Johnson lithium oxygen electrochemical engine

- JOHNSON IP HOLDING, LLC

A rechargeable lithium air battery is provided. The battery contains a ceramic separator forming an anode chamber, a molten lithium anode contained in the anode chamber, an air cathode, and a non-aqueous electrolyte. The cathode has a temperature gradient comprising a low temperature region and a high temperature region, and the temperature gradient provides a flow system for reaction product produced by the battery.

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Description
CROSS-REFERENCE TO RELATED APPLICATION

This application is a reissue of U.S. Pat. No. 10,218,044, issued on Feb. 26, 2019 from U.S. application Ser. No. 15/408,991, filed Jan. 18, 2017, which claims priority to U.S. Provisional Application No. 62/281,875, filed Jan. 22, 2016, the disclosure disclosures of which is are herein incorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

The need for high performance and reliable energy storage in the modern society is well documented. Lithium batteries represent a very attractive solution to these energy needs due to their superior energy density and high performance. However, available Li-ion storage materials limit the specific energy of conventional Li-ion batteries. While lithium has one of the highest specific capacities of any anode (3861 mAh/g), typical cathode materials such as MnO2, V2O5, LiCoO2 and (CF)n have specific capacities less than 200 mAh/g.

Recently, lithium/oxygen (Li/O2) or lithium air batteries have been suggested as a means for avoiding the limitations of today's lithium ion cells. In these batteries, lithium metal anodes are used to maximize anode capacity and the cathode capacity of Li air batteries is maximized by not storing the cathode active material in the battery. Instead, ambient O2 is reduced on a catalytic air electrode to form O22−, where it reacts with Li+ ions conducted from the anode. Aqueous lithium air batteries have been found to suffer from corrosion of the Li anode by water and suffer from less than optimum capacity because of the excess water required for effective operation.

Abraham and Jiang (J. Electrochem. Soc., 1996, 143 (1), 1-5) reported a non-aqueous Li/O2 battery with an open circuit voltage close to 3 V, an operating voltage of 2.0 to 2.8 V, good coulomb efficiency, and some re-chargeability, but with severe capacity fade, limiting the lifetime to only a few cycles. Further, in non-aqueous cells, the electrolyte has to wet the lithium oxygen reaction product in order for it to be electrolyzed during recharge. It has been found that the limited solubility of the reaction product in available organic electrolytes necessitates the use of excess amounts of electrolyte to adequately wet the extremely high surface area nanoscale discharge deposits produced in the cathode. Thus, the required excess electrolyte significantly decreases high energy density that would otherwise be available in lithium oxygen cells.

Operation of Li/O2 cells depends on the diffusion of oxygen into the air cathode. Oxygen absorption is a function of the electrolyte's Bunsen coefficient (α), electrolyte conductivity (σ), and viscosity (η). It is known that as the solvent's viscosity increases, there are decreases in lithium reaction capacity and Bunsen coefficients. Additionally, the electrolyte has an even more direct effect on overall cell capacity as the ability to dissolve reaction product is crucial. This problem has persisted in one form or another in known batteries.

Indeed, high rates of capacity fade remain a problem for non-aqueous rechargeable lithium air batteries and have represented a significant barrier to their commercialization. The high fade is attributed primarily to parasitic reactions occurring between the electrolyte and the mossy lithium powder and dendrites formed at the anode-electrolyte interface during cell recharge, as well as the passivation reactions between the electrolyte and the LiO2 radical which occurs as an intermediate step in reducing Li2O2 during recharge.

During recharge, lithium ions are conducted across the electrolyte separator with lithium being plated at the anode. The recharge process can be complicated by the formation of low density lithium dendrites and lithium powder as opposed to a dense lithium metal film. In addition to passivation reactions with the electrolyte, the mossy lithium formed during recharge can be oxidized in the presence of oxygen into mossy lithium oxide. A thick layer of lithium oxide and/or electrolyte passivation reaction product on the anode can increase the impedance of the cell and thereby lower performance. Formation of mossy lithium with cycling can also result in large amounts of lithium being disconnected within the cell and thereby being rendered ineffective.

Lithium dendrites can penetrate the separator, resulting in internal short circuits within the cell. Repeated cycling causes the electrolyte to break down, in addition to reducing the oxygen passivation material coated on the anode surface. This results in the formation of a layer composed of mossy lithium, lithium-oxide and lithium-electrolyte reaction products at the metal anode's surface which drives up cell impedance and consumes the electrolyte, bringing about cell dry out.

Attempts to use active (non lithium metal) anodes to eliminate dendritic lithium plating have not been successful because of the similarities in the structure of the anode and cathode. In such lithium air “ion” batteries, both the anode and cathode contain carbon or another electronic conductor as a medium for providing electronic continuity. Carbon black in the cathode provides electronic continuity and reaction sites for lithium oxide formation. To form an active anode, graphitic carbon is included in the anode for intercalation of lithium and carbon black is included for electronic continuity. Unfortunately, the use of graphite and carbon black in the anode can also provide reaction sites for lithium oxide formation. At a reaction potential of approximately 3 volts relative to the low voltage of lithium intercalation into graphite, oxygen reactions would dominate in the anode as well as in the cathode. Applying existing lithium ion battery construction techniques to lithium oxygen cells would allow oxygen to diffuse throughout all elements of the cell structure. With lithium/oxygen reactions occurring in both the anode and cathode, creation of a voltage potential differential between the two is difficult. An equal oxidation reaction potential would exist within the two electrodes, resulting in no voltage.

As a solution to the problem of dendritic lithium plating and uncontrolled oxygen diffusion, known aqueous and non-aqueous lithium air batteries have included a barrier electrolyte separator, typically a ceramic material, to protect the lithium anode and provide a hard surface onto which lithium can be plated during recharge. However, formation of a reliable, cost effective barrier has been difficult. A lithium air cell employing a protective solid state lithium ion conductive barrier as a separator to protect lithium in a lithium air cell is described in U.S. Pat. No. 7,691,536 of Johnson. Thin film barriers have limited effectiveness in withstanding the mechanical stress associated with stripping and plating lithium at the anode or the swelling and contraction of the cathode during cycling. Moreover, thick lithium ion conductive ceramic plates, while offering excellent protective barrier properties, are extremely difficult to fabricate, add significant mass to the cell, and are rather expensive to make.

As it relates to the cathode, the dramatic decrease in cell capacity as the discharge rate is increased is attributed to the accumulation of reaction product in the cathode. At high discharge rate, oxygen entering the cathode at its surface does not have an opportunity to diffuse or otherwise transition to reaction sites deeper within the cathode. The discharge reactions occur at the cathode surface, resulting in the formation of a reaction product crust that seals the surface of the cathode and prevents additional oxygen from entering. Starved of oxygen, the discharge process cannot be sustained.

Another significant challenge with lithium air cells has been electrolyte stability within the cathode. The primary discharge product in lithium oxygen cells is Li2O2. During recharge, the resulting lithium oxygen radical, LiO2, an intermediate product which occurs while electrolyzing Li2O2, aggressively attacks and decomposes the electrolyte within the cathode, causing it to lose its effectiveness.

High temperature molten salts have been suggested as an alternative to organic electrolytes in non-aqueous lithium-air cells. U.S. Pat. No. 4,803,134 of Sammells describes a high lithium-oxygen secondary cell in which a ceramic oxygen ion conductor is employed. The cell includes a lithium-containing negative electrode in contact with a lithium ion conducting molten salt electrolyte, LiF—LiCl—Li2O, separated from the positive electrode by the oxygen ion conducting solid electrolyte. The ion conductivity limitations of available solid oxide electrolytes require that such a cell be operated in the 700° C. range or higher in order to have reasonable charge/discharge cycle rates. The geometry of the cell is such that the discharge reaction product accumulates within the molten salt between the anode and the solid oxide electrolyte. The required space is an additional source of impedance within the cell.

TABLE 1 Physical properties of Molten Nitrate Electrolytes Melt Temp κ (S/cm) System Mol % ° C. @570K at Mol % LiNO3—KNO3 42-58 124 0.687 50.12 mol % LiNO3 LiNO3—RbNO3 30-70 148 0.539 50 mol % RbNO3 NaNO3—RbNO3 44-56 178 0.519 50 mol % RbNO3 LiNO3—NaNO3 56-44 187 0.985 49.96 mol % NaNO3 NaNO3—KNO3 46-54 222 0.66  50.31 mol % NaNO3 KNO3—RbNO3 30-70 290 0.394 70 mol % RbNO3

Molten nitrates also offer a viable solution and the physical properties of molten nitrate electrolytes are summarized in Table 1 (taken from Lithium Batteries Using Molten Nitrate Electrolytes by Melvin H. Miles; Research Department (Code 4T4220D); Naval Air Warfare Center Weapons Division; China Luke, Calif. 93555-61000).

