Electrochemical energy storage devices and housings

Information

  • Patent Grant
  • 10608212
  • Patent Number
    10,608,212
  • Date Filed
    Wednesday, April 15, 2015
    9 years ago
  • Date Issued
    Tuesday, March 31, 2020
    4 years ago
Abstract
The disclosure provides electrochemical batteries, electrochemical battery housings and methods for assembling electrochemical batteries. The battery housing can include a container, a container lid assembly and an electrical conductor. The container can include a cavity that extends into the container from a cavity aperture. The lid assembly can seal the cavity, and can include an electrically conductive container lid and an electrically conductive flange. The container lid can cover the cavity aperture and can include a conductor aperture that extends through the container lid. The flange can cover the conductor aperture and can be electrically isolated from the container lid. The conductor can be connected to the flange and can extend through the conductor aperture into the cavity. The conductor can be electrically isolated from the container lid.
Description
BACKGROUND

A battery is a device capable of converting stored chemical energy into electrical energy. Batteries are used in many household and industrial applications. In some instances, batteries are rechargeable such that electrical energy (e.g., converted from non-electrical types of energy, such as mechanical energy) is capable of being stored in the battery as chemical energy (i.e., charging the battery).


SUMMARY

The disclosure provides energy storage devices (e.g., batteries) and housings that may be used within an electrical power grid or as part of a standalone system. The batteries may be charged from an electricity production source, for later discharge when there is a demand for electrical energy consumption.


Energy storage devices of the disclosure aid in alleviating at least some of the issues with renewable energy sources. Renewable energy may be intermittent, where energy supply and demand may not be matched time-wise (e.g., within instantaneous or near-instantaneous timeframes). For example, solar energy is only produced when the sun is shining and wind energy is only produced when the wind is blowing. Further, demand at any given time is a function of industrial, commercial, community and household activity. Using the batteries and battery housings described herein can offer a means for balancing intermittent electrical energy supply with demand.


The disclosure provides systems for directing electrical current through a metallic wall at elevated temperatures while minimizing the introduction of leaks or electrical contacts between the current flow path and the wall. In some cases this is achieved through the use of a mated flange connection with mica, vermiculite, glass, brazed ceramics, or other high-temperature dielectric sealing material, and may be secured with electrically-insulating fasteners (e.g., bolts, clamps) or through the mechanical and/or chemical adhesion of the seal with the metal flange surfaces. The feed-through assembly may be sealed onto an appropriate opening in the metallic wall (e.g., through secure weld). In some instances, the feed-through assembly distributes current evenly across the electrode.


Bolted flange assemblies provided herein can provide a compressive force that may be adequate to seal a cavity of a housing of an energy storage device. In some cases, use of a flange assembly can also provide a geometry that is amenable to the use of mica or vermiculite gaskets as the sealant and electrical isolation material. In some implementations, the geometry of the sealing surface is decoupled from the geometry of the housing (or vessel) being sealed. The size and shape of the housing, in some cases, may not dictate the size and shape of the seal.


In an aspect, an electrochemical cell comprises an electrically conductive housing and a conductor in electrical communication with a current collector, wherein the conductor protrudes through the housing through an aperture in the housing and is electrically isolated from the housing, wherein the electrochemical cell is capable of storing and/or taking in at least 25 Wh of energy. In some embodiments, the electrochemical cell comprises a liquid metal anode adjacent to said current collector. In some embodiments, the liquid metal comprises lithium.


In another aspect, a battery comprises a plurality of the electrochemical cells of claim 1, wherein the battery is capable of storing at least 100 kWh of energy.


In another aspect, a battery housing comprises an electrically conductive container and a conductor in electrical communication with a current collector, wherein the conductor protrudes through the housing through an aperture in the container and is electrically isolated from the container, wherein the housing is capable of enclosing an electrochemical cell that is capable of storing and or taking in at least 25 Wh of energy. In some embodiments, the housing is capable of hermetically sealing the electrochemical cell.


In another aspect, an electrochemical cell comprises an electrically conductive housing and a conductor in electrical communication with a current collector, wherein the conductor protrudes through the housing through an aperture of the housing and is electrically isolated from the housing, wherein the ratio of the area of the aperture to the area of the housing is less than 0.1. In some embodiments, the cell comprises a liquid metal anode adjacent to said current collector. In some embodiments, the liquid metal comprises lithium. In some embodiments, the cell is capable of storing and or taking in at least 25 Wh of energy.


In another aspect, a battery housing comprises an electrically conductive container and a conductor in electrical communication with a current collector, wherein the conductor protrudes through the container through an aperture in the container and is electrically isolated from the container, wherein the ratio of the area of the aperture to the area of the container is less than 0.1 and wherein the housing is capable of enclosing a battery that is capable of storing and or taking in at least 25 Wh of energy.


In another aspect, an electrochemical energy storage device comprises a housing, a liquid metal electrode, a current collector in contact with the liquid metal electrode, and a plurality of conductors that are in electrical communication with the current collector and protrude through the housing through apertures in the housing. In some embodiments, the current is distributed substantially evenly across the liquid metal electrode. In some embodiments, the liquid metal electrode is in contact with an electrolyte along a surface and the current flowing across the surface is uniform. In some embodiments, the maximum density of current flowing across an area of the surface is less than about 150% of the average density of current flowing across the surface. In some embodiments, the minimum density of current flowing across an area of the surface is greater than about 50% of the average density of current flowing across the surface.


In another aspect, a battery housing comprises an electrically conductive container, a plurality of container apertures and a plurality of conductors in electrical communication with a current collector, wherein the conductors pass through the container apertures and are electrically isolated from the electrically conductive container, wherein the housing is capable of enclosing an electrochemical cell comprising a liquid metal electrode in contact with the current collector. In some embodiments, the current is distributed substantially evenly across the liquid metal electrode. In some embodiments, the liquid metal electrode is in contact with an electrolyte along a surface and the current flowing across the surface is uniform. In some embodiments, the maximum density of current flowing across an area of the surface is less than about 150% of the average density of current flowing across the surface. In some embodiments, the minimum density of current flowing across an area of the surface is greater than about 50% of the average density of current flowing across the surface.


In another aspect, an electrochemical energy storage device comprises a liquid metal anode and a cathode, wherein the electrochemical energy storage device is capable of storing and or taking in at least 25 Wh of energy and is hermetically or non-hermetically sealed. In some embodiments, the device is capable of storing at least 100 kWh of energy. In some embodiments, the electrochemical energy storage device comprises a liquid anode comprising lithium. In some embodiments, the rate of oxygen transfer into the electrochemical energy storage device is less than 0.5 mL per hour when the electrochemical energy storage device is contacted with air at a pressure of 1 bar and temperature of 500° C. In some embodiments, the electrochemical energy storage device comprises less than 15 bolts or fasteners. In some embodiments, the electrochemical energy storage device comprises no bolts or fasteners.


In another aspect, a compilation of electrochemical cells, an individual cell of said compilation comprising a liquid lithium anode in a charged state, wherein the compilation is capable of storing and or taking in at least 25 Wh of energy and each of the cells are hermetically sealed. In some embodiments, the compilation is capable of storing at least 100 kWh of energy.


In another aspect, a battery housing comprises an electrically conductive container, a container aperture and a conductor in electrical communication with a current collector, wherein the conductor passes through the container aperture and is electrically isolated from the electrically conductive container, wherein the housing is capable of hermetically sealing a battery which is capable of storing and or taking in at least 25 Wh of energy. In some embodiments, the housing is capable of hermetically sealing a battery which is capable of storing at least 100 kWh of energy. In some embodiments, the battery comprises a liquid metal anode adjacent to said current collector.


In another aspect, an energy storage device, comprises: a first electrochemical cell adjacent to a second electrochemical cell, each of said first and second cells comprising an electrically conductive housing and a conductor in electrical communication with a current collector, wherein the conductor is electrically isolated from the housing and protrudes through the housing through an aperture in the housing such that the conductor contacts the housing of an adjacent electrochemical cell of the energy storage device. In some embodiments, the first and/or second electrochemical cells comprise a liquid metal anode adjacent to said current collector. In some embodiments, the conductor contacts the housing of an adjacent electrochemical cell of the energy storage device when the first and second cells are in a stacked configuration. In some embodiments, the first and second cells are capable of storing and or taking in at least 25 Wh of energy. In some embodiments, the energy storage device comprises a stack of 1 to 10 electrochemical cells. In some embodiments, the energy storage device comprises a stack of 11 to 50 electrochemical cells. In some embodiments, the energy storage device comprises a stack of 51 to 100 electrochemical cells, or more.


In another aspect, a battery housing comprises an electrically conductive container and a conductor in electrical communication with a current collector, wherein the conductor protrudes through the housing through an aperture in the container and is electrically isolated from the container, wherein the conductor of a first housing contacts the container of a second housing when the first and second housings are in a stacked configuration. In some embodiments, the housing is capable of hermetically sealing an electrochemical cell comprises a liquid metal electrode. In some embodiments, the housing is capable of hermetically sealing an electrochemical cell capable of storing and or taking in at least 25 Wh of energy.


In another aspect, an electrochemical energy storage device comprises an anode, a cathode, an electrolyte, a positive current collector and a negative current collector, wherein the negative current collector is in contact with the anode and the positive current collector is in contact with the cathode, wherein the electrolyte is disposed in-between said anode and cathode, and wherein the electrochemical energy storage device is capable of storing and or taking in at least 25 Wh of energy and comprises less than 15 bolts or fasteners. In some embodiments, the device is capable of storing at least 100 kWh of energy. In some embodiments, the electrochemical energy storage device comprises less than 5 bolts or fasteners. In some embodiments, the electrochemical energy storage device comprises no bolts or fasteners. In some embodiments, the electrochemical energy storage device comprises a liquid metal anode adjacent to said current collector.


In another aspect, a compilation of electrochemical cells, an individual cell of said compilation comprising a liquid lithium anode in a charged state, wherein the compilation is capable of storing and or taking in at least 25 Wh of energy and each of the batteries comprise less than 10 bolts or fasteners. In some embodiments, the compilation is capable of storing at least 100 kWh of energy.


In another aspect, a battery housing that hermetically seals an electrochemical energy storage device having a liquid metal anode, which electrochemical energy storage device is capable of storing and or taking in at least 25 Wh of energy, wherein the battery housing comprises less than 10 bolts or fasteners. In some embodiments, the housing is capable of hermetically sealing an electrochemical energy storage device capable of storing at least 100 kWh of energy.


In another aspect, an electrochemical cell comprises an electrically conductive housing and a conductor in electrical communication with a current collector, wherein the conductor protrudes through the housing through an aperture in the housing and is electrically isolated from the housing with a gasket, wherein the force on the gasket is at least 5,000 psi when the housing is sealed. In some embodiments, the force on the gasket is at least 10,000 psi when the housing is sealed. In some embodiments, the gasket is affixed with a flange and no more than 10 bolts or fasteners. In some embodiments, the gasket is adhesive and the cell comprises no bolts or fasteners.


In another aspect, a battery housing comprises an electrically conductive container and a conductor in electrical communication with a current collector, wherein the conductor protrudes through the container through an aperture in the container and is electrically isolated from the container with a gasket, wherein the force on the gasket is at least 5,000 psi when the battery housing is sealed. In some embodiments, the force on the gasket is at least 10,000 psi when the battery housing is sealed. In some embodiments, the gasket is affixed with a flange and no more than 10 bolts or fasteners. In some embodiments, the housing is capable of enclosing an electrochemical cell that is capable of storing and or taking in at least 25 Wh of energy. In some embodiments, the housing is capable of hermetically or non-hermetically sealing the battery.


In another aspect, an electrochemical battery housing, comprises: (a) a container including a cavity that extends into the container from a cavity aperture; (b) a container lid assembly sealing the cavity, the lid assembly including an electrically conductive container lid and an electrically conductive flange, wherein the container lid covers the cavity aperture and includes a conductor aperture that extends through the container lid, and wherein the flange covers the conductor aperture and is electrically isolated from the container lid; and (c) an electrical conductor connected to the flange and extending through the conductor aperture into the cavity, wherein the conductor is electrically isolated from the container lid.


In some embodiments, (a) the conductor aperture is one of a plurality of conductor apertures extending through the container lid; (b) the flange is one of a plurality of electrically conductive flanges respectively covering the conductor apertures and electrically isolated from the container lid; and/or (c) the conductor is one of a plurality of electrical conductors respectively connected to the flanges, respectively extending through the conductor apertures, and electrically isolated from the container lid. In some embodiments, the housing further comprises a current collector within the cavity and connected to the conductors. In some embodiments, the housing further comprises a gasket arranged between and electrically isolating the flange and the container lid. In some embodiments, the gasket comprises dielectric material. In some embodiments, the container lid is fixedly and/or securely connected to the container, and the flange is removably connected to the container lid. In some embodiments, the container lid includes a mounting ring connected to a base, and the conductor aperture extends through the mounting ring, and wherein the flange is removably connected to the mounting ring with a plurality of fasteners. In some embodiments, portions of the fasteners that engage the mounting ring are electrically isolated from the mounting ring. In some embodiments, the fasteners are electrically isolated from the flange by dielectric material. In some embodiments, the housing further comprises an insulating sheath attached to an interior sidewall surface of the container. In some embodiments, the container has one of a circular cross-sectional geometry and a rectangular cross-sectional geometry. In some embodiments, the cavity aperture has a cavity aperture diameter, and wherein the conductor aperture has a conductor aperture diameter that is about two (2) times less than that cavity aperture diameter. In some embodiments, the container lid assembly hermetically seals said cavity.


In another aspect, an electrochemical battery, comprises: (a) a container including a cavity that extends into the container from a cavity aperture; (b) an electrochemical battery cell arranged within the cavity; (c) a container lid assembly sealing the battery cell in the cavity, the lid assembly including an electrically conductive container lid and an electrically conductive flange, wherein the container lid covers the cavity aperture and includes a conductor aperture that extends through the container lid, and wherein the flange covers the conductor aperture and is electrically isolated from the container lid; and (d) an electrical conductor extending through the conductor aperture, and electrically coupled to the battery cell and the flange, wherein the conductor is electrically isolated from the container lid. In some embodiments, the battery cell comprises a liquid electrolyte arranged between a negative liquid metal electrode and a positive liquid metalloid electrode. In some embodiments, the battery further comprises a current collector electrically coupled to the negative liquid metal electrode, wherein the current collector is connected to the conductor which is connected to the top flange in the assembly, which is electrically isolated from the cell lid.


In some embodiments, (a) the conductor aperture is one of a plurality of conductor apertures extending through the container lid; (b) the flange is one of a plurality of electrically conductive flanges respectively covering the conductor apertures and electrically isolated from the container lid; and/or (c) the conductor is one of a plurality of electrical conductors respectively electrically coupled to the battery cell and the flanges, respectively extending through the conductor apertures, and electrically isolated from the container lid. In some embodiments, the battery further comprises a gasket arranged between and electrically isolating the flange and the container lid. In some embodiments, the gasket comprises dielectric material. In some embodiments, the container lid includes a mounting ring connected to a base that is fixedly and/or securely connected to the container, and the conductor aperture extends through the mounting ring, and wherein the flange is removably connected to the mounting ring with a plurality of bolts or fasteners. In some embodiments, the container lid assembly hermetically or non-hermetically seals said battery cell in said cavity.


