- Electrolyte Cell SampleCarbon Teflon M Al 03 Conc.tM) (g) (%) (~) 1 0.045 15% --- 1.0 2 0.045 15% --- 1.3 3 0.045 15% ___ 1.5 4 0.045 15~ 15% 1.0 0.047 15% 15% 1.3 6 0.047 15% 15% 1.5 ;
.
23.
~ 1 5~ 7 2 5 12296 xamPle 5 Scver-l lots of three cells were constructed u~ing lithium node, a cathote-electrolyte of lM LlAlC14 in S02C12 nd cathode collector of 0 65 g carbon nd 10 perce~t Teflon, Tn some ,ots, the cathote collector also containet 10 ~ A1203 Each cell was t~scharged Jcross varlous loads to a 2 7-volt cutoff The dat-ver ge~ ob~crved and calculated for e ch lot of 3 eell6 re ~hown ~n T ble 7.
Table 7 Lo~d Te~t Lot Without ~1203 Test Lot with A1203 kmpere Watt Hr~ per Ampere Watt Hrs per HoursCublc Inch ~ours Cubic Inch 35 ohms 0 68 7 1 1 15 11 8 75 ohms 1 31 14 1 1 31 14 8 2S0 ohm~ 1 24 15 0 1 23 14 6 S00 ohms 1 27 16 0 1 28 16 2 The ~-t- show that the catalyst adtition pro-duc-d c~ th-t had a cubstantially higher output on high dr-~n conditions Several cells were produced using a lithium anode, a c-thode-electrolyte of IM LiAlCl in S02C12 TM
nd c-thode collector o$ car~on and Te$10n Some of the cclls had 10% by weight nickel oxide added to the cathode collcctor The cells were d~scharged across various loads and the voltag~ observed re reportet in T~ble 8 ~6 evident from the data, the greatest i~proYe-ment was observed at the higher current drains 24.
~ o ~
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~1517Z5 12296 While the present invention has been described with reference to many particular details thereof, it is not intended that these details should be construed as limiting the scope of the invention.
26.
;,
Claims (13)
1. A nonaqueous cell comprising an active metal anode, an ionically conductive cathode-electrolyte solution containing a solute dissolved in a liquid active cathode and a porous carbonaceous cathode collector containing at least one metal oxide.
2. The nonaqueous cell of claim 1 wherein the metal oxide in the cathode collector ranges from about 1 to about 30 percent by weight based on the weight of the carbonaceous material in the cathode collector.
3. The nonaqueous cell of claim 2 wherein the metal oxide in the cathode collector ranges from about 5 to about 20 percent by weight based on the weight of the carbonaceous material in the cathode collector.
4. The nonaqueous cell of claim 2 wherein the metal oxide is selected from the group consisting of aluminum oxide, kaolin, and nickel oxide.
5. The nonaqueous cell of claims 1, 2 or 3 wherein the metal oxide is aluminum oxide.
6. The nonaqueous cell of claim 1 wherein the cathode-electrolyte contains at least one liquid oxyhalide selected from the group consisting of thionyl chloride, sulfuryl chloride, phosphorous oxychloride, thionyle bromide,chromyl chloride, vanadyl tribromide and 27.
selenium oxychloride.
selenium oxychloride.
7. The nonaqueous cell of claims 1 or 2 wherein the at least one liquid oxyhalide is selected from the group consisting of thionyl chloride and sulfuryl chloride.
8. The nonaqueous cell of claims 1 or 6 wherein the anode is selected from the group consisting of lithium, sodium, calcium, potassium and aluminum.
9. The nonaqueous cell of claims 1 or 6 wherein the cathode-electrolyte contains an inorganic cosolvent.
10. The nonaqueous cell of claims 1 or 6 wherein the cathode-electrolyte contains an organic cosolvent.
11. The nonaqueous cell of claims 2, 3, or 4 wherein the anode is lithium and the liquid oxyhalide is thionyl chloride.
12. The nonaqueous cell of claims 2, 3 or 4 wherein the anode is lithium and the liquid oxyhalide is sulfuryl chloride.
13. The nonaqueous cell of claims 3 or 4 werein the solute is a complex salt of a Lewis acid and an inorganic ionizable salt.