The electrochemical oxidation of the molten LiNO3 occurs at about 1.1 V vs. Ag+/Ag or 4.5 V vs. Li+/Li. The electrochemical reduction of LiNO3 occurs at about −0.9V vs. Ag+/Ag, and thus these two reactions define a 2.0V electrochemical stability region for molten LiNO3 at 300° C. and are defined as follows:
LiNO3→Li++NO2+½O2+e  (Equation 1)
LiNO3+2e→LiNO2+O−−  (Equation 2)

This work with molten nitrates was not performed with lithium air cells in mind; however, the effective operating voltage window for the electrolyte is suitable for such an application. As indicated by the reaction potential line in FIG. 1, applying a recharge voltage of 4.5V referenced to the lithium anode can cause lithium nitrate to decompose to lithium nitrite, releasing oxygen. On the other hand, lithium can reduce LiNO3 to Li2O and LiNO2. This reaction occurs when the LiNO3 voltage drops below 2.5V relative to lithium. As long as there is dissolved oxygen in the electrolyte, the reaction kinetics will favor the lithium oxygen reactions over LiNO3 reduction. Oxide ions are readily converted to peroxide (O22−) and aggressive superoxide (O2) ions in NaNO3 and KNO3 melts (M. H. Miles et al., J. Electrochem. Soc., 127,1761 (1980)).

A need remains for a lithium air cell which overcomes problems associated with those of the prior art.

BRIEF SUMMARY OF THE INVENTION

A rechargeable lithium air battery comprises a ceramic separator forming an anode chamber, a molten lithium anode contained in the anode chamber, an air cathode, and a non-aqueous electrolyte, wherein the cathode has a temperature gradient comprising a low temperature region and a high temperature region, and wherein the temperature gradient provides a flow system for reaction product produced by the battery.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown.

In the drawings:

FIG. 1 is a diagram depicting electrochemical reaction potentials in molten lithium nitrate at 300° C.;

FIG. 2 is a schematic of a battery cell according to one embodiment of the present invention;

FIG. 3 is a schematic of a battery cell according to another embodiment of the present invention in discharge;

FIG. 4 is a schematic of the battery cell of FIG. 3 in recharge;

FIG. 5 is a schematic of a high performance battery cell according to a further embodiment of the invention in discharge;

FIG. 6 is a schematic of a high performance battery cell of FIG. 5 in recharge;

FIG. 7 is a schematic of a battery cell according to a further embodiment of the invention; and

FIG. 8 is an Arrhenius plot showing lithium ion conductivities of several solid ceramic electrolytes.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates generally to energy storage, and more particularly to a lithium air electrochemical cell. For the purposes of this disclosure, the terms lithium air cell, lithium air electrochemical engine and lithium oxygen battery are used interchangeably.

The present invention provides a rechargeable lithium air cell having a high rate of cell charge/discharge with limited capacity fade, high energy density, high power density, and the ability to operate on oxygen from ambient air. As such, it removes significant barriers that have prevented the commercialization of lithium air cells. For example, the formation of mossy lithium powder and dendrites at the anode-electrolyte interface during cell recharge are eliminated by the use of molten lithium supplied as a flow reactant to the anode side of a stable solid state ceramic electrolyte. The battery according to the invention also includes a flow system for removing reaction product from the cathode.

The reactions of lithium with oxygen are as follows:
2Li+O2→Li2O2 Eo=3.10 V
4Li+O2→2Li2O Eo=2.91V
To avoid problems associated with past approaches to lithium air cells, a lithium air cell according to the invention may be operated at a wide range of temperatures in the range of 20° C. to 700° C., which include elevated temperatures, such as the preferred temperatures of about 200° C. to 450° C., more preferably about 200° to about 250° C. The solvent in the electrolyte may be selected based on the preferred operating temperature of the specific battery. Operation at elevated temperature enables faster kinetics for higher power density, thus eliminating a major issue associated with lithium air technology. Further, operation at elevated temperature also allows for the use of high temperature organic electrolytes and inorganic, molten salt electrolyte solutions that have high electrochemical stability, thus avoiding another of the major problems that has plagued conventional approaches to lithium air cells. Selected inorganic molten salts have good solubility of lithium/oxygen reaction products, thus allowing better control of cell kinetics.

The rechargeable air battery according to the invention contains a ceramic separator which forms an anode chamber, a molten lithium anode contained in the anode chamber, an air cathode, and a non-aqueous electrolyte. Each of these components will be described in more detail below.

The cell further comprises a flow system which is provided by a temperature gradient across the cathode. More specifically, the cathode has two temperature regions: a high temperature region (preferably located near the anode, where the reaction takes place) and a low temperature region which is located further away from the anode. As the electrolyte circulates through the cell during discharge, the reaction product produced by the battery migrates from the high temperature region to the low temperature region.

The anode chamber is preferably formed by a sealed ceramic enclosure that is lithium ion conductive and which functions as the separator for the battery. Preferably, the ceramic material is stable in contact with lithium metal and protects the anode from ambient oxygen and moisture. Preferred materials include lithium ion conducting glasses such as lithium beta alumina, lithium phosphate glass, lithium lanthanum zirconium oxide (LLZO), Al2O3:Li7La3Zr2O12, lithium aluminum germanium phosphate (LAGP), and lithium aluminum titanium phosphate (LATP). In a preferred embodiment, the anode chamber is maintained at about 20° C. to about 200° C., more preferably at about 175° C. to about 200° C., most preferably about 175° C. to about 195° C.

The anode comprises metallic lithium in a molten state; lithium has a melting point of about 180° C. The benefit of the molten lithium anode is that it limits undesirable dendrite growth in the cell.

The non-aqueous electrolyte is chosen for stability in contact with lithium. Thus, a breach in the ceramic enclosure will not result in rapid reactions, particularly because air ingress into the cell will be controlled. Preferred electrolytes include molten inorganic salts, for example, alkali nitrates such as lithium and sodium nitrate, alkali chlorides and bromides such as lithium, potassium and sodium chlorides and bromides, alkali carbonates such as sodium and lithium carbonates, as well as sodium nitrate-potassium nitrate (NaNO3—KNO3) eutectic mixtures and silane and siloxane-based compounds including, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylhexatetrasiloxane with or without polyethylene oxide groups.

The inorganic salt, silane, or siloxane in the electrolyte is present in a solvent. The solvent is not limited, and may be selected based on the preferred operating temperature of the battery. A preferred solvent is LiCl—KCl eutectic, which works at a temperature of 350° C. to 450° C. The temperature of the electrolyte may be controlled with a heater and is preferably about 200° C. to 450° C.

The air cathode or positive electrode is porous so that oxygen can penetrate through the pores and form lithium peroxide as the reaction product; electrolyte also flows through the porous cathode. The cathode is preferably formed from a porous ceramic material which is lithium conductive and which is infiltrated or impregnated with a metal nitrate such as silver nitrate or a carbon material such as carbon fibers, carbon black, or carbon foam. Preferred porous ceramic materials include LLZO, LAGP, LATP, and lithium oxyanions such as lithium carbonate; most preferred is LLZO. In another preferred embodiment, the cathode contains a carbon material, a heat resistance polymer binder such as polyimide, and a metal oxide catalyst. An exemplary cathode material of this type contains about 60% by weight vapor grown carbon fibers, about 30% polyimide binder, and about 10% manganese dioxide. The cathode may also be constructed of electrically conductive sintered metal oxide powder, sintered metal nitride, carbon, or sintered silicon carbide.

As a preferred example, porous lithium lanthanum zirconium oxide (LLZO) ceramic substrates are prepared by pressing 10-15 grams of LLZO powder into a disc at 1000 psi. The disc is densified by placing in a furnace at 1000° C. for a period of 1 hour. The disc is then impregnated with a metal nitrate such as silver nitrate to form the cathode.

