IE49844B1 - Non-aqueous cells employing heat-treated manganese dioxide cathodes - Google Patents
Non-aqueous cells employing heat-treated manganese dioxide cathodesInfo
- Publication number
- IE49844B1 IE49844B1 IE1312/80A IE131280A IE49844B1 IE 49844 B1 IE49844 B1 IE 49844B1 IE 1312/80 A IE1312/80 A IE 1312/80A IE 131280 A IE131280 A IE 131280A IE 49844 B1 IE49844 B1 IE 49844B1
- Authority
- IE
- Ireland
- Prior art keywords
- cell
- manganese dioxide
- nonaqueous cell
- electrolyte
- lithium
- Prior art date
Links
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000006184 cosolvent Substances 0.000 claims abstract description 8
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims description 30
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 239000011734 sodium Chemical group 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- -1 polytetrafluorethylene Polymers 0.000 claims description 4
- 239000011591 potassium Chemical group 0.000 claims description 4
- 229910052700 potassium Chemical group 0.000 claims description 4
- AKUSZFPCJFNRSZ-UHFFFAOYSA-N 3,4-dimethyl-1,2-oxazole Chemical compound CC1=CON=C1C AKUSZFPCJFNRSZ-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 claims description 3
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 claims description 3
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FZKPQHFEMFIDNR-UHFFFAOYSA-N 2-hydroxyethyl hydrogen sulfite Chemical compound OCCOS(O)=O FZKPQHFEMFIDNR-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Chemical group 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 210000004027 cell Anatomy 0.000 description 64
- 239000000203 mixture Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- 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
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- 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
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
A nonaqueous cell comprising an active metal anode such as lithium, a manganese dioxide-containing cathode which contains less than 1 weight percent water in the manganese dioxide and a liquid organic electrolyte comprising 3-methyl- 2-oxazolidone in conjunction with a selected solute and optionally a cosolvent having a viscosity lower than that of the 3-methyl-2- oxazolidone.
Description
The development of high energy battery systems requires the compatibility of an electrolyte possessing desirable electrochemical properties with highly reactive anode materials, such as lithium, sodium, and the like, and the efficient use of high energy density cathode materials, such as manganese dioxide. 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 high energy density obtainable through use of these highly reactive anodes and high energy density cathodes, to turn to the Investigation of nonaqueous electrolyte systems and more particularly to nonaqueous organic electrolyte systems.
The term nonaqueous organic electrolyte in the prior art refers to an electrolyte which is composed of a solute, for example, a salt or complex salt of Group I-A, Group II-A or Group III-A elements of the Periodic Table, dissolved in an appropriate nonaqueous organic solvent. Conventional solvents include propylene carbonate, ethylene carbonate or γ-butyrolactone. The term Periodic Table as used herein refers to the Periodic Table of the 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 solutes is known and recommended for use but the selection of a suitable solvent has been particularly troublesome since many of those solvents which are used to prepare electrolytes sufficiently conductive to permit effective ion migration through the solution are reactive with the highly active anodes mentioned above. Most investigators in this area, in search of suitable solvents, have concentrated on aliphatic and aromatic nitrogen- and oxygen-containing compounds with some attention given to organic sulfur-, phosphorus- and arsenic5 containing compounds. The results of this search have not been entirely satisfactory since many of the solvents Investigated still could not be used effectively with high energy density cathode materials, such as manganese dioxide (MnOg), and were sufficiently corrosive to lithium anodes to prevent efficient performance over any length of time.
Although manganese dioxide has been mentioned as a possible cathode for cell applications, manganese dioxide inherently contains an unacceptable amount of water, both of the absorbed and bound (adsorbed) types, which is sufficient to cause anode (lithium) corrosion along with its associated hydrogen evolution. This type of corrosion that causes gas evolution is a serious problem in sealed cells, particularly in miniature type button cells. In order to maintain overall battery-powered electronic devices as compact as possible, the electronic devices are usually designed with cavities to accommodate the miniature cells as their power source. The cavities are usually made so that a cell can be snugly positioned therein thus making electronic contact with appropriate terminals within the device. A major potential problem in the use of cell-powered devices of this nature is that if the gas evolution causes the cell to bulge then the cell could become wedged within the cavity.
