CA1268809A - Cathode composition and method for solid state lithium battery - Google Patents
Cathode composition and method for solid state lithium batteryInfo
- Publication number
- CA1268809A CA1268809A CA000504129A CA504129A CA1268809A CA 1268809 A CA1268809 A CA 1268809A CA 000504129 A CA000504129 A CA 000504129A CA 504129 A CA504129 A CA 504129A CA 1268809 A CA1268809 A CA 1268809A
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- Prior art keywords
- cathode
- lithium
- polymer
- salt
- electrochemical cell
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
- Conductive Materials (AREA)
Abstract
HENRY F. HOPE
STEPHEN F. HOPE
CATHODE COMPOSITION AND METHOD FOR
SOLID STATE LITHIUM BATTERY
ABSTRACT OF THE DISCLOSURE
A cathode for a solid-state lithium battery comprising a layer of polymer spheres. Each polymer sphere consists of a vanadium oxide core encapsulated in an ionically and electronically conductive polymeric material.
STEPHEN F. HOPE
CATHODE COMPOSITION AND METHOD FOR
SOLID STATE LITHIUM BATTERY
ABSTRACT OF THE DISCLOSURE
A cathode for a solid-state lithium battery comprising a layer of polymer spheres. Each polymer sphere consists of a vanadium oxide core encapsulated in an ionically and electronically conductive polymeric material.
Description
68~309 HENRY F. HOPE
STEPHEN F. HOPE
CATHODE COMPOSITION AND METHOD FOR
SOLID STATE LITHIUM BATTERY
BACKGROUND OF THE INVENTION
Field of the Invention The invention is directed to a novel cathode construction for an all-solid state lithium electrochemical cell and a method of forming the cathode.
In particular, the invention is directed towards the cathode layer of a multilayer electrochemical lithium cell having a polymeric electrolyte layer, a cathode layer containing vanadium oxide, and a lithium or lithium/aluminum alloy anode layer.
DESCRIPTION OF THE PRIOR ART
Electrochemical cells and batteries have been constructed from a wide variety of materials. Both the electrodes and the dielectric layer have been made from plastic, metal, and other substances. The electrolyte has usually been a liquid but solid material, such as polymers, are now preferred in lithium battery construction.
A solid state battery will avoid many of the problems commonly associated with liquid electrolyte cells. Such problems include electrolyte leakage, dryout, anode passivation, and dendrite formation. In addition, the use of all solid state components simplifies fabrication of the cell and leads to a mechanically stable device. Operation at moderate temperature overcomes the severe problems of corrosion and sealing associated with high temperature fused salt electrolyte or molten electrode systems. Clearly a solid state battery is preferable for many applications to a 6l~
battery containing liquid electrolyte or electrolyte paste.
It has been preferred when fabricating lithium batteries to use a polymer/inorganic composite as both the cathode layer and the electrolyte layer, which layers may be formed as a film by continuous casting and solvent evaporation. Using this method, large area membranes of 25-50 micrometer thickness may be routinely fabricated.
This technique, commonly referred to as the "doctor-blade" technique, results in electrolyte layers which are substantially pinhole-free, retain their integrity over many cycles, and provide excellent interfacial characteristics.
Recent joint studies conducted by the Harwell Laboratory and the Energy Research Laboratory of Odense University have focused upon lithium batteries employing a polymer electrolyte composed of polyethylene oxide compounded with various lithium salts. In these cells, the cathode material is based on V6O13 and the preferred anode consists of a lithium metal foil or a lithium/aluminum foil. Specifically, the cathode is a composite structure formed by intimately mixing pre-milled vanadium oxide with acetylene black, in an electrolyte solution. The electrolyte solution contains polyethylene oxide polymer. The resulting cathode layer, when deposited as a film, consists of a random agglomerate of particles of polymer, carbon, and vanadium oxide. It is reported that the lithium cells so constructed showed improved performance in terms of current density, material utilization, and reproduceabilty. It is suggested that these cells may have application in the production of vehicle traction batteries. See, Hooper, A. et al., Advanced Battery o~
l Development (Odense University Press, 1984).
