ABSTRACT
Abstract
A high-performance rechargeable battery using ultra-fast ion conductors. In one embodiment the rechargeable battery apparatus includes an enclosure, a first electrode operatively connected to the enclosure, a second electrode operatively connected to the enclosure, a nanomaterial in the enclosure, and a heat transfer unit.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a Division of Co-pending U.S. Non-Provisional patent application Ser. No. 12/890,099 filed Sep. 24, 2010, entitled, âHigh-Performance Rechargeable Batteries with Nanoparticle Active Materials, Photochemically Regenerable Active Materials, and Fast Solid-State Ion Conductors,â which claims priority based upon U.S. Provisional Patent Application No. 61/246,018 filed Sep. 25, 2009, entitled âNovel High-Performance Rechargeable Batteries with Fast Solid-State Ion Conductors,â the disclosure of which is hereby incorporated by reference in its entirety for all purposes.
STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT
The United States Government has rights in this invention pursuant to Contract No. DE-AC52-07NA27344 between the United States Department of Energy and Lawrence Livermore National Security, LLC for the operation of Lawrence Livermore National Laboratory.
BACKGROUND
Field of Endeavor
The present invention relates to batteries, and more particularly to, high-performance rechargeable batteries with fast solid-state ion conductors.
State of Technology
Electrochemical energy storage is required for grid storage, wireless communications, portable computing, and will be essential for the realization of future fleets of electric and hybrid electric vehicles, which are now believed to be an essential part of the world's strategy for reducing our dependence on oil, and minimizing the impact of gaseous emissions of CO 2 on global warming. In looking at those possible materials that can be used for anodes in electrochemical energy conversion and storage systems, hydrogen and lithium have the highest specific capacities (Ah/kg). Hydrogen is of course used to power fuel cells, while lithium is used in advanced rechargeable batteries.
Most state of the art energy storage systems use lithium ion battery chemistry, with graphite anodes that intercalate lithium upon charging, mixed transition metal oxide cathodes that intercalate lithium during discharge, a micro-porous polyethylene electrode separator, and electrolyte formed from a dielectric mixed solvent composed of organic carbonates and high-mobility lithium salts. The movement of the lithium ions between the intercalation anodes and cathodes during charge and discharge is known as the ârocking chairâ mechanism.
Cells with liquid electrolytes are usually contained in cylindrical or prismatic metal cans, with stack pressure maintained by the walls of the can, while cells with polymer gel electrolytes are usually contained in soft-side aluminum-laminate packages, with stack pressure achieved through thermal lamination of the electrodes and separators, thereby forming a monolithic structure.
The active graphite or transition metal oxide materials used in the electrodes exist as fine powders, coated onto thin metal foils of copper and aluminum, respectively, and held in place by a PVDF binder. Both natural and manmade graphite such as MCMB have been used for the anodes, while Li x CoO 2 , LiNiO 2 , Li x Mn 2 O 4 , mixed transition metal oxides with cobalt, nickel and manganese, and iron-phosphates are common choices for the cathode.
Over the past decade, these systems have attained outstanding specific energy and energy density, exceptional cycle life and rate capabilities that enable them to now be considered for both vehicular and power tool applications, in addition to their early applications in wireless communications and portable computing. The best commercially available, polymer-gel lithium ion battery now has a specific energy of 180 to 200 Wh/kg, an energy density of 360 to 400 Wh/L, and a reasonably good rate capability, allowing discharge at C/2 or better.
Both liquid prismatic and polymer gel cells have been incorporated into large high-capacity power packs and used to power the mobile electric vehicles. Such high capacity systems have state-of-the-art computerized charge and discharge control, which includes graphical user interfaces, sensing for monitoring the health of individual cells, and charge balancing networks.
Such lithium ion batteries, which rely on the rocking chair mechanism, are generally believed to be safer than those where lithium exists in the reduced metallic state. However, the use of flammable liquid-phase and two-phase polymer gel electrolytes, coupled with a high energy density, a relatively delicate 20-micron thick polymeric separator, and the possibility of lithium plating and dendrite formation due to non-uniform stack pressure and electrode misalignment has led to safety problems with these energy storage systems. The possibility of such an event occurring on commercial airliners, where many passengers carry laptop computers and cell phones with such batteries, is especially disconcerting. These events have occurred on much larger scale, and have caused industry-wide concern in the continued use of this important technology.
Adequate and intelligent thermal management in these cells is essential. High rates of charge or discharge drives the temperature upward due to resistive heating of the electrolyte. When the core temperature of these cells exceeds approximately 150° F., the systems frequently become unstable, with the possible initiation of autocatalytic reactions, which can lead to thermal runaway and catastrophic results. Disproportionation of the transition metal oxides can liberate sufficient oxygen to support oxidation of the organic carbonate solvents used in the liquid or polymer-gel electrolytes. It is now recognized that while conventional systems provide high energy density, their safety remains problematic.
The treatise, Introduction to Nanotechnology , by Charles P. Poole, Jr., and Frank J. Owens. John Wiley &. Sons, 2003, states: âNanotechnology is based on the recognition that particles less than the size of 100 nanometers (a nanometer is a billionth of a meter) impart to nanostructures built from them new properties and behavior. This happens because particles which are smaller than the characteristic lengths associated with particular phenomena often display new chemistry and physics, leading to new behavior which depends on the size. So, for example, the electronic structure, conductivity, reactivity, melting temperature, and mechanical properties have all been observed to change when particles become smaller than a critical size.â
SUMMARY
Features and advantages of the present invention will become apparent from the following description. Applicants are providing this description, which includes drawings and examples of specific embodiments, to give a broad representation of the invention. Various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this description and by practice of the invention. The scope of the invention is not intended to be limited to the particular forms disclosed and the invention covers all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.
The present invention provides a high-performance rechargeable battery using ultra-fast ion conductors. In one embodiment, the present invention provides high-performance rechargeable batteries based upon ultra-fast solid-state ion conductors. The present invention will help the creation of a completely solid-state alternative to liquid-filled and polymer-gel lithium ion batteries. The scientific and technological advancement of the present invention will assist in enabling dramatic performance enhancements through the reduction of inert materials in the battery; huge improvements in safety through the elimination of flammable organic liquids; U.S. dominance in advanced battery technology through the introduction of a disruptive technology; and help secure the future of the U.S. automotive industry, which includes electric vehicles.
The present invention will also help result in the creation of a room-temperature sodium-beta (or equivalent) battery for electrical grid management and transportation. Additional scientific and technical advancement of the present invention will enable load leveling for better utilization of power from fossil and nuclear plants; introduction of power from green sources such as wind and solar that are characterized by fluctuations from day-tonight, and from season-to-season; and utilization of the benefits of sodium-beta batteries for such applications, without the heat losses associated with high-temperature operation, and without the need for thermal insulation which increases the volume required by such energy storage devices.
The present invention will also help provide a completely solid-state alternative to lithium ion batteries and a room-temperature alternative to conventional sodium-beta batteries, rely on solid-state fast ion-conductors. The present invention will therefore drive the development of new solid-state ion conductors. Some specific quantifiable goals of one embodiment of the present invention that will guarantee adoption of these next-generation technologies are to: develop one or more inherently safe, high-performance rechargeable batteries based upon ultra-fast solid ion conductors; develop viable energy storage devices with solid-state electrolytes with specific energies ranging from 500 to 2500 Wh/kg, thereby achieving as much as an order of magnitude enhancement in energy storage capability; eliminate the need for volatile flammable organic solvents for electrolytes, to the extent possible; and develop room-temperature variants of the high-temperature sodium-beta batteries now used for electrical grid management, and transportation.
The present invention has use in intelligent grid management for energy security, safe electric vehicles with dramatic range extension and energy storage. The present invention also has use in energy storage for battle field applications, including military bases, silent watch, propulsion for ships, directed energy weapons and other applications. The present invention has exceptional specific energy (ultimately, several times greater than that of conventional Li-ion batteries), is intrinsically safe, exhibits long cycle life due to exceptional reversibility and dimensional stability, and can operate at room temperature.
