WO2011015866A1 - Electrical device - Google Patents

Electrical device Download PDF

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Publication number
WO2011015866A1
WO2011015866A1 PCT/GB2010/051283 GB2010051283W WO2011015866A1 WO 2011015866 A1 WO2011015866 A1 WO 2011015866A1 GB 2010051283 W GB2010051283 W GB 2010051283W WO 2011015866 A1 WO2011015866 A1 WO 2011015866A1
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WO
WIPO (PCT)
Prior art keywords
electrolytically
active material
electrical device
conductive polymer
region
Prior art date
Application number
PCT/GB2010/051283
Other languages
French (fr)
Inventor
James Doyle
Graham Simpson Murray
Original Assignee
Bac2 Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bac2 Limited filed Critical Bac2 Limited
Publication of WO2011015866A1 publication Critical patent/WO2011015866A1/en

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    • H—ELECTRICITY
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    • H01M4/049—Manufacturing of an active layer by chemical means
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • 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
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Definitions

  • the present invention relates to electrical devices, and particularly to electrical devices comprising conductive polymer and an electrolytically-active material.
  • US 6 214 251 discloses a conductive polymer exhibiting ionic conductivity which can be used as a solid electrolyte.
  • a common method of forming such an electrolyte is to dissolve a salt in a polymer and solvent matrix. More specifically current solid polymer electrolytes are made most practically by dissolving the solid polymer and salts in high boiling point polar organic solvents prior to the casting of thin films. It is important that the solid electrolytes have sufficient mechanical and dimensional stability to separate the two electrodes.
  • existing solid polymer electrolytes for alkaline cells are prepared from mixtures of non-conducting polymers, non-volatile solvents and alkali metal salts.
  • Polymers such as poly(alkylene oxide) , poly (vinyl fluoride) , poly(vinylidene fluoride) , poly sulf one, polyacrylonitrile, polyester, polyether, poly (ethylene) imine, polymethacrylate, poly (ethylene succinate) , poly(N-propylaziridine) , poly(alkylene sulphide) s, poly (ethylene adipate) , or copolymers are known.
  • a major drawback with the commonly employed polymers is that they tend to be crystalline and therefore the ionic conductivity decreases when the temperature drops below the melting point of the matrix polymer.
  • the complex polymer film consisting of polyethylene oxide and alkali metal salt has an ionic conductivity of around 10 3 S cm 1 at temperatures of 100 0 C, or higher but an ionic conductivity of 10 8 S cm 1 at room temperatures.
  • These solid polymer electrolytes are therefore limited to high temperature operating conditions. This low conductivity at ambient temperatures is a major limitation for widespread application of solid polymer electrolytes. Conductive polymers exhibiting some ionic conductivity at low or ambient temperature are preferred for use in a solid state electrical device.
  • Acidic ionic conducting polymers are typically sulphonated and phosphonated polymers such as sulphonated tetrafluoroethylene, sulphonated novolak, sulphonated polystyrene, sulphonated polyurethane, phosphonated poly(arylene ether) s, phosphonated polysulfones. These polymers are usually supplied in the form of films or powders. [006] A way of ameliorating these problems has been sought.
  • an optionally solid state electrical device comprising an electrolytically active material and a conductive polymer.
  • An optionally solid-state electrical device has many attractive features. It can be moulded or cast into many different forms and sizes, does not require a separator, does not leak electrolyte, and has good common ion mobility and high ion concentration.
  • An example electrical device is an electrochemical cell.
  • Most electrochemical cell fabrication involves a three layer architecture whereby an electrolyte layer is sandwiched between a positive material layer and a negative material layer. Generally each of these layers is individually prepared from binding materials using various coating processes and the layers are adhered together to produce a unitary cell. Stacking or grouping a number of these cells results in high voltage/energy multi-cell battery operation.
  • a "cell” refers to an "electrochemical cell” and a “battery” refers to a combination of two or more cells.
  • a cell or battery may be a primary cell or a primary battery which are systems capable of a single discharge of energy. Alternatively a cell or battery may be a secondary cell or a secondary battery which are systems capable of multiple discharge and recharge of energy.
  • Cell configuration or structure refers to the manipulation and composition of the cell layers.
  • conductive may mean a conductivity of at least 1 x 10 5 Scnr 1 .
  • a conductive material as defined herein has a resistivity of 5 xlO 6 Ohms cm or less, for example a resistivity of 2 xlO 4 Ohms or less.
  • the resistivity may be a surface resistivity.
  • the electrolytically active material comprises a reducing material, optionally an oxidising material.
  • a reducing material optionally an oxidising material.
  • at least a portion of each of the reducing material and the oxidising material (where present) is embedded in the conductive polymer.
  • the oxidising material may be provided by at least partially exposing the electrical device to air.
  • the electrical device comprises a first electrolytically-active material which comprises a reducing material and a second electrolytically-active material which comprises an oxidising material.
  • a first volume of first electrolytically-active material and a second volume of second electrolytically-active material may be separated by a third volume of electrolyte comprising a conductive polymer which third volume is substantially free from an electrolytically- active material.
  • the electrical device may comprise more than one first volumes and more than one second volumes.
  • the electrical device comprises three regions: a first region comprising a first electrolytically-active material embedded in a host conductive polymer, a second region comprising the conductive polymer and a third region comprising a second electrolytically-active material embedded in a host conductive polymer.
  • the first region and the third region are generally separated by the second region.
  • the conductive polymer used in each region may be the same or different.
  • the conductive polymers in adjacent regions is the same or similar (e.g. similar to the extent that the polymeric components of each conductive polymer are the same) . This is because the interface between the regions is expected to be improved.
  • the first and third region may form electrodes.
  • the second region may form an electrolyte.
  • the region comprising the first electrolytically-active material is the cathode on discharge and the region comprising the second electrolytically-active material is the anode on discharge. If the electrical device is chargeable, on charge the material roles are reversed.
  • the electrical device may be a solid state electrical device. Solid polymer electrolytes are desirable in the construction of electrical devices in order to avoid leakage from liquid electrolytes. They also offer other advantages over liquid electrolytes in that they enable the fabrication of cheaper, safer, smaller and lighter solid state products which are suitable for use in many different applications.
  • the electrical device of the present invention comprises a conductive polymer which, in its pre-cured form, can wet and bind the electrolytically-active material.
  • the conductive polymer in its pre-polymer form can polymerise at low or ambient temperatures. It is also preferred that the pre-cured polymer composition which optionally contains an electrolytically-active material can be poured, cast, sprayed, moulded or spin coated into a shape or onto a substrate.
  • the conductive polymer may exhibit ion conductivity as the conductive polymer takes on the role of solid polymer electrolyte.
  • the electrolytically-active material may be in particulate form.
  • One advantage of having a particulate electrolytically-active material is that the transport of ions through the electrolyte between the cathode and anode during discharge and/or charge is improved. This is believed to be because of the increased surface area contact between the electrolytically-active material and the conductive polymer and/or electrolyte.
  • the conductive polymer may be a phenolic resole resin wherein the conductive polymer contains conducting alkaline salts.