A thermodynamic process is employed to remove and supply electrolyte to cathode reaction sites. In its basic configuration, a temperature gradient is maintained across the structure of the cathode wetted by the electrolyte. The active charge/discharge reaction region of the cell forms the higher temperature region of the gradient. As a result of the temperature gradient, during discharge, reaction product accumulated within the electrolyte at the higher temperature region migrates to the lower temperature region where it precipitates/solidifies. The configuration of the cell is such that reaction product can accumulate within the lower temperature region physically away from the higher temperature reaction region of the cell. Accumulation of reaction product in the lower temperature region prevents it from significantly affecting the charge/discharge cell kinetics occurring in the higher temperature cathode reaction region. Ultimately, the cooled and settled reaction product will become re-dissolved in the electrolyte. This flow system is a key attribute of the inventive batteries.

In an alternative embodiment, the cell contains a pump to circulate the electrolyte across the temperature gradient. Such a cell contains a molten or another appropriate electrolyte reservoir and a temperature control system for controlling the relative temperatures of the cathode and the reservoir. Further, a heating element is employed for electrolyte temperature control. The pump system cycles electrolyte between the cathode and the electrolyte reservoir, which are adjacent to and in fluid communication with each other. Operation is such that during discharge, the cathode is maintained at a temperature that is elevated above that of the electrolyte reservoir. Reaction product dissolved in the electrolyte at high temperature in the cathode is carried to the electrolyte reservoir where it precipitates due to the lower temperature therein. In contrast, during charge, heat is supplied to the reservoir to maintain solubility of reaction product into the electrolyte. During charge, the electrolyte carries dissolved reaction product from the reservoir to the cathode, where it is electrolyzed. Oxygen is released and lithium ions are conducted through the ceramic separator such that lithium metal is plated at the anode. Electrolyte depleted of reaction product circulates back to the reservoir where it dissolves and carries more reaction product to the cathode as the charge process continues. The configuration is such that the reaction product is temporarily stored as a solid in the electrolyte reservoir as opposed to the cathode. Operation in this manner enables the cathode to be maintained in an optimum configuration for maximum charge and discharge performance.

FIG. 2 is a schematic drawing of a molten lithium electrochemical cell according to an embodiment of the invention. The cell is cylindrical in shape with fins running lengthwise along the cylinder and radiating outward away from the core of the cell. The basic structure is supported by hollow solid electrolyte cylinder (anode chamber) 2 which extends the length of the cell and functions as the cell separator. Molten lithium metal 14 is contained within reservoir 18 at the top of the cell and inside annular cavity 4 such that molten lithium is free to flow down from reservoir 18 into annular cavity 4. The top level of the molten anode 16 is not expected to totally fill the headspace 20 of the cell. Electrical heater element 6 runs the length of the cell and is positioned to maintain the lithium in a molten state. Heater 6 is part of the core structure that forms annular cavity 4 between the heater and the inner wall of the solid electrolyte 2 where molten lithium 14 is contained. Lithium 14 serves as the anode of the cell. Fined cathode cylinder 8 is positioned over the outer surface of electrolyte cylinder 2. The core of the fin is shown by 9. Cathode 8 is a porous structure containing liquid electrolyte which, due to its finned structure, is configured to have a wicking effect to maintain distribution of electrolyte therein. The reaction in the cell occurs at the interface where the cathode touches the separator, which is the hotter (high temperature) region of the cathode. The reaction product will not settle in this hot portion of the cathode, but rather on the colder side of the cathode (low temperature region). This allows for deeper cathode access. The cell preferably operates at 250° C. to 700° C. such that the eutectic salt mixture or other electrolyte is maintained in a molten state. Fins 10 extend into the surrounding air to facilitate heat transfer to the air such that heat supplied to the core induces a temperature gradient radially outward that is maintained between tips 12 of the fins 10 and the molten lithium at the core of the cell.

Dissolved reaction product 11 generated during discharge will preferentially precipitate in the lower temperature regions of the fins as opposed to the warmer core region. Molten electrolyte reservoir 1 contains excess electrolyte 3 and electrolyte that has been displaced by reaction product as it is produced and deposited within fins 10. Reservoir 1 may be maintained at a temperature that is lower than the core of the cell such that the reaction product preferentially precipitates therein as well. The temperature of the reservoir is controlled by heater element 5. During recharge, reaction product re-dissolves into the molten salt electrolyte to maintain concentration equilibrium as product is electrolyzed and lithium is re-plated at the anode. Heater 5 is used during recharge to heat the electrolyte to redissolve reaction product. The heat source for core 6 of the cell is not shown but would maintain temperature for operation during both charge and discharge.

Reservoir 18 supplies lithium 14 to annular cavity 4 so that the cavity does not become depleted as the lithium is consumed during discharge. Similarly, as lithium is reduced into the annular section during recharge, lithium is resupplied and accumulated in the reservoir.

FIGS. 3 and 4 show expanded views of radial plane cross section 26 of the cell in FIG. 2 and illustrate the operation of the cell. These Figs. show heater/spacer 6 including heater element 7, finned cathode 8, annular lithium cavity 4, solid electrolyte cylinder 2 and molten lithium anode 14. Referring to FIG. 3, oxygen 47 dissolves into the molten salt electrolyte from the cell's environment. During discharge, lithium 44 is oxidized and conducted through electrolyte separator 2 into the molten salt contained within cathode 8, giving rise to electric current flow 45 through load 40 to cathode 8. The electrons 43 oxidize molecular oxygen that is dissolved in the molten salt electrolyte, producing oxygen ions 46 to complete the reaction, with the resulting reaction product being either lithium peroxide (Li2O2 as 2Li+ and O2−−) and/or lithium oxide (Li2O as 2Li+ and O−−) ions suspended in the molten salt electrolyte solution. The two lithium ions 42 are anticipated to be individually dispersed within the electrolyte. The illustration is not intended to convey a diatomic pair bonded to each other. When the molten salt becomes saturated with reaction product, lithium peroxide 48 and/or lithium oxide begins to precipitate out of solution.

Heater element 7 located in the center region of the cell maintains the lithium anode and the electrolyte salt contained in the cathode in a molten state. Because of its location and because of the loss of heat from the cathode fins to the air surrounding the cell, a decreasing temperature exists between the core of the cell 6 and fin tips 12. The molar equilibrium of dissolved lithium/oxygen reaction product in the molten salt will be lower at the lower temperature fin tips 12 than at the high temperature cathode material 45 that is closest to the core of the cell. As such, reaction product 48 will tend to precipitate out of solution in the region of fin tips 12, resulting in a buildup of reaction product 41 in that location. Although reaction kinetics will favor the high temperature region, creation of reaction product in high temperature region 14 will cause over saturation and precipitation of reaction product in lower temperature fin tip region 12. Migration to fin tips 12 will occur because the molar concentration of reaction product in the salt is continuous between the two regions. The salt level will naturally be uniformly distributed, limited only by mass transport rate across the concentration gradients of the dissolved product within the molten salt. Further production of reaction products in the solution in the higher temperature regions will cause precipitation of reaction product in the lower temperature region since the increase would cause over saturation in the low temperature region.

Having the reaction product accumulate in the fin tip regions of the cell is important because precipitation in this region has only very limited adverse impacts on operation of the cell. The invention thus avoids over accumulation of reaction product in the active region of the cell which could cause a reduction of ionic conductivity and could block access and diffusion of oxygen to reaction sites.

FIG. 4 depicts recharge operation of the cell. For recharge, power source 50 is connected in the circuit in place of the load. Dissolved lithium/oxygen reaction product 52, 54, 56 is electrolyzed as electrons 53 are stripped by the power source and coupled to the anode side of the cell. During the process, molecular oxygen 57 is released to the environment and lithium ions 54 are conducted through the solid state separator 2 to the anode side of the cell where electrons 53 reduce it to lithium metal.

As reaction product 58 is consumed from the molten salt electrolyte solution, its molar concentration level in the electrolyte eutectic tends lower, thus allowing additional reaction product precipitant 41 to dissolve into the electrolyte. The re-dissolved reaction product naturally migrates toward the core region of the cell due to the concentration gradient created as reaction product in the core region is removed by the recharge process. Continuous dissolving of reaction product 41 maintains a molar equilibrium concentration level of the reaction product in the electrolyte in fin tip region 12 until all of discharge reaction product 41 is re-dissolved and electrolyzed, whereby the cell will be fully charged.