The invention is susceptible to modifications and alternative forms. Specific embodiments are shown by way of example. It is to be understood that the invention is not limited to the particular forms disclosed. The invention covers all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated into and constitute a part of the specification, illustrate specific embodiments of the invention and, together with the general description of the invention given above, and the detailed description of the specific embodiments, serve to explain the principles of the invention.
FIG. 1 illustrates one embodiment a rechargeable battery of the present invention.
FIG. 2 illustrates another embodiment a rechargeable battery of the present invention.
FIG. 3 illustrates yet another embodiment a rechargeable battery of the present invention.
DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS
Referring to the drawings, to the following detailed description, and to incorporated materials, detailed information about the invention is provided including the description of specific embodiments. The detailed description serves to explain the principles of the invention. The invention is susceptible to modifications and alternative forms. The invention is not limited to the particular forms disclosed. The invention covers all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.
The present invention provides a rechargeable battery. The rechargeable battery includes an enclosure, a first electrode operatively connected to the enclosure, a second electrode operatively connected to the enclosure, a nanomaterial in the enclosure, and a heat transfer unit.
The nanomaterial is defined as: nanomaterial+dielectric. A wide range of nanoparticles can be used. For example the following nanoparticles can be used: metal and metal alloy particles for anodic dissolution and thermal transport; hydrides as source of hydrogen ions; lithium and lithium alloys; intercalated graphite and carbon aerogel as Li source (anodic material); intercalated transition metal oxide as Li sink (cathodic material); and semiconductors for photovoltaic conversion in photo-electrochemical or hybrid electrochemical cell.
The particle suspension is defined as: particle suspension=particles+dielectric or ionic fluid. A wide range of particles can be used. For example the following particles can be used: metal and metal alloy particles for anodic dissolution and thermal transport; hydrides as source of hydrogen ions; lithium and lithium alloys; graphite intercalated with lithium; and carbon aerogel with a coating of lithium as a lithium source (anodic material); intercalated transition metal oxides as lithium sink (cathodic material); and semiconductors for photovoltaic conversion in photo-electrochemical or hybrid electrochemical cell.
Nanoparticles or particles for the nanomaterial anolyte can be made of pure elemental materials including Pb, Cd, Zn, Fe, Na, Ca, Mg, Al, and Li, as well as any alloy formed from these pure elemental materials. In the case of a nanofluid flow cell using lithium-ion type chemistry, the nanoparticles in the anolyte could be Li-intercalated natural graphite, Li-intercalated synthetic graphite, LiâS; alloys, LiâSn alloys, or other Li-containing alloys or compounds. Similar compositions can be used for particles suspensions. In the case of a nanofluid flow cell using lithium-ion type chemistry, the nanoparticles in the catholyte could be a transition metal oxide such as Li x CoO 2 , Li x NiO 2 , Li x Mn 2 O 4 , a mixed transition metal oxide such as Li x (Co, Ni, Mn)O 2 , or a phosphate such as Li x FePO 4 . Similar compositions can be used for particle suspensions. Hydrides can also be used for anolyte nanoparticles or particles.
Referring now to the drawings and in particular to FIG. 1 , a solid-state cell for on-chip applications is illustrated. The cell is designated generally by the reference numeral 100 . Metal-air batteries provide advantages over systems where both reactants are carried with the device as payload. Since the systems are air breathing, taking one of the reactants from the atmosphere, they are able to provide large advantages in regard to energy density and specific energy. The present invention should be able to achieve 2500 Wh/kg, with a limit of approximately 5000 Wh/kg. Typically the electrochemical dissolution of a metal anode is depolarized by oxygen reduction at an air-breathing cathode. Unfortunately, these systems lack the reversibility required to serve as rechargeable batteries, and are usually used as primaries. Alternatively, mechanically refueling can be used, where anode material is continuously fed to the system.
Metal air batteries of the present invention can be built that are entirely analogous to solid oxide fuel cells. In these systems, YSZ (Y 2 O 3 -stabilized ZrO 2 ) electrolytes are be used, with the formation of oxygen anions at the outer surface of the YSZ at a porous catalytic metal electrode, such as platinum, and then transported through the YSZ to the anode compartment, where they react with metal cations to form oxides. One possibility is a high-temperature lithium-air battery. Rechargeability requires reversibility of the oxide-formation at the YSZ/anode interface. By using low-melting eutectics, the anode can be kept in liquid phase at ambient temperature, and oxides can be bathed in the molten metal, with the possibility of dimensional stability of the electrode, and reversibility of the oxidation reaction between the oxygen anions and the metal cations.
Sodium-Beta Batteries
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a Division of Co-pending U.S. Non-Provisional patent application Ser. No. 12/890,099 filed Sep. 24, 2010, entitled, âHigh-Performance Rechargeable Batteries with Nanoparticle Active Materials, Photochemically Regenerable Active Materials, and Fast Solid-State Ion Conductors,â which claims priority based upon U.S. Provisional Patent Application No. 61/246,018 filed Sep. 25, 2009, entitled âNovel High-Performance Rechargeable Batteries with Fast Solid-State Ion Conductors,â the disclosure of which is hereby incorporated by reference in its entirety for all purposes.
STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT
The United States Government has rights in this invention pursuant to Contract No. DE-AC52-07NA27344 between the United States Department of Energy and Lawrence Livermore National Security, LLC for the operation of Lawrence Livermore National Laboratory.
BACKGROUND
Field of Endeavor
The present invention relates to batteries, and more particularly to, high-performance rechargeable batteries with fast solid-state ion conductors.
State of Technology
Electrochemical energy storage is required for grid storage, wireless communications, portable computing, and will be essential for the realization of future fleets of electric and hybrid electric vehicles, which are now believed to be an essential part of the world's strategy for reducing our dependence on oil, and minimizing the impact of gaseous emissions of CO 2 on global warming. In looking at those possible materials that can be used for anodes in electrochemical energy conversion and storage systems, hydrogen and lithium have the highest specific capacities (Ah/kg). Hydrogen is of course used to power fuel cells, while lithium is used in advanced rechargeable batteries.
Most state of the art energy storage systems use lithium ion battery chemistry, with graphite anodes that intercalate lithium upon charging, mixed transition metal oxide cathodes that intercalate lithium during discharge, a micro-porous polyethylene electrode separator, and electrolyte formed from a dielectric mixed solvent composed of organic carbonates and high-mobility lithium salts. The movement of the lithium ions between the intercalation anodes and cathodes during charge and discharge is known as the ârocking chairâ mechanism.
Cells with liquid electrolytes are usually contained in cylindrical or prismatic metal cans, with stack pressure maintained by the walls of the can, while cells with polymer gel electrolytes are usually contained in soft-side aluminum-laminate packages, with stack pressure achieved through thermal lamination of the electrodes and separators, thereby forming a monolithic structure.
The active graphite or transition metal oxide materials used in the electrodes exist as fine powders, coated onto thin metal foils of copper and aluminum, respectively, and held in place by a PVDF binder. Both natural and manmade graphite such as MCMB have been used for the anodes, while Li x CoO 2 , LiNiO 2 , Li x Mn 2 O 4 , mixed transition metal oxides with cobalt, nickel and manganese, and iron-phosphates are common choices for the cathode.
Over the past decade, these systems have attained outstanding specific energy and energy density, exceptional cycle life and rate capabilities that enable them to now be considered for both vehicular and power tool applications, in addition to their early applications in wireless communications and portable computing. The best commercially available, polymer-gel lithium ion battery now has a specific energy of 180 to 200 Wh/kg, an energy density of 360 to 400 Wh/L, and a reasonably good rate capability, allowing discharge at C/2 or better.
Both liquid prismatic and polymer gel cells have been incorporated into large high-capacity power packs and used to power the mobile electric vehicles. Such high capacity systems have state-of-the-art computerized charge and discharge control, which includes graphical user interfaces, sensing for monitoring the health of individual cells, and charge balancing networks.