  • the conductive polymer is an ester-cured alkaline phenolic resole resin and contains conducting alkaline salts
  • the electrical device comprises two or more, preferably three, regions the conducting alkaline salt may be the same in two or more of the regions. Alternatively, the conducting alkaline salt may be different in each of the regions.
  • the conductive polymer is an ester-cured phenolic resole resin containing conducting alkaline salts
  • the conductive polymer is not doped with a conductive material such as graphite.
  • the phenolic resin may be an acid cured solvented resole which is substantially free from water or an ester-cured alkaline phenolic resole resin.
  • An acid cured solvented resole resin suitable for use in the present application is described in international patent publication WO 2008/001089.
  • an acid cured solvented resole resin may comprise (i) a phenolic resole, (ii) a solvent and (iii) an acid.
  • the solvent (ii) may be a solvent as defined in paragraphs [010] , [011] and [012] of WO 2008/001089, the contents of which paragraphs are incorporated herein by reference.
  • the phenolic resole (i) may be a reaction product of a phenol-reactive aldehyde with a compound of formula (II) as defined in paragraphs [016] and [017] of WO 2008/001089, the contents of which paragraphs are incorporated herein by reference.
  • the phenol- reactive aldehyde may be a compound of formula (III) as defined in paragraphs [019] to [021] of WO 2008/001089, the contents of which paragraphs are incorporated herein by reference.
  • the phenolic resole may be a compound as defined in paragraph [018] of WO 2008/001089, the contents of which paragraph are incorporated herein by reference.
  • the acid (iii) may be an acid as defined in paragraphs [023] to [025] of WO 2008/001089, the contents of which paragraphs are incorporated herein by reference.
  • the amount of acid used may be as defined in paragraphs [022] and [027] of WO 2008/001089, the contents of which paragraphs are incorporated herein by reference.
  • An ester-cured alkaline phenolic resole resin suitable for use in the present application is described in international patent publication WO 2004/091015.
  • the ester-cured alkaline phenolic resole resin may be a reaction product of (a) an ester curing agent with (b) a phenolic resole and (c) a base.
  • the phenolic resole (b) may be a reaction product of (d) a phenol-reactive aldehyde with (e) an alkaline compound of formula (I) defined at the section from page 10 line 15 to page 12 line 8 of WO 2004/091015, the contents of which section is incorporated herein by reference.
  • the phenol-reactive aldehyde (d) may be a compound of formula (II) defined at the section from page 12 lines 10 to 30 of WO 2004/091015, the contents of which section is incorporated herein by reference.
  • the phenolic resole (b) may be as defined in the section from page 11 line 30 to page 12 line 8 of WO 2004/091015, the contents of which section is incorporated herein by reference.
  • the base (c) may be as defined in the section at page 13 from line 1 to line 6 and in the section at page 15 from line 4 to line 10 of WO 2004/091015 , the contents of which sections are incorporated herein by reference.
  • the ester curing agent (a) may be as defined in the section from page 13 line 8 to page 15 line 2 of WO 2004/091015, the contents of which section is incorporated herein by reference.
  • ester-cured alkaline phenolic resole resin may be as defined in the section at page 15 from line 12 to line 30 of WO 2004/091015, the contents of which section is incorporated herein by reference.
  • the term substantially free from water in the present specification is intended to cover a water content which is sufficiently low for the phenolic resole to be cured by a sufficient amount of acid for the resin to have conductive properties without a violent exotherm when the acid and phenolic resole are mixed.
  • This water content may easily be determined by a person of skill in the art depending on the starting materials used.
  • the water content is less than 5% by weight, preferably less than 4% by weight, preferably less than 3% by weight, preferably less than 2% by weight, preferably less than 1% by weight.
  • the conductive polymer optionally includes a plasticiser to increase flexibility of the polymer.
  • the electrolytically-active material may be in the form of a powder.
  • a suitable first electrolytically- active material includes zinc for use as an anode/reducing material in a primary cell or battery.
  • Other common examples of a first electrolytically-active materials can be selected from Mg, Cd, Li, Pb, Fe, H 2 , Nickel Hydride, Li, Li x C 6 , Na, K, for the anode/reducing material.
  • Examples of a second electrolytically-active material include a catalytically active material, MnO 2 , HgO, AgO, SOCl 2 , SO 2 , FeS 2 , (CF) n , I 2 (P2VP) , PbO 2 , NiO 2 , FeS, NiCl 2 , S, for the cathode/oxidising material.
  • the catalytically active material may be a material that can function as an oxidising material by using oxygen in air. Examples of such catalytically active materials include zinc, platinum, iridium, gold, titanium, zirconium, tungsten and/or tantalum and/or an acidic salt thereof.
  • an electrical device wherein the first electrolytically-active material comprises zinc.
  • the conductive polymer may be an ester cured alkaline phenolic resole resin and may contain conducting alkaline salts.
  • the conducting alkaline salts are preferably one or a mixture of alkali metal hydroxides.
  • alkali metal hydroxide refers to lithium hydroxide, sodium hydroxide or potassium hydroxide.
  • the conducting alkaline salts are one or a mixture of lithium hydroxide and potassium hydroxide.
  • the ester curing agent may be triacetin or butyrolactone.
  • an electrical device wherein the first electrolytically-active material comprises lead and the oxidising material comprises lead oxide.
  • the conductive polymer may be an acid cured solvented resole wherein the solvented resole is substantially free from water.
  • the acid may be para-toluene sulphonic acid.
  • the electrical device may further comprise one or more separator and/or bipolar plates.
  • the one or more separator and/or bipolar plate may comprise said conductive polymer composition.
  • the electrical device may comprise a cathode and an anode which are positioned parallel and spaced apart from one another and have an electrolyte provided therebetween.
  • the cathode, anode and the electrolyte may be co-extensive.
  • the cathode, anode and the electrolyte may be planar.
  • the electrolyte preferably contacts each of the cathode and anode.
  • the electrical device may be fabricated in order to interconnect with a further electrical device.
  • the electrical device may have any suitable shape such as to facilitate good chemical conversion yet conform to the users requirements, for example the device may be a disc (sometimes referred to as coin or button shaped) , or it may be elliptical, spherical or cylindrical.
  • the electrical device may be connected in series or in parallel with one or more other suitable electrical devices.
  • the electrical device is preferably a cell or a battery.
  • a battery comprising a plurality of the electrical devices according to the invention connected in series and/or in parallel.
  • the battery according to the invention may include one or more of a casing and positive and negative terminals to provide an electrical connection to the electrical device.
  • the battery may comprise a layer profile, for example a laminated layer profile.
  • a stack is defined as having a cathode terminal of a first electrical device according to the invention connected directly to the anode terminal of a second electrical device according to the invention or vice versa.
  • This profile can be physically constructed in series or in parallel, which is achieved by connecting individual cell electrodes in the standard electronic series or parallel configurations.
  • Electrodes are made possible by the use of a conductive polymer to form the electrolyte and to bind the electrolytically-active material(s) , giving rise to increased surface area contact between the electrodes and the electrolyte.
  • a conductive polymer to form the electrolyte and to bind the electrolytically-active material(s) , giving rise to increased surface area contact between the electrodes and the electrolyte.
  • the choice of shapes and configurations allows the batteries or cells of the present invention to have a variety of end uses, for example elliptical or spherical batteries or cells may be of great use in surgical implantation or medical injection.