In another aspect, an electrochemical cell comprises an electrically conductive housing and a conductor in electrical communication with a current collector, wherein the conductor protrudes through the housing through an aperture in the housing and is electrically isolated from the housing with a seal that hermetically seals the electrochemical cell. In some embodiments, the seal is formed by brazing ceramic onto a metal substrate. In some embodiments, the seal is formed by mechanically and/or chemically bonded glass or glass-ceramic composite. In some embodiments, the seal is formed between dissimilar materials. In some embodiments, the seal is under compression at the operating temperature of the electrochemical cell. In some embodiments, the seal is formed between two surfaces in at least two planes. In some embodiments, the seal is formed from at least two different materials, at least one of which is resistant to degradation from contact with materials contained in the electrochemical cell.


In another aspect, a method for sealing an electrochemical cell comprises: (a) applying a sealant material between a housing and an article recessed into the housing, wherein the sealant is applied at a temperature at which the sealant material is malleable, viscous, or flowable, and wherein the housing and the article have different coefficients of thermal expansion; and (b) lowering the temperature to a temperature at which the sealant material is not malleable, viscous, or flowable, thereby creating a seal between the housing and the article that is under a compressive force. In some embodiments, the sealant material is a borosilicate glass. In some embodiments, the housing has a greater coefficient of thermal expansion than the article. In some embodiments, the seal is resistant to reactive metal vapors such as sodium (Na), lithium (Li) or magnesium (Mg). In some embodiments, the sealant material is a chalcogenide based compound. In some embodiments, the chalcogenide has the chemical formula CaAl2S4.


In another aspect, an electrochemical cell comprises an electrically conductive housing as a first current collector and a conductor in electrical communication with a second current collector, wherein the conductor protrudes through the housing through an aperture in the housing and is electrically isolated from the housing. In some embodiments, the electrochemical cell comprises a liquid metal anode adjacent to the first current collector or the second current collector.


In some embodiments, the liquid metal comprises lithium.


In another aspect, a battery comprises one or more electrochemical cells as described herein, wherein the battery is capable of storing at least 25 Wh of energy. In some embodiments, the battery is capable of storing at least 100 kWh of energy.


Additional aspects and advantages of the present disclosure will become readily apparent to those skilled in this art from the following detailed description, wherein only illustrative embodiments of the present disclosure are shown and described. As will be realized, the present disclosure is capable of other and different embodiments, and its several details are capable of modifications in various obvious respects, all without departing from the disclosure. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.


INCORPORATION BY REFERENCE

All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference.





BRIEF DESCRIPTION OF THE DRAWINGS

The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings (also “Figure” or “FIG.” herein), of which:



FIG. 1 is a illustration of an electrochemical cell (A) and a compilation (i.e., battery) of electrochemical cells (B and C);



FIG. 2 is a schematic cross sectional illustration of a battery housing having a conductor in electrical communication with a current collector pass through an aperture in the housing;



FIG. 3 is a schematic cross sectional illustration of an electrochemical cell;



FIG. 4 is a schematic cross sectional illustration of an embodiment of a cell lid assembly;



FIG. 5 is a schematic cross sectional illustration of an electrochemical cell having feed-throughs that are electrically insulated from a housing with a dielectric seal components;



FIG. 6, panels A & B, show that the current collector can be combined into a shared lid assembly and the invention can be used with cells of any size;



FIG. 7 is a schematic sectional illustration of an embodiment of an electrochemical battery;



FIG. 8 is a schematic perspective illustration of a first end of a container lid for the battery illustrated in FIG. 7;



FIG. 9 is a schematic perspective illustration of a second end of the container lid for the battery illustrated in FIG. 7;



FIG. 10 is a schematic perspective illustration of a first end of a flange for the battery illustrated in FIG. 7;



FIG. 11 is a schematic perspective illustration of a second end of the flange for the battery illustrated in FIG. 7;



FIG. 12 is a schematic exploded perspective illustration of a container lid assembly for the battery illustrated in FIG. 7;



FIG. 13 is a schematic partially exploded perspective illustration of an alternate embodiment electrochemical battery housing;



FIG. 14 is a schematic sectional illustration of the battery housing illustrated in FIG. 13;



FIG. 15 is a schematic sectional illustration of an electrochemical battery stack that can include a plurality of alternate embodiment electrochemical battery housings;



FIG. 16 is a schematic top view illustration of the battery stack illustrated in FIG. 15;



FIG. 17, panels A & B, are a schematic illustration where the conductive feed-throughs of a one cell are connected to the base of another cell;



FIG. 18 is a cross-sectional illustration of a seal of an electrochemical cell;



FIG. 19 is an exploded view illustration of a sealed electrochemical cell;



FIG. 20 is a top view illustration of the components of a seal of an electrochemical cell;



FIG. 21 is a cross-sectional illustration of a seal of an electrochemical cell with a recessed conductive feed-through;



FIG. 22 is an exploded view illustration of a seal of an electrochemical cell with a recessed conductive feed through; and



FIG. 23 is a top view illustration of the components of a seal of an electrochemical cell with a recessed conductive feed through.





DETAILED DESCRIPTION

While various embodiments of the invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions may occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed.


This disclosure provides electrochemical energy storage devices (or batteries) and electrochemical battery housings. An electrochemical battery can include an electrochemical battery cell sealed (e.g., hermetically sealed) within an electrochemical battery housing.


Electrochemical Cells and Housings


The term “cell,” as used herein, generally refers to an electrochemical cell. A cell can include a negative electrode of material ‘A’ and a positive electrode of material ‘B’, denoted as A∥B. The positive and negative electrodes can be separated by an electrolyte.


The term “module,” as used herein, generally refers to cells that are attached together in parallel by, for example, mechanically connecting the cell housing of one cell with the cell housing of an adjacent cell (e.g., cells that are connected together in an approximately horizontal packing plane). A module can include a plurality of cells in parallel. A module can comprise any number of cells (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or more). In some cases, a module comprises 9, 12, or 16 cells. In some cases, a module is capable of storing about 700 Watt-hours of energy and/or delivering about 175 Watts of power.


The term “pack,” as used herein, generally refers to modules that are attached through different electrical connections (e.g., vertically). A pack can comprise any number of modules (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or more). In some cases, a pack comprises 3 modules. In some cases, a pack is capable of storing about 2 kilo-Watt-hours of energy and/or delivering about 0.5 kilo-Watts of power.


The term “core,” as used herein generally refers to a plurality of modules or packs that are attached through different electrical connections (e.g., in series and/or parallel). A core can comprise any number of modules or packs (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or more). In some cases, the core also comprises mechanical, electrical, and thermal systems that allow the core to efficiently store and return electrical energy in a controlled manner. In some cases, a core comprises 12 packs. In some cases, a core is capable of storing about 25 kilo-Watt-hours of energy and/or delivering about 6.25 kilo-Watts of power.


The term “pod,” as used herein, generally refers to a plurality of cores that are attached through different electrical connections (e.g., in series and/or parallel). A pod can comprise any number of cores (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or more). In some cases, the pod contains cores that are connected in parallel with appropriate by-pass electronic circuitry, thus enabling a core to be disconnected while continuing to allow the other cores to store and return energy. In some cases, a pod comprises 4 cores. In some cases, a pod is capable of storing about 100 kilo-Watt-hours of energy and/or delivering about 25 kilo-Watts of power.


The term “system,” as used herein, generally refers to a plurality of cores or pods that are attached through different electrical connections (e.g., in series and/or parallel). A system can comprise any number of cores or pods (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or more). In some cases, a system comprises 20 pods. In some cases, a system is capable of storing about 2 megawatt-hours of energy and/or delivering about 500 kilowatts of power.


The term “battery,” as used herein, generally refers to one or more electrochemical cells connected in series and/or parallel. A battery can comprise any number of electrochemical cells, modules, packs, cores, pods or systems.


Electrochemical cells of the disclosure may include an anode, an electrolyte adjacent to the anode, and a cathode adjacent to the electrolyte. In some examples, an electrochemical cell is a liquid metal battery cell. A liquid metal battery cell may include a liquid electrolyte separator arranged between a negative liquid (e.g., molten) metal electrode and a positive liquid metalloid electrode. In some embodiments, a liquid metal battery cell has a molten alkali metal (e.g., lithium) anode, an electrolyte, and a molten metal (e.g. lead, lead-antimony alloy) cathode.


To maintain the electrodes in the liquid states, the battery cell may be heated to any suitable temperature. In some embodiments, the battery cell is heated to a temperature of about 200° C., about 250° C., about 300° C., about 350° C., about 400° C., about 450° C., about 500° C., about 550° C., about 600° C., about 650° C., or about 700° C. The battery cell may be heated to a temperature of at least about 200° C., at least about 250° C., at least about 300° C., at least about 350° C., at least about 400° C., at least about 450° C., at least about 500° C., at least about 550° C., at least about 600° C., at least about 650° C., or at least about 700° C. In some situations, the battery cell is heated to between 200° C. and about 500° C., between 200° C. and about 700° C. or between about 300° C. and 450° C.


Electrochemical cells of the disclosure may be adapted to cycle between charged (or energy storage) modes and discharged (or energy depleted) modes. In some examples, an electrochemical cell can be fully charged, partially discharged, or fully discharged.


In some implementations, during a charging mode, electrical current received from an external power source (e.g., a generator or an electrical grid) may cause metal atoms in the metalloid cathode to shed one or more electrons, dissolving into the electrolyte as a positively charged ion (i.e., cation). Simultaneously, cations of the same species can migrate through the electrolyte, and may accept electrons at the anode, causing them to transition to a neutral metal species, adding to the mass of the electrode. The removal of the active metal species from the cathode and the addition of the active metal to the anode stores electrical potential energy. During an energy discharge mode, an electrical load is coupled to the electrodes. The previously added metal species in the anode are released from the metal electrode (e.g. through melting), and pass through the electrolyte as ions. These ions in the electrolyte alloy with the cathode, with the flow of ions accompanied by the external and matching flow of electrons through the external circuit/load. This electrochemically facilitated metal alloying reaction discharges the previously stored electrical potential energy to the electrical load.


In a charged state, the anode can include anode material and the cathode can include cathode material. During discharging (e.g., when the battery is coupled to a load), the anode material yields one or more electrons and cations of the anode material. The cations migrate through the electrolyte to the cathode material and react with the cathode material to form an metal or metal alloy. During charging, the alloy disassociates to yield cations of the anode material, which migrates to the anode.


Electrochemical cells of the disclosure can include housings that may be suited for various uses and operations. A battery housing can be configured to electrically couple the electrodes to a switch, which is connected to the external power source and the electrical load. The battery cell housing may include, for example, an electrically conductive container that is electrically coupled to a first pole of the switch and/or another cell housing, and an electrically conductive container lid that is electrically coupled to a second pole of the switch and/or another cell housing. The container can be an electrode of the battery cell. The battery cell can be arranged within a cavity of the battery container. One of the electrodes contacts and/or is in electrical communication with an endwall of the battery container. A ceramic sheath may electrically insulate remaining portions of the battery cell from other portions of the battery container. A conductor electrically couples a second one of the electrodes to the container lid, which can seal (e.g., hermetically or non-hermetically) the battery cell within the cavity.


Batteries and Housings


A battery, as used herein can comprise a plurality of electrochemical cells. With reference to FIG. 1, an electrochemical cell (A) is a unit comprising an anode and a cathode. The cell may comprise an electrolyte and be sealed in a housing as described herein. In some cases, the electrochemical cells can be stacked (B) to form a battery (i.e., a compilation of electrochemical cells). The cells can be arranged in parallel, in series, or in both parallel and series (C). The cells can be made into different shapes and geometries that may differ from what is depicted.


Electrochemical cells of the disclosure may be capable of storing (and/or taking in) a suitably large amount of energy. In some instances, a cell is capable of storing (and/or taking in) about 1 Wh, about 5 Wh, 25 Wh, about 50 Wh, about 100 Wh, about 500 Wh, about 1 kWh, about 1.5 kWh, about 2 kWh, about 3 kWh, or about 5 kWh. In some instances, the battery is capable of storing (and/or taking in) at least about 1 Wh, at least about 5 Wh, at least about 25 Wh, at least about 50 Wh, at least about 100 Wh, at least about 500 Wh, at least about 1 kWh, at least about 1.5 kWh, at least about 2 kWh, at least about 3 kWh, or at least about 5 kWh. It is recognized that the amount of energy stored in an electrochemical cell and/or battery may be less than the amount of energy taken into the electrochemical cell and/or battery (e.g., due to inefficiencies and losses).


The compilation of cells (i.e., battery) can include any suitable number of cells, such as at least about 2, at least about 5, at least about 10, at least about 50, at least about 100, at least about 500, at least about 1000, at least about 5000, at least about 10000, and the like. In some examples, a battery includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 5000, 10,000, 20,000, 50,000, 100,000, 500,000, or 1,000,000 cells.


Batteries of the disclosure may be capable of storing a suitably large amount of energy for use with a power grid (i.e., a grid-scale battery) or other loads or uses. In some instances, a battery is capable of storing (and/or taking in) about 5 kWh, 25 kWh, about 50 kWh, about 100 kWh, about 500 kWh, about 1 MWh, about 1.5 MWh, about 2 MWh, about 3 MWh, or about 5 MWh. In some instances, the battery is capable of storing (and/or taking in) at least about 5 kWh, at least about 25 kWh, at least about 50 kWh, at least about 100 kWh, at least about 500 kWh, at least about 1 MWh, at least about 1.5 MWh, at least about 2 MWh, at least about 3 MWh, or at least about 5 MWh.


In some instances, the cells and cell housings are stackable. Any suitable number of cells can be stacked. Cells can be stacked side-by-side, on top of each other, or both. In some instances, at least about 10, 50, 100, or 500 cells are stacked. In some cases, a stack of 100 cells is capable of storing at least 50 kWh of energy. A first stack of cells (e.g., 10 cells) can be electrically connected to a second stack of cells (e.g., another 10 cells) to increase the number of cells in electrical communication (e.g., 20 in this instance). In some instances, the energy storage device comprises a stack of 1 to 10, 11 to 50, 51 to 100, or more electrochemical cells.


Cell Lid Assemblies


An electrochemical cell can be housed in a container, which can include a container lid. In some cases, the container is an electrode of the electrochemical cell. The container lid may utilize, for example, a seal or gasket (e.g., annular dielectric gasket) to electrically isolate the battery container from the container lid. Such a gasket may be constructed from a relatively hard electrically insulating material, such as, for example, glass, silicon oxide, aluminum oxide, boron nitride, aluminum nitride, or other oxides comprising of lithium oxide, calcium oxide, barium oxide, yttrium oxide, silicon oxide, aluminum oxide, lithium nitride, or other ceramics. The gasket may be subject to relatively high compressive forces (e.g., greater than 10,000 psi) between the container lid and the battery container in order to provide the seal in addition to the electrical isolation. In order to subject the dielectric gasket to such high compressive forces, the fasteners may have relatively large diameters and may be closely spaced together. Such large diameter fasteners may be expensive and, thus, may significantly increase the cost to build a relatively large diameter battery container. In addition, as the diameter of the dielectric gasket is increased to accommodate a large diameter battery container, the gasket may become more and more fragile and difficult to maneuver.