FIG. 5 is a schematic diagram of a high performance lithium oxygen or lithium air cell according to a further embodiment of the invention. Lithium reservoir 62 contains molten lithium 64 at a preferred temperature of 350° C. A portion 72 of lithium reservoir 62 extends into reactor reaction chamber and molten salt electrolyte reservoir 68 where separator 71 interfaces with the contents of reaction chamber and molten salt electrolyte reservoir 68. Reservoir 62 optionally includes ullage pressurized gas 66 to ensure flow of molten lithium into contact with solid state electrolyte separator 71. Reservoir 62 maintains the supply 101 of lithium to separator 71 as the cell is discharged. Separator 71 is a solid lithium ion conductive material and may be lithium beta alumina or lithium lanthanum zirconium oxide (LLZO). It is preferably a solid ceramic and/or a glass electrolyte. Cathode 98 and embedded current collector 74 are coupled to the surface of separator 71 on the external side of reservoir 62. Cathode 98 includes lithium/oxygen reaction sites for charge and discharge of the cell. Current collector 74 is connected to positive terminal 69 which allows electrons 81 to travel. Power is applied to terminals 82. Reactor Reaction chamber and molten salt electrolyte reservoir 68 contains molten salt electrolyte 78. Pump 75 supplies molten salt electrolyte solution 78 through supply tube 76 to nozzle 80. Nozzle 80, tube 85 and port 87 comprise a jet pump whereby fluid supplied by pump 75 creates a low pressure region that draws air 84 into port 87 such that it flows through conduit 86 to port 87. The fluid injection process creates a turbulent mixture region of air and molten electrolyte. It produces a washing effect as the resulting spray 104 exits the jet pump and impinges on cathode 98. This process creates an electrochemical potential between the lithium inside reservoir 62 on one side of electrolyte 71 (electrode terminal 70) and the oxygen dissolved and dispersed within electrolyte/air mixture washing through cathode 98 on the other side.

Operation of the cell is such that molten salt electrolyte 102 washing through cathode 98 dissolves lithium-air reaction products produced therein as the cell is discharged. Oxygen depleted air 99 exits the reactor chamber through port 100. Air 84 enters the cell at port 91 and passes through heat exchanger 90, heat exchanger 105 and heat exchanger 92 prior to entering reaction chamber and molten salt electrolyte reservoir 68. The flow rate can be controlled by valve 108. The heat exchangers preheat air 84 to a level such that it enters nozzle 87 near the temperature of molten salt electrolyte 78 exiting nozzle 80. Air entering the reaction chamber and molten salt electrolyte reservoir 68 is heated within heat exchangers 90 and 92 by oxygen depleted air 99 exiting the reaction chamber through conduit 88. Air passing through heat exchanger 105 inside reactor reaction chamber and molten salt electrolyte reservoir 68 is heated by molten electrolyte salt 78. Extraction of heat from electrolyte 78 in the electrolyte reservoir maintains its temperature below the temperature of the electrolyte 102 that is washing through cathode 98. Electric heater 96 is thermally coupled to separator 71 and supplies energy as needed to maintain the temperature of cathode 98 above the temperature the reservoir electrolyte 78 that is thermally coupled to heat exchanger 105. The effect of the thus maintained temperature difference is that electrolyte 102 washing through cathode 98 is raised to a higher temperature than electrolyte 78 that is in the reservoir. Continuous flow of electrolyte continuously dissolves and washes away reaction product being produced in cathode 98. On the other hand, when the electrolyte leaves cathode 98 and is cooled by heat exchanger 105 in the reservoir, its saturation limit for dissolved reaction product decreases, which causes a portion of the reaction product to precipitate, 97. The electric heater 94 is used to control the temperature of the electrolyte. The discharge process continues as pump 75 resupplies electrolyte 78, now depleted of reaction product, to nozzle 80 where it entrains more air and carries it to cathode 98, is reheated, and dissolves more reaction product as it occurs from lithium air reactions ongoing therein.

FIG. 6 illustrates operation of the cell under recharge conditions. Power is supplied to heater 94 to increase the solubility level of reaction product 107 in electrolyte 78. The dissolving of reaction product 107 in electrolyte 78 increases with temperature. Pump 75 pumps electrolyte 78 containing dissolved reaction product to nozzle 80 whereby it is sprayed 114 onto cathode 98. Power is applied to terminals 82 to electrolyze lithium/air reaction product in cathode 98. With the extraction of electrons 59 by a positive voltage applied to terminal 69 relative to terminal 70, reaction product is electrolyzed with oxygen 110 being released to escape reactor reaction chamber and molten salt electrolyte reservoir 68 via port 100. It exits the cell through port 78 106 after passing through heat exchanger 92 and 90 to preheat incoming air. During the recharge process, lithium ions are conducted through solid electrolyte separator 71 into reservoir 62 where it is reduced to lithium by electron flow via terminal 70. The recharge process continuously electrolyzes dissolved reaction product from molten salt in cathode 98 as reaction product depleted electrolyte 112 returns to reaction chamber and molten salt electrolyte reservoir 78 68, dissolves more reaction product, 107, and is pumped back to cathode 98. Molten lithium is re-supplied to reservoir 62 as indicated by arrow 103. Under recharge condition, valve 108 may optionally be closed since air intake into the reaction chamber is not needed.

In an exemplary cell shown in FIG. 7, solid electrolyte cylinder 2 with terminals 122 and 19 has an inner diameter of 2.54 cm and length of 50 cm. The volume of lithium would be 0.253 L (π(2.54(D)/2)2*50 cm(L)=253.35 cm3). The electrochemical potential for the lithium/oxygen reaction is 3.14V. Assuming an under load operating output voltage of 2.5V to allow for internal impedances, the energy capacity can be determined considering the Amp-Hour capacity of lithium being 3,860 Ah/kg (2,084 Ah/ltr). At an output voltage of 2.5V, the energy available from the cell would be 9650 Wh/kg (5210 Wh/ltr). Given the 0.253 L lithium volume in the example, the cell could supply 1.3 kWh of energy.

In a cell operating at 300° C. with NaNO3—KNO3 molten salt eutectic electrolyte, the conductivity of the electrolyte is 0.66 S/cm. Similarly, the conductivity of the solid electrolyte containment cylinder 2 at 300° C. is 0.1 S/cm as shown in FIG. 7. Assuming that the thickness 74 in FIG. 7 of the porous cathode 8 on the surface of the solid cylinder electrolyte 2 is 0.2 cm and that the thickness 72 of the solid electrolyte is 0.1 mm, the area specific resistance of the solid electrolyte plus the liquid can be calculated as 0.403 Ohm-cm2 (1/(0.66 S/cm)*0.2 cm+1/(0.1 S/cm)*0.01 cm). Given the 0.7 Volt allowance for internal IR loss, the net output current under load would be 1.73 A assuming other polarization losses are negligible. In such a case, the area specific power of the cell would be 4.34 Watts. This example cell has a surface area of 399 cm2(π*2.54*50), therefor its power output capability would be 1.73 kW.

FIG. 8 is an Arrhenius plot showing the conductivity of several solid state ionic conductive materials that would be suitable for use as the electrolyte cylinder 2. Impedance line 83 is for lithium beta alumina (data from J. L. Briant, J. Electrochem. Soc.: Electrochemical Science And Technology; 1834 (1981)) and line 84 is for lithium phosphate glass (data from B. Wang, Journal of Non-Crystalline Solids, Volume 183, Issue 3, 2; 297-306 (1995). Conductivity values 82 for aluminum oxide doped lithium lanthanum zirconium oxide (Al2O3:Li7La3Zr2O12) are from M Kotobuki, et. al.; Journal of Power Sources 196 7750-7754 (2011)).

Sintered LLZO electrolyte had been demonstrated to be stable with lithium in all solid state batteries. (See T. Yoshida, et. al.; Journal of The Electrochemical Society, 157-10, A1076-A1079 (2010)). The cyclic voltammogram of the Li/LLZO/Li cell showed that the dissolution and deposition reactions of lithium occurred reversibly without any reaction with LLZO. This indicates that a Li metal anode can be employed in contact with LLZO electrolyte.

In an exemplary embodiment, a 1 kWh battery is designed to operate at a discharge rate of 1 C, i.e. battery totally discharged in 1 hour. Lithium has a specific energy of 11,580 Wh/kg. If the mass of the oxygen is included, the net energy density is 5,200 Wh/kg. For a 1 kWh battery, 86 g of lithium would be needed. Lithium has a discharge current capacity of 3.86 Ah/g. At a discharge rate of 1 C, the required discharge current would be 332 A (86 g*3.86 Ah/g/1 hr). In this example, the area of the separator may be defined as 100 cm2 and the solid separator as LLZO or other suitable substitute thereof. In this example the use of a 100 cm2 separator results in a net current density of 3.32 A/cm2. As indicated in FIG. 8, the lithium ion conductivity, σ, of LLZO is approximately 0.1 S/cm. A separator made of this material and at a thickness, t, of 100 um would have an impedance of 0.1 Ohm-cm2, (1/σ*t). The output current supplied at 1 C would have a maximum drop in voltage of 0.4V relative to the cell's open circuit voltage. The primary reaction product of the cell is Li2O2. The amount of air flow required to sustain a 1 C discharge rate can be determined from the required oxygen flow.

