The present invention relates generally to polymer batteries and, more specifically, to a method and an apparatus for making positive electrode films for polymer batteries.
Rechargeable batteries manufactured from laminates of polymer electrolytes and sheet-like electrodes display many advantages over conventional liquid electrolyte batteries. These advantages include lower overall battery weight, high power density, high specific energy, and longer service life. In addition, they are more environmentally friendly since the danger of spilling toxic liquid into the environment is eliminated.
Polymer battery components generally include positive electrodes (also referred to as cathodes), negative electrodes (also referred to as anodes), and an insulating material capable of permitting ionic conductivity, such as an electrolyte separator, sandwiched therebetween. The negative electrodes are usually made of light-weight metal foils, such as alkali metals and alloys thereof typically lithium metal, lithium oxide, lithium-aluminum alloys and the like or insertion materials such as carbon or graphite. The composite cathodes or positive electrodes are usually formed of a mixture of active material such as a transitional metal oxide, an electronically conductive filler, usually carbon particles, an ionically conductive polymer electrolyte material, and a current collector, usually a thin sheet of aluminum.
Composite cathode films are usually obtained by coating onto a current collector a mixture of a solvent and cathode materials with a doctor blade, for instance, and evaporating the solvent. This process is inefficient for the mass production of cathode films since it requires recycling the. solvent evaporated and the resulting cathode films have a relatively high porosity, and therefore decreased density.
One of the most efficient manufacturing processes for obtaining thin films is the process of continuous extrusion. However, the extrusion of positive electrode material into thin films is rendered extremely difficult by the high percentage of solids (active material and conductive filler) necessary to produce high energy density cathode films. The difficulty increases dramatically when attempting to directly extrude cathode films of less than 50 μm. The pressure required to extrude cathode material with over 40% solid content through a sheet die opening of less than 50 μm is such that the die itself may not resist and a gear pump capable of generating the required pressure may not be available on the market and therefore must be custom built.
In automotive applications such as hybrid vehicle applications, it is highly desirable to assemble very thin films of less than 50 μm and preferably less than 30 μm. Unfortunately, it is extremely difficult to process through an extruder cathode materials having a high solid content of active cathodic material and conductive filler (above 30%) to form a thin positive electrode composite film of less than 50 μm and preferably less than 30 μm.
Thus, there is a need for a method and an apparatus for manufacturing thin positive electrode films of less than 50 μm and preferably less than 30 μm having a high solid content.
In accordance with a first broad aspect, the invention seeks to provide a method for manufacturing through an extruder a composite positive electrode film of less than 50 μm having a high solid content.
In accordance with a second broad aspect, the invention seeks to provide an apparatus which can be combined with an extruder to manufacture a composite positive electrode film of less than 50 μm having a high solid content.
In accordance with a third broad aspect, the invention seeks to provide a method of making a positive electrode film having a thickness of less than 50 μm. The method comprises compounding in an extruder a composite positive electrode mixture of active cathode material, an electronically conductive additive, and an ionically conductive polymer electrolyte. The method also comprises extruding the composite positive electrode mixture through a sheet die into a film having a thickness of more than 50 μm. The method further comprises reducing the thickness of the extruded film through at least one pair of nip rollers to obtain a composite positive electrode film having a thickness of less than 50 μm.
In a particular example of implementation, the thickness of the extruded film is reduced to less than 30 μm.
In accordance with a fourth broad aspect, the invention seeks to provide an apparatus for reducing a thickness of an extruded positive electrode film to less than 50 μm. The apparatus comprises a pair of nip rollers defining a nip distance of less than 50 μm, at least one nip roller of the pair of nip rollers being adapted to be heated.
In accordance with a fifth broad aspect, the invention seeks to provide an apparatus for reducing a thickness of an extruded positive electrode film to less than 50 μm. The apparatus comprises a series of at least two pairs of nip rollers. The at least two pairs of nip rollers include a first pair of nip rollers defining a first nip distance, at least one nip roller of the first pair of nip rollers being adapted to be heated. The at least two pairs of nip rollers also include a second pair of nip rollers defining a second nip distance less than the first nip distance, at least one nip roller of the second pair of nip rollers being adapted to be heated.
In a particular example of implementation, the apparatus further comprises a pair of cooling nip rollers, positioned after the first and second pair of nip rollers and adapted to solidify the extruded positive electrode film when the latter has reach a desired thickness of less than 50 μm.
The apparatus may further comprise a belt connecting the nip rollers of each side of the at least two pairs of nip rollers or in another embodiment a polypropylene film to separate the extruded film from the nip rollers.