28.
28.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/052,845 US4367266A (en) | 1979-06-28 | 1979-06-28 | Cathode collectors for nonaqueous cell having a metal oxide catalyst |
| US052,845 | 1979-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1151725A true CA1151725A (en) | 1983-08-09 |
Family
ID=21980270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000354570A Expired CA1151725A (en) | 1979-06-28 | 1980-06-23 | Cathode collectors for nonaqueous cell having a metal oxide catalyst |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US4367266A (en) |
| EP (1) | EP0021427B1 (en) |
| JP (1) | JPS567361A (en) |
| AU (1) | AU538302B2 (en) |
| BR (1) | BR8003985A (en) |
| CA (1) | CA1151725A (en) |
| DE (1) | DE3069410D1 (en) |
| DK (1) | DK280980A (en) |
| ES (1) | ES492816A0 (en) |
| HK (1) | HK29685A (en) |
| IL (1) | IL60386A (en) |
| IN (1) | IN154393B (en) |
| NO (1) | NO150938C (en) |
| SG (1) | SG5585G (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4264687A (en) * | 1979-09-24 | 1981-04-28 | Duracell International Inc. | Fluid depolarized cell |
| US4461814A (en) * | 1982-02-08 | 1984-07-24 | Gte Laboratories Incorporated | Electrochemical cell |
| JPH0636376B2 (en) * | 1982-08-09 | 1994-05-11 | 東洋紡績株式会社 | Metal-halogen secondary battery |
| US4540641A (en) * | 1983-07-18 | 1985-09-10 | Gte Communications Products Corporation | Electrochemical cell |
| US4543305A (en) * | 1983-10-24 | 1985-09-24 | The United States Of America As Represented By The Secretary Of The Army | Method of pretreating carbon black powder to improve cathode performance and lithium sulfuryl chloride cell including the pretreated carbon black powder |
| US4808497A (en) * | 1983-12-28 | 1989-02-28 | Eveready Battery Company | Organic electrolyte for nonaqueous cells |
| EP0296589B1 (en) * | 1987-06-24 | 1993-09-01 | Hitachi Maxell Ltd. | Non-aqueous electrochemical cell |
| US4968393A (en) * | 1988-04-18 | 1990-11-06 | A. L. Sandpiper Corporation | Membrane divided aqueous-nonaqueous system for electrochemical cells |
| JP3077218B2 (en) * | 1991-03-13 | 2000-08-14 | ソニー株式会社 | Non-aqueous electrolyte secondary battery |
| JP3921768B2 (en) * | 1997-12-22 | 2007-05-30 | ソニー株式会社 | Non-aqueous electrolyte secondary battery |
| US8067108B1 (en) | 2007-02-14 | 2011-11-29 | Electrochem Solutions, Inc. | Hybrid battery for use over extended temperature range |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL76387C (en) * | 1949-03-24 | |||
| FR1527783A (en) * | 1966-12-30 | 1968-06-07 | Accumulateurs Fixes | Process for preparing an ionized nonaqueous electrolyte, in particular for primary electrochemical generators and electrolytes and generators thus obtained |
| US3578500A (en) * | 1968-07-08 | 1971-05-11 | American Cyanamid Co | Nonaqueous electro-chemical current producing cell having soluble cathode depolarizer |
| US3644145A (en) * | 1969-10-02 | 1972-02-22 | American Cyanamid Co | Incorporation of valve metals into current-producing cell constructions |
| DE2263115C2 (en) * | 1971-12-27 | 1982-04-22 | Gte Laboratories Inc., Wilmington, Del. | Galvanic cell |