Such lithium ion batteries, which rely on the rocking chair mechanism, are generally believed to be safer than those where lithium exists in the reduced metallic state. However, the use of flammable liquid-phase and two-phase polymer gel electrolytes, coupled with a high energy density, a relatively delicate 20-micron thick polymeric separator, and the possibility of lithium plating and dendrite formation due to non-uniform stack pressure and electrode misalignment has led to safety problems with these energy storage systems. The possibility of such an event occurring on commercial airliners, where many passengers carry laptop computers and cell phones with such batteries, is especially disconcerting. These events have occurred on much larger scale, and have caused industry-wide concern in the continued use of this important technology.
Adequate and intelligent thermal management in these cells is essential. High rates of charge or discharge drives the temperature upward due to resistive heating of the electrolyte. When the core temperature of these cells exceeds approximately 150° F., the systems frequently become unstable, with the possible initiation of autocatalytic reactions, which can lead to thermal runaway and catastrophic results. Disproportionation of the transition metal oxides can liberate sufficient oxygen to support oxidation of the organic carbonate solvents used in the liquid or polymer-gel electrolytes. It is now recognized that while conventional systems provide high energy density, their safety remains problematic.
The treatise, Introduction to Nanotechnology , by Charles P. Poole, Jr., and Frank J. Owens. John Wiley &. Sons, 2003, states: âNanotechnology is based on the recognition that particles less than the size of 100 nanometers (a nanometer is a billionth of a meter) impart to nanostructures built from them new properties and behavior. This happens because particles which are smaller than the characteristic lengths associated with particular phenomena often display new chemistry and physics, leading to new behavior which depends on the size. So, for example, the electronic structure, conductivity, reactivity, melting temperature, and mechanical properties have all been observed to change when particles become smaller than a critical size.â
SUMMARY
Features and advantages of the present invention will become apparent from the following description. Applicants are providing this description, which includes drawings and examples of specific embodiments, to give a broad representation of the invention. Various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this description and by practice of the invention. The scope of the invention is not intended to be limited to the particular forms disclosed and the invention covers all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.
The present invention provides a high-performance rechargeable battery using ultra-fast ion conductors. In one embodiment, the present invention provides high-performance rechargeable batteries based upon ultra-fast solid-state ion conductors. The present invention will help the creation of a completely solid-state alternative to liquid-filled and polymer-gel lithium ion batteries. The scientific and technological advancement of the present invention will assist in enabling dramatic performance enhancements through the reduction of inert materials in the battery; huge improvements in safety through the elimination of flammable organic liquids; U.S. dominance in advanced battery technology through the introduction of a disruptive technology; and help secure the future of the U.S. automotive industry, which includes electric vehicles.
The present invention will also help result in the creation of a room-temperature sodium-beta (or equivalent) battery for electrical grid management and transportation. Additional scientific and technical advancement of the present invention will enable load leveling for better utilization of power from fossil and nuclear plants; introduction of power from green sources such as wind and solar that are characterized by fluctuations from day-tonight, and from season-to-season; and utilization of the benefits of sodium-beta batteries for such applications, without the heat losses associated with high-temperature operation, and without the need for thermal insulation which increases the volume required by such energy storage devices.
The present invention will also help provide a completely solid-state alternative to lithium ion batteries and a room-temperature alternative to conventional sodium-beta batteries, rely on solid-state fast ion-conductors. The present invention will therefore drive the development of new solid-state ion conductors. Some specific quantifiable goals of one embodiment of the present invention that will guarantee adoption of these next-generation technologies are to: develop one or more inherently safe, high-performance rechargeable batteries based upon ultra-fast solid ion conductors; develop viable energy storage devices with solid-state electrolytes with specific energies ranging from 500 to 2500 Wh/kg, thereby achieving as much as an order of magnitude enhancement in energy storage capability; eliminate the need for volatile flammable organic solvents for electrolytes, to the extent possible; and develop room-temperature variants of the high-temperature sodium-beta batteries now used for electrical grid management, and transportation.
The present invention has use in intelligent grid management for energy security, safe electric vehicles with dramatic range extension and energy storage. The present invention also has use in energy storage for battle field applications, including military bases, silent watch, propulsion for ships, directed energy weapons and other applications. The present invention has exceptional specific energy (ultimately, several times greater than that of conventional Li-ion batteries), is intrinsically safe, exhibits long cycle life due to exceptional reversibility and dimensional stability, and can operate at room temperature.
The invention is susceptible to modifications and alternative forms. Specific embodiments are shown by way of example. It is to be understood that the invention is not limited to the particular forms disclosed. The invention covers all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated into and constitute a part of the specification, illustrate specific embodiments of the invention and, together with the general description of the invention given above, and the detailed description of the specific embodiments, serve to explain the principles of the invention.
FIG. 1 illustrates one embodiment a rechargeable battery of the present invention.
FIG. 2 illustrates another embodiment a rechargeable battery of the present invention.
FIG. 3 illustrates yet another embodiment a rechargeable battery of the present invention.
DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS
Referring to the drawings, to the following detailed description, and to incorporated materials, detailed information about the invention is provided including the description of specific embodiments. The detailed description serves to explain the principles of the invention. The invention is susceptible to modifications and alternative forms. The invention is not limited to the particular forms disclosed. The invention covers all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.
The present invention provides a rechargeable battery. The rechargeable battery includes an enclosure, a first electrode operatively connected to the enclosure, a second electrode operatively connected to the enclosure, a nanomaterial in the enclosure, and a heat transfer unit.
The nanomaterial is defined as: nanomaterial+dielectric. A wide range of nanoparticles can be used. For example the following nanoparticles can be used: metal and metal alloy particles for anodic dissolution and thermal transport; hydrides as source of hydrogen ions; lithium and lithium alloys; intercalated graphite and carbon aerogel as Li source (anodic material); intercalated transition metal oxide as Li sink (cathodic material); and semiconductors for photovoltaic conversion in photo-electrochemical or hybrid electrochemical cell.
The particle suspension is defined as: particle suspension=particles+dielectric or ionic fluid. A wide range of particles can be used. For example the following particles can be used: metal and metal alloy particles for anodic dissolution and thermal transport; hydrides as source of hydrogen ions; lithium and lithium alloys; graphite intercalated with lithium; and carbon aerogel with a coating of lithium as a lithium source (anodic material); intercalated transition metal oxides as lithium sink (cathodic material); and semiconductors for photovoltaic conversion in photo-electrochemical or hybrid electrochemical cell.
Nanoparticles or particles for the nanomaterial anolyte can be made of pure elemental materials including Pb, Cd, Zn, Fe, Na, Ca, Mg, Al, and Li, as well as any alloy formed from these pure elemental materials. In the case of a nanofluid flow cell using lithium-ion type chemistry, the nanoparticles in the anolyte could be Li-intercalated natural graphite, Li-intercalated synthetic graphite, LiâS; alloys, LiâSn alloys, or other Li-containing alloys or compounds. Similar compositions can be used for particles suspensions. In the case of a nanofluid flow cell using lithium-ion type chemistry, the nanoparticles in the catholyte could be a transition metal oxide such as Li x CoO 2 , Li x NiO 2 , Li x Mn 2 O 4 , a mixed transition metal oxide such as Li x (Co, Ni, Mn)O 2 , or a phosphate such as Li x FePO 4 . Similar compositions can be used for particle suspensions. Hydrides can also be used for anolyte nanoparticles or particles.
Referring now to the drawings and in particular to FIG. 1 , a solid-state cell for on-chip applications is illustrated. The cell is designated generally by the reference numeral 100 . Metal-air batteries provide advantages over systems where both reactants are carried with the device as payload. Since the systems are air breathing, taking one of the reactants from the atmosphere, they are able to provide large advantages in regard to energy density and specific energy. The present invention should be able to achieve 2500 Wh/kg, with a limit of approximately 5000 Wh/kg. Typically the electrochemical dissolution of a metal anode is depolarized by oxygen reduction at an air-breathing cathode. Unfortunately, these systems lack the reversibility required to serve as rechargeable batteries, and are usually used as primaries. Alternatively, mechanically refueling can be used, where anode material is continuously fed to the system.