This could result in damage to the device. Also, if electrolyte leaks from the cell it could cause damage to the device. Thus it is important that the physical dimensions of the cell's housing remain constant during discharge and that the cell with not leak any electrolyte into the device /
being powered.
U.S. Patent No. 4 133 856 discloses a process for producing a MnO? electrode (cathode) for nonaqueous cells whereby the Mn02 is initially heated within a range of 350° to 430°C so as to substantially remove both the absorbed and bound water and then, after being formed into an electrode with a conductive agent and bonder, it is further heated in a range of 200° to 350°C prior to its assembly into a cell. British Patent No. 1 199 426 also discloses the heat treatment of Mn02 in air at 250° to 450°C to substantially remove its water component.
U.S. Patents Nos. 3 871 916; 3 951 685 and 3 999 069 disclose a nonaqueous cell employing a 3-methyl-2-oxazolidone-based electrolyte in conjunction with a solid cathode selected from (CFx)n» CuO, FeS2,
Co^O^, ^2θ5’ Pb^O^, In2$3 CoS2·
While the theoretical energy, i.e., the electical energy potentially available from a selected anode-cathode couple, is relatively easy to calculate, there is a need to choose a nonaqueous electrolyte for a couple that permits the actual energy produced by an assembled battery to approach the theoretical energy. The problem usually encountered it that it is practically impossible to predict in advance how well, if at all, a nonaqueous electrolyte will function with a selected couple. Thus a cell must be considered as a unit having three parts: a cathode, an anode, and an electrolyte, and it is to be understood that the parts of one cell are not predictably interchangeable with parts of another cell to produce an efficient and workable cell.
It is al) object of the present invention to provide a manganese dioxide nonaqueous cell employing an active metal anode.
The invention provides a novel high energy density nonaqueous cell comprising a highly active metal anode, a manganese dioxide-containing cathode and a liquid organic electrolyte comprising 3-methyl-2oxazolidone together with a conductive solute with or without at least one cosolvent having a viscosity lower than that of 3-methyl-2-oxazolidone and wherein the manganese dioxide has a water content of less than 1 weight percent based on the weight of the manganese dioxide. Preferably the water content should be lower than 0.5 weight percent and most preferably below 0.2 weight percent.
The water inherently contained in both electrolytic and chemical types of manganese dioxide can be substantially removed by various treatments. For example, the manganese dioxide can be heated in air or an inert atmosphere at a temperature of 350°C for about 8 hours or at a lower temperature for a longer period of time. Care should be taken to avoid heating the manganese dioxide above its decomposition temperature which is about 400°C in air. In oxygen atmosphere, higher temperatures may be employed. To make it suitable for use in the cell of this invention the manganese dioxide should be heated for a sufficient period of time to ensure that the water content is reduced below 1 weight percent, preferably below about 0.5 and most preferably below about 0.2 weight percent based on the weight of the manganese dioxide. An amount of water above about 1 weight percent would react with the highly active metal anode, such as lithium, and cause it to corrode thereby resulting in hydrogen evolution. As stated above this could result in physical dis25 tortion of the cell and/or electrolyte leakige from the cell during storage or discharge.
— « a ο ί* <*
To effectively remove the undesirable water from Mni^, or MnOg mixed with a conductive agent and a suitable binder, to the level necessary to practice this invention, it is believed necessary that both the absorbed and bound water be substantially removed. After the water removal treatment has been completed, it is essential that the manganese dioxide be shielded to prevent absorption of water from the atmosphere. This could be accomplished by handling the treated manganese dioxide in a dry box or the like. Alternatively, the treated manganese dioxide or the manganese dioxide combined with a conductive agent and a suitable binder could be heat treated to remove water that could have been absorbed from the atmosphere.
