GB2335073A - Non-aqueous electrochemical cell containing conjugated polyimine functionality coupled to sulphur trioxide - Google Patents

Non-aqueous electrochemical cell containing conjugated polyimine functionality coupled to sulphur trioxide Download PDF

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Publication number
GB2335073A
GB2335073A GB9804958A GB9804958A GB2335073A GB 2335073 A GB2335073 A GB 2335073A GB 9804958 A GB9804958 A GB 9804958A GB 9804958 A GB9804958 A GB 9804958A GB 2335073 A GB2335073 A GB 2335073A
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Prior art keywords
cell according
electrochemical cell
poly
s03
polymeric substance
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GB9804958D0 (en
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Robin Alexander Angus Gilmour
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Lexcel Technology Ltd
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Lexcel Technology Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004Details
    • H01G9/04Electrodes or formation of dielectric layers thereon
    • H01G9/042Electrodes or formation of dielectric layers thereon characterised by the material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/44Preparation of metal salts or ammonium salts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/48Isomerisation; Cyclisation
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0563Liquid materials, e.g. for Li-SOCl2 cells
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137Electrodes based on electro-active polymers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/60Selection of substances as active materials, active masses, active liquids of organic compounds
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • H01M4/622Binders being polymers
    • H01M4/623Binders being polymers fluorinated polymers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/14Cells with non-aqueous electrolyte
    • H01M6/18Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/13Ultracapacitors, supercapacitors, double-layer capacitors

Abstract

A novel rechargeable lithium battery is disclosed wherein the positive electrode is comprised of conductive polymeric materials having conjugated imine functionality and the lithium salt of a sulphur oxy-acid as the active redox component. On charging, lithium metal is electrochemically split from the salt, e.g. Li2SO3, and is deposited at the negative electrode, the imine sites at the positive electrode acting as host for SO3 Complex formation. The system is optimized when the nitrogen content of the polyimine host material is present in an equimolar ratio with SO3.

Description

1 t .---i 2335073 Non-Aqueous Electrochemical Cell Containing Conjugated

Polyimine Functionality Coupled To Sulphur Trioxide 1

Background To The Invention:

An outstanding need exists for more efficient storage of electrical energy by redox chemical conversion. At present, most applications for a rechargeable or secondary battery system are met by either the lead-acid or the nickel-cadn-durn types, these being capable of storing a maximum of around 35 WhKg-' of battery weight. For electric vehicles to be viable. the energy density available from existing systems is totally inadequate and this restricts the development of vehicles to compete with those powered by internal combustion engines. In the field of portable communications equipment, the need for greater amounts of electrical energy to be stored in handsets is a top priority.

A target energy density of 100 WhKg-1 is generally regarded as being an acceptable and realistic value for the new generation of rechargeable batteries. In order to realize this threefold increase over existing electrochemical systems, it is necessary to resort to non-aqueous media. Primary, or non-rechargeable, battery systems based on lithium. metal as the negative electrode are capable of delivering over 1,000 WhKg"' are now well established. The lithium.thionyl chloride system is a good example of a high energy couple but is not rechargeable. Sodium / sulphur and sodium 1 metal chloride systems under development are reported to have good reversibility and to give energy densities in excess of 100 WhKg-'. These systems have an operating temperature of ca. 350T which limits their viability and increases safety concerns.

It is an important objective of the present invention that the chosen electrochemical system is operational at ambient temperatures. This obviates the need for the use of an external heating source. This is achieved by the use of electrolytes based m fion-aqueous solvents which remain in the liquid phase over a broad temperature window and also have good ionic conductivity. Suitable electrolytes consist of organic or inorganic solvents or mixtures thereof, with salts of the alkali or alkaline earth metal which forms the negative electrode dissolved therein.

A non-rechargeable lithium battery systern, well known as a power source for heart pacemakers, comprises a positive electrode which is a complex compound of iodine and poly(2vinyl pyridine), P(2NP)-12. In this system, the P(2-W) polymer material forms a solid solution with iodine and regulates reaction of the latter with lithium metal since there is no discrete separator present. This system is not reversible and has a very low rate capability.

By contrast, a very high rate primary lithium system uses liquid sulphur dioxide, S02, as active positive electrode material, the S02 also serves as electrolyte solvent or co-solvent. This system can be discharged at high rates down to -40T, but extensive development work aimed at making it rechargeable has met with only hinited success. It is a major objective of the present invention to provide a polymeric material comprised of imine fimctionality which forms an insoluble complex with a highly active Lewis acid such as S02 or S03 and confer much higher rate capability than that achieved in the PQ-VP)-12 system but be electrocheinically reversible.

