WO1991006132A1 - Element d'accumulateur destine a la fabrication de batteries secondaires - Google Patents

Element d'accumulateur destine a la fabrication de batteries secondaires Download PDF

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Publication number
WO1991006132A1
WO1991006132A1 PCT/US1990/005638 US9005638W WO9106132A1 WO 1991006132 A1 WO1991006132 A1 WO 1991006132A1 US 9005638 W US9005638 W US 9005638W WO 9106132 A1 WO9106132 A1 WO 9106132A1
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Prior art keywords
cell
sulfur
positive electrode
secondary batteries
solid
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PCT/US1990/005638
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English (en)
Inventor
Steven J. Visco
Meilin Liu
Lutgard C. Dejonghe
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The Regents Of The University Of California
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Application filed by The Regents Of The University Of California filed Critical The Regents Of The University Of California
Priority to BR909007750A priority Critical patent/BR9007750A/pt
Priority to SU5011317/07A priority patent/RU2099821C1/ru
Priority to CA002053887A priority patent/CA2053887C/fr
Publication of WO1991006132A1 publication Critical patent/WO1991006132A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/3909—Sodium-sulfur cells
    • H01M10/3918—Sodium-sulfur cells characterised by the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/3909—Sodium-sulfur cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/604—Polymers containing aliphatic main chain polymers
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/3909—Sodium-sulfur cells
    • H01M10/3954—Sodium-sulfur cells containing additives or special arrangement in the sulfur compartment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • 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
    • H01M4/669—Steels
    • 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