| US3926669A (en) * | 1972-11-13 | 1975-12-16 | Gte Laboratories Inc | Electrochemical cells having an electrolytic solution comprising a covalent inorganic oxyhalide solvent |
| FR2220883A1 (en) * | 1973-03-09 | 1974-10-04 | Mallory & Co Inc P R | Galvanic cell - contg negative active-metal electrode and positive electrode depolarised with nitrogen dioxide |
| US3964933A (en) * | 1974-04-08 | 1976-06-22 | Exxon Research And Engineering Company | Carbon article including electrodes and methods of making the same |
| US3925098A (en) * | 1974-11-27 | 1975-12-09 | Electric Power Res Inst | Positive electrode for electrical energy storage device |
| US4020248A (en) * | 1975-09-18 | 1977-04-26 | Gte Laboratories Incorporated | Primary electrochemical cell capable of high discharge rates |
| US4118334A (en) * | 1975-09-18 | 1978-10-03 | Gte Laboratories Incorporated | Primary electrochemical cell |
| US4048389A (en) * | 1976-02-18 | 1977-09-13 | Union Carbide Corporation | Cathode or cathode collector arcuate bodies for use in various cell systems |
| US4154902A (en) * | 1976-09-13 | 1979-05-15 | American Energizer Corporation | Electric battery cell, system and method |
| JPS5559667A (en) * | 1978-08-29 | 1980-05-06 | Binsento Oouen Kaatanzaraito | Adder to lithium cathode and chionyl chloride active positive electrode battery |
| US4219443A (en) * | 1978-12-20 | 1980-08-26 | Gte Laboratories Incorporated | Method of preparing a cathode current collector for use in an electrochemical cell |
-
1979
- 1979-06-28 US US06/052,845 patent/US4367266A/en not_active Expired - Lifetime
-
1980
- 1980-06-16 IN IN442/DEL/80A patent/IN154393B/en unknown
- 1980-06-20 NO NO801870A patent/NO150938C/en unknown
- 1980-06-23 CA CA000354570A patent/CA1151725A/en not_active Expired
- 1980-06-24 IL IL60386A patent/IL60386A/en unknown
- 1980-06-26 BR BR8003985A patent/BR8003985A/en unknown
- 1980-06-26 ES ES492816A patent/ES492816A0/en active Granted
- 1980-06-26 EP EP80103608A patent/EP0021427B1/en not_active Expired
- 1980-06-26 DE DE8080103608T patent/DE3069410D1/en not_active Expired
- 1980-06-27 JP JP8768380A patent/JPS567361A/en active Pending
- 1980-06-27 DK DK280980A patent/DK280980A/en not_active Application Discontinuation
- 1980-06-27 AU AU59721/80A patent/AU538302B2/en not_active Ceased
-
1985
- 1985-01-22 SG SG55/85A patent/SG5585G/en unknown
- 1985-04-11 HK HK296/85A patent/HK29685A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS567361A (en) | 1981-01-26 |
| NO801870L (en) | 1980-12-29 |
| EP0021427A2 (en) | 1981-01-07 |
| EP0021427B1 (en) | 1984-10-10 |
| ES8102690A1 (en) | 1981-01-16 |
| IN154393B (en) | 1984-10-20 |
| EP0021427A3 (en) | 1981-03-25 |
| NO150938C (en) | 1985-01-16 |
| IL60386A0 (en) | 1980-09-16 |
| BR8003985A (en) | 1981-01-13 |
| HK29685A (en) | 1985-04-19 |
| DK280980A (en) | 1980-12-29 |
| IL60386A (en) | 1983-07-31 |
| SG5585G (en) | 1985-06-14 |
| DE3069410D1 (en) | 1984-11-15 |
| ES492816A0 (en) | 1981-01-16 |
| NO150938B (en) | 1984-10-01 |
| US4367266A (en) | 1983-01-04 |
| AU5972180A (en) | 1981-01-08 |
| AU538302B2 (en) | 1984-08-09 |
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