Metal air batteries of the present invention can be built that are entirely analogous to solid oxide fuel cells. In these systems, YSZ (Y 2 O 3 -stabilized ZrO 2 ) electrolytes are be used, with the formation of oxygen anions at the outer surface of the YSZ at a porous catalytic metal electrode, such as platinum, and then transported through the YSZ to the anode compartment, where they react with metal cations to form oxides. One possibility is a high-temperature lithium-air battery. Rechargeability requires reversibility of the oxide-formation at the YSZ/anode interface. By using low-melting eutectics, the anode can be kept in liquid phase at ambient temperature, and oxides can be bathed in the molten metal, with the possibility of dimensional stability of the electrode, and reversibility of the oxidation reaction between the oxygen anions and the metal cations.
Sodium-Beta Batteries
Sodium-beta batteries are crucial energy storage devices that rely heavily on solid-state fast ion conductors. In general, these batteries have a molten sodium anode and a 3â³-alumina, sodium-ion conductive, high-temperature solid-state electrolyte and separator. Two variants exist, known as sodium/sulfur and sodium/metal-chloride cells. The sodium/metal-chloride battery is also known as the ZEBRA battery.
Background on NaâS Battery
The most well developed sodium-beta battery is the NaâS system, which uses a sodium ion-conductive electrolyte, operating at a high temperature to maintain the sodium anode and the sulfur cathode in a molten state. During discharge, the molten Na is oxidized at the Na/βâ³-Al 2 O 3 , forming Na+ ions. These ions migrate through the β-Al 2 O 3 electrolyte, which is usually in the form of a ceramic tube. The beta-alumina solid electrolyte is sometimes referred to as BASE.
After diffusion through the (3â³-Al 2 O 3 separator, Naâ³ ions combine with sulfur reduced at the positive electrode, thereby forming sodium pentasulfide (Na 2 S 5 ), which is immiscible with the remaining molten sulfur. A two-phase system is therefore formed during the initial stage of discharge. After all of the free sulfur is converted to Na 2 S 5 during the initial stage of discharge, the cell enters a second stage of discharge, with the formation of single-phase polysulfides with higher sulfur content (Na 2 S x , where x=2.7 to 5). If discharge continues, the cell enters the third stage with the formation of a second two-phase system consisting of residual Na 2 S,â² and Na 2 S 2 . Most cells are designed to prevent the formation of Na 2 S 2 during such over discharge.
Stationary Power Applications
The sodiumlsulfur (NaâS) battery has enjoyed widespread use for stationary applications, such as grid management. As pointed out by the California Energy Commission during their Energy Storage Workshop, in the presentation entitled Overview of NaâS Battery for Load Management, this generic type of battery is potentially very useful for electrical grid applications. Multi-megawatt class systems have been built and deployed. With the increasing uses of green sources of energy, such as solar, wind and tidal, with variable production rates, the need for reliable energy storage on the grid is becoming even greater.
The NaâS battery is very similar to the ZEBRA battery, and has enjoyed widespread use for stationary applications, such as grid management. As pointed out by the California Energy Commission during their Energy Storage Workshop, in the presentation entitled Overview of NaâS Battery for Load Management, this generic type of battery is potentially very useful for electrical grid applications. With the increasing uses of green sources of energy, such as solar, wind and tidal, with variable production rates, the need for reliable energy storage on the grid is becoming even greater.
Background on ZEBRA
The ZEBRA cell is considered to be a variant of the sodium-beta type since it also has a molten sodium anode and a 13â³-alumina, sodium-ion conductive, high-temperature solid-state electrolyte and separator, and is also referred to as a NaâNiCl 2 cell. Applications for the ZEBRA battery include a variety of electric vehicles, such as delivery vans, taxis, school buses, passenger cars, surface ships and submarines, and stationary applications similar to those for the NaâS cell
The ZEBRA battery was invented in 1985 by a group led by Dr. Johan Coetzer at the CSIR in Pretoria, South Africa, and is generally considered safer and more robust due to the replacement of the molten sulfur electrode with a metal/metalchloride electrode. Some authors state that the ZEBRA name stands for the âZeolite Battery Research Africa Projectâ which developed the technology, which seems most reasonable, while other authors state that ZEBRA name stands for âZero Emission Battery Research Activities.â
The ZEBRA cell is considered to be a variant of the sodium-beta type since it has a molten sodium anode and a (13â³-alumina, sodium-ion conductive, high-temperature solid-state electrolyte and separator, and is also referred to as a NaâNiCl 2 cell. The ZEBRA cell has an open circuit voltage of 2.58 volts, and consists of a molten sodium anode, an electrolyte of NaAICl 4 , which melts at 160° C. (320° F.) and freezes at 157° C. (315° F.), a sodium-ion conducting 3â³-Al 2 O 3 separator, and a NiCI 2 /Ni cathode. The shorthand notation for the ZEBRA cell is: Na/βâ³-Al 2 O 3 /NaAICI 4 /NiCl 2 /Ni. The range of operating temperature for this battery is given as 270° C. (517° F.) to 350° C. (662° F.). This battery technology had achieved a specific energy of 85 Whlkg and a specific power 150 W/kg.
Goals for Development of Disruptive Energy Storage Technology
Specific goals are: (1) to develop one or more inherently safe, high performance rechargeable batteries based upon ultra-fast solid ion conductors; (2) identify viable pathways to specific energies ranging from 1000 to 5000 Wh/kg thereby achieving as much as an order of magnitude enhancement in energy storage capability; and (3) where possible, eliminate the need for volatile flammable organic solvents for electrolytes. Such technology would provide an attractive and enabling alternative for advanced electric vehicles for domestic and military applications, as well as for mobile directed energy weapons.
Development of Solid-State Fast Ion Conductors for Advanced Battery Systems
The lithium-ion battery is mature, with a specific energy that is not expected to increase substantially above 200 Wh/kg, and is plagued with safety issues associated with the flammable organic solvents used in the liquid and polymer gel electrolytes, and gaseous products from fires such as HF. The ZEBRA battery is an inherently safe alternative, but requires a high operating temperature, between 270° C. and 350° C. Thermal insulation necessary for high temperature operation can limit energy losses from the battery to between 10% and 25% of the stored energy, but lower the energy density substantially.
Work is proposed here to systematically explore new cell chemistries that promise to provide substantially greater specific energy and energy density than either modern lithium-ion systems, or the sodium-beta (ZEBRA) battery, using the fastest solid-state ion-conductors known to replace liquid-phase electrolytes. Such solid state electrolytes include materials such as Lii (cep), a-Agl (bee), RbAg 4 I 5 (distorted cubic), (3â³-Al 2 O 3 (spine] blocks) and Y 2 O 3 -stabilized ZrO 2 . Note that the ionic crystal with the highest known ion conductivity is RbAg 4 Is. These are summarized below:
Silver Iodide (Mobile Agâ²)
T<146° C. y-Agl (Zinc Blende) & (3-Agl (Wurtzite)
T>146° C.-* a-Agl (Body Centered Cubic)-* a-100 S mâ²
Rubidiuim-Substituted Silver Iodide (Mobile Agâ²)
T 25° C.-RbAg 4 I. 5 (Fixed I & Rb; Mobile Ag)-cr-25 S m-â²
Activation Energy for 1-lopping r., 0.07 eV
Solid-State Battery: Ag & RbI 3 Electrodes
Beta Alumina (Mobile Naâ²)
T 300° C.-* Râ³-(Al 2 O 3 ) 11 (Na 2 O), (Spine] Blocks)âa 10 S m-â²
Sodium-Sulfur Cell: Na Anode & Sulfur Cathode
Stabilized Cubic Zirconia (Mobile O 2â )
T 900° C.-(ZrO 2 ) 9 (Y 2 O 3 ) 1 (Cubic)--6--1 S m-â²
T . . . , 500° C.---a (ZrO 2 ) 85.72 (CaO) 15 -28 (Cubic)--a 6-500 S n11
Oxygen Sensor & Solid Oxide Fuel Cell: O2 Cathode & H2 Anode
To achieve rate capabilities comparable Li-ion batteries, solid-state electrolytes that have ion conductivities comparable to the liquid-phase electrolytes are used. The Li-based sold-state electrolyte with the best performance appears to be Li 0.36 1 0 14O0.007P0.11S0.38 with a conductivity of 0.5 mS/cm at ambient temperature, though non Li-based compounds are seen that exceed this bench-mark by great margin.