C ",- -1, It has been Imown fbr some time that a solution of sulphur trioxide containing an ionically conducting lithium salt exhibits an EMF of ca. 4. 5 V. Attempts to utilise such an electrochemical cell have been unsuccessful primarily due to the high reactivity Of S03 to other cell constituents including separator, cell wall and lithium electrode itself. Solid complexes are formed by combination Of S03 With monomeric tertiary amines and imines, including heterocyclic compounds such as pyridine and these are stable in the absence of moisture to ca. 200T. Itese complexes are unsuitable as positive electrode materials because of their ready solubility in excess S02, S 03 and other highly polar solvents.

In UK Patent Application GB 2 266 179 A, electrochemical cells were claimed having complexes Of S03 and polymeric tertiary amines. The energy densities of these are low due to the high ratios of carbon to nitrogen fimetionality.

3 i m-Y i Invention:

This present invention is concerned with a novel positive electrode composition for electrochernical cells of the non-aqueous type. A high energy and power density together with superior charge retention over prior art systems are salient features of the new electrode composite as is the relatively low cost and non-toxicity of the starting materials. The invention offers an improved power storage device Wz. an electric battery or capacitor and is based on the use of an organic polymer having a C to N ratio of no more than 3 to 1 and in which conjugated imirie flinctionality is present in a 1: 1 molar ratio of N: S03. The positive electrode may be prepared by the thermal cyclization of nitrile containing polymers such as acrylonitrile or copolymers thereof such as flimaronitrile, or maleonitrile. When thermally restructured at temperatures of up to 600T in an anaerobic environment, conjugated arrays of imine functionality are incorporated into the material.

In one example of the invention, the organic polymer is finely ground with Li2S03 to form an intimate admixture in which there is a 1: 1 molar ratio of N: S03. This combination of polymer host and discharged product is pressed into a tablet and assembled in an arrangement where it is positioned between an aluminium plate positive electrode current collector and copper negative electrode; a conventional separator is also employed in the assembly. A non-aqueous electrolyte and background salt, such as LPF6, is employed to provide an ionic conduction pathway.

Charging causes lithium to be electroplated at the negative electrode while S03 is able to form stable complexes with imine functionality in the organic polymer. Discharging causes the recombination of lithium with S03 complexes. In this invention, S03 acts not only as polymer "dopant" but also as sites for the reversible redox electrochemistry of Li2S03.

The cell performance is improved when PVW, present by weight as 5%, is employed as binder with the polymer admixture. Carbon black, up to 20% by weight, is also employed to provide greater electronic conduction.

The present invention provides an electrochemical cell in which S03 is immobilised on a polymeric network comprised of a conjugated arrays of imine flinctionality. These tertiary nitrogen sites act as hosts to S03 complex formation. The requisite source materials are derived from the polymerization of monorners in which either (a) tertiary nitrogen is present in the form of an unsaturated side chain, as is the case in acrylonitrile, cyanoacetylene, dicyanoacetylene, etc., or (b) unsaturated tertiary nitrogen is present in the monomer backbone and it acts as sites for chain or addition growth polymerization, as is the case in fi=ronkffle, malononitrile, maleonitrile, etc., or (c) unsaturated tertiary nitrogen is formed from the oxidative dehydration 1 polymerization of monomers m which non-tertiary nitrogen is present, as is the case in oxamide etc., or (d) the thermal cyclization / polymerization of nitrile functionality contained within (a) - (c). A solid insoluble complex is formed by direct combination Of S 03 with such polymers.

4- Many polymeric structures fall within the scope of this invention. The examples below are selected bemuse they are either readily available or are synthesized either as homopolymer or as copolyiners with other monomers wMd this list of materials:

poly(2-vinyl pyridine) poly(4-vinyl pyridine) poly(acrylonitrile) thermally restructured poly(N- vinyl pyrrole) poly(N-methyl pyrrole) poly(flunaronitrile) thermally restructured poly(cyanoacetylene) thermally restructured poly(dicyanoacetylene) thermally restructured -The composite positive electrode is formed by the combination Of S03 with the polymer at imine (tertiary nitrogen) sites in an equimolar ratio, i.e. a 1: 1 equivalence of N: S03 functionality. In this invention, the specific discharge capacity of electrochernical cells is optin-dzed when positive electrode complexes are comprised of this ratio of imine host: S03, although other ratios approaching parity also yield cells with significantly high values fbr energy density. For the intended application, it is essential that the polymer and S03, used in preparation of the composite electrode, are completely anhydrous.

