Solid state batteries

Abstract: A material which is particularly suitable for use in a composite cathode and which includes a complex of a salt formed between a metal ion capable of existing in at least two stable valency states or an aluminium ion together with a suitable anion and a solid plastics polymeric composition capable of forming a donor acceptor type bond with the metal (or aluminium) ion, wherein the material exhibits both ionic and electronic conductivities to a substantial degree.

Description: This invention relates to electrochemical cells and substances for use in components thereof, and is especially relevant to solid state cells for use in particular in rechargeable lithium batteries. Electrochemical cells comprising a lithium-containing anode, a lithium ion-containing polymeric electrolyte with high ionic conductivity and a cathode containing an active catholyte together with an electronically conducting material are well known. Cells of this type are also known with a composite cathode in which the active catholyte, for example a vanadium oxide such as V₆O₁₃, and the electronically conducting material are distributed throughout polymeric electrolyte material, for example a complex between poly(ethylene oxide), referred to hereinafter as PEO, and lithium trifluoromethane sulphonate, i.e. (PEO) x LiF₃ CSO₃, the electronically conducting material, for example carbon black, forming an electronically conducting phase in the composite. However, problems can arise from a lack of continuity of the electronically conducting phase and/or poor contact between the conducting material and the active catholyte caused by unequal distribution of the conducting material within the polymeric electrolyte. GB-A-2157066 discloses a solid state polymer electrolyte comprising a complex of a metal salt and poly(ethylene oxide) PEO. The metal salt may comprise a magnesium, calcium, zinc or aluminium cation and a thiocyanate, perchlorate, trifluoromethane sulphonate or tetrafluorobonate anion. It is also known from "Solid State Ionics" volume 18/19, part 1, January 1986, pages 315-320, to dope a poly(ethylene oxide) electrolyte with copper chloride or perchlorate. In accordance with the invention, there is provided a material which includes a complex of a salt formed between a copper ion capable of existing in at least two stable valency states together with an anion of trifluoromethane sulphonate and a solid plastics polymeric composition poly(ethylene oxide) capable of forming a donor acceptor type bond with the copper ion characterised in that the material comprises (PEO) x (Cu(CF₃SO₃)₂ where x ≦ 8 and exhibits both ionic and electronic conductivities to a substantial degree. Preferably the ionic and electronic conductivities are comparable with each other and preferably the material of the invention provides an electronic conductivity at least equal to its ionic conductivity. Such materials are particularly suitable for use as composite cathode materials. However they may be employed in other applications in which combined ionic and electronic conductivities are required. Reference has previously been made in the art to the specific complex: (PEO)₉ Cu(CF₃SO₃)₂ in connection with its possible use as an electrolyte material, i.e. a use requiring high ionic conductivity, but is has been found that in this particular complex the electronic conductivity, as opposed to its ionic conductivity, is negligible. The electronic conductivity of the materials of the invention may be induced or enhanced either by a simple heat treatment, for example at or above 45°C, following which the conductivity remains high or by the presence of a source of copper, for example, copper metal. In accordance with further aspects of the invention, the material of the invention also includes (by mixing or otherwise) a lithium-ion containing polymeric substance, for example, an electrolyte substance. Advantageously, the lithium-ion containing substance is: (PEO) x LiCF₃SO₃ in which "x" can be varied over a range of, say, 3 to 25 and most preferably is from 8 to 10, for example 9. In particular, electronic conductivity of such complexes can also be generated in the poly(ethylene oxide) portion of the complexes. A material in which a mixed complex: PEO: x LiCF₃SO₃ : Cu (CF₃ SO₃)₂ is present and in which the value of "x" can again be varied is especially preferred. The materials of the invention and in particular those including a lithium-ion containing polymeric substance can be formed into useful composite cathodes by introducing therein an active catholyte. Examples of such catholytes are vanadium oxides; V₆ O₁₃ is preferred. Use of such a composite cathode can provide in general an improved electrochemical cell in view of the continuity of both ionic and electronic pathways in the composite cathode. In addition, because of the difficulties of trying to ensure a homogeneous distribution of previously employed electronic conducting agents in previously used cathodes, cell manufacturing techniques are less complicated. As with known cells, the composite cathode can usefully be employed in conjunction with a lithium, lithium alloy or other lithium-containing anodes, with an electrolyte, preferably a polymeric electrolyte and, if necessary, with relevant current collectors, for example nickel foil, and insulators. Batteries based on such cell constructions can be assembled by standard techniques. To illustrate the invention, certain tests were conducted on a variety of cells, all of which had a lithium anode and an electrolyte comprising (PEO)₉ LiCF₃ SO₃. The cathode of the various cells 1 to 7 contained V₆O₁₃ as active catholyte dispersed in the polymeric complex of the electrolyte above mixed with the complex: (PEO) x Cu (CF₃ SO₃)₂ where the value of "x" varies from cell to cell as shown below. A comparative cell "A" was also tested, which contained neither carbon nor the copper complex. The cells were vacuum laminated and were cycled at 120°C with a C/10 discharge rate and a C/20 charge rate. The results of these tests showed that the addition of the copper complex has a marked effect on cycle performance in terms of cell capacity retention on cycling even at the relatively small additions of Cell Nos. 1, 2 and 3; the tests showed that the cycling behaviour of Cells Nos. 4 to 7 is even better. In all cases the results showed the Cells 1 to 7 using cathode material in accordance with the invention to be superior to the carbon free Cell A.

Claims: A material which includes a complex of a salt formed between a copper ion capable of existing in at least two stable valency states together with an anion of trifluoromethane sulphonate and a solid plastics polymeric composition poly(ethylene oxide) capable of forming a donor acceptor type bond with the copper ion, characterised in that the material comprises (PEO) x Cu(CF₃SO₃)₂ where x ≦ 8 and exhibits both ionic and electronic conductivities to a substantial degree. A material according to any preceding claim which also contains a lithium-ion containing polymeric substance. A material according to claim 2 comprising the mixed complex (PEO) x : Li CF₃SO₃ : Cu(CF₃SO₃)₂ A composite cathode comprising the material according to any one of claims 1 to 3 in which an active catholyte is dispersed. A composite cathode according to claim 4 in which the active catholyte is a vanadium oxide. An electrochemical cell comprising the composite cathode of claim 4 or claim 5 together with a lithium-based anode and a polymeric electrolyte.

Inventors: HOOPER ALAN, NEAT ROBIN JOHN, NORTH JOHN MALCOLM, HOOPER, ALAN, NEAT, ROBIN JOHN, NORTH, JOHN MALCOLM
Applicants: DOWTY ELECTRONIC COMPONENTS, DOWTY ELECTRONIC COMPONENTS LIMITED
Application year: 1988
Main classification: H01M4
IPC codes: H01M4, H01M10