The atomic mass of lithium is 6.9 g/mole. The primary discharge reaction for the cell is 2Li+O2>Li2O2, 1 mole of oxygen is required for per mole of lithium. The number of moles of lithium in the reaction is 12.46, (86 g/6.9 g/mole). Therefore, 6.23 moles or 199.4 grams (6.23 moles *32 grams/mole) of oxygen are required to balance the reaction. Air is 23% oxygen by mass so that the total amount of air needed for the reaction is 866 g, (199.4 g O2/(0.23 g O2/gAir). For the 1 C discharge, the air mass flow rate is 866 g/hr or 0.24 g/sec. The density of air is 0.00123 g/cm3. This gives a volumetric flow rate of 195 cm3/sec.

It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.

Claims

1. A rechargeable lithium air battery comprising a ceramic separator forming an anode chamber, a molten lithium anode contained in the anode chamber, an air cathode, a non-aqueous electrolyte, and an electrolyte reservoir adjacent to the cathode, wherein the cathode has a temperature gradient comprising a low temperature region and a high temperature region, and wherein the temperature gradient provides a flow system for reaction product produced by the battery.

2. The battery according to claim 1, further comprising a pump and a temperature control system.

3. The battery according to claim 2, wherein the pump controls movement of the electrolyte between the cathode and the electrolyte reservoir.

4. The battery according to claim 2, wherein the temperature control system controls temperatures of the cathode and the electrolyte reservoir.

5. The battery according to claim 1, wherein during discharge the reaction product moves from the high temperature region of the cathode to the low temperature region of the cathode.

6. The battery according to claim 1, wherein the electrolyte comprises a molten inorganic salt.

7. The battery according to claim 1, wherein the electrolyte comprises a silane or siloxane compound.

8. The battery according to claim 1, wherein the cathode comprises a porous ceramic material.

9. The battery according to claim 8, wherein the cathode is impregnated with a metal nitride or a carbon material.

10. The battery according to claim 1, wherein the cathode comprises an electrically conductive sintered metal oxide, metal nitride, carbon, or silicon carbide.

11. The battery according to claim 1, wherein the cathode comprises carbon, a polymer binder, and a metal oxide.

12. The battery according to claim 8, wherein the porous ceramic material comprises lithium lanthanum zirconium oxide.

13. The battery according to claim 1, where the anode chamber is maintained at about 20° C. to 200° C.

14. The battery according to claim 1, wherein the ceramic separator comprises a lithium ion conducting glass.

15. The battery according to claim 14, wherein the lithium ion conducting glass is selected from lithium beta alumina, lithium phosphate glass, lithium lanthanum zirconium oxide, Al2O3:Li7La3Zr2O12, lithium aluminum germanium phosphate, and lithium aluminum titanium phosphate.

16. The battery according to claim 1, wherein the battery has an operating temperature of about 200° C. to about 450° C.

17. A rechargeable lithium air battery comprising a ceramic separator forming an anode chamber, a molten lithium anode and a heater contained in the anode chamber, an air cathode, and a non-aqueous electrolyte, wherein the cathode has a temperature gradient comprising a low temperature region and a high temperature region, and wherein the temperature gradient provides a flow system for reaction product produced by the battery.

18. A rechargeable lithium air battery comprising a ceramic separator forming an anode chamber, a molten lithium anode contained in the anode chamber, an air cathode, and a non-aqueous electrolyte, wherein the cathode has a temperature gradient comprising a low temperature region and a high temperature region, the temperature gradient provides a flow system for reaction product produced by the battery, wherein the cathode comprises a core adjacent to the ceramic separator and at least one fin extending radially outward from the core, and wherein the core is the high temperature region of the cathode and the at least one fin is the low temperature region of the cathode.

19. A rechargeable lithium air battery comprising a ceramic separator forming an anode chamber, a molten lithium anode contained in the anode chamber, an air cathode, a non-aqueous electrolyte, an electrolyte reservoir adjacent to the cathode, a pump and a temperature control system, wherein the temperature control system controls temperatures of the cathode and the electrolyte reservoir, the temperature of the electrolyte reservoir is about 200° C. to about 450° C., the cathode has a temperature gradient comprising a low temperature region and a high temperature region, and wherein the temperature gradient provides a flow system for reaction product produced by the battery.

20. A rechargeable lithium air battery comprising a lithium reservoir, a reaction chamber, an air cathode, a temperature control system, and an electrolyte reservoir adjacent to the air cathode, wherein the lithium reservoir includes a ceramic separator and the electrolyte reservoir contains an inorganic non-aqueous electrolyte, the ceramic separator extends into the reaction chamber whereby lithium flows into the reaction chamber from the lithium reservoir and contacts the ceramic separator in the reaction chamber, the ceramic separator couples lithium to the inorganic non-aqueous electrolyte supplied from the electrolyte reservoir, and the inorganic non-aqueous electrolyte couples the reaction chamber to the electrolyte reservoir and carries reaction product therebetween whereby reaction product within the reaction chamber is removed.

21. The battery according to claim 20, wherein the temperature control system controls temperatures of the cathode and the electrolyte reservoir.

22. The battery according to claim 20, wherein the cathode comprises a core adjacent to the ceramic separator and at least one fin extending radially outward from the core.

23. The battery according to claim 22, and wherein the core is a high temperature region of the cathode and the at least one fin is a low temperature region of the cathode.

24. The battery according to claim 20, wherein the electrolyte comprises a molten inorganic salt.

25. The battery according to clam 20, wherein the electrolyte comprises a silane or siloxane compound.

26. The battery according to claim 20, wherein the cathode comprises a ceramic material.

27. The battery according to claim 20, wherein the cathode is impregnated with a metal nitride or a carbon material.

28. The battery according to claim 20, wherein the cathode comprises an electrically conductive sintered metal oxide, metal nitride, carbon, or silicon carbide.

29. The battery according to claim 20, wherein the cathode comprises carbon, a polymer binder, and a metal oxide.

30. The battery according to claim 26, wherein the ceramic material comprises lithium lanthanum zirconium oxide.

31. The battery according to claim 20, where the anode chamber is maintained at about 20° C. to 200° C.

32. The battery according to claim 20, wherein the ceramic separator comprises a lithium ion conducting glass.

33. The battery according to claim 32, wherein the lithium ion conducting glass is selected from lithium beta alumina, lithium phosphate glass, lithium lanthanum zirconium oxide, Al2O3:Li7La3Zr2O12, lithium aluminum germanium phosphate, and lithium aluminum titanium phosphate.

34. The battery according to claim 20, wherein the battery has an operating temperature of about 200° C. to about 450° C.

35. A rechargeable lithium air battery comprising:

a supply of air flow,
an air cathode,
a heat exchanger for transferring heat to air flowing to the air cathode from air leaving the air cathode,
a pump for supplying air to the air cathode,
a temperature control system,
a lithium ion conductive solid ceramic electrolyte
a lithium reservoir,
an inorganic electrolyte reservoir,
a molten lithium anode contained in the lithium reservoir, and
an inorganic electrolyte contained within the inorganic electrolyte reservoir,
wherein lithium flows to the lithium anode from the lithium reservoir during charge and from the lithium anode to the lithium reservoir during recharge, the solid ceramic electrolyte conducts lithium ions from the lithium reservoir to the inorganic electrolyte for reaction with oxygen supplied by air flow to the air cathode, and wherein lithium oxygen reaction product is accumulated within the electrolyte reservoir.

36. The battery according to clam 35, wherein the lithium oxygen reaction product has at least limited solubility in the inorganic salt electrolyte.

37. A rechargeable lithium air battery comprising:

a supply of air flow,
a heat exchanger,
a pump,
a cathode,
a temperature control system,
a reaction chamber,
a lithium reservoir,
a molten salt electrolyte reservoir,
a molten lithium anode contained in the lithium reservoir, and
a molten inorganic salt electrolyte contained within the molten salt electrolyte reservoir,
wherein lithium is supplied to the reaction chamber from the lithium reservoir, molten inorganic salt is supplied to the reaction chamber from the molten salt electrolyte reservoir and air is supplied to the reaction chamber by the heat exchanger, the heat exchanger transfers heat from oxygen-depleted air leaving the cathode to ambient air flowing to the cathode, and wherein lithium oxygen reaction product accumulates within the molten salt electrolyte reservoir.

