# Patent

## Title
Lithium ion secondary battery having firmly adherent layers

## Abstract

The invention encompasses batteries, battery electrodes and methods of forming batteries and battery electrodes. In one aspect, the invention includes a method of forming a battery electrode comprising: a) forming an electrode material mix comprising electrode active material, a conductive medium, and polymeric binder materials consisting essentially of PVDF, copolymers of vinylidene fluoride and hexafluoropropylene, or mixtures thereof; b) curing the electrode mix to form a compressible material; and c) compressing the compressible material into an electrode. In another aspect, the invention encompasses a method of forming a battery comprising: a) forming a first electrode, the forming the first electrode comprising: i) forming an electrode material mixture, the electrode material mixture comprising an electrode active material, a conductive medium, and polymeric binder materials consisting essentially of PVDF, copolymers of vinylidene fluoride and hexafluoropropylene, or mixtures thereof; ii) forming the electrode material mixture into a sheet; iii) curing the sheet into a layer having a thickness; iv) compressing the material of the layer to decrease the thickness of the layer; and v) forming the first electrode from the material; b) providing a second electrode; and c) incorporating the first and second electrodes into a battery.

## Background
The invention pertains to batteries, battery electrodes and methods of forming batteries and battery electrodes. The invention has particular application to methods of forming very thin batteries, such as button-type batteries.

Small, thin batteries, such as button-type batteries, are commonly used in modern devices. For instance, button-type batteries are utilized as power sources for calculators and watches.

A prior art button-type battery 10 is shown in FIG. 1. Battery 10 comprises a lower terminal housing member, or can 12, and an upper terminal housing member, or lid 14. Can 12 and lid 14 are sealingly joined together at a crimp 16. Battery 10 is typically in the shape of a circle, with crimp 16 extending entirely around a periphery of the circle. A gasket material 18 is provided within crimp 16 to form a fluid-tight seal within the crimp. A cathode 20 and an anode 22 are provided between terminal housing members 12 and 14. Cathode 20 has a thickness of greater than 13 mils. Cathode 20 and anode 22 are separated by a porous separator 24. An electrolyte 26 is provided within the battery and within porous separator 24.

Battery cathode 20 typically comprises a mixture of an active material and a conductive medium, or diluent. The active material can be, for example at one manganese dioxide and (CF).sub.x. The manganese dioxide provides a source of oxidizing component in a battery cell. As manganese dioxide is itself a poor conductor, the conductive medium is added to provide electrical conductivity. The conductive medium can be, for example, elemental carbon. The elemental carbon is typically in the form of graphite, although other materials, such as, acetylene black may also be used. Natural graphites can be used in alkaline cells, but typically cells are made with very pure synthetic graphite to reduce impurities which might lead to corrosion in a battery cell.

A difficulty in forming battery cathodes occurs in binding a conductive medium with an active material. A goal is to develop binders which produce dense, stable cathodes having good electronic and ionic conductivity, and efficient discharge even at high discharge rates. Another goal is to develop binders which form cathodes which can be very thin, and yet durable enough to be utilized with pick and place automation. Also, a goal is to develop binders which are simple to incorporate into manufacturing processes by which battery cathodes are produced. It would be desirable to develop methods of forming battery cathodes which achieve one or more of the above-discussed goals.

There is a continuing goal in small battery fabrication to form the batteries increasingly thinner, while maintaining efficient power discharge. Limitations in battery thickness are imposed by limitations of the thicknesses of battery components, such as the anode and the cathode. Accordingly, it would be desirable to develop methods for forming thinner battery components.

The invention encompasses batteries, battery electrodes and methods of forming batteries and battery electrodes.

In one aspect, the invention includes a method of forming a battery electrode. An electrode material mixture is formed. The electrode material mixture comprises electrode active material, a conductive medium, and polymeric binder materials. All polymeric binder materials within the mix consist essentially of polyvinylidene fluoride (PVDF), copolymers of vinylidene fluoride and hexafluoropropylene, or mixtures thereof. The electrode mixture is cured to form a compressible material. The compressible material is compressed into at least one electrode shape to form an electrode.

In another aspect, the invention includes a method of forming a battery. A first electrode is formed as follows. An electrode material mixture is formed. The electrode material mixture comprises an electrode active material, a conductive medium, and polymeric binder materials. All polymeric binder materials in the mix consisting essentially of PVDF, copolymers of vinylidene fluoride and hexafluoropropylene, or mixtures thereof. The electrode material mixture is formed into a sheet. The sheet is cured into a layer having a thickness. After curing the sheet, the material of the layer is compressed to decrease the thickness of the layer. Material is cut from the layer, and the first electrode is formed from the cut material. A second electrode is provided. The first and second electrodes are incorporated into a battery.