  • One or more of the electrodes may be connected to an external current collector.
  • the current collector is optionally formed from graphite, conductive polymer, semi-metal, an inorganic compound or complex, an organic species supported on carbon (for example: SOCl 2 , LiAlCl 4 , LiAg 2 CrO 4 ) and/or metal (e.g Pb, Zn, Pt, PtO etc) .
  • the graphite may be provided as a layer or volume of graphite, as a conductive polymer composite.
  • graphite may be doped with a metal, semi-metal, inorganic compound or complex or organic species supported on carbon (e.g. Pb, Zn, Pt, PtO, Pb) .
  • the metal may be provided as a metal grid, a metal foil or a metal mesh.
  • an integrated circuit board comprising the electrical device of the present invention.
  • Such an integrated circuit board can be interfaced with computer or circuit board equipment.
  • the curing steps generally each take place under ambient conditions.
  • the curing steps may be accelerated by heating. Temperatures of 30 to 70 0 C, preferably 40 to 60 0 C, most preferably 50 0 C may be appropriate to accelerate curing.
  • Steps (a) , (b) and/or (c) may be performed by depositing the conductive polymer or the conductive polymer mixed with the first or second electrolytically-active material.
  • a depositing step is preferably achieved by moulding or casting.
  • the conductive polymer and the mixtures of the conductive polymer with the first or second electrolytically-active material may be cast or deposited as layers.
  • a mould may be any suitable mould, for example a picture frame mould or a plate.
  • the mould may have contours or be planar.
  • the electrical device of the present invention may lack an adhesive to adhere the electrode layers to the electrolyte.
  • An adhesive may not be necessary if in the process according to the invention the electrodes and electrolyte are cast or deposited directly against one another.
  • the electrical device may have no separator.
  • Figures IA and 2A are respectively a perspective view and a side view of an electrochemical, galvanic cell according to an embodiment of the invention.
  • Figures 2A and 2B are respectively a perspective view and a side view of vertically stacked galvanic cells connected in series forming a battery according to an embodiment of the invention.
  • Figure 1 shows a three layer electrochemical galvanic cell 1. The anode 2 and cathode 3 are separated by electrolyte 4.
  • Figure 2 shows a plurality of cells 1 of Figure 1 vertically stacked and connected in series forming a battery 10.
  • the invention is illustrated by the following Examples which are not intended to limit the scope of the invention claimed.
  • alkaline cells according to an embodiment of the invention comprising: a positive electrode, a negative electrode, and a solid electrolyte, wherein the conductive polymer is an ester-cured alkaline phenolic resole resin which polymer contains conducting alkaline salts and the positive and negative electrodes each contain an electrolytically-active material.
  • the conductive polymer is an ester-cured alkaline phenolic resole resin which polymer contains conducting alkaline salts and the positive and negative electrodes each contain an electrolytically-active material.
  • the Examples also illustrate how to prepare acid cells according to an embodiment of the invention comprising: a positive electrode, a negative electrode, and a solid electrolyte, wherein the conductive polymer composition is an acid cured solvented resole wherein the solvented resole is substantially free from water and the positive and negative electrodes each contain an electrolytically-active material.
  • Resin 1 - Fenotec a potassium hydroxide based alkaline phenolic resole ex Dynea
  • Active materials zinc powder, flake graphite (ex Branwell Graphite) , lead powder, lead oxide, manganese dioxide, magnesium powder, lithium cobalt oxide and acetone.
  • the electrical device of this Example has a cathode layer, electrolyte layer and anode layer.
  • the cathode layer was made by mixing resin 1 , triacetin and a second electrolytically-active material in the form of 150-500 ⁇ m graphite flakes (20:5: 100 parts by weight) , in a Kenwood mixer. The mixture was then moulded under 20 MPa (200 bar) pressure at 60 0 C for 10 minutes in a "picture frame" mould 150 x 150 x 3 mm in dimension. The moulded cathode layer was cut down to 40 x 40 x 3mm for the tests. For ease of layer fabrication additional composites were prepared in solution.
  • the electrolyte layer was made by mixing resin 1 (5 parts) and triacetin (1 part) for 1 minute then doctor blading technique was employed to deposit the electrolyte layer of resin 1 and triacetin (5: 1 parts by weight) mixture onto the cathode plate. The deposited electrolyte layer took 4-5 minutes to harden. Scotch tape was added as a mask to control layer film thickness and deposition area. Finally the anode electrode layer, a mixture of resin 1 , triacetin and a first electrolytically-active material in the form of zinc metal powder having a particle size of 3 ⁇ m (5: 1 :4 parts by weight) , was deposited on top of this electrolyte layer. All layers were allowed to cure under ambient conditions.
  • the electrical device of this Example has a cathode layer, electrolyte layer and anode layer.
  • the cathode layer was made using a hand mixed combination of resin 1 , triacetin and a second electrolytically- active material in the form of graphite (5: 1 :20 parts by weight) and pressed onto a glass slide as a base plate.
  • the electrolyte and anode layers were made as in Example 1.
  • the electrical device of this Example has a cathode layer, electrolyte layer and anode layer.
  • the cathode electrode layer was fabricated by mixing resin 1 , triacetin, a second electrolytically-active material comprising manganese dioxide powder having a particle size of lO ⁇ m and graphite fibre having a size of 150 ⁇ m (10:2:7: 1 ratio in parts by weight) , in a Kenwood mixer. The mixture was then moulded under 20 MPa (200 bar) pressure at 60 0 C for 10 minutes in a 40x60x2 mm mould. For ease of layer fabrication, additional composites were prepared in solution.
  • the electrolyte layer was made by mixing resin 1 (5 parts by weight) and triacetin (5: 1 parts by weight) for 1 minute followed by depositing via the doctor blade technique onto the cathode plate. The deposited electrolyte layer took 4-5 minutes to harden. Scotch tape was added as a mask to control layer film thickness and deposition area. Finally the anode electrode layer - a mixture of resin 1 , triacetin and a first electrolytically-active material in the form of zinc metal powder having a particle size of 3 ⁇ m (10:2:7 parts by weight) , was deposited on top of this electrolyte layer. [072] The resulting three layer device was tested using a multimeter at room temperature to probe the current flowing through and the potential difference across the device. The results obtained are shown in Table 1.
  • the electrical device of this Example has a cathode layer, electrolyte layer and anode layer.
  • the cathode layer was made using a mechanically mixed combination of resin 1 , triacetin and a second electrolytically-active material in the form of a manganese dioxide powder having a particle size of less than 4 ⁇ m (10:2:7 parts by weight) and pressed as in Example 1.
  • the electrolyte was made as in Example 1.
  • the anode layer was fabricated using a hand mixed combination of resin
  • the electrical device of this Example has a cathode layer, electrolyte layer and anode layer.
  • the cathode layer was made using a hand mixed combination of resin 1 , triacetin and a second electrolytically- active material in the form of lithium cobalt oxide powder having a particle size of less than 4 ⁇ m (10:2:7 parts by weight) and cast into a mould to form a base plate.
  • the electrolyte and anode layers were made as in Example 3.