EXAMPLE(S)
One embodiment of the present invention includes construction of practical three-dimensional cell architectures with solid-state fast ion conducting electrolytes and completely reversible, dimensionally-stable liquid electrodes, with the demonstration of a I Ah cell including the following steps:
Coating nanostructural material such as carbon with materials necessary for metal-halogen electrode (Fe/FeCl 2 , Ni/NiCl 2 , Ag/AgCl, Ag1Agl, Rb/RbI, Rb/RbI 3s etc.) using appropriate techniques, which may include CVD, PVD, including but not limited to ALD.
Overcoating of the resultant structure with appropriate film and/or coating of solid-state fast ion conductor. If insurmountable dimensional stability problems are encountered with homogenous inorganic ion-conducting films, a coating with dispersed particles with a polymeric binder can be used.
Infiltration of the pore structure with liquid-phase low-melting eutectic metal anode, thereby forming the second electrode in a unique three-dimensional battery system with unparalleled rate capability, and none of the problems of self shielding usually encountered with porous electrode systems.
Performance testing of three-dimensional system with novel low-melting eutectic metal electrode infiltrated into pores of nanostructural battery.
Applications in Terrestrial Vehicles
Applications for these rechargeable batteries have focused primarily on their potential used in electric vehicles, including delivery vans, taxis, ships and submarines. Individual cells with the nominal cell voltage of 2.58 volts and capacity of 32 Ah have been configured in series-parallel arrays, thereby achieving an OCV of 300 volts. Module voltages from 24 to 1000 volts, and module stored energy of 2 to 50 kWh are discussed in the literature.
Surface Ship and Submarine Applications
Despite the history of the lead acid battery (LAB) in marine and submarine applications, it is considered to be somewhat unreliable. Problems are still encountered with short circuits that can lead to self-discharge, sudden-death and cell replacement. The failure of a single cell can significantly degrade the overall performance of a larger battery.
In marine and submarine applications, the ZEBRA battery appears to alloy the battery, once charged, to retain 100% of its charge, regardless of whether the battery is maintained at its operating temperature, or allowed to cool down (to a frozen state). From a mission readiness point-of-view, it is conceivable that the batteries on a submarine could be charge to 100% SOC, and then placed in a frozen state for a period of years. With a 24-hour heating period, the cells would be ready to go.
ExampleâAir or Oxygen Breathing Battery
An example of an electro-chemical energy conversion and storage system constructed in accordance with the present invention is illustrated in FIG. 2 . The air or oxygen breathing nanofluid or particle suspension flow battery is designated generally by the reference numeral 200 . The air or oxygen breathing nanofluid or particle suspension flow battery 200 includes the following components: electro- catalytic anode 201 , nanofluid or particle suspension anolyte 202 , nanofluid or particle suspension anolyte storage tank & heat transfer 203 , heat rejection 204 , electrolyte & separator 205 , oxygen cathode 206 , oxygen or air 207 , selective transport of molecular oxygen 208 , oxygen selective membrane 209 , load 210 , pump 211 , fluid lines 212 , electrical connectors 213 , and housing 214 . The housing is made at least in part of a non-conductive material. The air or oxygen breathing nanofluid or particle suspension flow battery 200 provides a new inherently safe, high-energy, high-rate rechargeable battery.
The air or oxygen breathing nanofluid or particle suspension flow battery 200 includes electro- oxygen cathode 206 , and electro- catalytic anode 201 . The electro- oxygen cathode 206 and electro- catalytic anode 201 are electrically connected across load 206 by electrical connectors 213 .
Oxygen or air 207 provides selective transport of molecular oxygen 208 through oxygen selective membrane 209 to electrolyte and separator 205 .
The nanofluid or particle suspension anolyte 202 is contained within housing 214 adjacent oxygen cathode 206 and electro- catalytic anode 201 .
The electro- catalytic anode 201 gives up electrons at a potential above that of the electro- oxygen cathode 206 . The conductive link via the load 210 through electrical connectors 213 carries electrons from the electro- catalytic anode 201 to the electro- oxygen cathode 206 . The nanofluid or particle suspension anolyte 202 dissociates ions. These ions serve to deliver electrons and chemical matter through the nanofluid or particle suspension anolyte 202 to balance the flow of electric current through the load 210 during operation.
The nanofluid or particle suspension anolyte 202 is circulated to a nanofluid or particle suspension anolyte storage tank and heat transfer unit 203 through fluid lines 212 by pump 211 . Nanofluid or particle suspension anolyte storage tank and heat transfer unit 203 provides heat rejection 204 . The nanofluid or particle suspension anolyte 202 is a nanofluid or particle suspension.
The nanofluid is defined as: nanofluid=nanoparticles+dielectric or ionic fluid. A wide range of nanoparticles can be used. The particle suspension is defined as: particle suspension=particles+dielectric or ionic fluid. A wide range of particles can be used.
Referring now to FIG. 3 , a suitable solid-state fast ion conducting film is deposited over the interdigitated 2D electrodes with chemical vapor deposition (CVD), a physical vapor deposition (PVD) process such as thermal evaporation, electron beam evaporation, magnetron sputtering, and/or atomic layer deposition (ALD). Practical processes such as multi-magnetron sputtering as a means of building high-performance thin-film thermoelectric devices, including super-lattices formed from low-melting and difficult to process semiconductors can be used. The same technology can be readily applied to the fabrication of thin-film solid-state energy storage devices.
A practical three-dimensional cell architecture has been obtained with a solid-state fast ion conducting electrolyte and completely reversible, dimensionally-stable liquid electrodes, with the demonstration of a I Ah cell. A nanostructural material such as carbon aerogel is coated with those materials necessary for formation of an appropriate metal-halogen electrode (Fe/FeCl 2 , Ni/NiCl 2 , AggAgCl, Ag/Agt, Rb/Rbl, Rb/Rbl 3 , etc.), or another appropriate electrode, using techniques such as CVD, PVD, and ALD. The resultant structure is then be over-coated with an appropriate film and/or coating of solid-state fast ion conductor. If insurmountable dimensional stability problems are encountered with homogenous inorganic ion-conducting films, a coating with dispersed particles with a polymeric binder could be used. Finally, liquid-phase metallic alloys (low-melting eutectics) are infiltrated into the pore structure, thereby forming the second electrode in a unique three-dimensional battery system with unparalleled rate capability, and none of the problems of self shielding usually encountered with porous electrode systems. Performance testing of the three-dimensional system, with novel low-melting eutectic metal electrode infiltrated into pores of nanostructural battery, is performed. Ultimately, the cells are included in the integration of three-dimensional cell architectures into larger 10-Ah battery.
The graphitic intercalation anode (LiC 6 ) has a specific capacity of 372 Ah/kg, a capacity density of 937 Ah/L, and a self-diffusion coefficient of approximately 10â² 9 cm/sec. The transition metal intercalation cathode (LiCoO 2 ) has a specific capacity of 274 Ah/kg, a capacity density of 1017 Ah/L, and a self-diffusion coefficient of approximately 10 â9 cm 2 /sec. These cells have now been developed to the point where specific energies of 180 to 200 W/kg and energy densities of 380-400 Wh/L can be achieved. The OCV of these cells is approximately 3.1 volts, with a nominal operating voltage of 3.8 volts, and an end voltage of approximately 3.0 volts. Work during the past decade has now increased the charge-discharge cycle life of these cells to the point where 1500 deep discharge cycles can be achieved (defined as the point where the cell capacity is 80% of the initial capacity immediately following formation). Microporous polyolefin separators with thicknesses of about 20 microns are easily penetrated by foreign objects and debris, or by lithium dendrites that can form during unplanned plating within the cells during cycling. The Li-ion systems continue to be plagues by serious safety issues with volatile and flammable organic solvents, with the formation of hazardous vapors from such fires that include not only CO and CO 2 , but also HF. Battery fires with these systems have proven to be injurious, damaging, and very costly.