SUMMARY OF THE INVENTION
It has now been found that the performance characteristics of the above-described lithium cells may be dramatically increased by the use of a novel cathode construction. In particular, the present invention is directed towards a composite cathode based on V6Ol3 having increased surface area, increased performance characteristics, and increased life.
These objectives are achieved by forming the cathode layer of the solid-state battery as a layer of polymer-encapsulated vanadium oxide spheres. The prefe~red polymer, polyethylene oxide, additionally contains a lithium salt and activated carbon. The spheres, in the form of an emulsion, may be applied as a layer to an electrically conductive substrate.
In one of its aspects the present invention provides a solid state electrochemical cell compris,ing an anode, a polymeric electrolyte, and a cathode comprising a composite including an active cathode material, wherein said composite comprises a plurality of spheres formed by encapsulating said active cathode material in an electronic and ionic conducting polymeric film, said plurality of particles forming an electronic and conducting network.
~ r ~L26~38~9 1 DESCRIPTION OF TH~ DRAWINGS
The nature and characteristic features of the invention will be more readily understood from the following description taken in connection with the accompanying drawings forming part hereof in which:
Fig. 1 shows the polymer spheres of the invention as they exist in a layer, i.e. in each sphere in contact with neighboring spheres to form an electronic network; and FigO 2 shows a solid state lithium battery employin~ a layer of polymer spheres as the cathode.
It should, of course, be understood that the description and drawings herein are illustrative merely and that various modifications and changes can be made in the structure disclosed without departing from the spirit of the invention. .
- 3a -DESCRIPTION OF THE INVENTION
A lithium solid-state battery consists of an anode layer, a cathode layer and a polymer dielectric layer.
The three-layer structure, in the form of a sheet, roll, tape, etc. forms a simple cell or battery. Such structures can employ various additional layers, including current conducting backing layers, insulating layers, and/or bipolar electrode connections. Such simple batteries may be connected or combined in stacks to form multi-cell electrochemical devices.
Typically, electrochemical cells are formed as simple disc sandwiches with an active area of approximately 0.75 cm2. However, large area cells of approximately 85 to 200 cm2 may be fabricated using a "swiss-roll" technique around a central mandrel, or a "concertina" configuration, sandwiched between two stainless steel plates. Both of these methods are well-known to the artisan.
The cathode and electrolyte layers of the laminate are produced from the appropriate polymer film using the so-called "doctor-blade" technique. According to this method, a solution of the polymer (or polymer compounded with inorganic material) is prepared in a suitable solvent and cast as a film onto a sheet, for example, of waxed paper, passing beneath a fixed reservoir positioned at one end of a flat platform. The front face of the reservoir is adjustable in height and the setting of the gap between the doctor-blade and the paper sheet determines the thickness of the cast film. Evaporation of the solvent causes a uniform reduction in film thickness by an amount which is dependent on the concentration of the solution. This technique of creating a thin film layer is familiar to those skilled in the art, and can be used to form very thin films of approximately 25-50 micrometer thickness.
The anode layer used in lithium batteries comprises a lithium metal foil or a lithium/aluminum alloy foil.
In electrochemical lithium cells a battery grade lithium foil of 350 micrometer thickness has previously been used. Use of this foil represents a large excess of lithium and it is preferable to use a thin anode in the form of a lithium/aluminum alloy formed by cathodic reduction of alumin~lm foil in a lithium salt solution.
Lithium deposited on the surface of the foil is allowed to accumulate to a thickness of 10 to 20 micrometers on the surface of the aluminum foil. The structural integrity of the anode layer is maintained by allowing more than one half of the thickness of the aluminum foil to be unconverted. Aluminum on copper foils, formed by bonding, for example, an 80 micrometer copper foil and a 20 micrometer aluminum foil, will also serve as a satisfactory anode. The anode is then fabricated by the electrochemical conversion of the aluminum foil in non-aqueous liquid electrolyte solution containing lithium salts. Both of these anode structures are compatible with the construction of large area, thin film cells.