Preferably, the manganese dioxide should be heat treated to remove its water content to below 1 weight percent and then it can be mixed with a conductive agent such as a graphite, or carbon and a binder such as
Teflon (trade mark for polytetrafluoroethylene) or ethylene acrylic acid polymer to produce a solid cathode electrode. If desired, a small amount of electrolyte can be incorporated into the manganese dioxide mix.
An added possible benefit in the removal of substantially all the water from manganese dioxide is that if small amounts of water are present in the cell's electrolyte then the manganese dioxide will absorb the main portion of that water from the electrolyte and thereby prevent or substantially delay the reaction of the water with the anode such as lithium. In this situation, the manganese dioxide will act as an extracting agent for the water impurities in the organic solvents.
The electrolyte for use in this invention is a 3-methyl-2oxazolidone-based electrolyte. Liquid organic 3-methyl-2-oxazolidone material, (3Me20X)
9 0 4
Γ-1 ch2-ch2-o-co-n-ch3, is an excellent nonaqueous solvent because of its high dielectric constant, chemical inertness to battery components, wide liquid range and low toxicity.
However, it has been found that when metal salts are dissolved in liquid 3Me20x for the purpose of improving the conductivity of 3Me20x, the viscosity of the solution may be too high for its efficient use as an electrolyte for some nonaqueous cell applications other than those requiring very low current drains. Thus, in some applications in accordance with this invention, the addition of a low viscosity cosolvent would be desirable if 3Me20x is to be used as an electrolyte for nonaqueous cells which can operate or perform at a high energy density level. Specifically, in order to obtain a high energy density level in accordance with this invention, it is essential to use a heat-treated MnO2 cathode along with a highly active metal anode. Thus this invention is directed to a novel high energy density cell having a highly active metal anode, such as lithium, a heat-treated MnO2 cathode, and an electrolyte comprising 3Me20x in combination with a conductive solute with or without at least one low viscosity cosolvent.
The low viscosity cosolvents if used in this invention include tetrahydrofuran (THF), dioxolane (DIOX), dimethoxyethane (DME), propylene carbonate (PC), dimethyl isoxazole (DM1), diethyl carbonate (DEC), ethylene glycol sulfite (ESS), dioxane and dimethyl sulfite (DMS). Dimethoxyethane (DME), dioxolane (DIOX) and propylene carbonate (PC) are preferred cosolvents because of their compatibility with metal salts dissolved in liquid 3Me20x and their chemical inertness to cell components. Specifically, the total amount of the low viscosity cosolvent added could be between about 20% and about 80% based on total solvent volume, i.e. exclusive of solute, so as to lower the viscosity to a level suitable for use in a high drain cell.
Conductive solutes (metal salts) for use in this invention with the liquid 3M620x may be selected from MCF^SO^, MBF^, MCTO^, and
MM'F- wherein M is lithium, sodium or potassium, and M‘ is phosphorus, 0 arsenic or antimony. The addition of the solute is necessary to improve 10 conductivity of 3Me20x so that said 3Me20x can be used as the electrolyte in nonaqueous cell applications. Thus the particular salt selected has to be compatible and nonreactive with 2Me20x and the electrodes of the cell. The amount of solute to be dissolved in the liquid 3Me20x should be sufficient to provide good conductivity,
e.g. at least 10-4 ohm'^cm1. Generally an amount of at least 0.5 molar would be sufficient for most cell applications.
Highly active metal anodes suitable for this invention include • lithium (Li), potassium (K), sodium (Na), calcium (Ca), magnesium (Mg), aluminium (Al), and their alloys. Of these active metals, lithium would be preferred because in addition to being a ductile, soft metal that can easily be assembled in a cell, it possesses the highest energy-to-weight ratio of the group of suitable anode metals.
The present invention of a high energy density cell with a
3-Me20x-based electrolyte, a solid MnOg-containing cathode having less than 1 weight percent water and a highly active metal anode will be further illustrated in the following examples.