38. The battery according to clam 37, wherein the reaction chamber surrounds an air cathode and a solid ceramic lithium ion conductive electrolyte, wherein the solid ceramic lithium ion conductive electrolyte is coupled between the lithium reservoir and the molten inorganic salt electrolyte, isolating lithium from the molten inorganic salt electrolyte, interfacing lithium to the molten salt electrolyte or cathode, and conducting lithium ions from the lithium reservoir to the molten salt electrolyte for reaction with oxygen supplied to the cathode with air flow from the heat exchanger.

39. A rechargeable lithium air battery comprising:

a supply of oxygen flow,
a ceramic lithium ion conductive electrolyte,
a pump,
a lithium reservoir,
an inorganic electrolyte reservoir,
a molten lithium anode,
a cathode, and
an inorganic electrolyte contained within the electrolyte reservoir,
wherein the ceramic electrolyte is coupled between the lithium anode and the cathode, lithium is supplied to the anode from the lithium reservoir, oxygen is supplied to the cathode, and lithium ions are conducted by the ceramic electrolyte to the cathode, whereby lithium reacts with oxygen at the cathode, the pump circulates the electrolyte between the cathode and the reservoir, and the electrolyte washes reaction product from the cathode during discharge and supplies reaction product to the cathode during recharge.

40. A rechargeable lithium air battery comprising: wherein the ceramic electrolyte is coupled between the lithium anode and the cathode, lithium is supplied to the anode from the lithium reservoir, oxygen is supplied to cathode with air supplied by the pump, and lithium ions are conducted by the ceramic electrolyte to the cathode, whereby lithium reacts with oxygen at the cathode, and wherein lithium oxygen reaction product accumulates within the inorganic electrolyte reservoir.

a supply of oxygen flow,
a cathode,
a ceramic lithium ion conductive electrolyte,
a heat exchanger for transferring heat to air flowing to the cathode from air leaving the cathode,
a lithium reservoir,
an inorganic electrolyte reservoir,
a molten lithium anode,
a pump for supplying air to the cathode, and
an inorganic electrolyte contained within the electrolyte reservoir,