Definitions

  • the present invention relates to metal-sulfur type cells for making secondary batteries, and particularly to cells operating with all components thereof in the solid state.
  • the batteries have the advantage of being capable of operating for many charge cycles without any significant loss of performance.
  • these batteries have a low power to weight ratio.
  • lithium batteries have been thoroughly investigated, and certain of these systems are promising in certain applications. As improvements are made, it will be appreciated that more widespread use will follow.
  • a typical example of such a cell is to be found in U. S. Patent No. 4,589,197 describing a lithium/polyethylene battery system in which the electroactive material is an intercalation compound. This type of battery has also been shown to be capable of scaling up to large sizes without any significant loss of performance.
  • the present invention provides a cell having a FOH of the order of 120 along with capability of operation at room or ambient temperatures.
  • Another object of the invention is to provide a cell in which all of the components are in the solid state, and which may be reliably fabricated into units having reproducible performance values.
  • a further object of the invention is to provide a battery having an energy to weight ratio far in excess of the demands for load leveling and/or electric vehicle applications.
  • a composite positive electrode and a battery system constructed with the composite positive electrode system are provided.
  • the positive electrode comprises a 1-dimensional, 2-dimensional, or 3- dimensional polymeric electroactive component.
  • this component can be formulated as (SRS), n which R is an organic moiety as hereinafter defined and n is greater than 2 and preferably greater than 20 in the charged state.
  • SRS single-cell reaction
  • + 2n r ⁇ n -SRS- the overall cell reaction can be described as follows:
  • the electroactive component of the, solid-state organosulfur electrode can be represented in the charged state by (RS y ), wherein y is 2 to 6, n is greater than 2 and preferably greater than 20, and R is one or more different aliphatic or aromatic moieties having 1 to 20 carbon atoms which may include one or more oxygen, phosphorus, silicon, sulfur or nitrogen heteroato s when R comprises one or more aromatic rings, or one or more oxygen, phosphorus, silicon, sulfur, nitrogen or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the aliphatic group may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon, and wherein said organosulfur positive electrode is further characterized by a large number of sulfur-sulfur bonds when in the charged state, which upon discharge of the cell are broken to form an organo-metal salt with metal ions in the cell.
  • the charge/discharge process in the positive electrode can be viewed as a reversible redox polymerization (or redox dimerization/scission in the case of monomeric RSSR compounds) .
  • An example of a 2-dimensional (ladder polymer) electrode can be illustrated by polyethyleneimine disulfide as follows:
  • the ranges of the materials in the polymeric positive electrode is from about 30% to 80% by weight of active organosulfur, from about 20% to about 70% by weight of polymeric electrolyte, and from about 1% to about 20% by weight of conductor particles.
  • the desired mixture is achieved by dissolving or dispersing the (SRS) B polymer, polyethylene oxide, and carbon black powder in acetonitrile, and subsequently evaporating the solvent to cast a thin film (say 10 to 200 microns) of solid composite electrode.
  • the positive electrode is a composite electrode composed of organosulfur redox polymer, polyethylene oxide, and carbon black.
  • the organosulfur positive electrode is of the general formula (SRS), with the important feature being the formation of the sulfur- sulfur bond upon oxidation of the alkali metal thio salt.
  • the preferred electrode is a polymeric di ⁇ ulfide, but it is believed that monomeric disulfides (RSSR) as described in U. S. Patent No. 4,833,048 will also be operative in solid state batteries.
  • the organosulfur electrode comprises polythio and/or dithio anions (-SRS-) dispersed in the polymer electrolytematrix.
  • the final discharge product depends, of course, on the type of R groups in the polymer chain and the dimensionality of the fully oxidized positive polymer electrode.
  • Another advantage of the invention resides in the capability of the solid state electrodes to be reversible to various metals. While lithium has the lowest equivalent weight and corresponding weight advantages, it is more costly than sodium. In addition, the conductivity of the preferredpolyether electrolytes such as polyethylene oxide is higher for sodium transport than for lithium transport. Accordingly, while the intercalation type cells require lithium as a practical matter, the negative electrode of the present electrode may be composed of many different metals. Accordingly, any of the alkali or alkaline earth metals or transition metals (the polyether electrolytes have been shown to transport dications such as Zn ++ ) are within the ambit of the invention, and particularly mixtures containing lithium and/or sodium.
  • the electrolyte used in the cells of this invention functions as a separator for the electrodes and as a transport medium for the metal ions. Therefore, any solid material capable of transporting metal ions may be used. For example, it has been shown that sodium beta alumina is operative.