EXAMPLE 1 «»β«4
Thermogravimetric analyses (TGA) were made of various samples of coimiercial manganese dioxide. Some of the samples were analyzed as obtained, other samples were heat treated at 350°C for 8 hours, and other samples were heated treated at 350°C for 8 hours and then blended with carbon and Teflon to produce cathode mixes. The data obtained from the thermogravimetric analyses (TGA) are shown in Table 1. The data clearly show that commercial types of manganese dioxide contain large amounts of water. In addition, the data show that even after the manganese dioxide had been heat treated as specified above, it will absorb water from the atmosphere even after only a small period of time.
* ·* «ρ ·* νι
EXAMPLE II
Each of two falt-type cells was constructed utilizing a nickel metal base having therein a shallow depression into which the cell contents were placed and over which a nickel metal cap was placed to close the cell.
The contents of each sample cell consisted of 1.0 inch (2.54 cm) diameter lithium discs consisting of five sheets of lithium foil having a total thickness of 0.10 inch (0.254 cm), about 4 ml of an electrolyte consisting of about 40 vol. % dioxolane, about 30 vol.2 dimethoxyethane (DME), about 30 vol.2 3Me20x plus about 0.12 dimethelisoxazole (DM1) and containing IM LiCF-jSO-j, a 1.0 inch (2.54 cm) diameter porous nonwoven polypropylene separator having a thickness of 0.01 inch (0.0254 cm) which absorbed some of the electrolyte and two grams of cathode mix compressed to form a cathode having an apparent interfacial area of 5 square centimeters. In the first cell the cathode mix consisted of Tekkosh.a electrolytic Mn02 heat treated at 35O°C for 20 hours, carbon black, and Teflon. The second cell employed the same type of components as in the first cell except that the Tekkosha Mn02 was untreated. Each cell was discharged across a 1200-ohm load to a 1-volt cutoff and the cathode efficiences assuming a 1-electron reaction were calculated along with the overall energy densities.
The data obtained are shown in Table II.
TABLE II
Cathode Efficiency* 1-electron Density (Wh/in3) Cathode Energy (J/cm3) Heat Treated Mn02 81.02 72.8 15,993.1 Unheated Mn02 48.22 35.2 7,732.9
*Coulombic
49S44
EXAMPLE III
Ten miniature button cells were constructed using a lithium anode, an electrolyte consisting of about 40 vol.% dioxolane, about 30 vol.%
DME, about 30 vol.%.3Me20x plus about 0.1% DM1 and containing 1 M LiCF-jSOg, and a cathode containing 80 wt.% unheated or heat-treated Mn02, 1.5 wt.% carbon black, 13.5 wt.% graphite and 5.0 wt.% ethylene acrylic acid binder. The heat-treated Mn02 was heated at a temperature of 350°C for 18 hours under an argon atmosphere. Each cell (0.452 inch (1.148 cm) diameter; 0.166 inch (0.422 cm) height) contained 0.3045 gram of the untreated MnOg-containing cathode mix, or 0.3036 gram of the heat-treated Mn02~containing cathode^ mix, 0.037 gram of lithium, a polypropylene separator, and 140 pi of the electrolyte. Each cell was placed on a continuous 6200-ohm background load and was pulsed on a 250-ohm load for 2 seconds once a week. Upon reaching a cutoff voltage of 1 volt, the cell capacity and cathode coulombic efficiency for each cell were calculated and are shown in Table III.
TABLE III
Cell Sample Mn02 Cell Capability (mAh) Cathode Efficiency 1 Heat Treated 37.6 50.0 2 Heat Treated 30.2 40.3 3 Heat Treated 39.2 52.2 4 Heat Treated 46.0 61.4 5 Heat Treated 41.4 55.3 6 Not Heated 6.1 8.2 7 Not Heated 26.4 35.5 8 Not Heated 34.2 45.7 9 Not Heated 10.9 14.5 10 Not Heated 4.9 6.6
EXAMPLE IV
Two cells were constructed similar to cells in Example II except that 1.5 ml of the electrolyte was used and in the first cell the cathode mix (33% porosity) consisted of 80 wt.% Tekkosha Mn02, 10 wt.% carbon black and 10% Teflon, and in the second cell the cathode mix (45% porosity) was the same except that the Mn02 was electrolytic Mn02 made by Union Carbide Corporation. The Mn02 in each cell was heat treated and then blended into cathode pellets which were dried at 120°C in vacuum. The nominal interfacial electrode area for each electrode was 2 square centimeters. The cells were continuously discharged across a
3000-ohm load and the cathode coulombic efficiency of utilization to a
2.0 volt cutoff was calculated to be 88% for the Tekkosha Mn02 containing cell and 993! for the other cell.