  • the electrical device of this Example is an acid cell and has a cathode layer, electrolyte layer and anode layer. It was made by first laying down the anode layer consisting of a mixture of a second electrolytically-active material comprising lead powder having a particle size of about 44 ⁇ m, resin 3 and acetone (10:2.5:0.5 parts by weight) in a plastic cup. To this mix, 1.25 parts by weight of para-toluene sulphonic acid was added. The mixture was poured onto a polythene plastic card (used as a base during fabrication) and placed in an oven at 50 0 C to accelerate the hardening process.
  • a polythene plastic card used as a base during fabrication
  • the electrolyte layer consisting of a mixture of resin 3, para- toluene sulphonic acid and acetone (10: 10: 1.1 parts by weight) was poured over the anode layer and allowed to harden.
  • the cathode layer was laid on top of the electrolyte layer by mixing a first electrolytically- active lead oxide powder having a particle size of less than 4 ⁇ m with resin 3 and acetone (8:5: 1 parts by weight) , adding 2.5 parts by weight of para-toluene sulphonic acid and pouring over the electrolyte layer then allowing to harden.
  • the electrical device of this Example has a cathode layer, electrolyte layer and anode layer.
  • the cathode layer was prepared by hand mixing a combination of resin 3, a second electrolytically-active material in the form of manganese dioxide powder having a particle size of lO ⁇ m and para-toluene sulphonic acid in a ratio of 10:7:5 parts by weight. This was pressed under 4MPa of pressure into 60xl5x3mm moulded plates. After curing the electrolyte layer was prepared consisting of resin 3 and para-toluene sulphonic acid (2: 1 parts by weight) . This was deposited using the doctor blade technique as outlined in Example 1.
  • the anode layer consisted of a hand mixed combination of resin 3, a first electrolytically-active material comprising Mg powder and para-toluene sulphonic acid (10:7:5 parts by weight) .
  • a first electrolytically-active material comprising Mg powder and para-toluene sulphonic acid (10:7:5 parts by weight) .
  • the electrical device of this Example has a cathode layer, electrolyte layer and anode layer.
  • the cathode layer consisted of resin 3, a second electrolytically-active material comprising manganese dioxide powder and graphite, and para-toluene sulphonic acid (10:7: 1 :5 parts by weight) .
  • the plate was prepared as outlined in Example 6.
  • the electrolyte layer was fabricated as outlined in Example 6.
  • a hand mixed combination of resin 3, a first electrolytically-active material comprising Zn powder, and para-toluene sulphonic acid (10:7:5 parts by weight) was prepared and deposited to form a t-layer device.
  • the electrical device of this Example has a cathode layer, electrolyte layer and anode layer.
  • the cathode layer consisted of a hand mixed composition of resin 1 diluted with isopropanol (IPA) , a second electrolytically-active material comprising manganese dioxide and carbon fibre, and cured with triacetin (10:2:7: 1 :2 parts by weight ratio, respectively) .
  • IPA isopropanol
  • This composite was spun cast onto lOxlOmm conductive glass (1.1mm thick Sodalime glass with 15 Ohm/Sq indium tin oxide coating) at a speed of > 2500rpm for 60 seconds. The sample was then placed in an oven at 80 0 C for 30 minutes.
  • the electrolyte layer consisted of resin 1 , diluted with IPA and cured with triacetin (5: 1 : 1 parts by weight) .
  • the resulting film was spun cast and post cured under the same conditions as the cathode layer.
  • the anode layer consisted of resin 1 diluted with IPA, with a first electrolytically-active material comprising zinc powder having a particle size of 3 ⁇ m and cured with triacetin (10:2:7:2 parts by weight) .
  • the resulting film was spun cast and post cured under the same conditions as the cathode layer.
  • the resulting three layer device was as represented in Figure 1. It was tested as described in Example 1 and the results obtained are shown in Table 1.

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Abstract

The invention relates to an optionally solid state electrical device comprising an electrolytically active material and a conductive polymer; a battery and integrated circuit comprising the device; and a method for its preparation.

Description

ELECTRICAL DEVICE
[001] The present invention relates to electrical devices, and particularly to electrical devices comprising conductive polymer and an electrolytically-active material.
[002] US 6 214 251 discloses a conductive polymer exhibiting ionic conductivity which can be used as a solid electrolyte. In alkaline cells, a common method of forming such an electrolyte is to dissolve a salt in a polymer and solvent matrix. More specifically current solid polymer electrolytes are made most practically by dissolving the solid polymer and salts in high boiling point polar organic solvents prior to the casting of thin films. It is important that the solid electrolytes have sufficient mechanical and dimensional stability to separate the two electrodes.
[003] Typically, existing solid polymer electrolytes for alkaline cells are prepared from mixtures of non-conducting polymers, non-volatile solvents and alkali metal salts. Polymers such as poly(alkylene oxide) , poly (vinyl fluoride) , poly(vinylidene fluoride) , poly sulf one, polyacrylonitrile, polyester, polyether, poly (ethylene) imine, polymethacrylate, poly (ethylene succinate) , poly(N-propylaziridine) , poly(alkylene sulphide) s, poly (ethylene adipate) , or copolymers are known.
[004] A major drawback with the commonly employed polymers is that they tend to be crystalline and therefore the ionic conductivity decreases when the temperature drops below the melting point of the matrix polymer. For example, the complex polymer film consisting of polyethylene oxide and alkali metal salt has an ionic conductivity of around 10 3 S cm 1 at temperatures of 1000C, or higher but an ionic conductivity of 10 8 S cm 1 at room temperatures. These solid polymer electrolytes are therefore limited to high temperature operating conditions. This low conductivity at ambient temperatures is a major limitation for widespread application of solid polymer electrolytes. Conductive polymers exhibiting some ionic conductivity at low or ambient temperature are preferred for use in a solid state electrical device. [005] Acidic ionic conducting polymers are typically sulphonated and phosphonated polymers such as sulphonated tetrafluoroethylene, sulphonated novolak, sulphonated polystyrene, sulphonated polyurethane, phosphonated poly(arylene ether) s, phosphonated polysulfones. These polymers are usually supplied in the form of films or powders. [006] A way of ameliorating these problems has been sought.
[007] According to the present invention there is provided an optionally solid state electrical device comprising an electrolytically active material and a conductive polymer.
[008] An optionally solid-state electrical device according to the invention has many attractive features. It can be moulded or cast into many different forms and sizes, does not require a separator, does not leak electrolyte, and has good common ion mobility and high ion concentration.
[009] An example electrical device is an electrochemical cell. Most electrochemical cell fabrication involves a three layer architecture whereby an electrolyte layer is sandwiched between a positive material layer and a negative material layer. Generally each of these layers is individually prepared from binding materials using various coating processes and the layers are adhered together to produce a unitary cell. Stacking or grouping a number of these cells results in high voltage/energy multi-cell battery operation. [010] In the context of the present specification a "cell" refers to an "electrochemical cell" and a "battery" refers to a combination of two or more cells. A cell or battery may be a primary cell or a primary battery which are systems capable of a single discharge of energy. Alternatively a cell or battery may be a secondary cell or a secondary battery which are systems capable of multiple discharge and recharge of energy. "Cell configuration or structure" refers to the manipulation and composition of the cell layers.