The polymeric electrolyte composition is formed by compounding a lithium salt and a polymeric material such as polyethylene oxide. The polyethylene oxide and lithium salt are compounded by, for example, milling the heated polymer with crystals of lithium perchlorate, to achieve substantially uniform mixing. Alternatively, a solvent is combined with the polymer to improve its film-forming qualities and the salt introduced into the polymer in solution. The resulting mixture may be ~8~09 deposited as a film directly onto the cathode layer of the cell. The mixture is applied by the doctor-blade technique referred to previously. This leads to good reproducibility of the electrolyte layer, which is optimally in the order of 25 micrometers.
The cathode layer, formed in accordance with the present invention, consists of a thin layer of polymer spheres. At the core of each polymer sphere is the active cathode material, vanadium oxide. The preferred vanadium oxide compound, V6013, is prepared by the thermal decomposition of ammonium metavanadate and has an average agglomerated particle size of 100-500 microns.
The agglomerates can be further ground to reduce the particle size to the order of several microns.
The finely ground V6013 particles are encapsulated within conductive polymer to form spheres, as illustrated in FIG. 1. Referring to FIG. 1, polymer spheres 10 consist of a vanadium oxide core 13 encapsulated with conductive polymer material 12. The preferred conductive polymer consists of polyethylene oxide containing an inorganic salt to render the polymer ionically conductive, and carbon black to render the polymer electronically conductive.
The primary advantage of the polymer spheres of the present invention is a large increase in the available active surface area of the cathode. Also, the vanadium oxide cathode material is mechanically fixed within each sphere, which increases the active life of the cathode layer. Further, since each sphere is in contact with other conductive spheres, an electronic network or grid exists across and through the cathode, as shown in FIG.
1. The voids existing between the spheres allow diffusional access to any part of the cathode.
STEPHEN F. HOPE
CATHODE COMPOSITION AND METHOD FOR
SOLID STATE LITHIUM BATTERY
BACKGROUND OF THE INVENTION
Field of the Invention The invention is directed to a novel cathode construction for an all-solid state lithium electrochemical cell and a method of forming the cathode.
In particular, the invention is directed towards the cathode layer of a multilayer electrochemical lithium cell having a polymeric electrolyte layer, a cathode layer containing vanadium oxide, and a lithium or lithium/aluminum alloy anode layer.
DESCRIPTION OF THE PRIOR ART
Electrochemical cells and batteries have been constructed from a wide variety of materials. Both the electrodes and the dielectric layer have been made from plastic, metal, and other substances. The electrolyte has usually been a liquid but solid material, such as polymers, are now preferred in lithium battery construction.
A solid state battery will avoid many of the problems commonly associated with liquid electrolyte cells. Such problems include electrolyte leakage, dryout, anode passivation, and dendrite formation. In addition, the use of all solid state components simplifies fabrication of the cell and leads to a mechanically stable device. Operation at moderate temperature overcomes the severe problems of corrosion and sealing associated with high temperature fused salt electrolyte or molten electrode systems. Clearly a solid state battery is preferable for many applications to a 6l~
battery containing liquid electrolyte or electrolyte paste.
It has been preferred when fabricating lithium batteries to use a polymer/inorganic composite as both the cathode layer and the electrolyte layer, which layers may be formed as a film by continuous casting and solvent evaporation. Using this method, large area membranes of 25-50 micrometer thickness may be routinely fabricated.
This technique, commonly referred to as the "doctor-blade" technique, results in electrolyte layers which are substantially pinhole-free, retain their integrity over many cycles, and provide excellent interfacial characteristics.