  • the solid electrolyte separator is any suitable polymeric electrolyte such as polyether ⁇ , polyimines, polythioethers, polyphosphazenes, polymer blends, and the like in which an appropriate electrolyte salt has been added.
  • Figure 1 is a cross-sectional view of the main components of a cell constructed according to the invention.
  • Figure 2 shows data in graphical form illustrating the operation of one embodiment of the invention and comparing it with data of a prior art embodiment.
  • the metal-sulfur type cell as shown in Figure l comprises a current collector 11 in juxtaposition to a negative electrode 12, a current collector 13 in juxtaposition to a positive electrode 14, and an electrolyte 15 sandwiched betweenthe negative electrode 12 and the positive electrode 14.
  • a typical cell all of these components will be enclosed in a suitable case of plastic or the like (not shown) with only the current collectors extending beyond the enclosure. In this way, reactive metals such as sodium or lithium in the negative electrode areprotected. Similarly, protection is provided for the other parts of the cell.
  • Suitable battery constructions may be made according to the known art for assembling cell components and cells as desired, and any of the known configurations may be fabricated utilizing the invention. The exact structures will depend primarily upon the intended use for the battery unit. However, it will be appreciated that the cell units are all in a substantially solid state at ambient temperatures and in operation.
  • current collectors 11 and 13 are sheets of conductive material such as stainless steel which remain substantially unchanged during discharge and charge of the cell, and which provide current connections to the cathode and anode of the cell.
  • Negative electrode 12 is preferably an alkali metal such as lithium or sodium with sodium being preferred over lithium.
  • the organo-sulfur cathode or positive electrode 14 is foiled onto the current collector 13 as described above, and the entire unit pressed together with the electrolyte 15 sandwiched between electrodes as shown.
  • the thicknesses of all of the cell components are exaggerated for the sake of illustration, and all of these components are typically rather thin sheets.
  • a typical lithium or sodium solid anode 12 will be about 10 to 50 microns thick
  • a typical solid composite polymeric cathode 14 will be about 50 to 100 microns thick
  • a typical PEO electrolyte 15 will be about 10 to 100 microns thick.
  • the preferred electrolyte is a polyalkylene oxide such as polyethylene oxide into which a plasticizing electrolyte salt such as LiN(CF 3 S0 2 ) 2 has been added.
  • a plasticizing electrolyte salt such as LiN(CF 3 S0 2 ) 2 has been added.
  • the effect of the plasticizing electrolyte salt is to maintain the polyether in the amorphous (conductive) state at low temperatures, thereby allowing low temperature operation of the cell.
  • the organo-sulfur compound which comprises the novel positive electrode of the invention is characterized by an organosulfur material having at least one sulfur atom which forms a first bond with an organic moiety and a second bond, when the material is in its charged state, with another sulfur atom which is also bonded to an organic moiety.
  • an organosulfur material having at least one sulfur atom which forms a first bond with an organic moiety and a second bond, when the material is in its charged state, with another sulfur atom which is also bonded to an organic moiety.
  • a metal ion such as sodium
  • the positive electrode material comprises an organosulfur material which includes the basic or backbone formula R-S-.
  • the sulfur atom (or atoms, as will be explained below) forms a -S-S- bond with a sulfur atom of another R-S- group forming R-S-S-R.
  • the S-S-bond is broken and each R-S- group forms a salt with a metal ion such as, for example, sodium, i.e., R-S-Na.
  • the R group may also have more than one sulfur atom bonded thereto by single bonds thus making polymerization possible, for example in the case of -S-R-S-. Branching may also occur when the R group has three or more of such sulfur atoms single bonded thereto.
  • the general formula for the organosulfur material comprising the novel positive electrode of the invention may be written, in its charged state, as: (R(S) y ) a wherein y is 2 to 6; and is greater than 20; and R is one or more of the same or different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms, which may include one or more oxygen, sulfur, phosphorus, silicon, or nitrogen heteroatoms when R comprises one or more aromatic rings, or one or more oxygen, phosphorus, silicon, sulfur, nitrogen, or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the aliphatic group may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereor.
  • the organo-sulfur positive electrode material comprises organicmoieties containingmorethan one sulfur atom, attached to the same organic moiety, and capable of forming a sulfur-sulfur bond with a sulfur attached to another organic moiety.
  • a polymer-like material may be formed with the length of the polymer depending upon the presence of impurities or chain stoppers such as mono sulfide organic moieties, e.g., CH 3 -CH 2 -S-Na, to terminate polymerization.