[Oil] In the context of the present specification the term conductive may mean a conductivity of at least 1 x 10 5 Scnr1. Optionally, a conductive material as defined herein has a resistivity of 5 xlO6 Ohms cm or less, for example a resistivity of 2 xlO4 Ohms or less. The resistivity may be a surface resistivity.
[012] Optionally the electrolytically active material comprises a reducing material, optionally an oxidising material. Optionally at least a portion of each of the reducing material and the oxidising material (where present) is embedded in the conductive polymer. The oxidising material may be provided by at least partially exposing the electrical device to air.
[013] In some embodiments, substantially all of the electrolytically- active material is embedded in the conductive polymer. In some embodiments, the electrical device comprises a first electrolytically-active material which comprises a reducing material and a second electrolytically-active material which comprises an oxidising material.
[014] In some embodiments, there is provided a first volume of first electrolytically-active material and a second volume of second electrolytically-active material. The first and second volumes may be separated by a third volume of electrolyte comprising a conductive polymer which third volume is substantially free from an electrolytically- active material. [015] The electrical device may comprise more than one first volumes and more than one second volumes.
[016] In one embodiment the electrical device comprises three regions: a first region comprising a first electrolytically-active material embedded in a host conductive polymer, a second region comprising the conductive polymer and a third region comprising a second electrolytically-active material embedded in a host conductive polymer. The first region and the third region are generally separated by the second region. The conductive polymer used in each region may be the same or different. Optionally the conductive polymers in adjacent regions is the same or similar (e.g. similar to the extent that the polymeric components of each conductive polymer are the same) . This is because the interface between the regions is expected to be improved.
[017] The first and third region may form electrodes. The second region may form an electrolyte. The region comprising the first electrolytically-active material is the cathode on discharge and the region comprising the second electrolytically-active material is the anode on discharge. If the electrical device is chargeable, on charge the material roles are reversed. [018] In some embodiments, the electrical device may be a solid state electrical device. Solid polymer electrolytes are desirable in the construction of electrical devices in order to avoid leakage from liquid electrolytes. They also offer other advantages over liquid electrolytes in that they enable the fabrication of cheaper, safer, smaller and lighter solid state products which are suitable for use in many different applications.
[019] In some embodiments, the electrical device of the present invention comprises a conductive polymer which, in its pre-cured form, can wet and bind the electrolytically-active material. In some embodiments, the conductive polymer in its pre-polymer form can polymerise at low or ambient temperatures. It is also preferred that the pre-cured polymer composition which optionally contains an electrolytically-active material can be poured, cast, sprayed, moulded or spin coated into a shape or onto a substrate. [020] In some embodiments, the conductive polymer may exhibit ion conductivity as the conductive polymer takes on the role of solid polymer electrolyte.
[021] None of the alkaline solid polymer electrolyte combinations disclosed in US 6 214 251 which are of dissolved polymer and salt in high boiling point solvent are suitable for use as binders of active electrode materials as no crosslinking mechanism is available to bind the active material and to maintain ionic conductivity at low or ambient temperatures. The acidic polymer electrolytes disclosed in US 6 214 251 are not binders of the active materials for the same reason. Additionally they are not in a form allowing wetting and binding of the electrolytically-active materials .
[022] In some embodiments, the electrolytically-active material may be in particulate form. One advantage of having a particulate electrolytically-active material is that the transport of ions through the electrolyte between the cathode and anode during discharge and/or charge is improved. This is believed to be because of the increased surface area contact between the electrolytically-active material and the conductive polymer and/or electrolyte.
[023] The conductive polymer may be a phenolic resole resin wherein the conductive polymer contains conducting alkaline salts.
[024] Where the conductive polymer is an ester-cured alkaline phenolic resole resin and contains conducting alkaline salts, and the electrical device comprises two or more, preferably three, regions the conducting alkaline salt may be the same in two or more of the regions. Alternatively, the conducting alkaline salt may be different in each of the regions. Where the conductive polymer is an ester-cured phenolic resole resin containing conducting alkaline salts, the conductive polymer is not doped with a conductive material such as graphite.
[025] The phenolic resin may be an acid cured solvented resole which is substantially free from water or an ester-cured alkaline phenolic resole resin. An acid cured solvented resole resin suitable for use in the present application is described in international patent publication WO 2008/001089. In some embodiments, an acid cured solvented resole resin may comprise (i) a phenolic resole, (ii) a solvent and (iii) an acid.
[026] The solvent (ii) may be a solvent as defined in paragraphs [010] , [011] and [012] of WO 2008/001089, the contents of which paragraphs are incorporated herein by reference. [027] In some embodiments, the phenolic resole (i) may be a reaction product of a phenol-reactive aldehyde with a compound of formula (II) as defined in paragraphs [016] and [017] of WO 2008/001089, the contents of which paragraphs are incorporated herein by reference. The phenol- reactive aldehyde may be a compound of formula (III) as defined in paragraphs [019] to [021] of WO 2008/001089, the contents of which paragraphs are incorporated herein by reference. The phenolic resole may be a compound as defined in paragraph [018] of WO 2008/001089, the contents of which paragraph are incorporated herein by reference.
[028] The acid (iii) may be an acid as defined in paragraphs [023] to [025] of WO 2008/001089, the contents of which paragraphs are incorporated herein by reference. The amount of acid used may be as defined in paragraphs [022] and [027] of WO 2008/001089, the contents of which paragraphs are incorporated herein by reference. [029] An ester-cured alkaline phenolic resole resin suitable for use in the present application is described in international patent publication WO 2004/091015. In some embodiments, the ester-cured alkaline phenolic resole resin may be a reaction product of (a) an ester curing agent with (b) a phenolic resole and (c) a base.
[030] In some embodiments, the phenolic resole (b) may be a reaction product of (d) a phenol-reactive aldehyde with (e) an alkaline compound of formula (I) defined at the section from page 10 line 15 to page 12 line 8 of WO 2004/091015, the contents of which section is incorporated herein by reference. The phenol-reactive aldehyde (d) may be a compound of formula (II) defined at the section from page 12 lines 10 to 30 of WO 2004/091015, the contents of which section is incorporated herein by reference. The phenolic resole (b) may be as defined in the section from page 11 line 30 to page 12 line 8 of WO 2004/091015, the contents of which section is incorporated herein by reference.
[031] The base (c) may be as defined in the section at page 13 from line 1 to line 6 and in the section at page 15 from line 4 to line 10 of WO 2004/091015 , the contents of which sections are incorporated herein by reference. [032] The ester curing agent (a) may be as defined in the section from page 13 line 8 to page 15 line 2 of WO 2004/091015, the contents of which section is incorporated herein by reference.
[033] The preparation of the ester-cured alkaline phenolic resole resin may be as defined in the section at page 15 from line 12 to line 30 of WO 2004/091015, the contents of which section is incorporated herein by reference.
[034] The term substantially free from water in the present specification is intended to cover a water content which is sufficiently low for the phenolic resole to be cured by a sufficient amount of acid for the resin to have conductive properties without a violent exotherm when the acid and phenolic resole are mixed. This water content may easily be determined by a person of skill in the art depending on the starting materials used. Preferably, the water content is less than 5% by weight, preferably less than 4% by weight, preferably less than 3% by weight, preferably less than 2% by weight, preferably less than 1% by weight.