Recent joint studies conducted by the Harwell Laboratory and the Energy Research Laboratory of Odense University have focused upon lithium batteries employing a polymer electrolyte composed of polyethylene oxide compounded with various lithium salts. In these cells, the cathode material is based on V6O13 and the preferred anode consists of a lithium metal foil or a lithium/aluminum foil. Specifically, the cathode is a composite structure formed by intimately mixing pre-milled vanadium oxide with acetylene black, in an electrolyte solution. The electrolyte solution contains polyethylene oxide polymer. The resulting cathode layer, when deposited as a film, consists of a random agglomerate of particles of polymer, carbon, and vanadium oxide. It is reported that the lithium cells so constructed showed improved performance in terms of current density, material utilization, and reproduceabilty. It is suggested that these cells may have application in the production of vehicle traction batteries. See, Hooper, A. et al., Advanced Battery o~
l Development (Odense University Press, 1984).
SUMMARY OF THE INVENTION
It has now been found that the performance characteristics of the above-described lithium cells may be dramatically increased by the use of a novel cathode construction. In particular, the present invention is directed towards a composite cathode based on V6Ol3 having increased surface area, increased performance characteristics, and increased life.
These objectives are achieved by forming the cathode layer of the solid-state battery as a layer of polymer-encapsulated vanadium oxide spheres. The prefe~red polymer, polyethylene oxide, additionally contains a lithium salt and activated carbon. The spheres, in the form of an emulsion, may be applied as a layer to an electrically conductive substrate.
In one of its aspects the present invention provides a solid state electrochemical cell compris,ing an anode, a polymeric electrolyte, and a cathode comprising a composite including an active cathode material, wherein said composite comprises a plurality of spheres formed by encapsulating said active cathode material in an electronic and ionic conducting polymeric film, said plurality of particles forming an electronic and conducting network.
~ r ~L26~38~9 1 DESCRIPTION OF TH~ DRAWINGS
The nature and characteristic features of the invention will be more readily understood from the following description taken in connection with the accompanying drawings forming part hereof in which:
Fig. 1 shows the polymer spheres of the invention as they exist in a layer, i.e. in each sphere in contact with neighboring spheres to form an electronic network; and FigO 2 shows a solid state lithium battery employin~ a layer of polymer spheres as the cathode.
It should, of course, be understood that the description and drawings herein are illustrative merely and that various modifications and changes can be made in the structure disclosed without departing from the spirit of the invention. .
- 3a -DESCRIPTION OF THE INVENTION
A lithium solid-state battery consists of an anode layer, a cathode layer and a polymer dielectric layer.
The three-layer structure, in the form of a sheet, roll, tape, etc. forms a simple cell or battery. Such structures can employ various additional layers, including current conducting backing layers, insulating layers, and/or bipolar electrode connections. Such simple batteries may be connected or combined in stacks to form multi-cell electrochemical devices.
Typically, electrochemical cells are formed as simple disc sandwiches with an active area of approximately 0.75 cm2. However, large area cells of approximately 85 to 200 cm2 may be fabricated using a "swiss-roll" technique around a central mandrel, or a "concertina" configuration, sandwiched between two stainless steel plates. Both of these methods are well-known to the artisan.
The cathode and electrolyte layers of the laminate are produced from the appropriate polymer film using the so-called "doctor-blade" technique. According to this method, a solution of the polymer (or polymer compounded with inorganic material) is prepared in a suitable solvent and cast as a film onto a sheet, for example, of waxed paper, passing beneath a fixed reservoir positioned at one end of a flat platform. The front face of the reservoir is adjustable in height and the setting of the gap between the doctor-blade and the paper sheet determines the thickness of the cast film. Evaporation of the solvent causes a uniform reduction in film thickness by an amount which is dependent on the concentration of the solution. This technique of creating a thin film layer is familiar to those skilled in the art, and can be used to form very thin films of approximately 25-50 micrometer thickness.
The anode layer used in lithium batteries comprises a lithium metal foil or a lithium/aluminum alloy foil.
In electrochemical lithium cells a battery grade lithium foil of 350 micrometer thickness has previously been used. Use of this foil represents a large excess of lithium and it is preferable to use a thin anode in the form of a lithium/aluminum alloy formed by cathodic reduction of alumin~lm foil in a lithium salt solution.