The apparatus may also comprise a dispenser for applying lubricant to a surface of at least one nip roller of the pairs of nip rollers.
The rotational speed of the second pair of nip rollers may be set to exceed the rotational speed of the first pair of nip rollers in order to control the width of the extruded film being processed.
Advantageously, during the process of calendering or thickness reduction through the nip rollers, the extruded film is maintained at or above the melting point of its polymer electrolyte constituent in order to prevent separation of the polymer electrolyte from the active cathode material.
In one embodiment, the positive electrode film comprises more than 40%/wt of active cathode material and electronically conductive additive. The positive electrode film may be laminated onto a current collector when it has reached a desired thickness of less than 50 μm.
The active cathode material may be selected from cobalt oxide, nickel oxide, nickel cobalt oxide, nickel cobalt aluminum oxide, manganese oxide (LiMn2O4) or their analogs for so-called 4 V cathodes or among cathodes of less than 4 V such as phosphates or other polyanions of transition metals such as LiFePO4, Nasicon structures also including V2O5, LiV3O8 and MnO2. Various other choices are possible as the nature of the active material is not a limitation of the present invention.
Advantageously, a lubricant is used on the surfaces that directly contact the positive electrode film in order to prevent or at least inhibit adhesion of the positive electrode film to the contact surfaces. In a particular embodiment, the lubricant has the chemical formula of C7H16.
The apparatus may comprise a plurality of nip rollers wherein the nip distance between pairs of rollers is progressively smaller. A metallic belt surrounding the rollers of each side of the nips may be used as contact surfaces. In one specific embodiment, a polypropylene film is used to separate the positive electrode film from the contact surfaces.
These and other aspects and features of the present invention will now become apparent to those of ordinary skill in the art upon review of the following description of specific embodiments of the invention in conjunction with the accompanying drawings.
A detailed description of embodiments of the present invention is provided herein below with reference to the following drawings, in which:
In the drawings, embodiments of the invention are illustrated by way of examples. It is to be expressly understood that the description and the drawings are only for the purpose of illustration and as an aid to understanding. They are not intended to be a definition of the limits of the invention.
With reference to
In a particular embodiment, in order for the composite positive electrode sheet 20 to maintain some malleability which enables it to be calendered with minimum stress, at least one of the nip rollers 14A and 14B is heated to a temperature near the temperature of the composite positive electrode sheet 20 when it exits the sheet die 10. Advantageously, both nip rollers 14A and 14B are heated to a temperature near the temperature of the composite positive electrode sheet 20 when it exits the sheet die 10. Maintaining the composite positive electrode sheet 20 at a temperature near the temperature when it exits the sheet die 10 maintains the electrochemical integrity of the composite positive electrode sheet 20 by preventing microscopic separation of the polymer electrolyte constituent from the active cathode material. If the composite positive electrode sheet 20 is allowed to cool substantially, its polymer constituent may harden enough that it loses its malleability and pliability such that when it is deformed through the nip rollers 14A and 14B, its bond with the solid active cathode material may be severed, thereby partially breaking the electrochemical link between the polymer and the active cathode material.
The second pair of cylindrical nip rollers 16A and 16B picks up the composite positive electrode sheet 20 of reduced thickness and moves it to a further processing station. At least one of the nip rollers 16A and 16B (and advantageously both rollers 16A and 16B) is maintained at a cool temperature such that, when the composite positive electrode sheet 20 passes through, it is cooled down to a temperature that allows it to maintain its physical integrity. In this example, the distance between rollers 16A and 16B is set at the same distance as the distance ‘x’ between the rollers 14A and 14B (x<30 μm) such that no reduction of thickness occurs at the second pair of nip rollers 16A and 16B.
In one example of implementation, a lubricant is used on the surfaces of nip rollers 14A, 14B and 16A, 16B which directly contact the positive electrode film 20 in order to inhibit adhesion of the positive electrode film 20 to the surfaces of the nip rollers. The lubricant is dispensed by any method known to those skilled in the art. In a specific embodiment, the lubricant has the chemical formula of C7H16.
In a variant of the process, the composite positive electrode sheet 20 exiting nip rollers 16A and 16B may be maintained in contact with the surface of one of the cylindrical rollers 16A or 16B in order to increase the cooling time.