41. A rechargeable lithium air battery comprising:

a supply of air flow,
an air cathode,
an electrolyte pump,
a temperature control system,
a lithium ion conductive solid ceramic electrolyte
a lithium reservoir,
a molten salt electrolyte reservoir,
a molten lithium anode contained in the lithium reservoir, and
a molten inorganic salt electrolyte contained within the molten salt electrolyte reservoir,
wherein the solid ceramic electrolyte conducts lithium ions from the lithium reservoir to the molten inorganic salt electrolyte for reaction with oxygen supplied by air flow to the cathode, and the electrolyte pump promotes electrolyte flow to contact the cathode and to remove and carry lithium oxygen reaction product to the electrolyte reservoir.
Referenced Cited
U.S. Patent Documents
3237078 February 1966 Mallory
3393355 July 1968 Whoriskey et al.
4299682 November 10, 1981 Oda et al.
4303877 December 1, 1981 Meinhold
4352068 September 28, 1982 Weppner
4386020 May 31, 1983 Hartwig et al.
4419421 December 6, 1983 Wichelhaus et al.
4495078 January 22, 1985 Bell et al.
4513069 April 23, 1985 Kreuer et al.
4526855 July 2, 1985 Hartwig et al.
4614905 September 30, 1986 Petersson et al.
4654281 March 31, 1987 Anderman et al.
4704341 November 3, 1987 Weppner et al.
4710848 December 1, 1987 Schlechtriemen et al.
4719401 January 12, 1988 Altmejd
4728590 March 1, 1988 Redey
4777119 October 11, 1988 Brault et al.
4792752 December 20, 1988 Schlechtriemen et al.
4803134 February 7, 1989 Sammells
4885267 December 5, 1989 Takahara et al.
4931214 June 5, 1990 Worrell et al.
5023153 June 11, 1991 Weppner
5202788 April 13, 1993 Weppner
5238761 August 24, 1993 Ryan
5260821 November 9, 1993 Chu et al.
5270635 December 14, 1993 Hoffman et al.
5291116 March 1, 1994 Feldstein
5314765 May 24, 1994 Bates
5322601 June 21, 1994 Liu et al.
5336573 August 9, 1994 Zuckerbrod et al.
5338625 August 16, 1994 Bates et al.
5362581 November 8, 1994 Chang et al.
5387857 February 7, 1995 Honda et al.
5411592 May 2, 1995 Ovshinsky et al.
5432026 July 11, 1995 Sahm et al.
5445906 August 29, 1995 Hobson et al.
5455126 October 3, 1995 Bates et al.
5474959 December 12, 1995 Schafer et al.
5512147 April 30, 1996 Bates et al.
5522955 June 4, 1996 Brodd
5561004 October 1, 1996 Bates et al.
5567210 October 22, 1996 Bates et al.
5569520 October 29, 1996 Bates
5597660 January 28, 1997 Bates et al.
5612152 March 18, 1997 Bates
5654084 August 5, 1997 Egert
5677081 October 14, 1997 Iwamoto et al.
5705293 January 6, 1998 Hobson
5778515 July 14, 1998 Menon
5783333 July 21, 1998 Mayer
5783928 July 21, 1998 Okamura
5811205 September 22, 1998 Andrieu et al.
5821733 October 13, 1998 Turnbull
6022642 February 8, 2000 Tsukamoto et al.
6136472 October 24, 2000 Barker et al.
6139986 October 31, 2000 Kurokawa et al.
6168884 January 2, 2001 Neudecker et al.
6182340 February 6, 2001 Bishop
6201123 March 13, 2001 Daikai et al.
6242129 June 5, 2001 Johnson
6255122 July 3, 2001 Duncombe et al.
6387563 May 14, 2002 Bates
6413285 July 2, 2002 Chu et al.
6413672 July 2, 2002 Suzuki et al.
6541161 April 1, 2003 Scanlon, Jr.
6679926 January 20, 2004 Kajiura et al.
6827921 December 7, 2004 Singhal et al.
6852139 February 8, 2005 Zhang et al.
6886240 May 3, 2005 Zhang et al.
6887612 May 3, 2005 Bitterlich et al.
7230404 June 12, 2007 Kimoto et al.
7276308 October 2, 2007 Formanski et al.
7510800 March 31, 2009 Yoshida et al.
7524580 April 28, 2009 Birke et al.
7540886 June 2, 2009 Zhang et al.
7557055 July 7, 2009 Zhang et al.
7674559 March 9, 2010 Min et al.
7691536 April 6, 2010 Johnson
7732096 June 8, 2010 Thackeray et al.
7776478 August 17, 2010 Klaassen
7824795 November 2, 2010 Yoshida et al.
7901658 March 8, 2011 Weppner et al.
7914932 March 29, 2011 Yoshida et al.
7998622 August 16, 2011 Inda
8092941 January 10, 2012 Weppner et al.
8173292 May 8, 2012 Kato
8192869 June 5, 2012 Teramoto
8211496 July 3, 2012 Johnson et al.
8221916 July 17, 2012 Inda
8313721 November 20, 2012 Thackeray et al.
8383268 February 26, 2013 Inda
8431287 April 30, 2013 Teramoto
8476174 July 2, 2013 Inda
8568921 October 29, 2013 Johnson
8778546 July 15, 2014 Farmer
8795868 August 5, 2014 Miles
8808407 August 19, 2014 Inda
8822077 September 2, 2014 Katoh
8852816 October 7, 2014 Ogasa
8883355 November 11, 2014 Inda
8951681 February 10, 2015 Katoh
9034525 May 19, 2015 Babic et al.
9153838 October 6, 2015 Ogasa
9159989 October 13, 2015 Ogasa
9178255 November 3, 2015 Kumar et al.
9203123 December 1, 2015 Prochazka, Jr. et al.
9263770 February 16, 2016 Boxley et al.
9266780 February 23, 2016 Ogasa
9379375 June 28, 2016 Sugiura et al.
9385405 July 5, 2016 Murata et al.
9413033 August 9, 2016 Ogasa
9413036 August 9, 2016 Bhavaraju et al.
9425454 August 23, 2016 Sugiura et al.
9450278 September 20, 2016 Kim et al.
9680191 June 13, 2017 Lee et al.
9711822 July 18, 2017 Nakashima et al.
9917304 March 13, 2018 Lee et al.
9954260 April 24, 2018 Ho
9997813 June 12, 2018 Park et al.
10566611 February 18, 2020 Allie et al.
10686224 June 16, 2020 Angell et al.
10693170 June 23, 2020 Jin et al.
10734686 August 4, 2020 Robins et al.
10797340 October 6, 2020 Lee et al.
20010014505 August 16, 2001 Duncombe et al.
20010036578 November 1, 2001 Nishida et al.
20020000541 January 3, 2002 Sasaki et al.
20020008706 January 24, 2002 Mayes et al.
20020119375 August 29, 2002 Zhang
20030012996 January 16, 2003 Bitterlich et al.
20030030039 February 13, 2003 Sasaki et al.
20030118897 June 26, 2003 Mino et al.
20030157407 August 21, 2003 Kosuzu et al.
20040081888 April 29, 2004 Thackeray et al.
20040101761 May 27, 2004 Park et al.
20040111874 June 17, 2004 Schierle-Arndt et al.
20040118700 June 24, 2004 Schierle-Arndt et al.
20040151986 August 5, 2004 Park et al.
20040191617 September 30, 2004 Visco et al.
20050084758 April 21, 2005 Yamamoto et al.
20050095506 May 5, 2005 Klaassen
20050100793 May 12, 2005 Jonghe et al.
20050147890 July 7, 2005 Shembel et al.
20050266150 December 1, 2005 Yong et al.
20060046149 March 2, 2006 Yong et al.
20060068282 March 30, 2006 Kishi et al.
20060093916 May 4, 2006 Howard et al.
20060165578 July 27, 2006 Sasaki et al.
20060246355 November 2, 2006 Min et al.
20060287188 December 21, 2006 Borland et al.
20070031323 February 8, 2007 Baik et al.
20070048617 March 1, 2007 Inda
20070087269 April 19, 2007 Inda
20070148545 June 28, 2007 Amine et al.
20070148553 June 28, 2007 Weppner
20070231704 October 4, 2007 Inda
20070264579 November 15, 2007 Ota
20080131781 June 5, 2008 Yong et al.
20080220334 September 11, 2008 Inda
20080241698 October 2, 2008 Katoh
20080268346 October 30, 2008 Inda
20090004371 January 1, 2009 Johnson et al.
20090068563 March 12, 2009 Kanda et al.
20090081554 March 26, 2009 Takada et al.
20090081555 March 26, 2009 Teramoto
20090092903 April 9, 2009 Johnson et al.
20090098281 April 16, 2009 Zhang et al.
20090142669 June 4, 2009 Shinohara et al.
20090162755 June 25, 2009 Neudecker
20090194222 August 6, 2009 Teramoto
20090197178 August 6, 2009 Inda
20090197182 August 6, 2009 Katoh
20090214957 August 27, 2009 Okada et al.
20090274832 November 5, 2009 Inda
20100028782 February 4, 2010 Inda
20100047696 February 25, 2010 Yoshida et al.
20100104948 April 29, 2010 Skotheim et al.
20100203383 August 12, 2010 Weppner
20100291443 November 18, 2010 Farmer
20100308278 December 9, 2010 Kepler et al.
20110053001 March 3, 2011 Babic et al.
20110059369 March 10, 2011 Nan et al.
20110076542 March 31, 2011 Farmer
20110086274 April 14, 2011 Chang et al.
20110133136 June 9, 2011 Weppner et al.
20110177397 July 21, 2011 Ogasa
20110209859 September 1, 2011 Reinke et al.
20110223460 September 15, 2011 Farmer
20110223467 September 15, 2011 Shacklette et al.
20110223487 September 15, 2011 Johnson et al.
20110300451 December 8, 2011 Inda
20110318650 December 29, 2011 Zhang et al.
20120100433 April 26, 2012 Suyama et al.
20120141881 June 7, 2012 Geier et al.
20120196189 August 2, 2012 Babic et al.
20120237834 September 20, 2012 Ogasa
20120251882 October 4, 2012 Moon et al.
20120264021 October 18, 2012 Sugiura et al.
20120270115 October 25, 2012 Johnson
20130011751 January 10, 2013 Nakada et al.
20130011752 January 10, 2013 Tanaami et al.
20130017454 January 17, 2013 Sato et al.
20130095394 April 18, 2013 Tanaami et al.
20130157149 June 20, 2013 Peled
20130164616 June 27, 2013 Nakada et al.
20130230777 September 5, 2013 Babic et al.
20130273437 October 17, 2013 Yoshioka et al.
20130309551 November 21, 2013 Ogasa
20130344416 December 26, 2013 Sakamoto et al.
20140008006 January 9, 2014 Lee et al.
20140011080 January 9, 2014 Lee et al.
20140011095 January 9, 2014 Lee et al.
20140023933 January 23, 2014 Chiga et al.
20140038058 February 6, 2014 Holzapfel et al.
20140065456 March 6, 2014 Bhavaraju
20140099538 April 10, 2014 Johnson et al.
20140099556 April 10, 2014 Johnson et al.
20140287305 September 25, 2014 Wachsman et al.
20150037688 February 5, 2015 Otsuka et al.
20150056518 February 26, 2015 Babic et al.
20150056520 February 26, 2015 Thokchom et al.
20150099187 April 9, 2015 Cui et al.
20150099197 April 9, 2015 Nakashima et al.
20150333307 November 19, 2015 Thokchom et al.
20160028133 January 28, 2016 Miles
20160036109 February 4, 2016 Kim et al.
20160149261 May 26, 2016 Zaghib et al.
20160164153 June 9, 2016 Kim et al.
20160181657 June 23, 2016 Kawaji et al.