Lithium deposited on the surface of the foil is allowed to accumulate to a thickness of 10 to 20 micrometers on the surface of the aluminum foil. The structural integrity of the anode layer is maintained by allowing more than one half of the thickness of the aluminum foil to be unconverted. Aluminum on copper foils, formed by bonding, for example, an 80 micrometer copper foil and a 20 micrometer aluminum foil, will also serve as a satisfactory anode. The anode is then fabricated by the electrochemical conversion of the aluminum foil in non-aqueous liquid electrolyte solution containing lithium salts. Both of these anode structures are compatible with the construction of large area, thin film cells.
The polymeric electrolyte composition is formed by compounding a lithium salt and a polymeric material such as polyethylene oxide. The polyethylene oxide and lithium salt are compounded by, for example, milling the heated polymer with crystals of lithium perchlorate, to achieve substantially uniform mixing. Alternatively, a solvent is combined with the polymer to improve its film-forming qualities and the salt introduced into the polymer in solution. The resulting mixture may be ~8~09 deposited as a film directly onto the cathode layer of the cell. The mixture is applied by the doctor-blade technique referred to previously. This leads to good reproducibility of the electrolyte layer, which is optimally in the order of 25 micrometers.
The cathode layer, formed in accordance with the present invention, consists of a thin layer of polymer spheres. At the core of each polymer sphere is the active cathode material, vanadium oxide. The preferred vanadium oxide compound, V6013, is prepared by the thermal decomposition of ammonium metavanadate and has an average agglomerated particle size of 100-500 microns.
The agglomerates can be further ground to reduce the particle size to the order of several microns.
The finely ground V6013 particles are encapsulated within conductive polymer to form spheres, as illustrated in FIG. 1. Referring to FIG. 1, polymer spheres 10 consist of a vanadium oxide core 13 encapsulated with conductive polymer material 12. The preferred conductive polymer consists of polyethylene oxide containing an inorganic salt to render the polymer ionically conductive, and carbon black to render the polymer electronically conductive.
The primary advantage of the polymer spheres of the present invention is a large increase in the available active surface area of the cathode. Also, the vanadium oxide cathode material is mechanically fixed within each sphere, which increases the active life of the cathode layer. Further, since each sphere is in contact with other conductive spheres, an electronic network or grid exists across and through the cathode, as shown in FIG.
1. The voids existing between the spheres allow diffusional access to any part of the cathode.
2~881)9 The spheres are prepared by forming an emulsion using the polyethylene oxide polymer as a binder. The polymer may be compounded with a lithium salt and a carbon black prior to its introduction into the emulsion.
Inorganic salts which are preferred are of the type employed in the electrolyte layer of lithium batteries, and include LiCl04, NaCl04, LiF3CS03, and LiBF4. Carbon or acetylene black is added to the polymer, to approximately 5% by weight, to provide electrical conductivity.
The compounded polymer and finely divided V60l3 are emulsified in a suitable organic solvent.
As a result, each particle or agglomerate of vanadium oxide becomes encapsulated by polymer and retains the resulting spherical form within the emulsion.
Accordingly, when the emulsion is applied as a thin film and the solvent removed, a layer of spheres is deposited on the substrate. The film is applied by, for example, the "doctor-blade" method, and the resulting film may be of any desired thickness.
Referring to FIG~ 2, a solid state lithium battery structure which embodies the invention is shown. Layer 14 corresponds to the anode, which as described previously, may consist of a lithium or lithium/aluminum foil. The layer shown as 16 corresponds to the electrolyte layer, which preferably consists of polyethylene oxide and an inorganic salt. Layer lO
comprises the cathode formed of a multiplicity of polymer spheres containing vanadium oxide, as disclosed herein.
Layer 18 represents a current-collecting base layer, which may consist of, for example, a nickel or copper foil.
The 4-layer laminate shown in FIG. 2 may be prepared as a continuous sheet or roll. Preferably, one ~ ~ :IL2~8~()9 layer is laminated directly onto the underlying layer in a continous process.
In a preferred embodiment of the present invention, additional ionically conductive polyethylene oxide is applied to the layer of spheres to form a matrix around the spheres and fill the voids therebetween. This increases the mechanical stability of the layer and provides improved diffusional properties.