[035] The conductive polymer optionally includes a plasticiser to increase flexibility of the polymer. [036] In some embodiments, the electrolytically-active material may be in the form of a powder. Examples of a suitable first electrolytically- active material includes zinc for use as an anode/reducing material in a primary cell or battery. Other common examples of a first electrolytically-active materials can be selected from Mg, Cd, Li, Pb, Fe, H2, Nickel Hydride, Li, LixC6, Na, K, for the anode/reducing material. Examples of a second electrolytically-active material include a catalytically active material, MnO2, HgO, AgO, SOCl2, SO2, FeS2, (CF)n, I2(P2VP) , PbO2, NiO2, FeS, NiCl2, S, for the cathode/oxidising material. The catalytically active material may be a material that can function as an oxidising material by using oxygen in air. Examples of such catalytically active materials include zinc, platinum, iridium, gold, titanium, zirconium, tungsten and/or tantalum and/or an acidic salt thereof.
[037] It is possible through the selection of suitable electrolytically- active material (s) and conductive polymer to fabricate an anode, a cathode and a solid electrolyte from the same conductive polymer enabling the manufacture of novel and inventive optionally solid-state battery and cell configurations and architectures.
[038] In one embodiment there is provided an electrical device wherein the first electrolytically-active material comprises zinc. The conductive polymer may be an ester cured alkaline phenolic resole resin and may contain conducting alkaline salts. The conducting alkaline salts are preferably one or a mixture of alkali metal hydroxides. The term "alkali metal hydroxide" refers to lithium hydroxide, sodium hydroxide or potassium hydroxide. In some embodiments, the conducting alkaline salts are one or a mixture of lithium hydroxide and potassium hydroxide. The ester curing agent may be triacetin or butyrolactone.
[039] In a further embodiment there is provided an electrical device wherein the first electrolytically-active material comprises lead and the oxidising material comprises lead oxide. The conductive polymer may be an acid cured solvented resole wherein the solvented resole is substantially free from water. The acid may be para-toluene sulphonic acid.
[040] The electrical device may further comprise one or more separator and/or bipolar plates. The one or more separator and/or bipolar plate may comprise said conductive polymer composition.
[041] In the following paragraphs the word "electrode" is to be interpreted to include regions or volumes of electrolytically-active material. [042] The electrical device may comprise a cathode and an anode which are positioned parallel and spaced apart from one another and have an electrolyte provided therebetween.
[043] The cathode, anode and the electrolyte may be co-extensive. The cathode, anode and the electrolyte may be planar. [044] The electrolyte preferably contacts each of the cathode and anode. The electrical device may be fabricated in order to interconnect with a further electrical device. [045] The electrical device may have any suitable shape such as to facilitate good chemical conversion yet conform to the users requirements, for example the device may be a disc (sometimes referred to as coin or button shaped) , or it may be elliptical, spherical or cylindrical.
[046] The electrical device may be connected in series or in parallel with one or more other suitable electrical devices. The electrical device is preferably a cell or a battery.
[047] According to the invention there is also provided a battery comprising a plurality of the electrical devices according to the invention connected in series and/or in parallel. The battery according to the invention may include one or more of a casing and positive and negative terminals to provide an electrical connection to the electrical device.
[048] The battery may comprise a layer profile, for example a laminated layer profile. A stack is defined as having a cathode terminal of a first electrical device according to the invention connected directly to the anode terminal of a second electrical device according to the invention or vice versa. This profile can be physically constructed in series or in parallel, which is achieved by connecting individual cell electrodes in the standard electronic series or parallel configurations.
[049] All of these cell and battery configurations are made possible by the use of a conductive polymer to form the electrolyte and to bind the electrolytically-active material(s) , giving rise to increased surface area contact between the electrodes and the electrolyte. [050] The choice of shapes and configurations allows the batteries or cells of the present invention to have a variety of end uses, for example elliptical or spherical batteries or cells may be of great use in surgical implantation or medical injection. [051] One or more of the electrodes may be connected to an external current collector. The current collector is optionally formed from graphite, conductive polymer, semi-metal, an inorganic compound or complex, an organic species supported on carbon (for example: SOCl2, LiAlCl4, LiAg2CrO4) and/or metal (e.g Pb, Zn, Pt, PtO etc) . Where the current collector is formed from graphite, the graphite may be provided as a layer or volume of graphite, as a conductive polymer composite. Optionally, graphite may be doped with a metal, semi-metal, inorganic compound or complex or organic species supported on carbon (e.g. Pb, Zn, Pt, PtO, Pb) . Where the current collector is formed from metal, the metal may be provided as a metal grid, a metal foil or a metal mesh.
[052] According to the invention there is also provided an integrated circuit board comprising the electrical device of the present invention. Such an integrated circuit board can be interfaced with computer or circuit board equipment.
[053] According to the invention there is also provided a method of preparing the electrical device according to the invention which method comprises the steps of:
(a) providing a first electrode comprising a mixture of a conductive polymer with a first electrolytically-active material;
(b) providing an electrolyte comprising a conductive polymer;
(c) providing a second electrode comprising a conductive polymer with a second electrolytically-active material; and
(d) curing the conductive polymer. [054] The curing steps generally each take place under ambient conditions. The curing steps may be accelerated by heating. Temperatures of 30 to 700C, preferably 40 to 600C, most preferably 500C may be appropriate to accelerate curing.
[055] Steps (a) , (b) and/or (c) may be performed by depositing the conductive polymer or the conductive polymer mixed with the first or second electrolytically-active material. A depositing step is preferably achieved by moulding or casting. The conductive polymer and the mixtures of the conductive polymer with the first or second electrolytically-active material may be cast or deposited as layers. A mould may be any suitable mould, for example a picture frame mould or a plate. The mould may have contours or be planar.
[056] In some embodiments, the electrical device of the present invention may lack an adhesive to adhere the electrode layers to the electrolyte. An adhesive may not be necessary if in the process according to the invention the electrodes and electrolyte are cast or deposited directly against one another. In some embodiments, the electrical device may have no separator.
[057] The invention is illustrated by reference to the following Figures of the drawings which are not intended to limit the scope of the invention claimed: Figures IA and 2A are respectively a perspective view and a side view of an electrochemical, galvanic cell according to an embodiment of the invention; and
Figures 2A and 2B are respectively a perspective view and a side view of vertically stacked galvanic cells connected in series forming a battery according to an embodiment of the invention.
[058] The figures show possible electrical device structures or configurations that could be achieved as part of the present invention. [059] Figure 1 shows a three layer electrochemical galvanic cell 1. The anode 2 and cathode 3 are separated by electrolyte 4.
[060] Figure 2 shows a plurality of cells 1 of Figure 1 vertically stacked and connected in series forming a battery 10. [061] The invention is illustrated by the following Examples which are not intended to limit the scope of the invention claimed.