In general, systems relying on conventional liquid-filled, or polymer-gel lithium ion batteries could benefit greatly from a completely solid-state rechargeable battery. Such a battery would be available to achieve enhanced specific energy and energy density, through the elimination of an abundance of inert (non energy storing materials) present in the lithium-ion system, and would be able to operate far more safely due to the elimination of volatile and flammable organic solvents used in the electrolytes. While fast-ion conductors exist, and have been used for very small on-chip rechargeable batteries for memory backup in computers and other electronic devices, no solid-state battery exists that can be scaled up for applications in portable computing, wireless communications, electric vehicles, and the battlefield needs of the soldier and sailor. The proposed work will seek to develop a completely solid-state alternative to the modern lithium-ion battery. This battery, if developed, will be to the lithium-ion battery what transistors and integrated circuits were to the vacuum tube.
Microporous polyolefin separators with thicknesses of about 20 microns are easily penetrated by foreign objects and debris, or by lithium dendrites that can form during unplanned plating within the cells during cycling. The Li-ion systems continue to be plagues by serious safety issues with volatile and flammable organic solvents, with the formation of hazardous vapors from such fires that include not only CO and CO 2 , but also HF. Battery fires with these systems have proven to be injurious, damaging, and very costly.
While the invention may be susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and have been described in detail herein. However, it should be understood that the invention is not intended to be limited to the particular forms disclosed. Rather, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the following appended claims.
Claims ( 2 )
The invention claimed is:
1. A rechargeable battery apparatus, comprising:
an enclosure,
a first electrode operatively connected to said enclosure wherein said first electrode is an electro-catalytic anode,
a second electrode operatively connected to said enclosure wherein said second electrode is an oxygen cathode,
a suspended flowing material in said enclosure wherein said suspended flowing material comprises intercalated transition metal oxide nanoparticles and wherein said suspended flowing material is directly connected to said first electrode wherein said first electrode is an electro-catalytic anode,
an electrolyte and separator between said first electrode and said second electrode,
an oxygen selective membrane between said first electrode and said second electrode,
a suspended flowing material storage tank containing said suspended flowing material wherein said suspended flowing material storage tank is connected to said enclosure by flow lines for flowing said suspended flowing material into and out of said enclosure,
a pump for circulating said suspended flowing material from said suspended flowing material storage tank into and out of said enclosure, and
a heat transfer unit connected to said suspended flowing material in said suspended flowing material storage tank.
2. A rechargeable battery apparatus, comprising:
an enclosure,
a first electrode operatively connected to said enclosure wherein said first electrode is an electro-catalytic anode,
a second electrode operatively connected to said enclosure wherein said second electrode is an oxygen cathode,
a flowing material in said enclosure wherein said flowing material comprises intercalated transition metal oxide nanoparticles and wherein said flowing material is directly connected to said first electrode wherein said first electrode is an electro-catalytic anode,
an electrolyte and separator between said first electrode and said second electrode,
an oxygen selective membrane between said first electrode and said second electrode, and
a circulation system for circulating said flowing material into and out of said enclosure, said circulation system including
a storage tank containing said flowing material wherein storage tank is connected to said enclosure by flow lines for flowing said flowing material into and out of said enclosure,
a pump for pumping said flowing material from said storage tank into and out of said enclosure,
a heat transfer unit connected to said flowing material in said storage tank.
US15/358,518
2009-09-25
2016-11-22
High-performance rechargeable batteries with fast solid-state ion conductors
Expired - Fee Related
US9692078B2
( en )
Priority Applications (1)
Application Number
Priority Date
Filing Date
Title
US15/358,518
US9692078B2
( en )
2009-09-25
2016-11-22
High-performance rechargeable batteries with fast solid-state ion conductors
Applications Claiming Priority (3)
Application Number
Priority Date
Filing Date
Title
US24601809P
2009-09-25
2009-09-25
US12/890,099
US9614251B2
( en )
2009-09-25
2010-09-24
High-performance rechargeable batteries with nanoparticle active materials, photochemically regenerable active materials, and fast solid-state ion conductors
US15/358,518
US9692078B2
( en )
2009-09-25
2016-11-22
High-performance rechargeable batteries with fast solid-state ion conductors
Related Parent Applications (1)
Application Number
Title
Priority Date
Filing Date
US12/890,099
Division
US9614251B2
( en )
2009-09-25
2010-09-24
High-performance rechargeable batteries with nanoparticle active materials, photochemically regenerable active materials, and fast solid-state ion conductors
Publications (2)
Publication Number
Publication Date
US20170149094A1
US20170149094A1 ( en )
2017-05-25
US9692078B2
true
US9692078B2 ( en )
2017-06-27
Family
ID=43037008
Family Applications (2)
Application Number
Title
Priority Date
Filing Date
US12/890,099
<span it
CLAIMS
Claims ( 2 )
The invention claimed is:
1. A rechargeable battery apparatus, comprising:
an enclosure,
a first electrode operatively connected to said enclosure wherein said first electrode is an electro-catalytic anode,
a second electrode operatively connected to said enclosure wherein said second electrode is an oxygen cathode,
a suspended flowing material in said enclosure wherein said suspended flowing material comprises intercalated transition metal oxide nanoparticles and wherein said suspended flowing material is directly connected to said first electrode wherein said first electrode is an electro-catalytic anode,
an electrolyte and separator between said first electrode and said second electrode,
an oxygen selective membrane between said first electrode and said second electrode,
a suspended flowing material storage tank containing said suspended flowing material wherein said suspended flowing material storage tank is connected to said enclosure by flow lines for flowing said suspended flowing material into and out of said enclosure,
a pump for circulating said suspended flowing material from said suspended flowing material storage tank into and out of said enclosure, and
a heat transfer unit connected to said suspended flowing material in said suspended flowing material storage tank.
2. A rechargeable battery apparatus, comprising:
an enclosure,
a first electrode operatively connected to said enclosure wherein said first electrode is an electro-catalytic anode,
a second electrode operatively connected to said enclosure wherein said second electrode is an oxygen cathode,
a flowing material in said enclosure wherein said flowing material comprises intercalated transition metal oxide nanoparticles and wherein said flowing material is directly connected to said first electrode wherein said first electrode is an electro-catalytic anode,
an electrolyte and separator between said first electrode and said second electrode,
an oxygen selective membrane between said first electrode and said second electrode, and
a circulation system for circulating said flowing material into and out of said enclosure, said circulation system including
a storage tank containing said flowing material wherein storage tank is connected to said enclosure by flow lines for flowing said flowing material into and out of said enclosure,
a pump for pumping said flowing material from said storage tank into and out of said enclosure,
a heat transfer unit connected to said flowing material in said storage tank.
US15/358,518
2009-09-25
2016-11-22
High-performance rechargeable batteries with fast solid-state ion conductors
Expired - Fee Related
US9692078B2
( en )
Priority Applications (1)
Application Number
Priority Date
Filing Date
Title
US15/358,518
US9692078B2
( en )
2009-09-25
2016-11-22
High-performance rechargeable batteries with fast solid-state ion conductors
Applications Claiming Priority (3)
Application Number
Priority Date
Filing Date
Title
US24601809P
2009-09-25
2009-09-25
US12/890,099
US9614251B2
( en )
2009-09-25
2010-09-24
High-performance rechargeable batteries with nanoparticle active materials, photochemically regenerable active materials, and fast solid-state ion conductors
US15/358,518
US9692078B2
( en )
2009-09-25
2016-11-22
High-performance rechargeable batteries with fast solid-state ion conductors
Related Parent Applications (1)
Application Number
Title
Priority Date
Filing Date
US12/890,099
Division
US9614251B2
( en )
2009-09-25
2010-09-24
High-performance rechargeable batteries with nanoparticle active materials, photochemically regenerable active materials, and fast solid-state ion conductors
Publications (2)
Publication Number
Publication Date
US20170149094A1
US20170149094A1 ( en )
2017-05-25
US9692078B2
true
US9692078B2 ( en )
2017-06-27
Family
ID=43037008
Family Applications (2)
Application Number
Title
Priority Date
Filing Date
US12/890,099
Expired - Fee Related
US9614251B2
( en )
2009-09-25
2010-09-24
High-performance rechargeable batteries with nanoparticle active materials, photochemically regenerable active materials, and fast solid-state ion conductors
US15/358,518
Expired - Fee Related
US9692078B2
( en )
2009-09-25
2016-11-22
High-performance rechargeable batteries with fast solid-state ion conductors
Family Applications Before (1)
Application Number
Title
Priority Date
Filing Date
US12/890,099
Expired - Fee Related
US9614251B2
( en )
2009-09-25
2010-09-24
High-performance rechargeable batteries with nanoparticle active materials, photochemically regenerable active materials, and fast solid-state ion conductors
Country Status (2)
Country
Link
US
( 2 )
US9614251B2
( en )
WO
( 1 )
WO2011038233A1
( en )
Families Citing this family (42)
* Cited by examiner, â Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
US9705136B2
( en )
2008-02-25
2017-07-11
Traverse Technologies Corp.