It has been found preferable to employ vanadium oxide as approximately 50%, by volume, of the total cathode, including the added matrix material, if used.
When forming a lithium battery, it is preferred to deposit the cathode layer directly onto the current-collecting base layer. Accordingly, in the present invention, the emulsion of polymer spheres may be applied directly to the foil base as a thin layer.
Inorganic salts which are preferred are of the type employed in the electrolyte layer of lithium batteries, and include LiCl04, NaCl04, LiF3CS03, and LiBF4. Carbon or acetylene black is added to the polymer, to approximately 5% by weight, to provide electrical conductivity.
The compounded polymer and finely divided V60l3 are emulsified in a suitable organic solvent.
As a result, each particle or agglomerate of vanadium oxide becomes encapsulated by polymer and retains the resulting spherical form within the emulsion.
Accordingly, when the emulsion is applied as a thin film and the solvent removed, a layer of spheres is deposited on the substrate. The film is applied by, for example, the "doctor-blade" method, and the resulting film may be of any desired thickness.
Referring to FIG~ 2, a solid state lithium battery structure which embodies the invention is shown. Layer 14 corresponds to the anode, which as described previously, may consist of a lithium or lithium/aluminum foil. The layer shown as 16 corresponds to the electrolyte layer, which preferably consists of polyethylene oxide and an inorganic salt. Layer lO
comprises the cathode formed of a multiplicity of polymer spheres containing vanadium oxide, as disclosed herein.
Layer 18 represents a current-collecting base layer, which may consist of, for example, a nickel or copper foil.
The 4-layer laminate shown in FIG. 2 may be prepared as a continuous sheet or roll. Preferably, one ~ ~ :IL2~8~()9 layer is laminated directly onto the underlying layer in a continous process.
In a preferred embodiment of the present invention, additional ionically conductive polyethylene oxide is applied to the layer of spheres to form a matrix around the spheres and fill the voids therebetween. This increases the mechanical stability of the layer and provides improved diffusional properties.
It has been found preferable to employ vanadium oxide as approximately 50%, by volume, of the total cathode, including the added matrix material, if used.
When forming a lithium battery, it is preferred to deposit the cathode layer directly onto the current-collecting base layer. Accordingly, in the present invention, the emulsion of polymer spheres may be applied directly to the foil base as a thin layer.
Claims (18)
1. In a solid-state lithium battery of the type comprising a lithium or lithium/aluminum anode, a polymeric electrolyte, and a cathode based on vanadium oxide, the improvement comprising:
a cathode comprising a multiplicity of spheres, each sphere consisting of a vanadium oxide core encapsulated in a polymer film, said polymer film containing an inorganic salt and an activated carbon.
a cathode comprising a multiplicity of spheres, each sphere consisting of a vanadium oxide core encapsulated in a polymer film, said polymer film containing an inorganic salt and an activated carbon.
2. The battery as set forth in claim 1 wherein said polymer film consists of polyethylene oxide.
3. The battery as set forth in claim 2, wherein said inorganic salt is selected from the group consisting of LiClO4, NaClO4, LiF3CSO3, and LiBF4.
4. The battery as set forth in claim 2 wherein said spheres are prepared by emulsifying vanadium oxide powder in an organic solvent using said polyethylene oxide as a binder.
5. The battery set forth in claim 1 wherein the cathode consists of approximately 50% by volume of vanadium oxide.
6. A solid-state electrochemical cell comprising an anode, a polymeric electrolyte, and a cathode comprising a composite including an active cathode material, wherein said composite comprises a plurality of spheres formed by encapsulating said active cathode material in an electronic and ionic conducting polymeric film, said plurality of spheres forming an electronic and ionic conducting network.
7. The electrochemical cell of claim 6 wherein said electronic and ionic conductive polymer includes an ionically conductive salt and an electronically conductive filler.