With reference to FIG. 2, a battery comprises an electrically conductive housing 201 and a conductor 202 in electrical communication with a current collector 203. The conductor may be electrically isolated from the housing and may protrude through the housing through an aperture in the housing such that the conductor of a first cell contacts the housing of a second cell when the first and second cells are stacked.


In an aspect, a cell housing comprises an electrically conductive container and a conductor in electrical communication with a current collector. The conductor may protrude through the housing through an aperture in the container and is electrically isolated from the container. The conductor of a first housing may contact the container of a second housing when the first and second housings are stacked.


In some instances, the area of the aperture through which the conductor protrudes from the housing and/or container is small relative to the area of the housing and/or container. In some cases, the ratio of the area of the aperture to the area of the housing is about 0.001, about 0.005, about 0.01, about 0.05, about 0.1, about 0.15, about 0.2, about 0.3, about 0.4, or about 0.5. In some cases, the ratio of the area of the aperture to the area of the housing is less than 0.001, less than 0.005, less than 0.01, less than 0.05, less than 0.1, less than 0.15, less than 0.2, less than 0.3, less than 0.4, or less than 0.5.


In an aspect, a cell comprises an electrically conductive housing and a conductor in electrical communication with a current collector. The conductor protrudes through the housing through an aperture in the housing and may be electrically isolated from the housing. The ratio of the area of the aperture to the area of the housing may be less than about 0.1.


In an aspect, a cell housing comprises an electrically conductive container and a conductor in electrical communication with a current collector. The conductor protrudes through the container through an aperture in the container and is electrically isolated from the container. The ratio of the area of the aperture to the area of the container may be less than 0.1. The housing can be capable of enclosing a cell that is capable of storing and or taking in at least 25 Wh of energy.


In some instances, the conductor is electrically isolated from the housing with a gasket or seal. FIG. 3 shows a cell lid assembly 301 that can be welded onto a container 305. At least one conductive feed-through (i.e., conductor) passes through the lid assembly and is in electrical communication with a liquid anode 302. In some embodiments, the current collector is an electrically conductive foam, wherein the anode comprises a liquid metal (e.g. lithium, magnesium, sodium). The anode is in contact with a molten salt electrolyte 304, which is in contact with a liquid metal cathode 303. In some embodiments the liquid metal cathode comprises lead and antimony.



FIG. 4 shows a conductor 401, housing aperture and associated structures for electrically isolating the conductor from the housing 402 and sealing the electrochemical cell. In some embodiments, at least one bolt 403 holds the assembly in place. The bolt can be in electrical communication with the housing and electrically insulated from the conductive feed-through. In some embodiments, the bolt compresses a top flange 404 with a bottom flange 405. The bottom flange is welded to the cell lid in some instances. An electrically insulating washer or washer assembly 406 can insulate the bolt from the top flange. In some cases, a dielectric gasket 407 insulates the top flange from the bottom flange. A dielectric sheath (not shown) can be used to prevent the bolt from contacting the top flange in some cases. In some cases, the feed-through conductor has negative polarity (e.g., is in electrical communication with the anode) and the bolts and housing have positive polarity (e.g., is in electrical communication with the cathode).


When sealed, the force applied to the gasket can be about 1,000 psi, about 2,000 psi, about 5,000 psi, about 10,000 psi, about 15,000 psi, or about 30,000 psi. In some instances, the force applied to the gasket is at least 1,000 psi, at least 2,000 psi, at least 5,000 psi, at least 10,000 psi, at least 15,000 psi, or at least 30,000 psi.


In some cases, a cell comprises an electrically conductive housing and a conductor in electrical communication with a current collector. The conductor can protrude through the housing through an aperture in the housing and is electrically isolated from the housing with a gasket. The force on the gasket may be at least 1,000 psi, at least 5,000 psi, at least 10,000 psi, and the like.


A cell housing can comprise an electrically conductive container and a conductor in electrical communication with a current collector. The conductor may protrude through the container through an aperture in the container and may be electrically isolated from the container with a gasket. The force on the gasket can be at least 1,000 psi, at least 5,000 psi, at least 10,000 psi, and the like.


Few Bolts and Fasteners


Bolts and fasteners can add to the cost of the battery and/or housing substantially. In some instances, the battery or battery housing comprises few bolts or fasteners. In some embodiments, the battery or housing comprises about 50, about 40, about 30, about 20, about 10, about 5, or about 2 bolts or fasteners. The battery or battery housing may comprise no bolts or fasteners. In some embodiments, the battery or housing comprises less than 50, less than 40, less than 30, less than 20, less than 10, less than 5, or less than 2 bolts or fasteners. In other embodiments, the dielectric sealing material may be mechanically and/or chemically adhered to the surfaces of the cell lid and the feed through leads, allowing the system to achieve a hermetic gas-tight seal without the need for any bolts or fasteners on the cell. Pressure may also be applied to the top of the feed-through, such as through cell stacking or adding a weight to the top of the cell, improving the performance and durability of the seal.


A battery can comprise an anode, a cathode, an electrolyte, a positive current collector, and a negative current collector. The negative current collector can be in contact with the anode and the positive current collector is in contact with the cathode. The battery can be capable of storing and or taking in at least 25 Wh of energy and comprises less than 10 bolts or fasteners.


In some cases, a compilation of cells is capable of storing at least 25 Wh, 200 Wh, 300 Wh, 400 Wh, 500 Wh, 600 Wh, 700 Wh, 800 Wh, 900 Wh, 1,000 Wh, 2,000 Wh, 3,000 Wh, 4,000 Wh, 4,000 Wh, 5,000 Wh, 6,000 Wh, 7,000 Wh, 8,000 Wh, 9,000 Wh, 10,000 Wh, 20,000 Wh, 30,000 Wh, 40,000 Wh, or 50,000 Wh of energy, and each of the cells comprises less than 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 bolt(s) or fastener(s). In some examples, cell components can be welded to one another.


A cell housing can be capable of hermetically sealing a cell which is capable of storing and or taking in at least 25 Wh of energy. The housing comprises less than 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 bolt(s) or fastener(s).


Cell lid assemblies can use adhesive seals instead of flanges and gaskets. In some cases, adhesive seals eliminate bolts from the electrochemical cell housing. As seen in FIG. 5, the conductive feed-through 501 is electrically isolated from the housing and the housing is sealed by an adhesive sealing material 502 disposed between the feed-through and the housing.


In some cases, for cells that are sealed with adhesive dielectric seals that do not use bolts, a pressure of less than 1 psi may be all that is required to maintain a gas tight seal. In some cases, at least part of the pressure can be supplied by the weight of one or more electrochemical cells stacked upon each other in a battery. The adhesive seal material can comprise a glass seal or a brased ceramic, such as Alumina with Cu—Ag braze alloy, or other ceramic-braze combination.


Sealing the electrochemical cell with an adhesive material rather than bolts and flanges can reduce the height at which the lid assembly can extend above the housing (“head space”). In a stacked battery configuration, it may be desirable to reduce the head space so that relatively more of the volume of the battery can comprise anode and cathode material (i.e., a higher energy storage capacity). In some instances, the width of the head space (as measured from the top of the feed-through to the top surface of the anode) is a small fraction of the width of the battery (as measured from the top of the feed-through to the bottom surface of the housing). In some embodiments, the head space is about 5%, about 10%, about 15%, about 20%, or about 25% of the height of the battery. In some embodiments, the head space is at most about 5%, at most about 10%, at most about 15%, at most about 20%, or at most about 25% of the height of the battery.


In some embodiments, the combined volume of anode and cathode material is about 50%, about 60%, about 70%, about 80%, about 90%, or about 95% of the volume of the battery (e.g., as defined by the outer-most housing of the battery, such as a shipping container). In some embodiments, the combined volume of anode and cathode material is at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, or at least about 95% of the volume of the battery.


In some situations, the use of a few or only a single conductive feed-through can result in uneven current distribution in the electrode. As described herein, a plurality of conductive feed-throughs can more evenly distribute the current in the electrode.


In an aspect, an electrochemical energy storage device comprises a housing, a liquid metal electrode, a current collector in contact with the liquid metal electrode, and a plurality of conductors that are in electrical communication with the current collector and protrude through the housing through apertures in the housing. In some embodiments, current is distributed substantially evenly across the liquid metal electrode.


In some embodiments, the liquid metal electrode is in contact with an electrolyte along a surface (and/or interface) and the current flowing across the surface (and/or interface) is uniform. The current flowing through any portion of the surface (and/or interface) does not deviate far from the average current. In some embodiments, the maximum density of current flowing across an area of the surface (and/or interface) is less than about 105%, less than about 115%, less than about 125%, less than about 150%, less than about 175%, less than about 200%, less than about 250%, or less than about 300% of the average density of current flowing across the surface (and/or interface). In some embodiments, the minimum density of current flowing across an area of the surface (and/or interface) is greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80%, greater than about 90%, or greater than about 95% of the average density of current flowing across the surface (and/or interface).



FIG. 6 shows multiple conductive feed-throughs. The electrochemical storage device and/or housings can comprise any number of conductive feed-throughs (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or more). In some cases, the conductive feed-throughs are separate (panel A). In some cases, the conductive feed-throughs share a common upper portion (panel B).


Hermetic Sealing of Cells


A hermetically sealed battery or battery housing may prevent an unsuitable amount of air, oxygen and/or water into the battery (e.g., an amount such that the battery maintains at least 80% of its energy storage capacity for at least one year, at least 2 years, at least 5 years, at least 10 or at least 20 years).


In some instances, the rate of oxygen, nitrogen, and water vapor transfer into the battery is less than about 0.25 mL per hour when the battery is contacted with air at a pressure of 1 bar and temperature of 400 to 700° C. In some embodiments, the number of moles of oxygen, nitrogen, or water vapor that leaks into the cell over a 10 year period is less than 10% of the number of moles of active metal material in the cell.


In an aspect, a battery comprises an anode and a cathode. The battery is capable of storing at least 10 Wh of energy and is hermetically or non-hermetically sealed. At least one of the anode and the cathode can be a liquid metal. In some cases, the anode is a liquid metal (e.g. lithium, magnesium, sodium).


In an aspect, a group of batteries is capable of storing at least 10 Wh of energy and each of the batteries are hermetically or non-hermetically sealed.


In an aspect, a battery housing comprises an electrically conductive container, a container aperture and a conductor in electrical communication with a current collector. The conductor may pass through the container aperture and is electrically isolated from the electrically conductive container. The housing may be capable of hermetically sealing a battery which is capable of storing at least 100 kWh of energy.


Embodiments of Electrochemical Cells, Batteries and Battery Housings



FIG. 7 illustrates an electrochemical cell 20, in accordance with an embodiment of the invention. The cell 20 includes at least one electrochemical cell 22 sealed (e.g., hermetically sealed) within an electrochemical cell housing 24. The cell housing 24 includes a cell container 26, a container lid assembly 28 and one or more electrical conductors 30 (e.g., conductor rods). The cell housing 24 can also include a thermally and/or electrically insulating sheath 32, a first (e.g., negative) current collector 34 and a second (e.g., positive) current collector 36.


The battery cell 22 may be configured as a liquid metal battery cell. The battery cell 22 may include, for example, a liquid separator 38 arranged axially between a liquid first (e.g., negative) electrode 40 and a liquid second (e.g., positive) electrode 42.


In some instances, the electrochemical battery departs from that in FIG. 7. For example, the top electrode 40 can be contained within the top current collector (e.g., foam) 34. In this embodiment, the salt layer comes up in contact with the bottom and sides of the foam 34, and the top metal in the foam is held away from the sidewalls 32 or 26, thus allowing the cell to run without the insulating sheath 32. In some cases, a graphite sheath is used to prevent ‘creeping’ of the cathode up the sidewall, which can prevent shorting of the cell.


The separator 38 may be an ionically conducting liquid electrolyte. An example of a liquid electrolyte is a liquid solution of one or more ionically conductive molten salts such as, for example, fluoride salt, chloride salt, bromide salt, iodide salt, or a combination thereof. The first electrode 40 may be a liquid (e.g., molten) metal. Examples of materials that may be used as the first electrode 40 include, without limitation, sodium (Na), potassium (K), lithium (Li), calcium (Ca), barium (Ba), magnesium (Mg), or combinations thereof. The liquid metal of the first electrode 40 may contain one or more of the listed examples. The second electrode 42 may be a liquid metal or metalloid. Examples of materials that may be used as the second electrode 42 include, without limitation, antimony (Sb), lead (Pb), tin (Sn), bismuth (Bi), tellurium (Te), selenium (Se), or combinations thereof. The second electrode 42 may contain one or more of metals or metalloid metals listed above. Other examples of separator, first electrode and second electrode materials and/or configurations are disclosed in U.S. Patent Application Publication Nos. 2008/0044725, 2011/0014503, 2011/0014505 and 2012/0104990, each of which is entirely incorporated by reference herein. The present invention, however, is not limited to any particular battery cell configurations and/or materials.


The battery container 26 can be constructed from an electrically conductive material such as, for example, steel, iron, stainless steel, graphite, nickel, nickel based alloys, titanium, aluminum, molybdenum, tungsten, or conductive glass. The cell container may also comprise of a structure component, and thinner lining component of a separate metal or electrically insulating coating, such as, for example, a steel container with a graphite lining, or a steel container with a boron nitride coating. The battery container 26 can have a cross-sectional geometry that can extend axially between a first container end (e.g., edge) 44 and a second container end (e.g., edge) 46. The cross-sectional geometry can be, for example, circular as illustrated in FIG. 13, rectangular (e.g., square) as illustrated in FIG. 16, or any other shape that may be selected based on design requirements for the battery 20. The battery container 26 includes a cell cavity 48 defined by a container (bottom) endwall 50 and a container sidewall 52. The cavity 48 can extend axially into the battery container 26 from a cavity aperture 54 that is located at the first container end 44 to the container endwall 50 that is located at the second container end 46. The cavity 48 can also extend laterally between opposing sides of the container sidewall 52.


The container lid assembly 28 can include an electrically conductive container lid 56, one or more electrically conductive flanges 58, and one or more electrically insulating gaskets 60 (e.g., annular dielectric gaskets).