High capacity energy storage
US11233234B2
( en )
2008-02-25
2022-01-25
Cf Traverse Llc
Energy storage devices
KR101503659B1
( en )
2008-02-25
2015-03-17
ë¡ë ë ì¤ìë ë¡ì ì¤í¤
High capacity electrodes
US9941709B2
( en )
2009-02-25
2018-04-10
Cf Traverse Llc
Hybrid energy storage device charging
US10727481B2
( en )
2009-02-25
2020-07-28
Cf Traverse Llc
Energy storage devices
US9412998B2
( en )
2009-02-25
2016-08-09
Ronald A. Rojeski
Energy storage devices
US10205166B2
( en )
2008-02-25
2019-02-12
Cf Traverse Llc
Energy storage devices including stabilized silicon
US9349544B2
( en )
2009-02-25
2016-05-24
Ronald A Rojeski
Hybrid energy storage devices including support filaments
US9917300B2
( en )
2009-02-25
2018-03-13
Cf Traverse Llc
Hybrid energy storage devices including surface effect dominant sites
US9431181B2
( en )
2009-02-25
2016-08-30
Catalyst Power Technologies
Energy storage devices including silicon and graphite
US9966197B2
( en )
2009-02-25
2018-05-08
Cf Traverse Llc
Energy storage devices including support filaments
US9979017B2
( en )
2009-02-25
2018-05-22
Cf Traverse Llc
Energy storage devices
US10056602B2
( en )
2009-02-25
2018-08-21
Cf Traverse Llc
Hybrid energy storage device production
US9362549B2
( en )
2011-12-21
2016-06-07
Cpt Ip Holdings, Llc
Lithium-ion battery anode including core-shell heterostructure of silicon coated vertically aligned carbon nanofibers
US10193142B2
( en )
2008-02-25
2019-01-29
Cf Traverse Llc
Lithium-ion battery anode including preloaded lithium
WO2011038233A1
( en )
2009-09-25
2011-03-31
Lawrence Livermore National Security, Llc
High-performance rechargeable batteries with fast solid-state ion conductors
GB2493511B
( en )
*
2011-07-29
2018-01-31
Sondex Wireline Ltd
Downhole energy storage system
KR101945968B1
( en )
2012-03-01
2019-02-11
ìì ë¼í¸ë¡ ì리ë ì¤í ì´í¸ ììì¨
High Capacity Solid State Composite Cathode, Solid State Composite Separator, Solid-State Rechargeable Lithium Battery and Methods of Making Same
RU2499961C1
( en )
*
2012-05-03
2013-11-27
ФедеÑалÑное гоÑÑдаÑÑÑвенное бÑджеÑное ÑÑÑеждение "ÐаÑионалÑнÑй иÑÑледоваÑелÑÑкий ÑенÑÑ "ÐÑÑÑаÑовÑкий инÑÑиÑÑÑ"
Method of energy generation in hybrid plant
US9490507B2
( en )
*
2012-05-22
2016-11-08
Lawrence Livermore National Security, Llc
Li-ion battery thermal runaway suppression system using microchannel coolers and refrigerant injections
DE112013003084T5
( en )
*
2012-06-19
2015-03-05
Robert Bosch Gmbh
Metal / air battery with gas-operated nanostructure
US9793525B2
( en )
2012-10-09
2017-10-17
Johnson Battery Technologies, Inc.
Solid-state battery electrodes
US9356314B2
( en )
2013-02-25
2016-05-31
Battelle Memorial Institute
Metallization pattern on solid electrolyte or porous support of sodium battery process
US9559388B2
( en )
2013-06-18
2017-01-31
Massachusetts Institute Of Technology
Electrochemical systems configured to harvest heat energy
US20150066228A1
( en )
*
2013-07-26
2015-03-05
Peaknrg
Building Management and Appliance Control System
CN113437282B
( en )
*
2014-01-03
2022-05-13
溧é³å¤©ç®å 导çµæ± ææç§ææéå ¬å¸
Nanoscale lithium-silicon alloy material and preparation method and application thereof
US20160190624A1
( en )
*
2014-12-29
2016-06-30
Wen Huang LIAO
Flow type zinc air fuel cell
WO2016160703A1
( en )
2015-03-27
2016-10-06
Harrup Mason K
All-inorganic solvents for electrolytes
JP6763965B2
( en )
2015-12-21
2020-09-30
ã¸ã§ã³ã½ã³ã»ã¢ã¤ãã¼ã»ãã¼ã«ãã£ã³ã°ã»ã¨ã«ã¨ã«ã·ã¼
Solid-state batteries, separators, electrodes and manufacturing methods
US10218044B2
( en )
2016-01-22
2019-02-26
Johnson Ip Holding, Llc
Johnson lithium oxygen electrochemical engine
WO2018025406A1
( en )
*
2016-08-05
2018-02-08
æåé»å·¥æ ªå¼ä¼ç¤¾
Redox flow battery
AU2017311235B2
( en )
2016-08-08
2022-03-10
Orison, Inc.
Plug and play with smart energy storage units
CN106340646B
( en )
*
2016-09-22
2019-07-12
åè¥å½è½©é«ç§å¨åè½æºæéå ¬å¸
Spherical multiphase lithium manganese iron phosphate material and preparation method thereof
US10707531B1
( en )
2016-09-27
2020-07-07
New Dominion Enterprises Inc.
All-inorganic solvents for electrolytes
US10903672B2
( en )
2017-03-30
2021-01-26
International Business Machines Corporation
Charge method for solid-state lithium-based thin-film battery
US10944128B2
( en )
2017-03-30
2021-03-09
International Business Machines Corporation
Anode structure for solid-state lithium-based thin-film battery
US10581109B2
( en )
2017-03-30
2020-03-03
International Business Machines Corporation
Fabrication method of all solid-state thin-film battery
US10622680B2
( en )
*
2017-04-06
2020-04-14
International Business Machines Corporation
High charge rate, large capacity, solid-state battery
WO2019014630A1
( en )
2017-07-13
2019-01-17
Orison Inc.
Energy monitor
US11085674B1
( en )
*
2018-08-06
2021-08-10
U.S.A, as represented by the Administrator of the National Aeronautics and Space Administration
Electrocaloric-based cooling system
CN111653759A
( en )
*
2020-06-15
2020-09-11
ä¸å½ç§å¦é¢å®æ³¢ææææ¯ä¸å·¥ç¨ç 究æ
A kind of silicon-based composite material and preparation method thereof
WO2024213073A1
( en )
*
2023-04-14
2024-10-17
æ±èæ°éå ç§ææéå ¬å¸
Molten lithium metal battery based on ceramic electrolyte sheet
Citations (16)
* Cited by examiner, â Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
US3443997A
( en )
1966-02-11
1969-05-13
North American Rockwell
Solid state electrochemical devices
US5372691A
( en )
1992-06-04
1994-12-13
Globe-Union Inc.
Thermocell
US20030069129A1
( en )
2001-10-09
2003-04-10
Lefebvre Mark C.
