Thermal evaporation process for manufacture of solid state battery devices

• US 9,127,344 B2
• Filed: 11/08/2011
• Issued: 09/08/2015
• Est. Priority Date: 11/08/2011
• Status: Active Grant

• Current Assignee: Sakti3, Inc
• Original Assignee: Sakti3, Inc
• Inventors: Chung, Myoungdo, Kim, Hyoncheol, Sastry, Ann Marie, Langlois, Marc
• Primary Examiner(s): WIECZOREK, MICHAEL P
• Application Number:
  US13/291,845
• Publication Number:
  US 20120058280A1
• Time in Patent Office: 1,400 Days
• Field of Search: 427/115, 427/126.3, 427/250, 427/251, 427/252, 427/255.5, 427/551, 427/592, 427/593, 429/188, 429/206, 429/218.1, 429/231.5
• US Class Current: 1/1
• CPC Class Codes: C23C 14/0031 Bombardment of substrates by reactive ion beams
• CPC Class Codes: C23C 14/0676 Oxynitrides
• CPC Class Codes: C23C 14/083 of refractory metals or yttrium
• CPC Class Codes: C23C 14/5833 Ion beam bombardment
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/0585 of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 4/0423 Physical vapour deposition
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/1391 of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 4/48 of inorganic oxides or hydroxides
• CPC Class Codes: H01M 4/483 for non-aqueous cells H01M4/485 takes precedence
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 50/403 Manufacturing processes of separators, membranes or diaphragms
• CPC Class Codes: H01M 6/40 Printed batteries , e.g. thin film batteries
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

A method for manufacturing a solid-state battery device. The method can include providing a substrate within a process region of an apparatus. A cathode source and an anode source can be subjected to one or more energy sources to transfer thermal energy into a portion of the source materials to evaporate into a vapor phase. An ionic species from an ion source can be introduced and a thickness of solid-state battery materials can be formed overlying the surface region by interacting the gaseous species derived from the plurality of electrons and the ionic species. During formation of the thickness of the solid-state battery materials, the surface region can be maintained in a vacuum environment from about 10-6 to 10-4 Torr. Active materials comprising cathode, electrolyte, and anode with non-reactive species can be deposited for the formation of modified modulus layers, such a void or voided porous like materials.

Claims

1. A method for manufacturing a cathode device for a solid-state battery device using a flash process, the method comprising:

providing a substrate including a surface region, the substrate being configured on a transfer device;

continuously applying at a controlled rate a cathode source comprising a metal oxide onto a hot wall reactor subjected to thermal energy to cause a portion of the cathode source to evaporate into a vapor phase within a time period of less than about one second to substantially evaporate the portion of the cathode source free from formation of undesirable metal oxide species;

forming a thickness of metal oxide material overlying the surface region at a rate of about 100 to 10,000 Angstroms per second per 100 square centimeters by condensing the vapor phase of the metal oxide species as the substrate moves either in a first direction or a second direction;

subjecting the thickness of the metal oxide material to an ion source comprising an oxygen species, an argon species, and a nitrogen species while the thickness of metal oxide material is being formed and/or after the thickness of metal oxide material has been formed, the ion source including an ion beam having a power to cause an electrical conductivity of the thickness of the metal oxide material to increase from about 10<sup>−

8</sup> Siemens/meter to about 10<sup>−

5</sup> Siemens/meter and to cause the thickness of the metal oxide material to be doped with approximately 4% nitrogen; and

maintaining the surface region in a vacuum environment from about 10<sup>−

6</sup> to 10<sup>−

4</sup> Torr during the formation of the thickness of the metal oxide material.

2. The method of claim 1 wherein the substrate moves at a rate of about 1 inches/min to about 10 feet/min in a continuous manner via the transfer device to form the solid state battery device configured in a roll.

3. The method of claim 1 wherein cathode source comprises a vanadium oxide having a purity.

4. The method of claim 1 wherein the metal oxide is selected from one of a vanadium oxide, a manganese oxide, an iron oxide, nickel oxide, sulfur oxide, cobalt oxide, or magnesium oxide.

5. The method of claim 1 further comprising introducing a dopant species into the thickness of metal oxide using an ion beam process to cause an increase in conductivity of the thickness of metal oxide material and cause an increase in ionic diffusivity of the thickness of the metal oxide material.

6. The method of claim 1 further comprising introducing an additional dopant species into the thickness of metal oxide, the additional dopant being selected from the group consisting of oxygen, carbon, fluorine, silver, molybdenum, copper, tin, aluminum, iodine, phosphorous, and silicon.

7. The method of claim 1 wherein the subjecting the thermal energy to the cathode source is provided on the hot wall reactor;

wherein the hot wall reactor is characterized by a temperature ranging from about 600 to 1200 Degrees Centigrade;

wherein the metal oxide is vanadium oxide;

wherein the ion source is provided at an energy from about 100 to about 400 electron volts.

8. The method of claim 1 wherein the transfer device comprises a first drum coupled to a second drum and configured in a reel to reel.