Referring to FIGS. 8 and 9, the container lid 56 can be constructed from an electrically conductive material such as, for example, steel, iron, copper, stainless steel, graphite, nickel, nickel based alloys, titanium, aluminum, molybdenum, tungsten, or conductive glass. The container lid 56 can extend axially between a first lid end 62 and a second lid end 64. The container lid 56 can include an electrically conductive base 66 and one or more electrically conductive mounting rings 68 (also referred to as “feed through flanges”). The base can extend axially between the first lid end 62 and a base end 70, which is located axially between the first lid end 62 and the second lid end 64. The base 66 can include one or more mounting ring apertures 72 that can extend axially through the base 66 between the first lid end 62 and the base end 70. The mounting rings 68 are respectively mated with the mounting ring apertures 72, and connected (e.g., welded, adhered or otherwise fastened) to the base 66. The mounting rings 68 can extend axially between the first lid end 62 and the second lid end 64. Each of the mounting rings 68 includes a first conductor aperture 74 that can extend axially therethrough between the first lid end 62 and the second lid end 64. The first conductor aperture 74 has a diameter that is, for example, at least 2 (e.g., between about 2 and 6) times less than a diameter of the cavity aperture 54 (see FIG. 7). Each of the mounting rings 68 may also include one or more threaded fastener apertures 76 arranged circumferentially around the respective first conductor aperture 74. The fastener apertures 76 extend axially into the respective mounting ring 68 from the first lid end 62.


Referring to FIGS. 10 and 11, each of the flanges 58 is constructed from an electrically conductive material such as, for example, steel, iron, stainless steel, graphite, nickel, nickel based alloys, titanium, aluminum, molybdenum, tungsten, or conductive glass. Each of the flanges 58 can extend axially from a first flange end 78 to a second flange end 80. Each of the flanges 58 may include an electrically conductive base 82 and an electrically conductive flange ring 84. The base 82 can extend axially between the first flange end 78 and the second flange end 80. The base 82 includes a threaded conductor aperture 86 that can extend axially into the base 82 from the second flange end 80 to a base endwall 88. The flange ring 84 can extend circumferentially around the base 82. The flange ring 84 can also extend axially between a first flange ring end 90 and a second flange ring end 92. The first flange ring end 90 may be offset from the first flange end 78 by a first axial distance, and/or the second flange ring end 92 may be offset from the second flange end 80 by a second axial distance. The flange ring 84 may include a plurality of fastener apertures 94 arranged circumferentially around the base 82. The fastener apertures 94 extend axially through the flange ring 84 between the first flange ring end 90 and the second flange ring end 92.


Referring to FIGS. 7 and 12, the gaskets 60 are constructed from a dielectric material such as, for example, glass, brazed ceramic, thermiculite, aluminum nitride, mica and/or vermiculite. Each of the gaskets 60 includes a second conductor aperture 96 that can extend axially therethrough between a first gasket end 98 and a second gasket end 100. The second conductor aperture 96 has a diameter that is substantially equal to or less than the diameter of a respective one of the first conductor apertures 74.


Referring to FIG. 7, the conductors 30 can be constructed from an electrically conductive material such as, for example, steel, iron, stainless steel, graphite, nickel, nickel based alloys, titanium, aluminum, molybdenum, or tungsten. The conductors 30 extend axially between a first conductor end 102 and a second conductor end 104. Each of the conductors 30 may include a threaded end region 106 adjacent the first conductor end 102.


Referring to FIG. 7, the sheath 32 can be constructed from a thermally insulating and/or electrically insulating material such as, for example, alumina, titania, silica, magnesia, boron nitride, or a mixed oxide including calcium oxide, aluminum oxide, silicon oxide, lithium oxide, magnesium oxide, etc. The sheath 32 has an annular cross-sectional geometry that can extend axially between a first sheath end (top) 108 and a second sheath end (bottom) 110.


As an alternative, the sheath can be used to prevent corrosion of the container and/or prevent wetting of the cathode material up the side wall, and may be constructed out of an electronically conductive material, such as steel, stainless steel, tungsten, molybdenum, nickel, nickel based alloys, graphite, or titanium. The sheath may be very thin and could be a coating. The coating can cover just the inside of the walls, and/or, can also cover the bottom of the inside of the container.


Referring to FIG. 7 and FIG. 12, the first current collector 34 is constructed from an electrically conductive material such as, for example, nickel-iron (Ni—Fe) foam, perforated steel disk, sheets of corrugated steel, sheets of expanded metal mesh, etc. The first current collector 34 may be configured as a plate that can extend axially between a first collector end 112 and a second collector end 114. The first current collector 34 has a collector diameter that is less than the diameter of the cavity aperture 54, and greater than the diameter of the first conductor aperture 74. Examples of other current collector configurations are disclosed in U.S. Patent Publication Nos. 2011/0014503, 2011/0014505, and 2012/0104990, which are entirely incorporated herein by reference. The present invention is not limited to any particular first current collector configurations.


The second current collector 36 may be configured as a part of the cell container 26. In the embodiment illustrated in FIG. 7, for example, the container endwall 50 is configured as the second current collector 36. As an alternative, the current collector may be discrete from and, for example, electrically connected to, the battery container. Examples of such a current collector arrangement are disclosed in the aforementioned U.S. Patent Publication Nos. 2011/0014503, 2011/0014505, and 2012/0104990, which are entirely incorporated herein by reference. The present invention is not limited to any particular second current collector configurations.



FIGS. 13 and 14 illustrate an alternative embodiment electrochemical battery housing 120. A sheath in such a case can in some cases be precluded. In contrast to the battery housing 24 of FIGS. 7 and 12, each of the flanges 58 of the battery housing 120 includes a flange ring 122 that is directly connected (e.g., welded, glued, fused, adhered and/or otherwise fastened) to a respective one of the conductors 30. Each of the gaskets 60 of the battery housing 120 may additionally include a plurality of fastener apertures 124, which receive the fasteners 116. Each of the fasteners 116 may be electrically isolated from the flange ring 122 via an electrically insulating sleeve 126 and an electrically insulating washer 128. The sleeve 126 and the washer 128 are each constructed from a dielectric such as, for example, mica or vermiculite. The battery housing 120 may also include one or more fluid ports 130 (e.g., quick connect gas fittings) that direct fluid (e.g., inert gas) into and/or out of the sealed cavity 48.



FIGS. 15 and 16 illustrate another alternative embodiment electrochemical battery housing 132. In contrast to the battery housing 24 of FIGS. 7 and 12, each of the flanges 58 of the battery housing 132 includes a base 134 that can extend axially between the first flange ring end 90 and the second flange end 80. Each of the flanges 58 can also include a protrusion 136 (e.g., a boss) that is connected to the base 134 and/or the flange ring 84, and can extend axially to the first flange end 78. Such a protrusion 136 may be utilized for vertically stacking and/or electrically interconnecting a plurality of the battery housing 132 as illustrated in FIG. 15.



FIG. 17 illustrates an embodiment that reduces the number of pieces of the electrochemical cells and/or batteries described herein (e.g., allows the assembly of a plurality of electrochemical cells using a single pre-assembled piece). In some cases, the conductors of a first electrochemical cell 1701 are connected to, and/or are formed from the same piece of metal as, the housing (e.g., positive current collector) of a second electrochemical cell 1702. In some cases, the top of a first electrochemical cell is directly connected to (e.g., welded or bolted) or formed from the same piece of metal as the bottom of a second electrochemical cell that is located on top of the first electrochemical cell. The cells can be assembled as shown in panel A in FIG. 17. As seen here, a plurality of pieces 1703 comprising a housing portion and a container lid assembly portion 1704 are put together (e.g., welded) one on top of another to form a plurality of electrochemical cells. The negative current collector 1705, positive electrode 1706 and electrolyte 1707 can be inserted and/or filled into the electrochemical cells as the cells are assembled from the pieces. The negative current collector 1705 can include (e.g., house, contain) the negative electrode. For example, the negative current collector 1705 can be a porous material that includes material of the negative electrode (e.g., lithium) in the pores of the negative current collector 1705.


The electrochemical cell can be hermetically and/or electrically sealed by placing a sealant material between two surfaces.


In an aspect, an electrochemical cell comprises an electrically conductive housing and a conductor in electrical communication with a current collector, wherein the conductor protrudes through the housing through an aperture in the housing and is electrically isolated from the housing with a seal that hermetically seals the electrochemical cell.


With reference to FIG. 18, the sealant 1800 can be disposed and/or placed between the housing of the electrochemical cell 1801 and another article 1802 (e.g., a conductive feed through). FIG. 19 shows that the two surfaces 1900 can be metal. In some cases, the seal and/or sealant 1901 is a ceramic, glass, or glass-ceramic composite. FIG. 20 shows a top view for each layer of the assembly with the electrochemical cell housing on the left 2000, the seal in the center 2001 and the article 2002 (e.g., conductive feed through) on the right.


In some cases, the surfaces are made of dissimilar materials (i.e., materials that are not the same, such as two different metal surfaces). The materials can have different coefficients of thermal expansion. The dissimilar materials can be inlaid and/or recessed into one another (e.g., one material surrounds the other on at least two planes, such as a flat surface and an edge). FIG. 21 shows an embodiment where a conductive feed-through 2100 is inlaid in the housing of the electrochemical cell 2101. In some cases, the feed-through is sealed from the housing along two planes including along a horizontal plane 2102 and along the edges 2103 (i.e., a vertical plane).


In some instances, the feed-through is recessed in the housing and electrically insulated from the housing on all sides, but only sealed along one plane. For example, a horizontal shim (e.g., made of ceramic material) can be put between the feed through and the housing in the horizontal direction and the sealant can be disposed along the vertical direction. In some embodiments, a vertical ring (e.g., made of ceramic material) is placed between the feed through and the housing in the vertical direction (e.g., along the edges) and the sealant can be disposed along the horizontal direction. FIG. 22 shows a 3-dimensional exploded view of the feed-through, housing and seal, horizontal shim 2201 and/or vertical ring 2200 along two planes (e.g., vertical and horizontal).



FIG. 23 shows a top view of each layer of the assembly including from left to right; the electrochemical cell housing 2300, the horizontal shim 2301, the conductive feed through 2302, and the vertical ring 2303 on the far right. In an embodiment, the layers of the assembly have relative dimensions as shown. In particular, the housing 2300 may have a hole with an inner diameter of one arbitrary unit (denoted by the symbol ϕ) 1.00 with a second diameter of 1.5 and an outer diameter of 4.00 (e.g., 4 inches). The base of the housing 2300 can be made of metal and be about 0.5 thick. In some cases, the horizontal shim 2301 has an inner diameter of 0.6 and an outer diameter of 1.5 with a thickness of 0.05. In some embodiments, the conductive feed through 2302 has a diameter of 1.38 and a thickness of 0.2. In some instances, the vertical ring 2303 has an inner diameter of 1.38, an outer diameter of 1.5 and a thickness of 0.2.


A compressive force can be established on the seal if the housing and feed-through are made of dissimilar materials that have a different coefficient of thermal expansion. In some embodiments, the housing has a greater coefficient of thermal expansion than the feed-through. The seal can be put between the materials when expanded at a high temperature. Upon cooling, the materials can shrink in volume (e.g., with the outer housing shrinking more than the inner feed-through) to establish a compressive force upon the seal. The force can be any suitable force (e.g., suitable for hermetically sealing the electrochemical cell). In some cases, the force is about 1,000 psi, about 2,000 psi, about 5,000 psi, about 10,000 psi, or about 20,000 psi. In some cases, the force is at least 1,000 psi, at least 2,000 psi, at least 5,000 psi, at least 10,000 psi, or at least 20,000 psi.


In an aspect, a method for sealing an electrochemical cell comprises (a) applying a sealant material between a housing and an article recessed into the housing, wherein the sealant is applied at a temperature at which the sealant material is malleable, viscous, and/or flowable, and wherein the housing and the article have different coefficients of thermal expansion; and (b) lowering the temperature to a temperature at which the sealant material is not malleable, viscous, and/or flowable, i.e. solidifies or hardens, thereby creating a seal between the housing and the article that is under a compressive force. In some embodiments, the seal is under compression at the operating temperature of the electrochemical cell.


The sealant can be any suitable material. In some instances, the seal is formed by brazing ceramic onto a metal substrate. In some embodiments, the seal is formed by solidifying ceramic and/or glass. In some embodiments, the seal is formed by mechanically and/or chemically bonded glass or glass-ceramic composite.


In some cases, the sealant material is a re-flowable material such as borosilicate glass (or other seal-specific glass). In such an embodiment, a hermetic seal can be established by sliding a borosilicate glass tube around the cell top as a horizontal spacer. After insertion of the re-flowable material into the inlaid space, heating to a temperature of about, for example, 700 to 800° C. can allow flow of the borosilicate glass to form a glass seal. The seal can be stable at the temperatures of battery operation. In some instances, the glass seal is suitably thick to hermetically seal the cell and be resilient to shear stress. In some embodiments, the cell is slowly and evenly cooled following melting such that the seal forms evenly without cracks, delamination, and the like.


In some cases, more than one sealant material can be used. In some embodiments, the seal is formed from at least two different materials, at least one of which is resistant to degradation from contact with materials contained in the electrochemical cell. In some embodiments, the seal is resistant to reactive metal vapors such as sodium (Na), lithium (Li) or magnesium (Mg). In some instances, the seal is a chalcogenide seal (e.g., comprises a chalgen such as CaAl2S4). In some embodiments, the sealant material is a chalcogenide based compound. In some cases, the chalcogenide has the chemical formula CaAl2S4.


Systems, apparatuses and methods of the disclosure may be combined with or modified by other systems, apparatuses and/or methods, such as batteries and battery components described in U.S. Patent Publication No. 2012/0104990 (“Alkali Metal Ion Battery with Bimetallic Electrode”), which is entirely incorporated herein by reference.


Energy storage devices of the disclosure may be used in grid-scale settings or stand-alone settings. Energy storage device of the disclosure can, in some cases, be used to power vehicles, such as scooters, motorcycles, cars, trucks, trains, helicopters, airplanes, and other mechanical devices, such as robots.


A person of skill in the art will recognize that the battery housing components may be constructed from materials other than the examples provided above. One or more of the electrically conductive battery housing components, for example, may be constructed from metals other than steel and/or from one or more electrically conductive composites. In another example, one or more of the electrically insulating components may be constructed from dielectrics other than the aforementioned glass, mica and vermiculite. The present invention therefore is not limited to any particular battery housing materials.


It is to be understood that the terminology used herein is used for the purpose of describing specific embodiments, and is not intended to limit the scope of the present invention. It should be noted that as used herein, the singular forms of “a”, “an” and “the” include plural references unless the context clearly dictates otherwise. In addition, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.


While preferred embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed in practicing the invention. It is intended that the following claims define the scope of the invention and that methods and structures within the scope of these claims and their equivalents be covered thereby.