In another aspect, the invention includes a battery electrode having a thickness of less than or equal to 13 mils. The battery electrode comprises electrode active material, a conductive medium, and polymeric binders consisting essentially of PVDF, copolymers of vinylidene fluoride and hexafluoropropylene, or mixtures thereof.

Preferred embodiments of the invention are described below with reference to the following accompanying drawings.

FIG. 1 is a diagrammatic cross-sectional view of a prior art button-type battery.

FIG. 2 is a flow chart of a process for forming a battery cathode according to the present invention.

FIG. 3 is a diagrammatic cross-sectional view of a cathode material being processed according to a first embodiment process of the present invention.

FIG. 4 is a diagrammatic cross-sectional view of the cathode material of FIG. 3 at a processing step subsequent to that of FIG. 3.

FIG. 5 is a diagrammatic cross-sectional view of the cathode material of FIG. 3 at a processing step subsequent to that of FIG. 4.

FIG. 6 is a perspective view of the cathode material of FIG. 3 at a processing step subsequent to that of FIG. 5.

FIG. 7 is a diagrammatic cross-sectional view of a cathode material being processed according to a second embodiment process of the present invention.

This disclosure of the invention is submitted in furtherance of the constitutional purposes of the U.S. Patent Laws "to promote the progress of science and useful arts" (Article 1, Section 8).

The present invention encompasses methods of forming thin cathodes for thin profile batteries. A first embodiment method of the present invention is described in a flow chart of FIG. 2, as well as with the diagrams of FIGS. 3-6. The method utilizes polymeric binder materials consisting essentially of polyvinylidene fluoride (PVDF), copolymers of vinylidene fluoride and hexafluoropropylene, or mixtures thereof, as a binding agents in a cathode to, for example, bind carbon and MnO.sub.2. The PVDF is a homopolymer of 1,1-difluoroethene (vinylidene fluoride).

Referring to FIG. 2, a first step in the process (step "A") is to mix the polymeric binder materials with an organic solvent to form a mixture. The organic solvent can comprise any solvent capable of dissolving the polymeric binder materials, such as, for example, acetone, methyl ethyl ketone, tetrahydrofuran (THF), or N-methyl pyrrolidone. The solvent can also be a blend of, for example, THF and N-methyl pyrrolidone. If the solvent is a blend of THF and N-methyl pyrrolidone, the ratio of THF to N-methyl pyrrolidone will preferably be from about 50:50 to about 99:1 (by volume), with about 94:6 being most preferred. Preferably, from about 4% to about 8% (by weight) of the polymeric binder materials is provided in the solvent at room temperature and room pressure to achieve dissolving. More preferably, about 6% (by weight) of the polymeric binder materials is provided in the solvent.

In step "B", the polymeric binder material mixture is combined with electrode active materials and a conductive medium to form an electrode material mixture. Examples of electrode active materials are MnO.sub.2 and (CF).sub.x. An example conductive medium is elemental carbon. If either the PVDF homopolymer, or polyvinylidene/hexafluoropropylene copolymer, is essentially the only polymeric binder material within the electrode material mixture, cathode manufacturing processes can be simplified. Many prior art cathode manufacturing processes utilize a combination of polymeric binder materials. The incorporation of only one polymeric binder material of the method of the present invention into such prior art processes can reduce manufacturing steps in the processes.

In step "C", the electrode material mixture is formed into a thin film of compressible material. Methods for forming the electrode material mixture into a thin film of compressible material include, for example, solvent casting, extrusion, or drying into a powder. FIG. 3 is a diagrammatic view of a thin compressible film 30 formed by solvent casting or extrusion over a removable substrate 32. Substrate 32 can comprise, for example, a polyester film. If thin film 30 is formed by solvent casting, the electrode material mixture can be applied to substrate 32 as a low viscosity liquid and then dried to remove organic solvents from the film and form the compressible material 30. Thin film 30 is preferably about 0.04 inches thick when it is initially cast as a wet film. The film is then dried at, for example, 80.degree. C. for about 30 minutes to remove organic solvent from the film and to decrease the thickness to a thickness of from about 13 mils to about 15 mils. The drying of thin film 30 is indicated as step "D" of FIG. 2.

If thin film 30 is formed by extrusion, the electrode material mixture can be passed through an extruder in a relatively high viscosity form to form the resultant thin film 30. A thin film 30 formed by an extrusion process can be placed on a removable substrate 32 as shown, or it can be fed directly to a pellet punch (described below with reference to FIG. 5).

Appropriate viscosities of an electrode material mixture for utilization in solvent casting processes or extrusion processes are known to persons of ordinary skill in the art.

Referring to FIG. 4, removable substrate 32 is separated from thin film 30 to release the thin film as a cathode material sheet. Methods for separating removable substrate 32 from thin film 30 are known to persons of ordinary skill in the art. Such methods can include adhering removable substrate 32 to a roller device 36 and pushing thin film 30 onto a support structure 38.