EXAMPLE V
Several 0.455 inch (1.156 cm) diameter, 0.165 inch (0.419 cm) high 5 cells were constructed using 0.36 gram of cathode mix containing wt.% Tekkosha Mn02, 8.5 wt.% carbon black, 2.5 wt.% graphite, and 3.0 wt.% Teflon; 0.03 gram lithium anode; and 140 pi of the electrolyte used in Example III. The MnOj, prior to forming the cathode mix, was heat treated at 350°C for 8 hours. Thereafter the moulded cathode mix pellets were exposed to various levels of humidity for various lengths of time and then assembled into cells. The bulge measurements, if any, and the leakage, if any, after storage for various periods of time as shown in Table IV. The bulge measurement is the deviation in mils or millineters of the height of the cell from the original height of the cell due to anode corrosion and/or gas evolution within the cell. Leakage is any electrolyte visually observable at the seal area of the cell. The cells were then discharged across a 15,000 ohm load until the voltage dropped to 2.4 volts. The average milliampere hours capacity delivered by the cells in each sample group is also shown in Table IV.
The data shown in Table IV demonstrate that the cells in which the heat-treated MnOg cathodes have been exposed to substantial levels of humidity begin to show bulging within 24 hours. Some decrease in bulge with time may be due to some of the gas escaping through the cover/gasket/container interface when leakage occurs.
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TABLE IV (METRIC)
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Claims (13)
1. A nonaqueous cell comprising an active metal anode, a manganese dioxide-containing cathode and a liquid organic electrolyte comprising 3-methyl-2-oxazolidone together with a solute and wherein the manganese 5 dioxide has a water content of less than 1 weight percent based on the weight of the manganese dioxide.
2. A nonaqueous cell as claimed in claim 1 wherein the water content is less than 0.5 weight percent based on the weight of the manganese dioxide. 10
3. A nonaqueous cell as claimed in claim 2 wherein the water content is less than 0.2 weight percent based on the weight of the manganese dioxide.
4. A nonaqueous cell as claimed in any one of claims 1 to 3 wherein the cathode comprises manganese dioxide, a conductive agent and a binder 15
5. A nonaqueous cell as claimed in claim 4 wherein the conductive agent is carbon or graphite and the binder is polytetrafluorethylene or ethylene acrylic acid polymer.
6. A nonaqueous cell as claimed in any one of claims 1 to 5 wherein at least one cosolvent is contained in the liquid organic electrolyte. 20
7. A nonaqueous cell as claimed in claim 6 wherein said solvent is selected from tetrahydrofuran, dioxolane, dimethoxyethane, dimethyl isoxazole, diethyl carbonate, propylene carbonate, ethylene glycol sulfite, dioxane and dimethyl sulfite.
8. A nonaqueous cell as claimed in any one of claims 1 to 7 wherein 25 said solute is selected from MCF 3 SO.j, MBF^, MCIO^, and ΜΜΤθ wherein M is lithium, sodium or potassium and M‘ is phosphorus, arsenic or antimony.
9. A nonaqueous cell as claimed in any one of claims 1 to 8 wherein said active metal anode is selected from lithium, potassium, sodium, calcium, mangnesium, aluminium and alloys thereof.
10. A nonaqueous cell as claimed in any one of claims 1 to 6 wherein 5 the anode is lithium and the electrolyte is LiCF^SO^ dissolved in 3. -methyl-2-oxazolidone, dloxolane, dimethoxyethane and dimethyl isoxazole.