Claims
  • 1. An electrochemical battery, comprising: a container including a cavity that extends into the container from a cavity aperture;an electrochemical battery cell arranged within the cavity, wherein the electrochemical battery cell comprises an electrolyte arranged between a negative electrode and a positive electrode, and wherein at least one of the negative electrode and the positive electrode is liquid at an operating temperature of the electrochemical battery greater than 250° C.;a container lid assembly sealing the battery cell in the cavity, the container lid assembly including an electrically conductive container lid and an electrically conductive flange, wherein the container lid covers the cavity aperture and includes a conductor aperture that extends through the container lid, wherein the electrically conductive flange covers the conductor aperture and is electrically isolated from the container lid, and wherein the electrically conductive flange is in electrical communication with the negative metal electrode and the container lid is in electrical communication with the positive electrode; andan electrical conductor extending through the conductor aperture and electrically coupled to the electrochemical battery cell and the electrically conductive flange, wherein the conductor is electrically isolated from the container lid.
  • 2. The battery of claim 1, further comprising a current collector electrically coupled to the negative electrode, wherein the current collector is connected to the conductor, and wherein the conductor is connected to the electrically conductive flange.
  • 3. The battery of claim 1, further comprising a gasket arranged between and electrically isolating the electrically conductive flange and the container lid.
  • 4. The battery of claim 3, wherein the gasket comprises dielectric material.
  • 5. The battery of claim 1, wherein said container lid assembly hermetically seals said battery cell in said cavity.
  • 6. The battery of claim 1, wherein the container is in electrical communication with an electrode of the electrochemical battery cell.
  • 7. The battery of claim 1, wherein the electrochemical battery is capable of storing at least 25 Wh of energy.
  • 8. The battery of claim 1, wherein a ratio of an area of the conductor aperture to an area of the container is less than 0.2.
  • 9. The battery of claim 1, wherein the flange covers a portion of the conductor aperture.
  • 10. The battery of claim 1, further comprising a current collector within the cavity and connected to the conductor.
  • 11. The battery of claim 3, wherein the gasket comprises a ceramic material.
  • 12. The battery of claim 3, wherein the gasket comprises aluminum nitride.
  • 13. The battery of claim 3, wherein the gasket is annular.
  • 14. The battery of claim 10, wherein the current collector is a metal foam or metal mesh.
  • 15. The battery of claim 1, wherein the positive electrode comprises antimony.
  • 16. The battery of claim 1, wherein the negative electrode comprises calcium.
  • 17. The battery of claim 1, wherein the electrically conductive flange is connected to the container lid with a brazed ceramic.
  • 18. The battery of claim 1, wherein the electrically conductive flange is connected to the container lid with a plurality of fasteners.
CROSS-REFERENCE

This application is a continuation application of PCT Application No. PCT/US2013/065086, filed Oct. 15, 2013, which claims the benefit of U.S. Provisional Patent Application Ser. No. 61/714,714, filed Oct. 16, 2012 and U.S. Provisional Patent Application Ser. No. 61/737,068, filed on Dec. 13, 2012, each of which is incorporated herein by reference in its entirety.