Referring to steps "E" and "F" of FIG. 2, a cathode disk is punched from the cathode material sheet, and compressed to form a cathode. In a preferred embodiment of the present invention, the punching and compressing occur in a common step as shown in FIG. 5. Thin film sheet 30 is placed within a punch 39 comprising a pair of spaced punch dies 40 and 42. Punched dies 40 and 42 are preferably circular in horizontal cross-sectional shape (not shown), and preferably comprise recesses 44 and 46, which are less than about 4 mils deep. Dies 40 and 42 are forced together to compress sheet 30 between them and to punch a cathode disk 50 (shown in FIG. 6) from sheet 30. Referring to FIG. 6, cathode disk 50 is preferably circular in shape, and preferably comprises a thickness of less than about 9 mils, and more preferably of less than about 8 mils. Cathode disk 50 is thus very thin. Cathode disk 50 is also durable enough to be utilized with pick and place automation. Cathode disk 50 may be incorporated into a button-type battery (such as the battery shown in FIG. 1) as an operable cathode. Once incorporated into a battery, cathode disk 50 is found to have efficient discharge properties. For example, a cathode disk of the present invention will have a discharge rate of about 5 milliamps/cm.sup.2.

Although the above-discussed process removed substrate 32 from thin film 30 prior to subjecting thin film 30 to punch 39, alternative processes can be used in which substrate 32 is not removed until after punching a cathode disk from material 30. In such alternative processes, the recesses formed in punch dies 40 and 42 can be deeper than 4 mils to accommodate the extra thickness of substrate 32.

Also, in alternative methods of the invention, the cutting of a cathode disk can occur before, or after, compressing cathode material 30 to a thickness of less than 9 mils. Methods for cutting cathode material 30 before or after compressing material 30 will be recognized by persons of ordinary skill in the art.

An alternative method of the present invention is described in reference to FIG. 7. In FIG. 7, a cathode powder material 60 is provided onto a conveyor sheet 62 which conveys the material to a press 64. Powder 60 can be formed from the above-discussed electrode mixture of polymeric binder materials, MnO.sub.2, and elemental carbon by drying the mixture and subsequently pulverizing or grinding the mixture into a powder. Press 64 comprises a die 66 and a die receptacle 68. Die receptacle 68 comprises an orifice 70 configured for receiving die 66. Die 66 and orifice 70 preferably have a circular cross-sectional shape along a horizontal cross-section (not shown). The powder within orifice 70 is compressed by die 66 to form a cathode disk having dimensions preferably identical to the preferable dimensions discussed above regarding disk 50 of FIG. 6. After the cathode disk is formed within orifice 70, the disk can be removed by methods known to persons of ordinary skill in the art. Such methods can include sliding a punch (not shown) into the bottom of orifice 70 to expel the cathode disk from the orifice.

An example composition of a cathode of the present invention is as follows. Component            Range ______________________________________ Manganese Dioxide    80-91% Carbon 6-10% Polymeric Binder material (PVDF) 3-10% ______________________________________

Although the invention has been discussed primarily with reference to applications in which a cathodes are formed, the invention also encompasses methods of forming other battery components, such as anodes. For instance, in applications in which anodes are formed from mixtures of materials, the mixtures can be bound together in accordance with the present invention with a polymeric binder consisting essentially of PVDF.

In compliance with the statute, the invention has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the invention is not limited to the specific features shown and described, since the means herein disclosed comprise preferred forms of putting the invention into effect. The invention is, therefore, claimed in any of its forms or modifications within the proper scope of the appended claims appropriately interpreted in accordance with the doctrine of equivalents.

## Claims

1. A battery electrode comprising: material including (CF).sub.x ; and fluoride and hexafluoropropylene.

2. A battery comprising: fluoride and hexafluoropropylene; and

3. A method of forming a battery electrode comprising: electrode active material that includes (CF).sub.x, a conductive medium, and polymeric binder materials, all polymeric binder materials within the mix consisting essentially of copolymers of vinylidene fluoride and hexafluoropropylene; form an electrode.

4. The method of claim 3 wherein the conductive medium comprises elemental carbon.

5. A method of forming a battery electrode comprising: comprising electrode active material which includes (CF).sub.x, a conductive medium, and polymeric binder materials, all polymeric binder materials within the mix consisting essentially of copolymers of vinylidene fluoride and hexafluoropropylene; the thickness of the layer; and material.

6. A method of forming a battery comprising: comprising an electrode active material which includes (CF).sub.x, a conductive medium, and polymeric binder materials, all polymeric binder materials in the mixture consisting essentially of copolymers of vinylidene fluoride and hexafluoropropylene; the thickness of the layer; and cut material;