11. A nonaqueous cell as claimed in any one of claims 1 to 6 wherein the anode is lithium and the electrolyte is LiBF^ dissolved in 3-methyl-2-oxazolidone and dimethoxyethane. 10
12. A nonaqueous cell as claimed in any one of claims 1 to 6 wherein the anode is lithium and the electrolyte is LiCFjSO^ dissolved in 3-methyl-2-oxazolidone and dimethoxyethane.
13. A nonaqueous cell as claimed in any one of claims 1 to 6 wherein the anode is lithium and the electrolyte is LiCF^SO^ dissolved in 15 3-methyl-2-oxazolidone and propylene carbonate. A nonaqueous cell substantially as hereinbefore described with reference to any one of the Examples II to IV.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US5149179A | 1979-06-25 | 1979-06-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE801312L IE801312L (en) | 1980-12-25 |
| IE49844B1 true IE49844B1 (en) | 1985-12-25 |
Family
ID=21971625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE1312/80A IE49844B1 (en) | 1979-06-25 | 1980-06-24 | Non-aqueous cells employing heat-treated manganese dioxide cathodes |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JPS566383A (en) |
| AU (1) | AU530502B2 (en) |
| BE (1) | BE883985A (en) |
| BR (1) | BR8003919A (en) |
| CA (1) | CA1149447A (en) |
| CH (1) | CH642779A5 (en) |
| DE (1) | DE3022977A1 (en) |
| DK (1) | DK270280A (en) |
| ES (1) | ES492687A0 (en) |
| FR (1) | FR2460046A1 (en) |
| GB (1) | GB2054253B (en) |
| HK (1) | HK33585A (en) |
| IE (1) | IE49844B1 (en) |
| IN (1) | IN154337B (en) |
| IT (1) | IT1132123B (en) |
| LU (1) | LU82543A1 (en) |
| MX (1) | MX153063A (en) |
| NL (1) | NL8003660A (en) |
| NO (1) | NO801877L (en) |
| SE (1) | SE8004657L (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4279972A (en) * | 1979-08-27 | 1981-07-21 | Duracell International Inc. | Non-aqueous electrolyte cell |
| US4401735A (en) * | 1979-12-28 | 1983-08-30 | Duracell International Inc. | Non-aqueous Li/MnO2 cell |
| EP0044240A1 (en) * | 1980-06-27 | 1982-01-20 | Union Carbide Corporation | Non-aqueous cells employing cathodes of heat-treated manganese dioxide and a propylene-carbonate-dimethoxy-ethane-lithium-trifluoro-methane sulfonate electrolyte |
| US4327166A (en) * | 1980-09-29 | 1982-04-27 | Union Carbide Corporation | Nonaqueous cell having a MNO2 /poly-carbon fluoride cathode |
| DE3242139C2 (en) * | 1982-11-13 | 1984-09-06 | Accumulatorenwerke Hoppecke Carl Zoellner & Sohn GmbH & Co KG, 5790 Brilon | Process for the production of positive electrodes for electrochemical elements, in particular Li / Mn0 2 cells and electrodes produced by this process |
| US4489144A (en) * | 1983-03-28 | 1984-12-18 | Union Carbide Corporation | Isoxazole derivative additive in organic electrolytes of nonaqueous cells employing solid cathodes |
| JPS62117271A (en) * | 1985-11-15 | 1987-05-28 | Sanyo Electric Co Ltd | non-aqueous electrolyte battery |
| JP2703338B2 (en) * | 1989-05-25 | 1998-01-26 | 三洋電機株式会社 | Non-aqueous electrolyte battery |
| EP0614239A3 (en) * | 1993-03-01 | 1996-10-16 | Tadiran Ltd | Non-aqueous safe secondary cell. |
| JP2002075446A (en) * | 2000-08-02 | 2002-03-15 | Samsung Sdi Co Ltd | Lithium-sulfur battery |