US Referenced Citations (429)
Number Name Date Kind
2587443 Crabtree Feb 1952 A
3057946 Eidensohn Oct 1962 A
3238437 Foster et al. Mar 1966 A
3245836 Agruss Apr 1966 A
3419432 Hesson Dec 1968 A
3488221 Shimotake et al. Jan 1970 A
3507703 Heredy Apr 1970 A
3535214 Rene Oct 1970 A
3607405 Christopher Sep 1971 A
3607407 Adams Sep 1971 A
3635765 Greenberg Jan 1972 A
3663295 Baker May 1972 A
3716409 Cairns et al. Feb 1973 A
3770506 Rightmire et al. Nov 1973 A
3775181 Ryerson Nov 1973 A
3833420 Will Sep 1974 A
3833421 Rubischko et al. Sep 1974 A
3833422 Will et al. Sep 1974 A
3870561 Charbonnier et al. Mar 1975 A
3877984 Werth Apr 1975 A
3878296 Vine et al. Apr 1975 A
3884715 Gay et al. May 1975 A
3887396 Walsh et al. Jun 1975 A
3898096 Heredy et al. Aug 1975 A
3907589 Gay et al. Sep 1975 A
3915742 Battles et al. Oct 1975 A
3926673 Saridakis Dec 1975 A
3930888 Bowser et al. Jan 1976 A
3933521 Vissers et al. Jan 1976 A
3941612 Steunenberg et al. Mar 1976 A
3947291 Yao et al. Mar 1976 A
3954504 Zellhoefer May 1976 A
3959012 Liang et al. May 1976 A
3960594 Fritz et al. Jun 1976 A
3969139 Lai Jul 1976 A
3980495 Roche et al. Sep 1976 A
3988164 Liang et al. Oct 1976 A
4002807 Ludwig Jan 1977 A
4011374 Kaun Mar 1977 A
4015054 Cleaver et al. Mar 1977 A
4018969 Fischer et al. Apr 1977 A
4029860 Vissers et al. Jun 1977 A
4032614 Lewis Jun 1977 A
4044194 Evans et al. Aug 1977 A
4060667 Askew et al. Nov 1977 A
4061841 Sharma Dec 1977 A
4065602 Roche et al. Dec 1977 A
4069372 Voinov Jan 1978 A
4107401 Goodson et al. Aug 1978 A
4125683 Beckford et al. Nov 1978 A
4130500 Melendres et al. Dec 1978 A
4164608 Coetzer Aug 1979 A
4169120 Miller Sep 1979 A
4189529 Birt et al. Feb 1980 A
4195123 Jumel Mar 1980 A
RE30353 Voinov Jul 1980 E
4216273 Cadart et al. Aug 1980 A
4238553 Weddigen et al. Dec 1980 A
4265984 Kaye May 1981 A
4287268 Coetzer Sep 1981 A
4287269 Coetzer et al. Sep 1981 A
4299890 Rea et al. Nov 1981 A
4338380 Erickson et al. Jul 1982 A
4367159 Mrazek et al. Jan 1983 A
4405433 Payne Sep 1983 A
4407912 Virkar et al. Oct 1983 A
4457989 Coetzer Jul 1984 A
4510210 Hunt Apr 1985 A
4565751 Faust et al. Jan 1986 A
4582553 Buchta Apr 1986 A
4588663 Mason et al. May 1986 A
4596637 Kozarek et al. Jun 1986 A
4622111 Brown et al. Nov 1986 A
4657830 Kagawa Apr 1987 A
4692390 Roy Sep 1987 A
4764437 Kaun Aug 1988 A
4800143 Harbach et al. Jan 1989 A
4818638 Roy Apr 1989 A
4833046 Roy May 1989 A
4849682 Bauer et al. Jul 1989 A
4877695 Cipriano et al. Oct 1989 A
4886715 McCullough, Jr. et al. Dec 1989 A
4929521 Cipriano et al. May 1990 A
4945012 Bugga et al. Jul 1990 A
4945257 Marrocco Jul 1990 A
H000816 Carder et al. Sep 1990 H
4954403 Plichta et al. Sep 1990 A
4965146 McCullough, Jr. et al. Oct 1990 A
4975344 Wedlake et al. Dec 1990 A
4999097 Sadoway Mar 1991 A
5011748 Shacklette et al. Apr 1991 A
5024737 Claus et al. Jun 1991 A
5039351 Cooper et al. Aug 1991 A
5139895 Roy et al. Aug 1992 A
5185068 Sadoway Feb 1993 A
5254232 Sadoway Oct 1993 A
5284562 Beck et al. Feb 1994 A
5286359 Richards et al. Feb 1994 A
5369547 Evans Nov 1994 A
5380406 Horton et al. Jan 1995 A
5392191 Thomas et al. Feb 1995 A
5407119 Churchill et al. Apr 1995 A
5429895 Lian et al. Jul 1995 A
5469325 Evans Nov 1995 A
5476733 Coetzer et al. Dec 1995 A
5491037 Kawakami et al. Feb 1996 A
5532078 Redey et al. Jul 1996 A
5536600 Kaun Jul 1996 A
5538813 Li Jul 1996 A
5549989 Anani Aug 1996 A
5559667 Evans Sep 1996 A
5563765 Lian et al. Oct 1996 A
5578389 Tsuchimoto et al. Nov 1996 A
5587872 Lian et al. Dec 1996 A
5597331 Gable et al. Jan 1997 A
5604053 Coetzer et al. Feb 1997 A
5658447 Watson et al. Aug 1997 A
5661403 Mackenzie Aug 1997 A
5687056 Harshe et al. Nov 1997 A
5688613 Li et al. Nov 1997 A
5688614 Li et al. Nov 1997 A
5693434 Li et al. Dec 1997 A
5714283 Briscoe et al. Feb 1998 A
5735933 Yokoyama et al. Apr 1998 A
5737181 Evans Apr 1998 A
5763117 Wright et al. Jun 1998 A
5807412 Li et al. Sep 1998 A
5856041 Inoue et al. Jan 1999 A
5874183 Uematsu Feb 1999 A
5972533 Coetzer et al. Oct 1999 A
5982609 Evans Nov 1999 A
6007943 Coetzer Dec 1999 A
PP11374 Leue May 2000 P
6083296 Innes et al. Jul 2000 A
6143054 Dry Nov 2000 A
6180284 Shah et al. Jan 2001 B1
6218055 Shah et al. Apr 2001 B1
6221513 Lasater Apr 2001 B1
6267799 Innes et al. Jul 2001 B1
6270553 Innes Aug 2001 B1
6289034 Bates Sep 2001 B1
6322745 Leigh et al. Nov 2001 B1
6328783 Bates Dec 2001 B1
6368486 Thompson et al. Apr 2002 B1
6379422 Dry Apr 2002 B1
6379424 Dry Apr 2002 B1
6379840 Kitoh Apr 2002 B2
6387153 Burke May 2002 B1
6402808 Dry Jun 2002 B1
6419812 Beck et al. Jul 2002 B1
6419813 Brown et al. Jul 2002 B1
6423114 Burke Jul 2002 B1
6423115 McCarthy et al. Jul 2002 B1
6428603 Batterham Aug 2002 B1
6440195 Dry Aug 2002 B1
6475264 Dry Nov 2002 B1
6478848 McCarthy et al. Nov 2002 B1
6498406 Hoeriuchi et al. Dec 2002 B1
6517605 Bates et al. Feb 2003 B1
6548212 Heider et al. Apr 2003 B1
6549423 Brodnick et al. Apr 2003 B1
6558525 Bradford et al. May 2003 B1
6579817 Harada et al. Jun 2003 B2
6585929 Bates et al. Jul 2003 B1
6602321 Dry et al. Aug 2003 B2
6692620 Duruz et al. Feb 2004 B2
6692631 Bergsma Feb 2004 B2
6692870 Miyake et al. Feb 2004 B2
6706239 Haack et al. Mar 2004 B2
6719889 Brown Apr 2004 B2
6723222 Bergsma et al. Apr 2004 B2
6730210 Thompson et al. May 2004 B2
6733924 Skotheim et al. May 2004 B1
6906436 Jenson et al. Jun 2005 B2
6924164 Jenson Aug 2005 B2
6962613 Jenson Nov 2005 B2
6963186 Hobbs Nov 2005 B2
6986965 Jenson et al. Jan 2006 B2
7055733 Weil et al. Jun 2006 B2
7077945 Bergsma et al. Jul 2006 B2
7131189 Jenson Nov 2006 B2
7144655 Jenson et al. Dec 2006 B2
7157187 Jenson Jan 2007 B2
7184903 Williams et al. Feb 2007 B1
7194801 Jenson et al. Mar 2007 B2
7211351 Klaassen May 2007 B2
7250233 Choi et al. Jul 2007 B2
7274118 Jenson et al. Sep 2007 B2
7294209 Shakespeare Nov 2007 B2
7328831 Topolski Feb 2008 B1
7344804 Klaassen Mar 2008 B2
7373222 Wright et al. May 2008 B1
7389189 Williams et al. Jun 2008 B2
7389580 Jenson et al. Jun 2008 B2
7433655 Jacobs et al. Oct 2008 B2
7504017 Cardarelli Mar 2009 B2
7513219 Louden Apr 2009 B2
7568537 King Aug 2009 B2
7603144 Jenson et al. Oct 2009 B2
7612537 Wynne et al. Nov 2009 B2
7632604 Iacovangelo et al. Dec 2009 B2
7678484 Tao et al. Mar 2010 B2
7776190 Hiltmann et al. Aug 2010 B2
7776191 Hiltmann et al. Aug 2010 B2
7776478 Klaassen Aug 2010 B2
7808131 Hurst et al. Oct 2010 B2
7877120 Jacobs et al. Jan 2011 B2
7883796 Kida et al. Feb 2011 B2
7931989 Klaassen Apr 2011 B2
7939205 Klaassen May 2011 B2
7943270 Blake et al. May 2011 B2
8034484 Inatomi et al. Oct 2011 B2
8044508 Jenson et al. Oct 2011 B2
8080326 Chan et al. Dec 2011 B2
8101293 Chan et al. Jan 2012 B2
8110301 Iacovangelo et al. Feb 2012 B2
8142569 Kalynushkin et al. Mar 2012 B2
8178231 Soloveichik et al. May 2012 B2
8202641 Winter et al. Jun 2012 B2
8219140 Jacobs et al. Jul 2012 B2
8221912 Fujiwara Jul 2012 B2
8236440 Bendert Aug 2012 B2
8237407 Hurst et al. Aug 2012 B2
8268471 Sadoway et al. Sep 2012 B2
8281877 Shahin et al. Oct 2012 B2
8298701 Whitacre et al. Oct 2012 B2
8306671 Marcus Nov 2012 B1
8311681 Marcus Nov 2012 B1
8313719 Barker et al. Nov 2012 B2
8323816 Bradwell et al. Dec 2012 B2
8329336 Soloveichik et al. Dec 2012 B2
8334053 Shapiro et al. Dec 2012 B2
8343646 Wilkins et al. Jan 2013 B1
8409744 Ijaz et al. Apr 2013 B2
8436489 Stahlkopf et al. May 2013 B2
8457800 Marcus Jun 2013 B2
8460814 Deane et al. Jun 2013 B2
8471520 Coe et al. Jun 2013 B2
8475954 Ijaz et al. Jul 2013 B2
8504214 Gene et al. Aug 2013 B2
8537581 Wagoner et al. Sep 2013 B2
8539763 McBride et al. Sep 2013 B2
8568915 Fuhr et al. Oct 2013 B2
8642201 Cheng et al. Feb 2014 B2
8643500 Lee et al. Feb 2014 B2
8652672 Whitacre et al. Feb 2014 B2
8722226 Chiang et al. May 2014 B2
8764962 Allanore et al. Jul 2014 B2
8766642 Bogdan et al. Jul 2014 B2
8806866 McBride et al. Aug 2014 B2
8815445 Sugiura et al. Aug 2014 B2
9000713 Boysen et al. Apr 2015 B2
9076996 Bradwell et al. Jul 2015 B2
9106980 Parakulam et al. Aug 2015 B2
9153803 Chung et al. Oct 2015 B2
9312522 Bradwell et al. Apr 2016 B2
9502737 Bradwell et al. Nov 2016 B2
9520618 Bradwell et al. Dec 2016 B2
9559386 Bradwell et al. Jan 2017 B2
9787119 Yamauchi et al. Oct 2017 B2
9825265 Bradwell et al. Nov 2017 B2
9876258 Bradwell et al. Jan 2018 B2
9893385 Nayar et al. Feb 2018 B1
9925881 Manotas, Jr. et al. Mar 2018 B2
20020009649 Sato et al. Jan 2002 A1
20020051912 Fitter May 2002 A1
20020064704 Thackeray et al. May 2002 A1
20030008212 Akashi et al. Jan 2003 A1
20030044686 Bushong et al. Mar 2003 A1
20030186111 Tamakoshi Oct 2003 A1
20030196908 Brown Oct 2003 A1
20030203279 Tsukamoto Oct 2003 A1
20030207161 Rusta-Sallehy et al. Nov 2003 A1
20030228520 Kaun Dec 2003 A1
20040061841 Black et al. Apr 2004 A1
20040076885 Sato et al. Apr 2004 A1
20040229116 Malinski et al. Nov 2004 A1
20040258953 Kido et al. Dec 2004 A1
20050079411 Kairawicz et al. Apr 2005 A1
20050237029 Takezawa et al. Oct 2005 A1
20060127735 Sabin Jun 2006 A1
20060151333 Banek Jul 2006 A1
20070215483 Johansen et al. Sep 2007 A1
20070252556 West et al. Nov 2007 A1
20080023321 Sadoway Jan 2008 A1
20080044725 Sadoway et al. Feb 2008 A1
20080050295 Uchida et al. Feb 2008 A1
20080053838 Yamaguchi et al. Mar 2008 A1
20080118428 Awano et al. May 2008 A1
20080145755 Iacovangelo et al. Jun 2008 A1
20080264565 Sun et al. Oct 2008 A1
20080308415 Hiltmann et al. Dec 2008 A1
20090011331 Stringer et al. Jan 2009 A1
20090014320 Chiang et al. Jan 2009 A1
20090029236 Mailley et al. Jan 2009 A1
20090162736 Vallance Jun 2009 A1
20090208836 Fuhr et al. Aug 2009 A1
20090212743 Hagiwara et al. Aug 2009 A1
20090253017 Larsen et al. Oct 2009 A1
20090297892 Ijaz et al. Dec 2009 A1
20100028723 Haba Feb 2010 A1
20100047671 Chiang et al. Feb 2010 A1
20100058578 Vallance et al. Mar 2010 A1
20100068610 Sudworth Mar 2010 A1
20100089547 King et al. Apr 2010 A1
20100119847 Wu et al. May 2010 A1
20100154205 Nakagawa et al. Jun 2010 A1
20100178532 Shapiro et al. Jul 2010 A1
20100233518 Kwon et al. Sep 2010 A1
20100240517 Ashkin et al. Sep 2010 A1
20100243017 Normann et al. Sep 2010 A1
20100291443 Farmer Nov 2010 A1
20110014503 Bradwell et al. Jan 2011 A1
20110014505 Bradwell Jan 2011 A1
20110027624 Deane et al. Feb 2011 A1
20110027627 Deane et al. Feb 2011 A1
20110027633 Deane et al. Feb 2011 A1
20110027637 Deane et al. Feb 2011 A1
20110027638 Deane et al. Feb 2011 A1
20110027639 Deane et al. Feb 2011 A1
20110048066 Gielda et al. Mar 2011 A1
20110050235 Bogdan, Jr. et al. Mar 2011 A1
20110052968 Venkataramani et al. Mar 2011 A1
20110086258 Yaginuma et al. Apr 2011 A1
20110104570 Galloway et al. May 2011 A1
20110111296 Berdichevsky et al. May 2011 A1
20110135975 Fuhr et al. Jun 2011 A1
20110177413 Tao et al. Jul 2011 A1
20110189520 Carter et al. Aug 2011 A1
20110200848 Chiang et al. Aug 2011 A1
20110262794 Yoon Oct 2011 A1
20120003508 Narbonne et al. Jan 2012 A1
20120003513 Fuhr Jan 2012 A1
20120015235 Fuhr et al. Jan 2012 A1
20120077095 Roumi et al. Mar 2012 A1
20120104990 Boysen et al. May 2012 A1
20120107675 Kim May 2012 A1
20120125784 Berlin et al. May 2012 A1
20120129056 Majima et al. May 2012 A1
20120146585 Darcy Jun 2012 A1
20120161083 Jha et al. Jun 2012 A1
20120183838 An et al. Jul 2012 A1
20120191262 Marcus Jul 2012 A1
20120194140 Rijssenbeek et al. Aug 2012 A1
20120196170 Ijaz et al. Aug 2012 A1
20120217032 Beaupre et al. Aug 2012 A1
20120244404 Obasih et al. Sep 2012 A1
20120244418 Cheng et al. Sep 2012 A1
20120264021 Sugiura et al. Oct 2012 A1
20120265397 Aliberti et al. Oct 2012 A1
20120282501 Haynes et al. Nov 2012 A1
20120282508 Bendert Nov 2012 A1
20120297772 McBride et al. Nov 2012 A1
20120319653 Kumar et al. Dec 2012 A1
20120328910 Ia et al. Dec 2012 A1
20130009602 Hoff et al. Jan 2013 A1
20130017417 Whitacre et al. Jan 2013 A1
20130022845 Davis et al. Jan 2013 A1
20130022852 Chang et al. Jan 2013 A1
20130029195 Peace Jan 2013 A1
20130045408 Sadoway et al. Feb 2013 A1
20130049466 Adams Feb 2013 A1
20130049478 Wagoner et al. Feb 2013 A1
20130055559 Slocum et al. Mar 2013 A1
20130057220 Whitacre Mar 2013 A1
20130059176 Stefani et al. Mar 2013 A1
20130059185 Whitacre et al. Mar 2013 A1
20130065122 Chiang et al. Mar 2013 A1
20130069001 Luo et al. Mar 2013 A1
20130071306 Camp et al. Mar 2013 A1
20130074485 McBride et al. Mar 2013 A1
20130074488 McBride et al. Mar 2013 A1
20130074940 McBride et al. Mar 2013 A1
20130074941 McBride et al. Mar 2013 A1
20130074949 McBride et al. Mar 2013 A1
20130084474 Mills Apr 2013 A1
20130119937 Arseneault et al. May 2013 A1
20130130085 Choi May 2013 A1
20130136980 Bartling May 2013 A1
20130143139 Tao et al. Jun 2013 A1
20130145764 McBride et al. Jun 2013 A1
20130166085 Cherian et al. Jun 2013 A1
20130183544 Yoshioka et al. Jul 2013 A1
20130295435 Vu Nov 2013 A1
20140000251 McBride et al. Jan 2014 A1
20140038012 Alimario et al. Feb 2014 A1
20140038038 Vallance et al. Feb 2014 A1
20140099522 Spatocco et al. Apr 2014 A1
20140113181 Bradwell et al. Apr 2014 A1
20140162090 Whitacre et al. Jun 2014 A1
20140220428 Zinck et al. Aug 2014 A1
20140248521 Chiang et al. Sep 2014 A1
20140272481 Chung et al. Sep 2014 A1
20140272508 Musetti Sep 2014 A1
20140349159 Bartling et al. Nov 2014 A1
20150004455 Bradwell et al. Jan 2015 A1
20150010792 Amendola et al. Jan 2015 A1
20150015210 Bradwell et al. Jan 2015 A1
20150037670 Tanaka et al. Feb 2015 A1
20150132627 Bradwell et al. May 2015 A1
20150132628 Bradwell et al. May 2015 A1
20150214579 Boysen et al. Jul 2015 A1
20150249273 Bradwell et al. Sep 2015 A1
20150249274 Bradwell et al. Sep 2015 A1
20150303525 Bradwell et al. Oct 2015 A1
20150318586 Rahmane et al. Nov 2015 A1
20150380713 Kimura et al. Dec 2015 A1
20160006090 Licht Jan 2016 A1
20160156068 Burke et al. Jun 2016 A1
20160172714 Ouchi et al. Jun 2016 A1
20160211555 Bradwell et al. Jul 2016 A9
20160254512 Yin et al. Sep 2016 A1
20160301038 Modest et al. Oct 2016 A1
20160336623 Nayar et al. Nov 2016 A1
20160344066 Sudworth et al. Nov 2016 A1
20160365612 Bradwell et al. Dec 2016 A1
20160372763 Lu et al. Dec 2016 A1
20170018811 Bradwell et al. Jan 2017 A1
20170104244 Bull et al. Apr 2017 A1
20170149095 Amendola et al. May 2017 A1
20170222273 Bradwell et al. Aug 2017 A1
20170248041 Lenk et al. Aug 2017 A1
20170263951 Kanno et al. Sep 2017 A1
20170338451 Bradwell et al. Nov 2017 A9
20180034110 Sudworth et al. Feb 2018 A1
20180083274 Martin Mar 2018 A1
20180090726 Thompson et al. Mar 2018 A1
20180097259 Bradwell et al. Apr 2018 A1
20180159179 Bradwell Jun 2018 A1
Foreign Referenced Citations (108)
Number Date Country
2014229643 Sep 2015 AU
2016225020 Sep 2017 AU
2767920 Jan 2011 CA
2811218 Mar 2012 CA
2887201 Apr 2014 CA
703320 Dec 2011 CH
1429417 Jul 2003 CN
101436780 May 2009 CN
101828285 Sep 2010 CN
101942676 Jan 2011 CN
201809448 Apr 2011 CN
201908137 Jul 2011 CN
102181883 Sep 2011 CN
102498589 Jun 2012 CN
102646808 Aug 2012 CN
103001239 Mar 2013 CN
105190984 Dec 2015 CN
105659415 Jun 2016 CN
3239964 May 1984 DE
19618609 Nov 1997 DE
0078404 May 1983 EP
0078404 Oct 1985 EP
0327959 Aug 1989 EP
0343333 Nov 1989 EP
1096593 May 2001 EP