EXAMPLES
[062] The following Examples, which are not intended to limit the scope of the invention claimed, illustrate how to prepare alkaline cells according to an embodiment of the invention comprising: a positive electrode, a negative electrode, and a solid electrolyte, wherein the conductive polymer is an ester-cured alkaline phenolic resole resin which polymer contains conducting alkaline salts and the positive and negative electrodes each contain an electrolytically-active material. The Examples also illustrate how to prepare acid cells according to an embodiment of the invention comprising: a positive electrode, a negative electrode, and a solid electrolyte, wherein the conductive polymer composition is an acid cured solvented resole wherein the solvented resole is substantially free from water and the positive and negative electrodes each contain an electrolytically-active material.
[063] In these Examples the materials used are:
Resin 1 - Fenotec, a potassium hydroxide based alkaline phenolic resole ex Dynea
Resin 2 - lithium hydroxide based alkaline phenolic resole ex Dynea
Resin 3 - a solvented resole ex Dynea
Esters - butyrolactone and triacetin Catalyst - para-toluene sulphonic acid 65 weight% aqueous solution Plasticiser - polyethylene glycol
Active materials - zinc powder, flake graphite (ex Branwell Graphite) , lead powder, lead oxide, manganese dioxide, magnesium powder, lithium cobalt oxide and acetone.
[064] The preparation of the electrochemical cell examples were as follows. Examples 1-4 and 8 were of alkaline cells whereas Example 5-7 are of acid cells. EXAMPLE 1
[065] The electrical device of this Example has a cathode layer, electrolyte layer and anode layer. The cathode layer was made by mixing resin 1 , triacetin and a second electrolytically-active material in the form of 150-500μm graphite flakes (20:5: 100 parts by weight) , in a Kenwood mixer. The mixture was then moulded under 20 MPa (200 bar) pressure at 600C for 10 minutes in a "picture frame" mould 150 x 150 x 3 mm in dimension. The moulded cathode layer was cut down to 40 x 40 x 3mm for the tests. For ease of layer fabrication additional composites were prepared in solution. [066] The electrolyte layer was made by mixing resin 1 (5 parts) and triacetin (1 part) for 1 minute then doctor blading technique was employed to deposit the electrolyte layer of resin 1 and triacetin (5: 1 parts by weight) mixture onto the cathode plate. The deposited electrolyte layer took 4-5 minutes to harden. Scotch tape was added as a mask to control layer film thickness and deposition area. Finally the anode electrode layer, a mixture of resin 1 , triacetin and a first electrolytically-active material in the form of zinc metal powder having a particle size of 3μm (5: 1 :4 parts by weight) , was deposited on top of this electrolyte layer. All layers were allowed to cure under ambient conditions.
[067] The resulting three layered electrical device was as represented in Figure 1 tested using a multimeter at room temperature to probe the current through and voltage across the device. The results obtained are shown in Table 1.
EXAMPLE 2
[068] The electrical device of this Example has a cathode layer, electrolyte layer and anode layer. The cathode layer was made using a hand mixed combination of resin 1 , triacetin and a second electrolytically- active material in the form of graphite (5: 1 :20 parts by weight) and pressed onto a glass slide as a base plate. The electrolyte and anode layers were made as in Example 1.
[069] The resulting three layered device was as represented in Figure 1. It was tested as described in Example 1 and the results obtained are shown in Table 1.
EXAMPLE 3
[070] The electrical device of this Example has a cathode layer, electrolyte layer and anode layer. The cathode electrode layer was fabricated by mixing resin 1 , triacetin, a second electrolytically-active material comprising manganese dioxide powder having a particle size of lOμm and graphite fibre having a size of 150μm (10:2:7: 1 ratio in parts by weight) , in a Kenwood mixer. The mixture was then moulded under 20 MPa (200 bar) pressure at 600C for 10 minutes in a 40x60x2 mm mould. For ease of layer fabrication, additional composites were prepared in solution. [071] The electrolyte layer was made by mixing resin 1 (5 parts by weight) and triacetin (5: 1 parts by weight) for 1 minute followed by depositing via the doctor blade technique onto the cathode plate. The deposited electrolyte layer took 4-5 minutes to harden. Scotch tape was added as a mask to control layer film thickness and deposition area. Finally the anode electrode layer - a mixture of resin 1 , triacetin and a first electrolytically-active material in the form of zinc metal powder having a particle size of 3μm (10:2:7 parts by weight) , was deposited on top of this electrolyte layer. [072] The resulting three layer device was tested using a multimeter at room temperature to probe the current flowing through and the potential difference across the device. The results obtained are shown in Table 1.
EXAMPLE 4
[073] The electrical device of this Example was fabricated as outlined in Example 1 with the exception that the compositions were hand mixed.
[074] The resulting three layer device was tested as described in Example 1 and the results obtained are shown in Table 1.
EXAMPLE 5
[075] The electrical device of this Example has a cathode layer, electrolyte layer and anode layer. The cathode layer was made using a mechanically mixed combination of resin 1 , triacetin and a second electrolytically-active material in the form of a manganese dioxide powder having a particle size of less than 4μm (10:2:7 parts by weight) and pressed as in Example 1. The electrolyte was made as in Example 1. The anode layer was fabricated using a hand mixed combination of resin
2, conductive material in the form of graphite (10: 1 parts by weight) and a first electrolytically-active material in the form of oxygen, deposited as in Example 1.
[076] The resulting three layer device was as represented in Figure 1. It was tested as described in Example 1 and the results obtained are shown in Table 1.
EXAMPLE 6
[077] The electrical device of this Example has a cathode layer, electrolyte layer and anode layer. The cathode layer was made using a hand mixed combination of resin 1 , triacetin and a second electrolytically- active material in the form of lithium cobalt oxide powder having a particle size of less than 4μm (10:2:7 parts by weight) and cast into a mould to form a base plate. The electrolyte and anode layers were made as in Example 3.
[078] The resulting three layer device was as represented in Figure 1. It was tested as described in Example 1 and the results obtained are shown in Table 1.
EXAMPLE 7
[079] The electrical device of this Example is an acid cell and has a cathode layer, electrolyte layer and anode layer. It was made by first laying down the anode layer consisting of a mixture of a second electrolytically-active material comprising lead powder having a particle size of about 44μm, resin 3 and acetone (10:2.5:0.5 parts by weight) in a plastic cup. To this mix, 1.25 parts by weight of para-toluene sulphonic acid was added. The mixture was poured onto a polythene plastic card (used as a base during fabrication) and placed in an oven at 500C to accelerate the hardening process. When the cathode layer was firm to touch, the electrolyte layer, consisting of a mixture of resin 3, para- toluene sulphonic acid and acetone (10: 10: 1.1 parts by weight) was poured over the anode layer and allowed to harden. The cathode layer was laid on top of the electrolyte layer by mixing a first electrolytically- active lead oxide powder having a particle size of less than 4μm with resin 3 and acetone (8:5: 1 parts by weight) , adding 2.5 parts by weight of para-toluene sulphonic acid and pouring over the electrolyte layer then allowing to harden.
[080] The resulting three layer device was as represented in Figure 1. It was tested as described in Example 1 and the results obtained are shown in Table 1.