9. The method of claim 1 further comprising moving the substrate in a single pass or multiple passes using the transfer device in a continuous manner, wherein the transfer device is configured for the single pass or the multiple pass passes of the substrate between a pair of reels:

wherein the substrate is moved through a single chamber or multiple chambers in the first direction or the first direction and the second direction.

10. The method of claim 1 wherein the specific cathode material is characterized by a mixture of cathode and anode material co-deposited so as to form a cathode layer in a partially or fully discharged state having a modified intercalation stress.

11. The method of claim 1 wherein the evaporated material contains entrained non-reactive species in the shape of nano rods, cones, columns, fibers, spheres, with or without binder, comprising a void or voided porous cathode or cathode modification layer.

12. The method of claim 1 wherein the cathode source is provided in a containment vessel comprising a plurality of containment vessels and the thermal energy is provided by an energy source comprising a plurality of energy sources;

each of the containment vessels may be specific to a different surface to volume ratio of materials;

the materials may be mixtures of other materials; and

the containment vessels being suitable for producing co deposited or multi deposited materials, including graded materials for the cathode layer or cathode modification layer of an electrochemical device.

13. The method of claim 1 further comprising a shaped mask device configured between the hot wall reactor providing the thermal energy and the substrate, the shaped mask device may be coupled to a heating device to maintain the mask device essentially free from a residue from the metal oxide and is so positioned as to allow either demarcation of the cathode material or oblique angle deposition for the formation of a void or voided porous like cathode or cathode modification layer.

14. A method for manufacturing a cathode device for a solid-state battery device using a flash process, the method comprising:

providing a substrate including a surface region, the substrate being configured on a transfer device;

continuously applying at a controlled rate a cathode source comprising a metal oxide onto a hot wall reactor subjected to thermal energy to cause a portion of the cathode source to evaporate into a vapor phase within a time period of less than about one second to substantially evaporate the portion of the cathode source free from formation of undesirable metal oxide species;

forming a thickness of metal oxide material overlying the surface region by condensing the gaseous species as the substrate moves either in a first direction or a second direction, and at a rate of about 100 to 10,000 Angstroms per second per 100 square centimeters;

subjecting the thickness of the metal oxide material to an ion source comprising an oxygen species, an argon species, and a nitrogen species while the thickness of metal oxide material is being formed and/or after the thickness of metal oxide material has been formed in order to dope the thickness of the metal oxide material with approximately 4% nitrogen, which causes an electrical conductivity of the thickness of the metal oxide material to increase from about 10<sup>−

8</sup> Siemens/meter to about 10<sup>−

5</sup> Siemens/meter;

maintaining the surface region in a vacuum environment from about 10<sup>−

6</sup> to 10<sup>−

4</sup> Torr during the formation of the thickness of the metal oxide material.

15. The method of claim 14 wherein the ion source is an ion beam or an ion shower;

and wherein the substrate moves at a rate of about 1 inches/min to about 10 feet/min; and

wherein cathode source comprises a vanadium oxide having a purity.

16. The method of claim 14 wherein the metal oxide is selected from one of a vanadium oxide, a manganese oxide, an iron oxide, nickel oxide, sulfur oxide, cobalt oxide, or magnesium oxide.

17. The method of claim 14 further comprising introducing a dopant species into the thickness of metal oxide using an ion beam process to cause an increase in conductivity of the thickness of metal oxide material and cause an increase in ionic diffusivity of the thickness of the metal oxide material;

and further comprising introducing a dopant species into the thickness of metal oxide, the additional dopant being selected from the group consisting of, oxygen, carbon, fluorine, silver, molybdenum, copper, tin, aluminum, iodine, phosphorous, and silicon.

18. A method for manufacturing a cathode device for a solid-state battery device using a flash process comprising:

providing a substrate including a surface region, the substrate being configured on a transfer device for a roll to roll process;

continuously applying thermal energy from a hot wall reactor region at a temperature ranging from about 600 to 1200 Degrees Centigrade to a cathode source comprising a metal oxide species to cause a portion of the cathode source to evaporate into a vapor phase within a time period of less than about one second to substantially evaporate the portion of the cathode source free from formation of undesirable metal oxide species;

forming a thickness of metal oxide material overlying the surface region by condensing the gaseous species as the substrate moves either in a first direction or a second direction, and at a rate of about 100 to 10,000 Angstroms per second per 100 square centimeters;

subjecting the thickness of the metal oxide material to an ion source at an energy of 100 eV to 400 eV and comprising an oxygen species, an argon species, and a nitrogen species while the thickness of metal oxide material is being formed and/or after the thickness of metal oxide material has been formed, in order to dope the thickness of the metal oxide material with approximately 4% nitrogen, which causes an electrical conductivity of the thickness of the metal oxide material to increase from about 10<sup>−

8</sup> Siemens/meter to about 10<sup>−

5</sup> Siemens/meter;

maintaining the surface region in a vacuum environment from about 10<sup>−

6</sup> to 10<sup>−

4</sup> Torr during the formation of the thickness of the metal oxide material; and

moving the substrate in a continuous manner while the cathode source is continuously applied to the hot wall reactor region to evaporate the cathode source into the vapor phase.