1469536 Oct 2004 EP
1548912 Jun 2005 EP
2408083 Jan 2012 EP
2416464 Feb 2012 EP
2499507 Sep 2012 EP
2709188 Mar 2014 EP
2062939 May 1981 GB
S4933815 Sep 1974 JP
S 55-053877 Apr 1980 JP
S61114664 Jun 1986 JP
H06223872 Aug 1994 JP
H 06310171 Nov 1994 JP
H1012270 Jan 1998 JP
H117923 Jan 1999 JP
2001115369 Apr 2001 JP
2001243994 Sep 2001 JP
3355377 Dec 2002 JP
2007-157373 Jun 2007 JP
2010535942 Nov 2010 JP
2011508379 Mar 2011 JP
2012124009 Jun 2012 JP
2012-226866 Nov 2012 JP
2012533865 Dec 2012 JP
2013537361 Sep 2013 JP
2014154337 Aug 2014 JP
2016510936 Apr 2016 JP
2016535392 Nov 2016 JP
10-2012-0059106 Jun 2012 KR
2013111960 Oct 2014 RU
188400 Apr 2013 SG
WO-9965642 Dec 1999 WO
WO 0005774 Feb 2000 WO
WO 2008045996 Apr 2008 WO
WO 2008105811 Sep 2008 WO
WO-2008105807 Sep 2008 WO
WO 2008045996 Oct 2008 WO
WO 2008105811 Dec 2008 WO
WO 2009046533 Apr 2009 WO
WO 2009151639 Dec 2009 WO
WO 2010130583 Nov 2010 WO
WO 2011011056 Jan 2011 WO
WO 2011014242 Feb 2011 WO
WO 2011014243 Feb 2011 WO
WO 2011022390 Feb 2011 WO
WO 2011025574 Mar 2011 WO
WO 2011047067 Apr 2011 WO
WO 2011022390 May 2011 WO
WO 2011050924 May 2011 WO
WO 2011079548 Jul 2011 WO
WO 2011082659 Jul 2011 WO
WO 2011047067 Aug 2011 WO
WO 2011100686 Aug 2011 WO
WO-2011116236 Sep 2011 WO
WO 2011148347 Dec 2011 WO
WO 2011153312 Dec 2011 WO
WO 2012003649 Jan 2012 WO
WO 2012009145 Jan 2012 WO
WO 2012033692 Mar 2012 WO
WO 2012040176 Mar 2012 WO
WO 2011153312 Apr 2012 WO
WO 2012009145 Apr 2012 WO
WO 2012051790 Apr 2012 WO
WO 2012033692 Jun 2012 WO
WO 2012129827 Oct 2012 WO
WO 2012145314 Oct 2012 WO
WO-2012138576 Oct 2012 WO
WO 2012158751 Nov 2012 WO
WO 2012158781 Nov 2012 WO
WO 2013025608 Feb 2013 WO
WO 2013032667 Mar 2013 WO
WO 2013048704 Apr 2013 WO
WO 2013052494 Apr 2013 WO
WO 2014055873 Apr 2014 WO
WO 2014062702 Apr 2014 WO
WO 2014062706 Apr 2014 WO
WO 2014140792 Sep 2014 WO
WO 2014190318 Nov 2014 WO
WO 2015042295 Mar 2015 WO
WO 2015058010 Apr 2015 WO
WO 2015058165 Apr 2015 WO
WO 2015063588 May 2015 WO
WO 2015066359 May 2015 WO
WO-2016138499 Sep 2016 WO
Non-Patent Literature Citations (217)
Entry
U.S. Appl. No. 14/178,806, filed Feb. 12, 2014, Bradwell et al.
U.S. Appl. No. 14/286,369, filed May 23, 2014, Bradwell et al.
U.S. Appl. No. 14/536,549, filed Nov. 7, 2014, Bradwell et al.
U.S. Appl. No. 14/536,563, filed Nov. 7, 2014, Bradwell et al.
Biswas, et al. Towards Implementation of Smart Grid: An Updated Review on Electrical Energy Storage Systems. Smart Grid and Renewable Energy. 2013; 4:122-132. Published online Feb. 2013.
Bradwell, et al. Magnesium-antimony liquid metal battery for stationary energy storage. J Am Chem Soc. Feb. 1, 2012;134(4):1895-7. doi: 10.1021/ja209759s. Published on web Jan. 6, 2012.
Bradwell, et al. Recycling ZnTe, CdTe, and Other Compound Semiconductors by Ambipolar Electrolysis. J. Am. Chem. Soc., 2011, 133, 19971-19975. Published Oct. 28, 2011.
Bradwell, et al. Supporting Information: Recycling ZnTe, CdTe, and other compound semiconductors by ambipolar electrolysis. J. Am. Chem. Soc., 2011, 133, S1-S8. Published Oct. 28, 2011.
Bradwell, et al. Supporting Material: Magnesium-antimony liquid metal battery for stationary energy storage. J Am Chem Soc. Feb. 1, 2012;134(4):S1-S11. doi: 10.1021/ja209759s. Published on web Jan. 6, 2012.
Bradwell. Liquid metal batteries: ambipolar electrolysis and alkaline earth electroalloying cells. Thesis. Massachusetts Institute of Technology. Dept. of Materials Science and Engineering. 2011.
Bradwell. Technical and economic feasibility of a high-temperature self-assembling battery. Thesis. Department of Material Science and Engineering. MIT. 2006.
Cairns, et al. Galvanic Cells with Fused-Salt Electrolytes. AEC Research and Development. 220 pages, Nov. 1967.
Cairns, et al. High Temperature Batteries Research in high-temperature electrochemistry reveals compact, powerful energy-storage cells. Science. Jun. 20, 1969; 164(3886):1347-1355.
Chuang. Floating capacitor active charge balancing for PHEV application. Thesis. Ohio State University. 2010.
Crowley, B. New battery could be solar power's BFF video. http://money.cnn.com/video/technology/2012/08/16/bsg-liquid-metal-battery- energy.cnnmoney. CNN Money, 2012. Accessed Jun. 29, 2015.
Donald Sadoway: The Colbert Report video. http://thecolbertreport.cc.com/videos/8uddyg/donald-sadoway. The Colbert Report, Oct. 22, 2012. Accessed Jun. 29, 2015.
Donald Sadoway: The missing link to renewable energy Youtube Video. https://www.youtube.com/watch?v=Sddb0Khx0yA. TED, Mar. 2012. Accessed Jun. 29, 2015.
Electroville: Grid-Scale Batteries. MIT Electroville: High Amperage Energy Storage Device—Energy for the Neighborhood. http://arpa-e.energy.gov/?q=slick-sheet-project/electroville-grid-scale-batteries. Accessed Jul. 2, 2015.
Electroville: High-Amperage Energy Storage Device—Energy Storage for the Neighborhood Project. U.S. Department of Energy Categorical Exclusion Determination Form. http://arpa-e.energy.gov/sites/default/files/25A1089%20MIT%20-%20Electroville.pdf. Accessed Jul. 2, 2015.
Energy 2064 with Professor Donald R. Sadoway Youtube Video. https://www.youtube.com/watch?v=0iwG32R2R5o. Alger, Oct. 7, 2014. Accessed Jun. 29, 2015.
GE Energy Storage Durathon Battery Durathon E620 Battery Module Technical Specifications. Available at http://www.geenergystorage.com/images/ge/PDF/DurathonGridE620ModuleSpecSheet.pdf. 2012, Accessed on Oct. 18, 2012.
Hall-heroult cell. Wikimedia Commons. Accessed Nov. 10, 2014. http://commons.wikimedia.org/wiki/File:Hall-heroult-kk-2008-12-31.png. Dec. 30, 2008.
Intermetallic—Wikipedia Website. https://en.wikipedia.org/wiki/Intermetallic. Accessed Jul. 2, 2015.
International preliminary report on patentability and written opinion dated Apr. 7, 2015 for PCT Application No. US2013/063472.
International preliminary report on patentability and written opinion dated Apr. 21, 2015 for PCT Application No. US2013/065086.
International preliminary report on patentability and written opinion dated Apr. 21, 2015 for PCT Application No. US2013/065092.
International preliminary report on patentability and written opinion dated Jan. 24, 2012 for PCT Application No. US2010/002035.
International preliminary report on patentability and written opinion dated Mar. 26, 2013 for PCT Application No. US2011/052316.
International preliminary report on patentability and written opinion dated Feb. 17, 2009 for PCT Application No. US2007/018168.
International search report and written opnion dated Jun. 11, 2015 for PCT Application No. IB2014/002608.
Jarret, et al. Advances in the Smelting of aluminum. Metallurgical Treatises, pp. 137-157, 1981.
Kane, et al. Electrochemical Determination of the Theimodynamic Properties of Lithium-Antimony Alloys. Journal of the Electrochemical Society, 162 (3) A421-A425 (2015). Published Dec. 31, 2014.
Kelley, et al. Mixing in a liquid metal electrode. Physics of Fluids 26, 2014, 057102, pp. 1-12. Published online May 20, 2014.
Kim, et al. Calcium-bismuth electrodes for large-scale energy storage (liquid metal batteries). Journal of Power Sources, vol. 241, 2013, pp. 239-248. Available online Apr. 19, 2013.
Kim, et al. Liquid Metal Batteries: Past, Present, and Future. Chemical Reviews, vol. 113, No. 3, Mar. 13, 2013, pp. 2075-2099. Published on web Nov. 27, 2012.
Lalau, et al. Sodium-bismuth-lead low temperature liquid metal battery. Journal for Electrochemistry and Plating Technology, Jun. 2015, pp. 1-7.
Liquid Metal Battery Research Company website. http://www.lmbrc.com/. 2015. Accessed Jul. 7, 2015.
Liquid-metal batteries get boost from molten lead. Nature news website. Sep. 21, 2014. Accessed Dec. 9, 2014. http://www.nature.com/news/liquid-metal-batteries-get-boost-from-molten-lead-1.15967.
Magnuski, H. Innovations in Energy Storage—Professor Sadoway Video. https://vimeo.com/20906061. MIT Club of Northern California, Mar. 8, 2011. Accessed Jun. 29, 2015.
MIT Electroville—Liquid Metal Battery wesite. http://www.ct-si.org/events/EnergyInnovation/showcase/popt.html?id=198. 2011. Accessed Jul. 2, 2015.
Molten metal batteries aimed at the grid. BBC News website. Sep. 21, 2014. Accessed Dec. 9, 2014. http://www.bbc.com/news/science-environment-29284934.
NAS Sodium Sulfur Battery Energy Storage System website, accessed Jul. 13, 2015. https://www.ngk.co.jp/nas/specs/#topto_specs.
Ning, et al. Self-healing Li—Bi liquid metal battery for grid-scale energy storage. Journal of Power Sourches 275 (2015) 370-376. Available online Oct. 29, 2014.
Nuvation BMS a Scalable and highly configurable battery management system for grid energy storage systems, 2014. http://nuvation.wpengine.netdna-cdn.com/img/nuvation-bms-web/downloads/NuvationBMS_Grid-Energy_20140922.pdf. Accessed Feb. 4, 2015.
Nuvation BMS Battery Management Systems. http://www.nuvation.com/battery-management-system. Accessed Feb. 4, 2015.
Nuvation Engineering Electronic Product Design Newsletter dated Jul. 9, 2014. http://us4.campaign-archive1.com/?u=d41c6a8dd772177f8c2976a94&id=d288872315&e=724575b634. Accessed Feb. 4, 2015.
Nuvation Engineering Electronic Product Design Newsletter dated Sep. 9, 2014. http://us4.campaign-archive1.com/?u=d41c6a8dd772177f8c2976a94&id=610713e05f&e=e9700170fc. Accessed Feb. 4, 2015.
Ouchi, et al. Calcium-Antimony Alloys as Electrodes for Liquid Metal Batteries. Journal of the Electrochemical Society. 2014; 161(12):A1898-A1904. Published Sep. 9, 2014.
Pflanz, K. A Liquid Layer Solution for the Grid. http://energy.gov/articles/liquid-layer-solution-grid. Sep. 15, 2011. Accessed Jul. 2, 2015.
Pongsaksawad, et al. Phase-Field Modeling of Transport-Limited Electrolysis in Solid and Liquid States. Journal of the Electrochemical Society, 154 (6) pp. F122-F133, 2007. Available electronically Apr. 18, 2007.
Sadoway, et al. Block and graft copolymer electrolytes for high-performance, solid-state, lithium batteries. Journal of Power Sources, Elsevier SA, CH, vol. 129, No. 1, Apr. 15, 2004, pp. 1-3. Available online Jan. 14, 2004.
Sadoway, et al. Innovation in Energy Storage: What I Learned in 3.091 was All I Needed to Know video. http://video.mit.edu/watch/innovation-in-energy-storage-what-i-learned-in-3091-was-all-i-needed-to-know-9601/. MIT Technology Day 2010, Jun. 5, 2010. (Originally posted at http://mitworld.mit.edu/video/800. Archived at http://archive.is/http://mitworld.mit.edu/video/800.) Accessed Jun. 29, 2015.
Shimotake, et al. Bimetallic Galvanic Cells With Fused-Salt Electrolytes. Advances in Energy Conversion Engineering. pp. 951-962. 1967 Intersociety Energy Conversion Engineering Conference. American Society of Mechanical Engineers, 1967.
Spatocco, et al. Cost-based discovery for engineering solutions. pp. 1-43. Adv. In Electrochemical Science and Technology (vol. XV), Feb. 9, 2015.
Staller, A. The Real Science of an Alkali Metal Explosion. The Electrochemical Society, Jan. 28, 2015. Accessed Apr. 20, 2015. http://www.ecsblog.org/uncategorized/the-real-science-behind-an-alkali-metal-explosion/.
Villar, et al. Assessment of high-temperature self-assembling battery implementation based on the aluminum smelting process. Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, Thesis, 2010. http://hdl.handle.net/1721.1/62677.
Wang, et al. Lithium-antimony-lead liquid metal battery for grid-level energy storage Nature. Oct. 16, 2014;514(7522):348-50. doi: 10.1038/nature13700. Epub Sep. 21, 2014.
Wesoff, E. Video: MIT's Don Sadoway and Energy Storage on the Colbert Report. http://www.greentechmedia.com/articles/read/Video-MITs-Don-Sadoway-and-Energy-Storage-on-the-Colbert-Report. Oct. 24, 2012. Accessed Jul. 2, 2015.
U.S. Appl. No. 14/688,179, filed Apr. 16, 2015, Bradwell et al.
U.S. Appl. No. 14/688,214, filed Apr. 16, 2015, Bradwell et al.
Advisory Action Before Filing of Appeal Brief dated May 10, 2012 for U.S. Appl. No. 12/839,130.
Advisory Action Before Filing of Appeal Brief dated Jun. 8, 2012 for U.S. Appl. No. 12/839,130.
Agruss. The Thermally Regenarative Liquid-Metal Cell, J. Electrochem. Soc. Nov. 1963; 110(11):1097-1103.
Atthey. A Mathematical Model for Fluid Flow in a Weld Pool at High Currents. J. Fluid Mech. 1980; 98(4):787-801.
Biswas, et al. Towards Implementation of Smart Grid: An Updated Review on Electrical Energy Storage Systems. Smart Grid and Renewable Energy. 2013; 4:122-132.
Bradwell, et al. Magnesium-antimony liquid metal battery for stationary energy storage. J Am Chem Soc. Feb. 1, 2012;134(4):1895-7. doi: 10.1021/ja209759s. Epub Jan. 18, 2012.
Bradwell. Liquid metal batteries: ambipolar electrolysis and alkaline earth electroalloying cells. Massachusetts Institute of Technology. Dept. of Materials Science and Engineering. 2011.
Bradwell. Technical and economic feasibility of a high-temperature self-assembling battery. Department of Material Science and Engineering. MIT. Thesis final copy. Aug. 2006.
Cairns, et al. Galvanic Cells with Fused-Salt Electrolytes. AEC Research and Development. 44 pages, Nov. 1967.
Cairns, et al. High Temperature Batteries Research in high-temperature electrochemistry reveals compact, powerful energy-storage cells. Science. Jun. 1969; 164(3886): 1347-1355.
Chuang. Floating capacitor active charge balancing for PHEV application. Master Thesis. Ohio State University. 2010.
Cubicciotti, et al. Metal-Salt Interactions at High Temperatures: The Solubilities of Some alkaline Earth Metals in their Halides. J. Am. Chem. Soc. 1949; 71(6):21492153.
Dworkin, et al. The Electrical Conductivity of Solutions of Metals in their Molten Halides. VIII. alkaline Earth Metal Systems. J. Phys. Chem. Jul. 1966; 70(7):2384.
European search report and search opinion dated Feb. 12, 2014 for EP Application No. 13196841.4.
Gay, et al. Lithium/Chalcogen Secondary Cells for Components in Electric Vehicular-Propulsion Generating Systems. Argonne National Laboratory, Argonne, Illinois, ANL-7863, 62 pages, Jan. 1972.
GE Energy Storage Durathon Battery Durathon E620 Battery Module Technical Specifications. Avallable at http://www.geenergystorage.com/images/ge/PDF/DurathonGridE620ModuleSpecSheet.pdf. Accessed on Oct. 18, 2012.
GE Energy Storage Durathon DC System Technical Specifications—MWh Series, 2014. Accessed Apr. 7, 2015. https://renewables.gepower.com/content/dam/gepower-enewables/global/en_US/documents/Durathon_DCMWh_Spec_Sheet_GEA-988123002A.pdf.
Hall-heroult cell. Wikimedia Commons. Dec. 31, 2008. Accessed Nov. 10, 2014. http://commons.wikimedia.org/wiki/File:Hall-heroult-kk-2008-12-31.png.
International preliminary report on patentability and written opinion dated Apr. 16, 2015 for PCT Application No. US2013/063472.
International preliminary report on patentability and written opinion dated Jan. 24, 2014 for PCT Application No. US2013/065086.
International preliminary report on patentability and written opinion dated Dec. 26, 2013 for PCT Application No. US2013/065092.
International preliminary report on patentability and written opinion dated Feb. 7, 2011 for PCT Application No. US2010/002035.
International preliminary report on patentability and written opinion dated Dec. 29, 2011 for PCT Application No. US2011/052316.