8. The electrochemical cell of claim 7 wherein said electronically conductive filler is carbon black.
9. The electrochemical cell of claim 8 wherein said ionically conductive salt is a lithium or sodium salt.
10. The electrochemical cell of claim 9 wherein said salt is a lithium salt.
11. The electrochemical cell of claim 10 wherein said polymer is polyethylene oxide.
12. The electrochemical cell of claim 6 wherein said anode is a lithium or lithium alloy anode.
13. The electrochemical cell of claim 6 wherein said polymeric electrolyte comprises a salt and a polymer and said salt and said polymer are present in said ionically and electronically conductive film encapsulating said active cathode material.
14. A cathode comprising a composite including an active cathode material, wherein said composite comprises a plurality of spheres formed by encapsulating said active cathode material in an electronic and ionic conducting polymeric film, said plurality of spheres forming an electronic and ionic conducting network.
15, The cathode of claim 14 wherein said active cathode material is vanadium oxide.
16. The cathode of claim 15 wherein said electronic and ionic conductive polymer includes an ionically conductive salt and an electronically conductive filler.
17, The cathode of claim 16 wherein said electronically conductive filler is carbon black and said ionically conductive sale is a lithium salt.
18. The cathode of claim 17 wherein said polymer is polyethylene oxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US729,643 | 1985-05-02 | ||
| US06/729,643 US4576883A (en) | 1985-05-02 | 1985-05-02 | Cathode composition and method for solid state lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA1268809C CA1268809C (en) | 1990-05-08 |
| CA1268809A true CA1268809A (en) | 1990-05-08 |
Family
ID=24931963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000504129A Expired CA1268809A (en) | 1985-05-02 | 1986-03-14 | Cathode composition and method for solid state lithium battery |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4576883A (en) |
| JP (1) | JPS61256564A (en) |
| CN (1) | CN86102718A (en) |
| AU (1) | AU576948B2 (en) |
| BR (1) | BR8601185A (en) |
| CA (1) | CA1268809A (en) |
| DE (1) | DE3608643A1 (en) |
| DK (2) | DK155477C (en) |
| GB (1) | GB2175126B (en) |
| NZ (1) | NZ215394A (en) |
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| US4720910A (en) * | 1987-06-16 | 1988-01-26 | Mhb Joint Venture | Method for preparing encapsulated cathode material |
| US4794059A (en) * | 1988-02-29 | 1988-12-27 | Hope Henry F | Lightweight solid state rechargeable batteries |
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| ES2047573T3 (en) * | 1988-09-09 | 1994-03-01 | Hydro Quebec | PROCEDURE FOR THE MANUFACTURE OF THIN ELECTRODES ON A SHEET. |
| US4960655A (en) * | 1989-01-27 | 1990-10-02 | Hope Henry F | Lightweight batteries |
| US5147985A (en) * | 1990-08-14 | 1992-09-15 | The Scabbard Corporation | Sheet batteries as substrate for electronic circuit |
| US5124508A (en) * | 1990-08-14 | 1992-06-23 | The Scabbard Corp. | Application of sheet batteries as support base for electronic circuits |
| US5348820A (en) * | 1992-07-10 | 1994-09-20 | Nippon Oil Company, Limited | Zinc electrode for alkaline storage battery |
| US5330856A (en) * | 1993-06-08 | 1994-07-19 | Valence Technology, Inc. | Method of making a cathode for use in an electrolytic cell |
| US5360686A (en) * | 1993-08-20 | 1994-11-01 | The United States Of America As Represented By The National Aeronautics And Space Administration | Thin composite solid electrolyte film for lithium batteries |