In accordance with the invention, there is provided an electrochemical cell, the positive electrode of which is comprised of an imine-containing polymer / S03 complex as previously described in contact with a suitable current collector. Certain polymers of the cotijugated type, an example of which is poly(N-methyl pyrrole) or thermally cyclized poly(acrylonitrile), are sufficiently electronically conductive to carry current from the reactive sites in the complex to the positive terminal. Non-conductive polymers require the use of carbon black or similar finely divided inert conductive material to be in intimate contact with the polymer complex. The negative electrode of the cell may be a light metal or light metal alloy. Lithium is the preferred negative electrode, yielding the greatest energy density and voltage. Alloys of lithium with aluminium or a carbon intercalate may be used to improve the electrochemical stability to the electrolyte. For high rate applications, anhydrous liquid electrolytes are required by virtue of their high ionic conductivity. Solid polymer electrolytes may also be used for low rate applications. Lithium ion conductivity is achieved in both instances by the incorporation of suitable salts such as LiCF3S03 and / or LiPF6. Liquid electrolytes may consist of mixtures of aprotic organic solvents and 1 or liquid S02. Preferred materials are fluoropolyiners such as Tefielm (Dupont) or poly(vinylidene fluoride) which resist attack from. the strongly oxidizing S03 1 polymer positive electrode complex.

Example:

Fresh, thermally restructured poly(acrylonitrile), or alternatively poly(acrylonitrileflimaronitrile) copolymer (of various comonomer mole % ratios), powder (ca. 5g) was transferred into a glove box maintained under a steady flow of dry nitrogen (white spot, BOC). Thermally restructured poly(acrylonitrile) (0.700g. acrylonitrile) was weighed into a quartz mortar and pestle. Lithium sulphite (1.242g.) was then added followed by graphite (0.225g. 9.2 % w/w, Timcal SFG44) carbon (0.225g. 9. 2 % w/w, Sederna NIMM Super P) and MF binder (0.053g. 2.2 % w/w, Elf- Atochern Kyriar 741). The five components were thoroughly ground together by use of the pestle to produce a very fine, homogeneous, charcoal coloured material. This was then heated on a hat plate (ca. 80 - I OOOC) for ca. 30 minutes under an anaerobic environment of dry Nzw..

After application of 30 niinutes of heating, the adduct (0.2g.) was pressed in to a small disc of diameter 25 mm and ca. 0.5 mm thick by the use of a Specac press operated at 15 tonnes. The electrochemical test cell (Figure 1) was then inverted so that copper piston (negative electrode) faed uppermost. A poly(propylene) separator (Celgard 3501, Hoecht Celanese) of diameter 27mm was cut out and placed on the surface of the copper piston. The stainless steel piston from the Specac press was used to press down gently on to the Celgard so that the excess of separator was creased to form a shallow cup. Dry (17 3 ppm H20) electrolyte (1 molArn7' LUT6 in equal weights of ethylene carbonate and diethyl carbonate, Merck) was carefWly added drop-wise onto the surface of the separator by the use of a pipette so that it was barely moistened. The disc of adduct was then placed onto the separator and a further addition of electrolyte was pipetted on the surface. A piece of expanded aluminium gauze was then placed on top of the adduct, This acted as an electrical contact to the aluminium base and it also provided torsional rigidity to the adduct. The remains of the test cell were then assembled and the six securing bolts (see Figure 1) were torqued evenly.

The active material of each adduct was formulated employing a 1: 1 ratio of N: S03 for each thermally restructured polymer tested. Owing to the low intrinsic electronic conductivity of both Li2S03 and the thermally treated polymers, an additional mass of graphite and carbon (up to 10 % by weight each) was introduced to all adducts. The brittle nature of the resultant materials meant that a binder was required to consolidate the electrodes into a suitable form. Finely divided poly(vinylidene fluoride), PVW, was employed to facilitate this need. After thorough mixing and grinding of thermally treated polymer, lithium sulphite, graphite, carbon and binder, admixtures were pressed into discs of diameter 2.5cm (area 4. 91Cm 2) to fit the internal bore of both cell types. Figure 1 is a pictorial representation of the cell assembly.