  • Such a polymer could comprise a linear aliphatic chain having such a sulfur atom at each end of that chain, e.g., -S-CH 2 CH 2 -S-, permitting the formation of diners, oligo ers, etc. such as, -S-CH 2 -CH 2 -S-S-CH 2 -CH 2 -S-S-CH 2 - CH 2 -S-, corresponding to the general formula (R(S)2) 3 .
  • the organo-sulfur compounds may comprise branched polysulfide materials containing more than two ⁇ ulfurs capable of forming sulfur-sulfur bond with adjacent sulfur atoms on other organo-sulfur materials.
  • the general formula could be written as (R(S) 3 ) n .
  • y has been given a value of 1 to 6 in the general formula in recognition of both the possibility of the existence of double bonded sulfur atoms on the R group as well as the presence of more than one sulfur atom thereon capable of forming sulfur-sulfur bonds with similar sulfur atoms on other molecules.
  • the value of n, in the general formula, while preferably greater than 20, has been given a range including 2 to 20 in recognition of the possibility of the lower stages of polymerization, such «s by ring formation, and because solid-state batteries have advantages with organosulfur compounds that do not polymerize. No upper limit was placed upon n because the degree of polymerization is limited under charging conditions by the nature of the organosulfur compound used.
  • organo-sulfur electrode The oxidation-reduction chemistry of the organo-sulfur electrode is explained ' fully in United States Patent No. 4,833,048, and the pertinent text therein is incorporated by reference.
  • the present invention while using similar organosulfur electrodes differs by operating at lower temperatures at solid state. Accordingly, the present invention prefers organosulfur polymer which are in excess of 20 monomer units and preferably higher than 50 units.
  • the positive electrode of this invention differs from that of the cited patent by utilizing special current transport additives.
  • the operating temperature of the solid-state cells is in the range of -40 to 145 ⁇ C, limited in the high range by the melting point of either electrode or the electrolyte.
  • the preferred temperature range is from ambient to 100°C.
  • Sodium negative electrodes are limited to temperatures below 98°C, but, sodium alloy electrodes such as Na 4 Pb can be used at solid form at well over 100°C.
  • the adhesiveness and elastomerity of the solid polymeric electrolyte and solid redox polymerization cathode prevent loss of or serious reduction of electrical contact between the solid electrolyte and the electrodes during cell cycling.
  • the invention provides improvements over the state of the art by replacement of certain liquid and corrosive materials with solid and safer compositions. This replacement makes batteries utilizing the invention far easier to manufacture and package by highly automated processes, and provides cells that are non-corrosive to containment materials.
  • the composite positive electrodes were cast to a thickness of approximately 100 microns, which translates to about 0.0115 g/cm 2 of electrode surface area.
  • the available capacity of the 100 micron polymer films was about 6.4 coulombs/cm 2 or 1.8 mAh/cm 2 .
  • the assembled cells were cycled to an end point of 6 coulombs (defined as 100% of capacity) . These cells were charged and discharged at a variety of temperatures and current densities for a total of 80 cycles with absolutely no discernible evidence of deterioration of performance.
  • the cells could be discharged to 100%.of available capacity at a current density of 4mA/cm 2 , and could be completely recharged at a current density of 3mA/cm 2 , with no adverse effects on subsequent cycles. Furthermore, the cells could be discharged at rates as high as 10 mA/cm 2 to 50% of available capacity, and charged at rates as high as 6 mA/cm 2 for 65% of available capacity. Moreover, these exceptionally high charge/discharge current densities did not harm the integrity of the solid polymer electrode. The results of these studies demonstrated the reversibility and reliability of the solid redox polarization electrodes, even under harsh electrochemical conditions.
  • LiCF 3 S0 3 lithium perchlorate
  • LiC10 4 lithium perchlorate
  • concentration of electrolyte salt was 8 PEO monomer units (CH 2 CH 2 0) per molecule of salt, abbreviated herein as PEOjLiX where
  • X is the salt anion.
  • the organosulfur polymer used was identical to that described above for the sodium cell.
  • Composite positive electrodes were constructed as described abode for the sodium-based cell, except that two thicknesses of electrode were cast; a high capacity 6 coulomb/cm 2 film (100 microns) , and a lower capacity 3 coulombs/cm 2 film (50 microns) for high power density batteries.
  • These Li/PEO/[ (SRS),/PEO/C] cells had theoretical energy densities of 1000 Wh/kg, and assembled cells had practical energy densities of 338 Wh/kg (zero current drain) for the high capacity films, and 304 Wh/kg or the low capacity films, based on the weight of the actual electrodes, PEO films, and a 4:1 excess of lithium (actual cells had a larger excess of lithium) .
  • the invention provides high specific energy and power cells that exceeds that of highly developed systems now known and in use. At the same time, the high energy and power are available at room temperature or ambient operation.