| US5418089A (en) * | 1993-12-06 | 1995-05-23 | Valence Technology, Inc. | Curable cathode paste containing a conductive polymer to replace carbon as the conductive material and electrolytic cells produced therefrom |
| JPH09245836A (en) * | 1996-03-08 | 1997-09-19 | Fuji Photo Film Co Ltd | Nonaqueous electrolyte secondary battery |
| DE69710787T2 (en) | 1996-05-22 | 2002-11-21 | Moltech Corp., Tucson | COMPOSITE CATHODES, ELECTROCHEMICAL CELLS WITH COMPOSITE CATHODES AND METHOD FOR THE PRODUCTION THEREOF |
| US7214446B1 (en) | 1997-07-21 | 2007-05-08 | Nanogram Corporation | Batteries with electroactive nanoparticles |
| US5952125A (en) * | 1997-07-21 | 1999-09-14 | Nanogram Corporation | Batteries with electroactive nanoparticles |
| US6132904A (en) * | 1997-07-24 | 2000-10-17 | Sanyo Electric Co., Ltd. | Polyelectrolytic battery having a polyelectrolyte based on a polystyrene main chain and polyethylene oxide side chain |
| US6673130B2 (en) * | 2001-06-15 | 2004-01-06 | The Regents Of The University Of California | Method of fabrication of electrodes and electrolytes |
| CN1260848C (en) * | 2002-03-28 | 2006-06-21 | Tdk株式会社 | Lithium secondary battery |
| US10411252B2 (en) * | 2016-02-09 | 2019-09-10 | GM Global Technology Operations LLC | Positive electrode composition, a positive electrode of a lithiumion electrochemical cell, and a method of forming the positive electrode |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2485274A1 (en) * | 1980-03-31 | 1981-12-24 | France Etat | SOLID ELECTROLYTE BASED ON ION-CONDUCTION MACROMOLECULAR MATERIAL |
| US4520086A (en) * | 1980-11-18 | 1985-05-28 | The United States Of America As Represented By The United States Department Of Energy | Rechargeable solid polymer electrolyte battery cell |
| JPS58169769A (en) * | 1982-03-30 | 1983-10-06 | Toshiba Corp | Solid electrolytic cell |
| US4471037A (en) * | 1982-04-16 | 1984-09-11 | United Kingdom Atomic Energy Authority | Solid state electrochemical cell |
| US4570086A (en) * | 1983-06-27 | 1986-02-11 | International Business Machines Corporation | High speed complementary NOR (NAND) circuit |
| US4496633A (en) * | 1983-11-01 | 1985-01-29 | Union Carbide Corporation | High density load bearing insulation peg |
-
1985
- 1985-05-02 US US06/729,643 patent/US4576883A/en not_active Expired - Fee Related
-
1986
- 1986-03-06 NZ NZ215394A patent/NZ215394A/en unknown
- 1986-03-07 AU AU54482/86A patent/AU576948B2/en not_active Ceased
- 1986-03-07 GB GB08605673A patent/GB2175126B/en not_active Expired
- 1986-03-14 CA CA000504129A patent/CA1268809A/en not_active Expired
- 1986-03-14 DE DE19863608643 patent/DE3608643A1/en not_active Withdrawn
- 1986-03-14 JP JP61055135A patent/JPS61256564A/en active Pending
- 1986-03-17 BR BR8601185A patent/BR8601185A/en unknown
- 1986-03-17 DK DK122386A patent/DK155477C/en active
- 1986-04-23 CN CN86102718A patent/CN86102718A/en active Pending
-
1988
- 1988-04-08 DK DK195088A patent/DK195088D0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE3608643A1 (en) | 1987-09-17 |
| DK155477C (en) | 1989-09-11 |
| DK155477B (en) | 1989-04-10 |
| BR8601185A (en) | 1987-01-13 |
| GB8605673D0 (en) | 1986-04-16 |
| AU576948B2 (en) | 1988-09-08 |
| CA1268809C (en) | 1990-05-08 |
| CN86102718A (en) | 1986-10-29 |
| DK122386D0 (en) | 1986-03-17 |
| GB2175126A (en) | 1986-11-19 |
| US4576883A (en) | 1986-03-18 |
| NZ215394A (en) | 1989-04-26 |
| DK195088A (en) | 1988-04-08 |
| DK122386A (en) | 1986-11-03 |
| AU5448286A (en) | 1986-11-06 |
| DK195088D0 (en) | 1988-04-08 |
| JPS61256564A (en) | 1986-11-14 |
| GB2175126B (en) | 1988-03-02 |
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| MKLA | Lapsed | ||
| MKLA | Lapsed |
Effective date: 19921110 |