All electrochemical cycling was performed at a constant current of ImA (i. e. 0.20 rnA.cfff 2). A Lee Dickens patentiostat regulated charge cycles between 2.4 and 4.3 V employing an intemal shunt which applied a variable impedance of 1000 mVnlKl for discharge cycles and lOniV / niA G9 for charge cycles. During discharge, current drain was ndintained at ImA and the voltage was permitted to operate in the 2.4 - 4.3 V window. Discharges were halted automatically by an internally programmed trip which was effected if the voltage dropped below 2.4 V. All charge and discharge cycles were conducted for 5 hours apiece such that a maximum of 5 niAh of charge was adniinistered or drained during any individual cycle. For each cell tested, the current density and operating voltage window was maintained at 0.20 mAcm-' and 2.4 - 4.3 V respectively such that the only significant varying parameter between experiments was the composition of the positive electrode complex.

Data was initially presented in the form of chart overlays of voltage versus time (units of 1cm also represented the flow of 1 mAh of charge). Accurate validation of charge flow was performed by the integration of numerical data performed by the Lee Dickens potentiostat. Thus, direct comparisons of charge and energy flow were possible for each thermally treated polymer. The mass of each adduct was measured so that values for specific energy were also expressed for each system. A control experiment was performed using an adduct of graphite, carbon and lithium sulphite (1: 1 molar equivalent Of S03: graphite and 20% carbon weight). This was intended to demonstrate the effect of no imine presence in the adduct and test the validity Of S03 / ffiline complex.

1

Claims (17)

Claims:
1. An electrochemical cell characterized in that the positive electrode consists of a macromolecular complex Of S03 and a polymeric substance comprised of arrays of imine functionality containing tertiary nitrogen as the recurring structural unit represented by the formula:
R R R R S03 S03 S03- n where R is an alkyI or alkylene group or R groups may be inter-linked to be representative of a closed 5 or 6 membered cyclic structures akin to the ring systems of pyrrole or pyridine, respectively. Additionally, R groups are inter-linked and form the mirror image of cariJugated imine, flinctionality already represented, i.e. the polymer as a whole is comprised of double ladders of imine moieties, as is representative of poly(pymzino-pymzine). The said positive electrode being used in conjunction with a non-aqueous electrolyte and a negative electrode consisting of a light inetal or light metal alloy.
2. An electrochermical cell according to claim 1, in which the polymeric substance is thermally restructured poly(acrylonitrile).
3. An electrochemical cell according to claim 1, in which the polymeric substance is thermally restructured poly(acrylonkffie-flimaronitrile) copolymer.
4. An electrochemical cell according to claim 1, in which the polymeric substance is thermally restructured poly(acrylonitrile-2-vinyl pyridine) copolymer.
5. An electrocheirdcal cell according to claim 1, in which the polymeric substance is thermally restructured poly(acrylonitrile-4-vinyl pyridine) copolymer.
6. An electrochemical cell according to claim 1, in which the polymeric substance is poly(pyrazinc-pyTazine).
7. An electrochemical cell according to claim 1, in which the polymeric substance is poly(cyanoacetylene).
8. An electrochemical cell according to claim 1, in which the polymeric substance is poly(dicyanoacetylene).
9. An electrochemical cell according to claim 1,2,3,4,5,6,7 and 8 in which the preferred ratio of S03 to nitrogen in the S03 / polymer complex is 1: 1.
10. An electrochemical cell according to claim 1, in which the polymer has a conjugated army of double bonds which confers intrinsic conductivity to the material and obviates the need to include carbon or other materials in the positive electrode which enhance electronic conductivity.
9
11. An electrochernical cell according to claims 1 to 10, in which the negative electrode is lithium metal and the electrolyte is a solution of a lithium salt in aprotic solvents.
12. An electrochemical cell according to claims 1 to 10, in which the negative electrode is magnesium metal and the electrolyte is a solution of a magnesium salt in aprotic solvents.
13. An electrochemical cell according to claims 1 to 11, in which the electrolyte consists essentially of a solution of lithium salts in liquid S02.
14. An electrochemical cell according to claims 1 to 9, in which the electrolyte consists of a solid polymer composition made ionically conductive by the incorporation of appropriate lithium salts.
15. An el"ochemical cell according to claims 1 to 14, which forms the unit for a rechargeable battery.
16. An electrochernical cell according to claims 1 to 14, which forms the unit for a super or ultracapacitor.
17. This invention is demonstrated to work according to claims 1 to 15, and be optimized in which the positive electrode is comprised of a polymeric material in which the ratio of ' carbon to imine fimctionality is present between the values 1: 1 and 3: 1, some examples of which are included in claims 2 to 6.
q
GB9804958A 1998-03-07 1998-03-07 Non-aqueous electrochemical cell containing conjugated polyimine functionality coupled to sulphur trioxide Withdrawn GB2335073A (en)