International preliminary report on patentability and written opinion dated Sep. 18, 2008 for PCT Application No. US2007/018168.
International search report and written opinion dated Jan. 22, 2015 for PCT Application No. US2014/061266.
International search report and written opinion dated Jan. 23, 2015 for PCT Application No. PCT/US2014/056367.
International search report and written opinion dated Jan. 24, 2014 for PCT/US2013/065086.
International search report and written opinion dated Jan. 27, 2014 for PCT Application No. US2013/063472.
International search report and written opinion dated Jan. 29, 2015 for PCT Application No. US2014/060979.
International search report and written opinion dated Feb. 7, 2011 for PCT/US2010/002035.
International search report and written opinion dated Sep. 18, 2008 for PCT/US2007/018168.
International search report and written opinion dated Oct. 20, 2014 for PCT Application No. US2014/039439.
International search report and written opinion dated Dec. 26, 2013 for PCT Application No. US2013/065092.
International search report and written opinion dated Dec. 29, 2011 for PCT/US2011/052316.
International search report and written opnion dated Feb. 13, 2015 for PCT Application No. US2014/063222.
International search report dated Oct. 15, 2014 for PCT Application No. IB2014/000617.
Javadekar, et al. Energy Storage in Electrochemical Cells with Molten Sb Electrodes. Journal of the Electrochemical Society, 159 (4) A386-A389 (2012); Jan. 24, 2012 http://repository.upenn.edu/cgi/viewcontent.cgi?article=1170&context=cbe_papers.
Jungblut, et al. Diffusion of lithium in highly oriented pyrolytic graphite at low concentrations and high temperatures. Phys Rev B Condens Matter. Dec. 1, 1989;40(16):10810-10815.
Kane, et al. Electrochemical Determination of the Thermodynamic Properties of Lithium-Antimony Alloys. Journal of the Electrochemical Society, 162 (3) A421-A425 (2015).
Kelley, et al. Mixing in a liquid metal electrode. Physics of Fluids 26, Jan. 2014, 057102, pp. 1-12.
Kim, et al. Calcium-bismuth electrodes for large-scale energy storage (liquid metal batteries). Journal of Power Sources, vol. 241, Apr. 2013, pp. 239-248.
Kim, et al. Liquid Metal Batteries: Past, Present, and Future. Chemical Reviews, vol. 113, No. 3, Mar. 13, 2013, pp. 2075-2099.
Liquid-metal batteries get boost from molten lead. Nature news website. Accessed Dec. 9, 2014. http://www.nature.com/news/liquid-metal-batteries-get-boost-from-molten-lead-1.15967.
Merriam-Webster's Medical Dictionary Website. http://merriam-webster.com/medical/room%20temperature. Apr. 2009.
Molten metal batteries aimed at the grid. BBC News website. Accessed Dec. 9, 2014. http://www.bbc.com/news/science-environment-29284934.
NAS Sodium Sulfur Battery Energy Storage System website, accessed Apr. 7, 2015. https://www.ngk.co.jp/nas/spees/#topto_specs.
Ning, et al. Self-healing Li—Bi liquid metal battery for grid-scale energy storage. Journal of Power Sourches 275 (2015) 370-376.
Notice of allowance dated Jan. 6, 2015 for U.S. Appl. No. 13/237,215.
Notice of allowance dated Mar. 12, 2015 for U.S. Appl. No. 12/839,130.
Notice of allowance dated Apr. 6, 2015 for U.S. Appl. No. 13/801,333.
Notice of allowance dated Apr. 20, 2012 for U.S. Appl. No. 12/505,937.
Notice of allowance dated Apr. 22, 2014 for U.S. Appl. No. 12/839,130.
Notice of allowance dated Apr. 30, 2015 for U.S. Appl. No. 13/801,333.
Notice of allowance dated Jul. 13, 2012 for U.S. Appl. No. 11/839,413.
Notice of allowance dated Aug. 2, 2012 for U.S. Appl. No. 12/505,937.
Office action dated Jan. 5, 2012 for U.S. Appl. No. 12/839,130.
Office action dated Jan. 10, 2014 for U.S. Appl. No. 12/839,130.
Office action dated Mar. 14, 2014 for U.S. Appl. No. 13/237,215.
Office action dated Mar. 16, 2012 for U.S. Appl. No. 12/839,130.
Office action dated May 13, 2011 for U.S. Appl. No. 11/839,413.
Office action dated Aug. 21, 2014 for U.S. Appl. No. 12/839,130.
Office action dated Sep. 3, 2014 for U.S. Appl. No. 13/801,333.
Office action dated Oct. 4, 2011 for U.S. Appl. No. 11/839,413.
Office action dated Dec. 5, 2014 for U.S. Appl. No. 12/839,130.
Office action dated Dec. 11, 2012 for U.S. Appl. No. 13/588,741.
Ouchi, et al. Calcium-Antimony Alloys as Electrodes for Liquid Metal Batteries. Journal of the Electrochemical Society. 2014; 161(12):A1898-A1904.
Pongsaksawad, et al. Phase-Field Modeling of Transport-Limited Electrolysis in Solid and Liquid States. Journal of the Electrochemical Society, 154 (6) pp. F122-F133, 2007.
Powell, et al. Modeling electrochemistry in metallurgical processes. Chemistry and Materials Science; JOM Journal of the Minerals, Metals and Materials Society vol. 59, No. 5 (2007), 35-43, DOI: 10.1007/s11837-007-0063-y http://lyre.mit.edu/˜powell/papers/jom-0705-35-43.pdf.
Response After Final Rejection dated Apr. 27, 2012 for U.S. Appl. No. 12/839,130.
Sadoway, et al. Block and graft copolymer electrolytes for high-performance, solid-state, lithium batteries. Journal of Power Sources, Elsevier SA, CH, vol. 129, No. 1, Apr. 15, 2004, pp. 1-3.
Shimotake, et al. Bimetallic Galvanic Cells With Fused-Salt Electrolytes. Argonne National Laboratory, Argonne, Illinois, pp. 951-962.
Shimotake, et al. Secondary Cells with Lithium Anodes and Immobilized Fused-Salt Electrolytes. I & EC ProcessDesign and Development, vol. 8, No. 1, Jan. 1969, pp. 51-56.
Spatocco, et al. Cost-based discovery for engineering solutions. pp. 1-43.
Supplemental Amendment After Final Rejection dated May 15, 2012 for U.S. Appl. No. 12/839,130.
The Colbert Report. Donald Sadoway interview. Oct. 22, 2012. http://www.colbertnation.com/full-episodes/mon-october-22/2012-donald-sadoway.
Villar, et al. Assessment of high-temperature self-assembling battery implementation based on the aluminum smelting process. Massachusetts Institute of Technology. Dept. of Materials Science and Engineering. Issue Date: 2010 http://hdl.handle.net/1721.1/62677.
Weaver, et al. The Sodium1Tin Liquid-Metal Cell. J. Electrochem. Soc., 109 (8), 653-657 (Aug. 1962).
Yu, et al. Determination of the Lithium Ion Diffusion Coefficient in Graphite. J. Electrochem. Soc. 1999 vol. 146, issue 1, 8-14.
Co-pending U.S. Appl. No. 15/136,337, filed Apr. 22, 2016.
Co-pending U.S. Appl. No. 15/289,857, filed Oct. 10, 2016.
European supplemental search report and opinion dated Mar. 16, 2017 for EP Application No. 14853610.
Fujiwara, et al. New molten salt systems for high temperature molten salt batteries: Ternary and quaternary molten salt systems based on LiF—LiCl, LiF—LiBr, and LiCl—LiBr. Journal of Power Sources. Apr. 15, 2011; 196(8):4012-4018.
International search report and written opinion dated Jun. 1, 2016 for PCT/US2016/019970.
International search report and written opinion dated Sep. 7, 2016 for PCT/US2016/021048.
Notice of allowance dated Apr. 11, 2017 for U.S. Appl. No. 14/688,214.
Notice of allowance dated Apr. 13, 2017 for U.S. Appl. No. 14/688,179.
Notice of allowance dated Aug. 22, 2016 for U.S. Appl. No. 14/536,549.
Notice of allowance dated Oct. 7, 2016 for U.S. Appl. No. 14/178,806.
Notice of allowance dated Mar. 22, 2017 for U.S. Appl. No. 14/536,563.
Office action dated May 1, 2017 for U.S. Appl. No. 14/678,602.
Office action dated Nov. 18, 2016 for U.S. Appl. No. 14/688,179.
Office action dated Nov. 22, 2016 for U.S. Appl. No. 14/688,214.
Shannon, Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica Section A: Crystal Physics, Diffraction, Theoretical and General Crystallography. Mar. 9, 1976, A32:751-767.
European search report and search opinion dated May 6, 2016 for EP Application No. 13847926.
European search report and search opinion dated May 13, 2016 for EP Application No. 13846301.
International preliminary report on patentability dated Apr. 28, 2016 for PCT Application No. PCT/US2014/060979.
International preliminary report on patentability dated Apr. 28, 2016 for PCT Application No. PCT/US2014/061266.
International preliminary report on patentability dated May 12, 2016 for PCT Application No. PCT/US2014/0063222.
Office action dated Jun. 7, 2016 for U.S. Appl. No. 14/045,967.
Cerablak™ technology. Atfi Surface Science Solutions. http://www.atfinet.com/index.php/technology. Accessed Feb. 24, 2016.
Co-pending U.S. Appl. No. 15/063,842, filed Mar. 8, 2016.
Co-pending U.S. Appl. No. 15/130,129, filed Apr. 15, 2016.
Co-pending U.S. Appl. No. 15/130,292, filed Apr. 15, 2016.
Co-pending U.S. Appl. No. 15/140,434, filed Apr. 27, 2016.
International preliminary report on patentability dated Mar. 31, 2016 for PCT Application No. PCT/US2014/056367.
Notice of allowance dated Mar. 8, 2016 for U.S. Appl. No. 13/801,333.
Allanore, A. Features and Challenges of Molten Oxide Electrolytes for Metal Extraction. Journal of the Electrochemical Society, 162 (1): E13-E22 (2015). Published Nov. 25, 2014.
Allanore, et al. A new anode material for oxygen evolution in molten oxide electrolysis. Nature, vol. 497, May 16, 2013, pp. 353-356 and Online Methods Section. Published online May 8, 2013.
International preliminary report on patentability and written opinion dated Sep. 15, 2015 for PCT Application No. IB2014/000617.
International preliminary report on patentability and written opinion dated Nov. 24, 2015 for PCT Application No. US2014/039439.
Kim, et al. Electrolysis of Molten Iron Oxide with an Iridium Anode: The Role of Electrolyte Basicity. Journal of the Electrochemical Society, 158 (10) E101-E105 (2011). Published Aug. 5, 2011.
Kipouros, et al. Toward new technologies for the production of Lithium. JOM, May 1998, pp. 24-26.
Notice of allowance dated Jul. 31, 2015 for U.S. Appl. No. 13/801,333.
Notice of allowance dated Sep. 18, 2015 for U.S. Appl. No. 13/801,333.
Notice of allowance dated Dec. 11, 2015 for U.S. Appl. No. 13/801,333.
Nuvation BMS—Grid Energy Storage. Battery Management System for Grid Energy Storage. Accessed Nov. 11, 2015. http://www.nuvation.com/battery-management-system/bms-for-grid-energy-storage-platforms.
Nuvation BMS. Grid Battery Controller Battery Management Solution for Multi-Stack Grid-Scale Energy Storage Systems. 2015.
Office action—Requirement for Restriction Election dated Aug. 13, 2015 for U.S. Appl. No. 14/045,967.
Office action dated Feb. 5, 2016 for U.S. Appl. No. 14/536,549.
Office action dated Nov. 5, 2015 for U.S. Appl. No. 14/178,806.
Office action dated Nov. 9, 2015 for U.S. Appl. No. 14/286,369.
Office action dated Nov. 24, 2015 for U.S. Appl. No. 14/045,967.
Spatocco, et al. Low-Temperature Molten Salt Electrolytes for Membrane-Free Sodium Metal Batteries. Published Oct. 20, 2015, available at http://jes.ecsdl.org/content/162/14/A2729.full.pdf+html.
Sadoway, D. The Electrochemical Processing of Refractory Metals. JOM, Jul. 1991, pp. 15-19.
Sadoway, Donald R. A Technical Feasibility Study of Steelmaking by Molten Oxide Electrolysis Presentation. Presented at 9th AISI/DOE TRP Industry Briefing Session, Oct. 10, 2007, Salt Lake City. http://steeltrp.com/Briefing07slides/09-TRP9956_MIT-071BS.pdf.
Sadoway, Donald R. Electrochemical Pathways Towards Carbon-Free Metals Production Presentation. Presented at GCEP Carbon Management in Manufacturing Industries workshop, Apr. 15-16, 2008, Stanford University. http://gcep.stanford.edu/pdfs/2RK4ZjKBF2f71uM4uriP9g/SadowayGCEP_reduced.pdf.
Sadoway, Donald R. New opportunities for metals extraction and waste treatment by electrochemical processing in molten salts. J. Mater. Res., vol. 10, No. 3, Mar. 1995, pp. 487-492.
Sadoway, Donald R. New opportunities for waste treatment by electrochemical processing in molten salts. Metals and Materials Waste Reduction, Recovery and Remediation, Edited by K.C. Liddell, R.G. Bautista and R.J. Orth, The Minerals, Metals & Materials Society, 1994, pp. 73-76.
Salois, Gretchen. Pursuing Metal Purity. Aug. 26, 2013, Modern Metals Website. Accessed Sep. 18, 2015. http://www.modernmetals.com/item/11618-pursuing-metal-purity.html.
Sodium Sulfur-Battery Definition; Wikipedia website. Accessed Sep. 3, 2015. https://en.wikipedia.org/wiki/Sodium%E2%80%93sulfur_battery.
Written opinion of the International Search Authority dated Oct. 15, 2014 for PCT Application No. IB2014/000617.
Xue, et al. Ionic Liquid Redox Catholyte for high Energy Efficiency, Low-cost Energy Storage. Advanced Energy Materials 2015, vol. 5, Issue 12,1500271, Published online Apr. 17, 2015.
Li, et al. High Performance Liquid Metal Battery with Environmentally Friendly Antimony-Tin Positive Electrode. ACS Appl Mater Interfaces. May 25, 2016;8(20):12830-5. doi: 10.1021/acsami.6b02576. Epub May 5, 2016. With supporting information.
Li, et al. Liquid Metal Electrodes for Energy Storage Batteries. Advanced Energy Materials (2016) 6:1600483-1-19. DOI: 10.1002/aenm.201600483. Published May 31, 2016.
Notice of allowance dated Jul. 5, 2016 for U.S. Appl. No. 14/178,806.
Notice of allowance dated Jul. 25, 2016 for U.S. Appl. No. 14/286,369.
Office action dated Jun. 30, 2016 for U.S. Appl. No. 14/536,563.
Ouchi, et al. Calcium-based multi-element chemistry for grid-scale electrochemical energy storage. Nat Commun. Mar. 22, 2016;7:10999. doi: 10.1038/ncomms10999. With supplementary materials.
Co-pending U.S. Appl. No. 15/690,863, filed Aug. 30, 2017.
“Notice of allowance dated May 11, 2017 for U.S. Appl. No. 14/688,214”.
“Notice of allowance dated Jul. 17, 2017 for U.S. Appl. No. 14/688,214”.
“Notice of allowance dated Jul. 28, 2017 for U.S. Appl. No. 14/688,214”.
“Notice of allowance dated Sep. 11, 2017 for U.S. Appl. No. 15/289,857”.
“Notice of allowance dated Sep. 28, 2017 for U.S. Appl. No. 14/688,214”.
Notice of allowance dated Oct. 4, 2017 for U.S. Appl. No. 15/136,337.
Notice of allowance dated Oct. 19, 2017 for U.S. Appl. No. 14/688,214.
McAlister, A. J. The Al—Li (Aluminum-Lithium) System. Bulletin of Alloy Phase Diagrams, vol. 3, No. 2, 1982, pp. 177-178. doi: 10.1007/BF02892377.
Zhang; et al. Pyrite FeS2 as an efficient adsorbent of lithium polysulfide for improved lithium-sulfur batteries. Journal of Materials Chemistry A, vol. 4, Feb. 23, 2016, pp. 4371-4374. doi: 10.1039/C6TA01214K. With supporting information.
Notice of allowance dated Jan. 11, 2018 for U.S. Appl. No. 15/136,337.
Notice of allowance dated Nov. 17, 2017 for U.S. Appl. No. 15/136,337.
Notice of allowance dated Dec. 20, 2017 for U.S. Appl. No. 15/136,337.
Notice of allowance dated Aug. 31, 2018 for U.S. Appl. No. 15/057,732.
Office action dated Mar. 27, 2018 for U.S. Appl. No. 15/140,434.
Office action dated Apr. 18, 2018 for U.S. Appl. No. 14/975,587.
Office action dated Apr. 20, 2018 for U.S. Appl. No. 15/057,732.
Office action dated Jun. 25, 2018 for U.S. Appl. No. 15/063,842.
Office action dated Nov. 13, 2017 for U.S. Appl. No. 14/678,602.
Related Publications (1)
Number Date Country
20150325821 A1 Nov 2015 US
Provisional Applications (2)
Number Date Country
61714714 Oct 2012 US
61737068 Dec 2012 US
Continuations (1)
Number Date Country
Parent PCT/US2013/065086 Oct 2013 US
Child 14687838 US