Methods of producing oxygen reduction catalyst
US6936185B1
( en )
1999-08-18
2005-08-30
Hydro-Quebec
Metal hydride bands and use thereof for storing hydrogen
US20060127731A1
( en )
2000-05-12
2006-06-15
Faris Sadeg M
Fuel containment and recycling system
US20060208692A1
( en )
2005-03-17
2006-09-21
Kejha Joseph B
Hybrid rechargeable battery having high power and high energy density lithium cells
US20070048619A1
( en )
2004-12-02
2007-03-01
Kabushiki Kaisha Ohara
All solid lithium ion secondary battery and a solid electrolyte therefor
US20080261116A1
( en )
2007-04-23
2008-10-23
Burton David J
Method of depositing silicon on carbon materials and forming an anode for use in lithium ion batteries
WO2008136296A1
( en )
2007-05-01
2008-11-13
Toyota Jidosha Kabushiki Kaisha
Air cell system
US20080311480A1
( en )
2007-03-29
2008-12-18
Tdk Corporation
All-solid-state lithium-ion secondary battery and production method thereof
US20090092903A1
( en )
2007-08-29
2009-04-09
Johnson Lonnie G
Low Cost Solid State Rechargeable Battery and Method of Manufacturing Same
US20090297895A1
( en )
2008-05-27
2009-12-03
Angstrom Power Incorporated
Systems and methods for managing heat in portable electronic devices
WO2009151639A1
( en )
2008-06-12
2009-12-17
Massachusetts Institute Of Technology
High energy density redox flow device
US20090325070A1
( en )
2008-06-30
2009-12-31
General Electric Company
Primary aluminum hydride battery
WO2011038233A1
( en )
2009-09-25
2011-03-31
Lawrence Livermore National Security, Llc
High-performance rechargeable batteries with fast solid-state ion conductors
US20120115046A2
( en )
2008-09-08
2012-05-10
Nanyang Technological University
Electrode materials for metal-air batteries, fuel cells and supercapacitors
2010
2010-09-24
WO
PCT/US2010/050205
patent/WO2011038233A1/en
not_active
Ceased
2010-09-24
US
US12/890,099
patent/US9614251B2/en
not_active
Expired - Fee Related
2016
2016-11-22
US
US15/358,518
patent/US9692078B2/en
not_active
Expired - Fee Related
Patent Citations (17)
* Cited by examiner, â Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
US3443997A
( en )
1966-02-11
1969-05-13
North American Rockwell
Solid state electrochemical devices
US5372691A
( en )
1992-06-04
1994-12-13
Globe-Union Inc.
Thermocell
US6936185B1
( en )
1999-08-18
2005-08-30
Hydro-Quebec
Metal hydride bands and use thereof for storing hydrogen
US20060127731A1
( en )
2000-05-12
2006-06-15
Faris Sadeg M
Fuel containment and recycling system
US20030069129A1
( en )
2001-10-09
2003-04-10
Lefebvre Mark C.
Methods of producing oxygen reduction catalyst
US20070048619A1
( en )
2004-12-02
2007-03-01
Kabushiki Kaisha Ohara
All solid lithium ion secondary battery and a solid electrolyte therefor
US20060208692A1
( en )
2005-03-17
2006-09-21
Kejha Joseph B
Hybrid rechargeable battery having high power and high energy density lithium cells
US20080311480A1
( en )
2007-03-29
2008-12-18
Tdk Corporation
All-solid-state lithium-ion secondary battery and production method thereof
US20080261116A1
( en )
2007-04-23
2008-10-23
Burton David J
Method of depositing silicon on carbon materials and forming an anode for use in lithium ion batteries
WO2008136296A1
( en )
2007-05-01
2008-11-13
Toyota Jidosha Kabushiki Kaisha
Air cell system
US20100151336A1
( en )
2007-05-01
2010-06-17
Shinji Nakanishi
Air battery system
US20090092903A1
( en )
2007-08-29
2009-04-09
Johnson Lonnie G
Low Cost Solid State Rechargeable Battery and Method of Manufacturing Same
US20090297895A1
( en )
2008-05-27
2009-12-03
Angstrom Power Incorporated
Systems and methods for managing heat in portable electronic devices
WO2009151639A1
( en )
2008-06-12
2009-12-17
Massachusetts Institute Of Technology
High energy density redox flow device
US20090325070A1
( en )
2008-06-30
2009-12-31
General Electric Company
Primary aluminum hydride battery
US20120115046A2
( en )
2008-09-08
2012-05-10
Nanyang Technological University
Electrode materials for metal-air batteries, fuel cells and supercapacitors
WO2011038233A1
( en )
2009-09-25
2011-03-31
Lawrence Livermore National Security, Llc
High-performance rechargeable batteries with fast solid-state ion conductors
Also Published As
Publication number
Publication date
US20110076542A1
( en )
2011-03-31
US20170149094A1
( en )
2017-05-25
WO2011038233A1
( en )
2011-03-31
US9614251B2
( en )
2017-04-04
Similar Documents
Publication
Publication Date
Title
US9614251B2
( en )
2017-04-04
High-performance rechargeable batteries with nanoparticle active materials, photochemically regenerable active materials, and fast solid-state ion conductors
US8778540B1
( en )
2014-07-15
Monolithic three-dimensional electrochemical energy storage system on aerogel or nanotube scaffold
US9673478B2
( en )
2017-06-06
Multi-layer coatings for bipolar rechargeable batteries with enhanced terminal voltage
AU2021333283B2
( en )
2025-09-18
Lithium metal anode and battery
US10403930B2
( en )
2019-09-03
Electrochemical nanofluid or particle suspension energy conversion and storage device
CN103238239B
( en )
2018-01-02
Rechargeable electrochemical energy storage device
Haas et al.
1999
Electrochemical energy storage
US8778546B2
( en )
2014-07-15
Air breathing lithium power cells
KR102246520B1
( en )
2021-04-30
Lithium battery with composite solid electrolyte
US8883339B2
( en )
2014-11-11
Alkali metal-cathode solution battery
US9647265B2
( en )
2017-05-09
All-solid state cell
KR102114716B1
( en )
2020-05-26
Sodium-halogen secondary cell
EP2859603B1
( en )
2017-12-20
Metal/oxygen battery with internal oxygen reservoir
US9799933B2
( en )
2017-10-24
Solid state battery with integrated rate booster
US10483586B2
( en )
2019-11-19
All-solid-state battery using sodium ion intercalation cathode with Li/Na exchanging layer
EP3063812A2
( en )
2016-09-07
Self healing liquid/solid state battery
US20100291444A1
( en )
2010-11-18
Multilayer coatings for rechargeable batteries
YANG et al.
2016
Next-generation energy storage technologies and their key electrode materials
US10320033B2
( en )
2019-06-11
Alkali metal ion battery using alkali metal conductive ceramic separator
US10230141B2
( en )
2019-03-12
Electrochemical energy store and method for operating the same
JP2016122650A5
( en )
2019-04-25
JP2015503187A
( en )
2015-01-29
Electrochemical cell
Julien
2019
Solid state batteries
US20190123343A1
( en )
2019-04-25
Bulk solid state batteries utilizing mixed ionic electronic conductors
WO2014087895A1
( en )
2014-06-12
Accumulation device, hybrid vehicle, and electric vehicle
Legal Events
Date
Code
Title
Description
2016-12-15
AS
Assignment
Owner name : LAWRENCE LIVERMORE NATIONAL SECURITY, LLC, CALIFOR
Free format text : ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:FARMER, JOSEPH C.;REEL/FRAME:040982/0616
Effective date : 20161215
2016-12-20
AS
Assignment
Owner name : U.S. DEPARTMENT OF ENERGY, DISTRICT OF COLUMBIA
Free format text : CONFIRMATORY LICENSE;ASSIGNOR:LAWRENCE LIVERMORE NATIONAL SECURITY, LLC;REEL/FRAME:040688/0102
Effective date : 20161215
2017-06-07
STCF
Information on status: patent grant
Free format text : PATENTED CASE
2020-09-09
MAFP
Maintenance fee payment
Free format text : PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY
Year of fee payment : 4
2025-02-17
FEPP
Fee payment procedure
Free format text : MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY
2025-08-04
LAPS
Lapse for failure to pay maintenance fees
Free format text : PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY
2025-08-04
STCH
Information on status: patent discontinuation
Free format text : PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362
2025-08-26
FP
Lapsed due to failure to pay maintenance fee
Effective date : 20250627