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GB9804958A GB2335073A (en) 1998-03-07 1998-03-07 Non-aqueous electrochemical cell containing conjugated polyimine functionality coupled to sulphur trioxide

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005015676A2 (en) * 2003-08-08 2005-02-17 Lexcel Technology Limited Electrochemical cell having 'in situ generated' component
WO2012025708A1 (en) 2010-08-27 2012-03-01 Qinetiq Limited Preparation of electrode compositions
GB2487036B (en) * 2010-08-27 2016-06-29 Qinetiq Ltd Preparation of electrode compositions
WO2018090097A1 (en) * 2016-11-18 2018-05-24 Newsouth Innovations Pty Limited Electrochemical cell

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4879192A (en) * 1983-09-21 1989-11-07 Hitachi Ltd. Secondary cell
DE4015147A1 (en) * 1989-10-10 1991-07-11 Ruhla Fahrzeugelektrik Polymer electrode for electrochemical storage elements - comprises at least 90 wt. per cent thermally-structured polyacrylonitrile with specific surface 500-1500 sq. m per g
GB2266179A (en) * 1992-04-03 1993-10-20 Alexander Gilmour Electrochemical cells with complex of sulphur trioxide and tertiary amine polymer as cathode
GB2309703A (en) * 1996-01-31 1997-08-06 Aea Technology Plc Polymer electrolyte
US5658586A (en) * 1994-10-28 1997-08-19 The Procter & Gamble Company Denture stabilizing compositions
EP0803925A1 (en) * 1995-01-18 1997-10-29 Japan Storage Battery Company Limited Nonaqueous polymer cell and method of producing polymer for nonaqueous polymer cell
US5693433A (en) * 1993-01-07 1997-12-02 Technology Resources International, Inc. Lithium-ion-conductive solid polymer electrolyte and method for its preparation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4879192A (en) * 1983-09-21 1989-11-07 Hitachi Ltd. Secondary cell
DE4015147A1 (en) * 1989-10-10 1991-07-11 Ruhla Fahrzeugelektrik Polymer electrode for electrochemical storage elements - comprises at least 90 wt. per cent thermally-structured polyacrylonitrile with specific surface 500-1500 sq. m per g
GB2266179A (en) * 1992-04-03 1993-10-20 Alexander Gilmour Electrochemical cells with complex of sulphur trioxide and tertiary amine polymer as cathode
US5693433A (en) * 1993-01-07 1997-12-02 Technology Resources International, Inc. Lithium-ion-conductive solid polymer electrolyte and method for its preparation
US5658586A (en) * 1994-10-28 1997-08-19 The Procter & Gamble Company Denture stabilizing compositions
EP0803925A1 (en) * 1995-01-18 1997-10-29 Japan Storage Battery Company Limited Nonaqueous polymer cell and method of producing polymer for nonaqueous polymer cell
GB2309703A (en) * 1996-01-31 1997-08-06 Aea Technology Plc Polymer electrolyte

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005015676A2 (en) * 2003-08-08 2005-02-17 Lexcel Technology Limited Electrochemical cell having 'in situ generated' component
WO2005015676A3 (en) * 2003-08-08 2008-01-03 Lexcel Technology Ltd Electrochemical cell having 'in situ generated' component
WO2012025708A1 (en) 2010-08-27 2012-03-01 Qinetiq Limited Preparation of electrode compositions
US9159498B2 (en) 2010-08-27 2015-10-13 Qinetiq Limited Preparation of electrode compositions
GB2487036B (en) * 2010-08-27 2016-06-29 Qinetiq Ltd Preparation of electrode compositions
WO2018090097A1 (en) * 2016-11-18 2018-05-24 Newsouth Innovations Pty Limited Electrochemical cell

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