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Abstract

On a mis au point des batteries au lithium et au sodium à l'état complètement solide, fonctionnant dans la plage de températures approximatives allant de la température ambiante à 145 °C (limitée par des points de fusion d'électrodes/électrolyte), dont les densités d'énergie de puissance dépassent de beaucoup les systèmes de batterie à haute température de l'art actuel. La batterie préférée comprend une électrode (12) au lithium ou au sodium solide, un électrolyte polymère (15) tel que de l'oxyde de polyéthylène dopé par du triflate de lithium (PEO8LiCF3SO3), ainsi que des électrodes (14) positives composites à l'état solide, contenant une électrode d'organosoufre polymère, (SRS)n, et du noir de carbone, dispersé dans un électrolyte polymère.
PCT/US1990/005638 1989-10-13 1990-10-09 Element d'accumulateur destine a la fabrication de batteries secondaires WO1991006132A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BR909007750A BR9007750A (pt) 1989-10-13 1990-10-09 Celula de metal-enxofre
SU5011317/07A RU2099821C1 (ru) 1989-10-13 1990-10-09 Элемент для изготовления вторичных батарей
CA002053887A CA2053887C (fr) 1989-10-13 1990-10-09 Pile servant a faire des batteries secondaires

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US42109189A 1989-10-13 1989-10-13
US421,091 1989-10-13

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WO1991006132A1 true WO1991006132A1 (fr) 1991-05-02

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EP (1) EP0495895A4 (fr)
JP (1) JP3102880B2 (fr)
KR (1) KR0137006B1 (fr)
CN (1) CN1023364C (fr)
AU (1) AU642676B2 (fr)
BR (1) BR9007750A (fr)
CA (1) CA2053887C (fr)
RU (1) RU2099821C1 (fr)
WO (1) WO1991006132A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0650208A1 (fr) * 1993-10-21 1995-04-26 Alcatel Matériau cathodique pour générateur électrochimique
US6709787B2 (en) 2000-02-09 2004-03-23 Hitachi Maxell, Ltd. Polycarbon sulfide, process for preparing the same and nonaqueous electrolyte battery comprising the same

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0713898D0 (en) * 2007-07-17 2007-08-29 Nexeon Ltd A method of fabricating structured particles composed of silcon or a silicon-based material and their use in lithium rechargeable batteries
CN103650215A (zh) * 2011-07-11 2014-03-19 巴斯夫欧洲公司 包含金属硫化物的电极材料
KR102035010B1 (ko) * 2012-04-13 2019-10-22 알케마 인코포레이티드 유기황 화학종-기반 배터리
WO2017079873A1 (fr) * 2015-11-09 2017-05-18 Robert Bosch Gmbh Cellules rechargeables au lithium tout solide
RU2755479C2 (ru) * 2016-12-02 2021-09-16 Аркема Инк. Аккумуляторная батарея на основе сероорганического соединения
WO2020152119A1 (fr) * 2019-01-25 2020-07-30 Shell Internationale Research Maatschappij B.V. Dispositif de stockage d'énergie électrique

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4681822A (en) * 1983-11-09 1987-07-21 The British Petroleum Company, P.L.C. Novel composites of an ionic conducting polymer and an electronic conducting polymer
US4833048A (en) * 1988-03-31 1989-05-23 The United States Of America As Represented By The United States Department Of Energy Metal-sulfur type cell having improved positive electrode

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1341507C (fr) * 1989-09-01 2006-06-13 Michel Gauthier Generateur a l'etat solide fonctionnant par polymerisation redox

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4681822A (en) * 1983-11-09 1987-07-21 The British Petroleum Company, P.L.C. Novel composites of an ionic conducting polymer and an electronic conducting polymer
US4833048A (en) * 1988-03-31 1989-05-23 The United States Of America As Represented By The United States Department Of Energy Metal-sulfur type cell having improved positive electrode

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0495895A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0650208A1 (fr) * 1993-10-21 1995-04-26 Alcatel Matériau cathodique pour générateur électrochimique
FR2711843A1 (fr) * 1993-10-21 1995-05-05 Alsthom Cge Alcatel Matériau cathodique pour générateur électrochimique.
US5496662A (en) * 1993-10-21 1996-03-05 Alcatel Alsthom Compagnie Generale D'electricite Cathode material for an electric cell
US6709787B2 (en) 2000-02-09 2004-03-23 Hitachi Maxell, Ltd. Polycarbon sulfide, process for preparing the same and nonaqueous electrolyte battery comprising the same

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KR0137006B1 (ko) 1998-06-15
JPH05501937A (ja) 1993-04-08
AU6611090A (en) 1991-05-16
BR9007750A (pt) 1992-09-01
CA2053887A1 (fr) 1991-04-14
CA2053887C (fr) 2001-12-11
JP3102880B2 (ja) 2000-10-23
AU642676B2 (en) 1993-10-28
EP0495895A1 (fr) 1992-07-29
CN1023364C (zh) 1993-12-29
CN1053324A (zh) 1991-07-24
RU2099821C1 (ru) 1997-12-20
EP0495895A4 (en) 1993-02-03

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