EXAMPLE 8
[081] The electrical device of this Example has a cathode layer, electrolyte layer and anode layer. The cathode layer was prepared by hand mixing a combination of resin 3, a second electrolytically-active material in the form of manganese dioxide powder having a particle size of lOμm and para-toluene sulphonic acid in a ratio of 10:7:5 parts by weight. This was pressed under 4MPa of pressure into 60xl5x3mm moulded plates. After curing the electrolyte layer was prepared consisting of resin 3 and para-toluene sulphonic acid (2: 1 parts by weight) . This was deposited using the doctor blade technique as outlined in Example 1. The anode layer consisted of a hand mixed combination of resin 3, a first electrolytically-active material comprising Mg powder and para-toluene sulphonic acid (10:7:5 parts by weight) . [082] The resulting three layer device was as represented in Figure 1. It was tested as described in Example 1 and the results obtained are shown in Table 1. EXAMPLE 9
[083] The electrical device of this Example has a cathode layer, electrolyte layer and anode layer. The cathode layer consisted of resin 3, a second electrolytically-active material comprising manganese dioxide powder and graphite, and para-toluene sulphonic acid (10:7: 1 :5 parts by weight) . The plate was prepared as outlined in Example 6. The electrolyte layer was fabricated as outlined in Example 6. For the anode layer, a hand mixed combination of resin 3, a first electrolytically-active material comprising Zn powder, and para-toluene sulphonic acid (10:7:5 parts by weight) was prepared and deposited to form a t-layer device.
[084] The resulting three layer device was tested as described in Example 1 and the results obtained are shown in Table 1.
EXAMPLE 10
[085] The electrical device of this Example has a cathode layer, electrolyte layer and anode layer. The cathode layer consisted of a hand mixed composition of resin 1 diluted with isopropanol (IPA) , a second electrolytically-active material comprising manganese dioxide and carbon fibre, and cured with triacetin (10:2:7: 1 :2 parts by weight ratio, respectively) . This composite was spun cast onto lOxlOmm conductive glass (1.1mm thick Sodalime glass with 15 Ohm/Sq indium tin oxide coating) at a speed of > 2500rpm for 60 seconds. The sample was then placed in an oven at 800C for 30 minutes. The electrolyte layer consisted of resin 1 , diluted with IPA and cured with triacetin (5: 1 : 1 parts by weight) . The resulting film was spun cast and post cured under the same conditions as the cathode layer. Finally the anode layer consisted of resin 1 diluted with IPA, with a first electrolytically-active material comprising zinc powder having a particle size of 3μm and cured with triacetin (10:2:7:2 parts by weight) . The resulting film was spun cast and post cured under the same conditions as the cathode layer. [086] The resulting three layer device was as represented in Figure 1. It was tested as described in Example 1 and the results obtained are shown in Table 1.
TABLE 1
Figure imgf000022_0001
Figure imgf000023_0001
[087] The results in Table 1 demonstrate that a conductive polymer can be used as an electrolytically active post matrix, housing electrolytically active materials within the cathode and anode volumes whilst also acting as the separating electrolyte system.

Claims

1. An optionally solid state electrical device comprising an electrolytically active material and a conductive polymer.
2. An electrical device as defined in Claim 1 which is a cell.
3. An electrical device as defined in Claim 1 or Claim 2 wherein the electrolytically active material comprises a reducing material and optionally an oxidising material, preferably the electrical device has one or more of the following features: at least a portion of the electrolytically-active material is embedded in the conductive polymer, preferably substantially all of the electrolytically-active material is embedded in the conductive polymer; the electrolytically-active material is in particulate form; and/or the electrical device comprises a first electrolytically-active material which comprises a reducing material and a second electrolytically-active material which comprises an oxidising material.
4. An electrical device as defined in Claim 3 wherein the first electrolytically-active material is Zn, Mg, Cd, Li, Pb, Fe, H2, Nickel Hydride, Li, LixC6, Na and/or K and/or the second electrolytically-active material is a catalytically active material, MnO2, HgO, AgO, SOCl2, SO2, FeS2, (CF)n, I2(P2VP) , PbO2, NiO2, FeS, NiCl2 and/or S.
5. An electrical device as defined in any one of the preceding Claims which has a first volume of first electrolytically-active material and a second volume of second electrolytically-active material, preferably the first and second volumes are separated by a third volume of electrolyte comprising a conductive polymer which third volume is substantially free from an electrolytically-active material.
6. An electrical device as defined in any one of the preceding Claims which comprises three regions which regions are a first region comprising a first electrolytically-active material embedded in a host conductive polymer, a second region comprising a conductive polymer and a third region comprising a second electrolytically-active material embedded in a host conductive polymer, preferably the electrical device has one or more of the following features: the first region and the third region are separated by the second region; the first and third region form electrodes; the second region forms an electrolyte; the region comprising the first electrolytically-active material is the cathode on discharge; and/or the region comprising the second electrolytically-active material is the anode on discharge.
7. An electrical device as defined in any one of the preceding Claims which is a solid state electrical device.
8. An electrical device as defined in any one of the preceding Claims wherein the conductive polymer is a phenolic resole resin wherein the conductive polymer contains conducting alkaline salts, preferably the electrical device has one or more of the following features: the conductive polymer is a phenolic resin which is an acid cured solvented resole wherein the solvented resole is substantially free from water or an ester-cured alkaline phenolic resole resin; and/or the conductive polymer includes a plasticiser to increase flexibility of the polymer.
9. An electrical device as defined in Claim 8 wherein the conductive polymer is an acid cured solvented resole resin which is substantially free from water, preferably the conductive polymer comprises (i) a phenolic resole, (ii) a solvent and (iii) an acid and/or the conductive polymer is an ester cured alkaline phenolic resole resin, preferably the conductive polymer is a reaction product of (a) an ester curing agent with (b) a phenolic resole and (c) a base.
10. An electrical device as defined in any one of the preceding Claims wherein the first electrolytically-active material comprises zinc, the conductive polymer is an ester cured alkaline phenolic resole resin containing conducting alkaline salts, preferably the electrical device has one or more of the following features: the conducting alkaline salts are one of or a mixture of alkali metal hydroxides and/or the ester curing agent is triacetin or butyrolactone.
11. An electrical device as defined in any one of the preceding Claims wherein the first electrolytically-active material comprises lead and the second electrolytically-active material comprises lead oxide, preferably the conductive polymer is an acid cured solvented resole wherein the solvented resole is substantially free from water, preferably the acid is para-toluene sulphonic acid.
12. An electrical device substantially as described herein or with reference to the drawings.
13. A battery comprising a plurality of the electrical devices as defined in any one of the preceding Claims connected in series and/or in parallel, preferably the battery has one or more of the following features: a casing; positive and negative terminals suitable to provide an electrical connection to the electrical device, preferably one or more of the electrodes is connected to an external current collector; and/or a layer profile, preferably a laminated layer profile.
14. A battery substantially as described herein or with reference to the drawings.
15. An integrated circuit board comprising the electrical device of the present invention. Such an integrated circuit board can be interfaced with computer or circuit board equipment.
16. An integrated circuit board substantially as described herein or with reference to the drawings.
17. A method of preparing an electrical device which method comprises the steps of: (a) providing a first electrode comprising a mixture of a conductive polymer with a first electrolytically-active material;
(b) providing an electrolyte comprising a conductive polymer;
(c) providing a second electrode comprising a conductive polymer with a second electrolytically-active material; and (d) curing the conductive polymer.
18. A method of manufacturing the solid-state electrical device as described herein or with reference to the drawings.
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