In the specific embodiment of
In
In one example of implementation, the distance x1 between nip rollers 24A and 24B is set at the final desired thickness of composite positive electrode sheet 20 of less than 30 μm (x1<30 μm) and the distance x2 between nip rollers 26A and 26B is set at the same distance (x1=x2) such that all the thickness reduction work is performed at the first pair of nip rollers 24A and 24B. As previously described for the example of implementation shown in
In another example of implementation, the distance x1 between nip rollers 24A and 24B is set at an intermediate distance (for example, x1=40 μm) and the distance x2 between nip rollers 26A and 26B is set at the final desired thickness for the composite positive electrode sheet 20 (for example, x2=20 μm). In such an example of implementation, the thickness reduction work is performed at the first pair of nip rollers 24A and 24B and at the second pair of nip rollers 26A and 26B. The nip rollers 24A and 24B and the nip rollers 26A and 26B are heated to a temperature that maintains the composite positive electrode sheet 20 soft and malleable. The metallic belts 28A and 28B are also heated by conduction throughout the thickness reduction process. The composite positive electrode sheet 20 of reduced thickness is cooled by any means known to those skilled in the art, such as through a series of cooling rollers.
It will be appreciated that, in the embodiment illustrated in
In a particular example of implementation, a lubricant is used on the surfaces of the metallic belts 28A and 28B which directly contact the composite positive electrode film 20 in order to prevent adhesion of the composite positive electrode film 20 to the surfaces of the metallic belts 28A and 28B. The lubricant is dispensed by any method known to those skilled in the art. In a specific embodiment, the lubricant has the chemical formula of C7H16.
In
In a particular example of implementation, a lubricant is used on the surfaces of nip rollers 32A and 32B, 34A and 34B, 36A and 36B, and 38A and 38B, which directly contact the composite positive electrode film 20 in order to prevent adhesion of the composite positive electrode film 20 to the surfaces of the nip rollers. The lubricant is dispensed by any method known to those skilled in the art. In a specific embodiment, the lubricant has the chemical formula of C7H16.
In
The metallic belts 50A and 50B circumscribing the two banks of nip rollers impose that the rotational speeds of nip rollers 42A and 42B, 44A and 44B, 46A and 46B, and 48A and 48B are equal (ω1=ω2=ω3=ω4). As such, the width of the composite positive electrode sheet 20 will increase with each step of reduction of thickness through the pairs of nip rollers 42A-42B, 44A-44B and 46A-46B such that d1<d2<d3<d4. However, since no work is performed at the pair of nip rollers 48A-48B other than cooling of composite positive electrode sheet 20, the width d5 should be substantially equal to the width d4.
In a particular example of implementation, a lubricant is used on the surfaces of metallic belts 50A and 50B which directly contact the composite positive electrode film 20 in order to prevent adhesion of the composite positive electrode film 20 to the surfaces of the metallic belts 50A and 50B. The lubricant is dispensed by any method known to those skilled in the art. In a specific embodiment, the lubricant has the chemical formula of C7H16.
In
In a particular example of implementation, a lubricant is used on the surfaces of polypropylene sheets 64 and 66 which directly contact the composite positive electrode film 20 in order to prevent adhesion of the composite positive electrode film 20 to the surfaces of polypropylene sheets 64 and 66. The lubricant is dispensed by any method known to those skilled in the art. In a specific embodiment, the lubricant has the chemical formula of C7H16.
In
In a particular example of implementation, a lubricant is used on the surfaces of rollers 76, 78, 80 and 82 which directly contact the composite positive electrode film 20 in order to prevent adhesion of the composite positive electrode film 20 to the surfaces of rollers 76, 78, 80 and 82. The lubricant is dispensed by any method known to those skilled in the art. In a specific embodiment, the lubricant has the chemical formula of C7H16.
In each of the previously described embodiments, the sheet die and calendering apparatus may be oriented horizontally or vertically without departing from the scope of the invention. Furthermore, the width of the composite positive electrode film 20 when exiting the calendering apparatus may further be controlled by a slitting process to ensure an exact width of the final product without departing from the scope of the invention.
It should be expressly understood that various mechanical and/or hydraulic means for mounting and adjusting the position of the nip rollers relative to each other to define the nip distances ‘x’ are contemplated and within the reach of a person skilled in the art, and as such are within the scope of the present invention.
Although the present invention has been described in relation to particular variations thereof, other variation and modifications are contemplated and are within the scope of the present invention Therefore, the present invention is not to be limited by the above description but is defined by the appended claims.
The present application claims priority from U.S. provisional application No. 60/535,828 filed on Jan. 13, 2004.
Number | Date | Country | |
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60535828 | Jan 2004 | US |