| GB2511743A (en) * | 2013-03-11 | 2014-09-17 | Craig Mclean-Anderson | Electrochemical cells |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2606915C3 (en) * | 1975-02-25 | 1979-09-20 | Union Carbide Corp., New York, N.Y. (V.St.A.) | Galvanic element with a non-aqueous electrolyte |
| JPS5342325A (en) * | 1976-09-29 | 1978-04-17 | Sanyo Electric Co | Method of making cathode of nonnaqueous battery |
| US4163829A (en) * | 1977-11-14 | 1979-08-07 | Union Carbide Corporation | Metallic reducing additives for solid cathodes for use in nonaqueous cells |
| US4129686A (en) * | 1977-11-16 | 1978-12-12 | Union Carbide Corporation | Pronged anode collector for internally shorting galvanic cells |
| US4142028A (en) * | 1977-12-23 | 1979-02-27 | Union Carbide Corporation | Nonaqueous cells utilizing aluminum, magnesium, and calcium anodes in amide-based electrolytes |
-
1980
- 1980-06-10 IN IN429/DEL/80A patent/IN154337B/en unknown
- 1980-06-13 CA CA000354021A patent/CA1149447A/en not_active Expired
- 1980-06-20 DE DE19803022977 patent/DE3022977A1/en not_active Ceased
- 1980-06-23 NO NO801877A patent/NO801877L/en unknown
- 1980-06-23 ES ES492687A patent/ES492687A0/en active Granted
- 1980-06-23 IT IT8022972A patent/IT1132123B/en active
- 1980-06-24 JP JP8582880A patent/JPS566383A/en active Pending
- 1980-06-24 GB GB802669A patent/GB2054253B/en not_active Expired
- 1980-06-24 AU AU59565/80A patent/AU530502B2/en not_active Ceased
- 1980-06-24 LU LU82543A patent/LU82543A1/en unknown
- 1980-06-24 FR FR8013989A patent/FR2460046A1/en active Granted
- 1980-06-24 DK DK270280A patent/DK270280A/en not_active Application Discontinuation
- 1980-06-24 MX MX182888A patent/MX153063A/en unknown
- 1980-06-24 BR BR8003919A patent/BR8003919A/en unknown
- 1980-06-24 NL NL8003660A patent/NL8003660A/en active Search and Examination
- 1980-06-24 SE SE8004657A patent/SE8004657L/en not_active Application Discontinuation
- 1980-06-24 IE IE1312/80A patent/IE49844B1/en unknown
- 1980-06-24 CH CH484780A patent/CH642779A5/en not_active IP Right Cessation
- 1980-06-24 BE BE0/201160A patent/BE883985A/en not_active IP Right Cessation
-
1985
- 1985-05-02 HK HK335/85A patent/HK33585A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS566383A (en) | 1981-01-22 |
| GB2054253B (en) | 1983-09-21 |
| IT8022972A0 (en) | 1980-06-23 |
| ES8102423A1 (en) | 1980-12-16 |
| GB2054253A (en) | 1981-02-11 |
| DK270280A (en) | 1980-12-26 |
| DE3022977A1 (en) | 1981-01-08 |
| FR2460046B1 (en) | 1984-05-25 |
| CA1149447A (en) | 1983-07-05 |
| FR2460046A1 (en) | 1981-01-16 |
| IE801312L (en) | 1980-12-25 |
| AU5956580A (en) | 1981-01-08 |
| IN154337B (en) | 1984-10-20 |
| BR8003919A (en) | 1981-01-13 |
| SE8004657L (en) | 1980-12-26 |
| LU82543A1 (en) | 1981-02-03 |
| HK33585A (en) | 1985-05-10 |
| NL8003660A (en) | 1980-12-30 |
| BE883985A (en) | 1980-12-24 |
| IT1132123B (en) | 1986-06-25 |
| CH642779A5 (en) | 1984-04-30 |
| ES492687A0 (en) | 1980-12-16 |
| NO801877L (en) | 1980-12-29 |
| MX153063A (en) | 1986-07-24 |
| AU530502B2 (en) | 1983-07-21 |
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