20160329539 November 10, 2016 Kawaji et al.
20160336583 November 17, 2016 Smith et al.
20170179521 June 22, 2017 Sakamoto
20170214106 July 27, 2017 Johnson et al.
20170222287 August 3, 2017 Suzuki et al.
20190296276 September 26, 2019 Bradwell et al.
20190372148 December 5, 2019 He et al.
20210218091 July 15, 2021 Uddin et al.
20210265616 August 26, 2021 Kim et al.
Foreign Patent Documents
1866583 November 2006 CN
101434417 May 2009 CN
101494299 July 2009 CN
102214827 October 2011 CN
102013536 October 2012 CN
102934279 February 2013 CN
104245624 December 2014 CN
206048735 March 2017 CN
107437636 December 2017 CN
206921981 January 2018 CN
207413450 May 2018 CN
4309070 September 1994 DE
102004010892 November 2005 DE
102007030604 January 2009 DE
102010019187 November 2011 DE
102015220354 April 2017 DE
0070020 January 1983 EP
0033935 August 1985 EP
0177062 April 1986 EP
0190605 August 1986 EP
0206339 December 1986 EP
0226955 July 1987 EP
0232513 August 1987 EP
0243975 November 1987 EP
0249802 December 1987 EP
238383 August 1989 EP
0408039 January 1991 EP
0227996 July 1991 EP
0470597 February 1992 EP
0693581 May 1998 EP
1271683 January 2003 EP
1431422 June 2004 EP
1431423 June 2004 EP
1237212 April 2005 EP
2037527 March 2009 EP
2086040 August 2009 EP
2181971 May 2010 EP
2685551 January 2014 EP
2706598 March 2014 EP
2903060 August 2015 EP
2466107 March 1981 FR
1329688 September 1973 GB
1599792 October 1981 GB
2226441 December 1992 GB
S628452 January 1987 JP
H05-310417 November 1993 JP
H07235291 September 1995 JP
2000311710 November 2000 JP
2000331680 November 2000 JP
2000331684 November 2000 JP
2001126757 May 2001 JP
2001126758 May 2001 JP
2001243954 September 2001 JP
2003132921 May 2003 JP
2004127613 April 2004 JP
2006260887 September 2006 JP
2006261008 September 2006 JP
2006310295 November 2006 JP
2008505458 February 2008 JP
2009176741 August 2009 JP
2010067499 March 2010 JP
2010080426 April 2010 JP
2010129190 June 2010 JP
2010132533 June 2010 JP
2010244729 October 2010 JP
2011134675 July 2011 JP
2011150817 August 2011 JP
2011249254 December 2011 JP
2012003940 January 2012 JP
2012099315 May 2012 JP
2012146479 August 2012 JP
2013037992 February 2013 JP
2013157084 August 2013 JP
2013532359 August 2013 JP
2015013775 January 2015 JP
2015138741 July 2015 JP
2015144061 August 2015 JP
2015204215 November 2015 JP
2015230801 December 2015 JP
20140006046 January 2014 KR
2126192 February 1999 RU
2005085138 September 2005 WO
2006005066 January 2006 WO
2006019245 February 2006 WO
2007004590 January 2007 WO
2007075867 July 2007 WO
2009003695 January 2009 WO
2009029746 March 2009 WO
2011007445 January 2011 WO
2011125481 October 2011 WO
2011150528 December 2011 WO
2011154869 December 2011 WO
2011156392 December 2011 WO
2012008422 January 2012 WO
2012016606 February 2012 WO
2012018831 February 2012 WO
2012128374 September 2012 WO
2012144553 October 2012 WO
2013049460 April 2013 WO
2013085557 June 2013 WO
2013130983 September 2013 WO
2013131005 September 2013 WO
2014058683 April 2014 WO
2014058684 April 2014 WO
2015007680 January 2015 WO
2015104538 July 2015 WO
2015128982 September 2015 WO
2015151144 October 2015 WO
2016102373 June 2016 WO
2016116400 July 2016 WO
2016141765 September 2016 WO
2020225313 November 2020 WO
Other references
  • Office Action dated Dec. 17, 2020 in CN Application No. 201780007783.8.
  • Extended European Search Report dated Feb. 12, 2020 in EP Application No. 19192837.3.
  • Kim et al., “A review of lithium and non-lithium based solid state batteries,” Journal of Power Sources, vol. 282, pp. 299-322 (2015).
  • Office Action dated Jun. 7, 2018 in U.S. Appl. No. 15/408,991, by Johnson.
  • Office Action dated Jun. 10, 2019 in JP Application No. 2018538203 (Partial English Translation).
  • “All-Solid-State Lithium-Ion Battery Using Li2.2C0.8B0 203 Electrolyte” External Program 20th Century International Conferencer, Presented on Poster Board, 2 pgs (Jun. 15, 2015).
  • Aaltonen et al., “Lithium Lanthanum Titanate Thin Films Grown by Atomic Layer Deposition for All-Solid-State Lithium Ion Battery Applications,” Abstract #688, The 15th International Meeting on Lithium Batteries (2010).
  • Adachi et al., “Ionic Conducting Lanthanide Oxides,” Chem. Rev., vol. 102, pp. 2405-2429 (2002).
  • Ahn et al., “Characteristics of Amorphous Lithium Lanthanum Titanate Electrolyte Thin Films Grown by PLD for Use in Rechargeable Lithium Microbatteries,” Electrochemical and Solid-State Letters, vol. 8, No. 2, pp. A75-A78 (2005).
  • Ahn et al., “Characteristics of Perovskite (Li0.5La0.5)TiO3 Solid Electrolyte Thin Films Grown by Pulsed Laser Deposition for Rechargeable Lithium Microbattery,” Electrochimica Acta, vol. 50, pp. 371-374 (2004).
  • Ahn et al., “Effect of Li0.5La0.5TiO3 Solid Electrolyte Films on Electrochemical Properties of LiCoO2 Thin Film Cathodes with Different Rapid-Thermal Annealing Conditions,” Journal of Vacuum Science & Technology B, vol. 23, No. 5, pp. 2089-2094 (2005).
  • Allen et al., “Effect of substitution (Ta, Al, Ga) on the conductivity of Li7La3Zr2012,” Journal of Power Sources, vol. 206, pp. 315-319(2012).
  • Allnatt et al., “Atomic Transport in Solids,” Cambridge University Press, pp. ix-xiii (2003).
  • Annamareddy et al., “Ion Hopping and Constrained Li Diffusion Pathways in the Superionic State of Antifluorite Li2O,” Entropy, vol. 19, No. 227, pp. 1-11 (2017).
  • Aruna et al., “Combustion Synthesis and Nanomaterials,” Current Opinion in Solid State and Materials Science, vol. 12, pp. 44-50 (2008).
  • Awaka et al., “Synthesis and Structure Analysis of Tetragonal Li7La3Zr2012 with the Garnet-Related Type Structure,” Journal of Solid State Chemistry, vol. 182, No. 8, pp. 2046-2052 (2009).
  • Balkanski et al., “Integrable lithium solid-state microbatteries,” Journal of Power Sources, vol. 26, pp. 615-622 (1989).
  • Bates et al., “Rechargeable Thin-Film Lithium Batteries,” Oak Ridge National Laboratory Publication, 9 pgs (1993).
  • Billinge, “The Nanostructure Problem,” Physics, vol. 3, No. 25, pp. 1-3 (2010).
  • Birke et al., “A first approach to a monolithic all solid state inorganic lithium battery,” Solid State Ionics, vol. 118, pp. 149-157 (1999).
  • Birke et al., “Electrolytic Stability Limit and Rapid Lithium Insertion in the Fast-Ion-Conducting Li0.29La0.57TiO3 Perovskite-Type Compound,” Journal of the Electrochemical Society, vol. 144, No. 6, pp. L167-L169 (1997).
  • Bohnke et al., “Mechanism of Ionic Conduction and Electrochemical Intercalation of Lithium into the Perovskite Lanthanum Lithium Titanate,” Solid State Ionics, vol. 91, pp. 21-31 (1996).
  • Boyd, “Thin Film Growth by Pulsed Laser Deposition,” Ceramics International, vol. 22, pp. 429-434 (1996).
  • Boyle et al., “All-Ceramic Thin Film Battery,” Sandia Report 2002-3615 Unlimited Release, 53 pages (Nov. 2002).
  • Brenier, “Stress and Moisture-Sorption in Ozone-Annealed Films of Zirconium Oxide Obtained from Sol-Gel,” Journal of Sol-Gel Science and Technology, vol. 25, pp. 57-63 (2002).
  • Brinker et al., “Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing,” Academic Press, pp. 21, 95, 153, 513, 675, 742, 787, and 837 (1990).
  • Buschmann et al., “Structure and dynamics of the fast lithium ion conductor 'Li7La3Zr2012,” Physical Chemistry Chemical Physics, vol. 13, p. 19378-19392 (2011) (Abstract Only).
  • Cao et al., “Microstructure and Ionic Conductivity of Sb-doped Li7La3Zr2012,” Journal of Inorganic Materials,vol. 29, No. 2, pp. 220-224 (2014).
  • Chabal et al., “Safer High-performance Electrodes, Solid Electrolytes, and Interface Reactions for Lithium-Ion Batteries,” Material Matters, vol. 8, No. 4, pp. 104-110 (2013).
  • Chen et al., “High Capacity and Cyclic Performance in a Three-Dimensional Composite Electrode Filled with Inorganic Solid Electrolyte,” Journal of Power Sources, vol. 249, pp. 306-310 (2014).
  • Chen et al., “Improving ionic conductivity of Li0.35La0.55Ti03 ceramics by introducing Li7La3Zr2012 sol into the precursor powder,” Solid State Ionics, vol. 235, pp. 8-13 (2013).
  • Cussen, “Structure and Ionic Conductivity in Lithium Garnets,” Journal of Materials Chemistry, vol. 20, pp. 5167-5173 (2010).
  • Davison et al., “Low Cost, Novel Methods for Fabricating All-Solid-State Lithium Ion Batteries,” downloaded from web page: <http://www.wpi.edu/Pubs/E-project/Available/E-project-042312-141301/unrestricted/SS_Lithium_Ion_Battery_MQP_Final_Report.pdf>, Download date: Apr. 23, 2012, original posting date unknown, 126 pages.
  • Decision to Grant dated Nov. 24, 2020 in KR Application No. 1020187020835.
  • Drabold, “Topics in the Theory of Amorphous Materials,” The European Physical Journal B, vol. 68, pp. 1-21 (2009).
  • Elliott, “Physics of Amorphous Materials,” Longman Scientific & Technical, Ed. 2, pp. v-vi (1990).
  • Examination Report dated Jun. 22, 2016 in EP Application No. 13776685.3.
  • Examination Report dated Nov. 30, 2016 in EP Application No. 13776685.3.
  • Extended European Search Report dated Feb. 8, 2017 in EP Application 16202541.
  • Extended European Search Report dated Mar. 16, 2017 in EP Application No. 17150717.
  • Furusawa et al., “Ionic Conductivity of Amorphous Lithium Lanthanum Titanate Thin Film,” Solid State Ionics, vol. 176, pp. 553-558 (2005).
  • Gao et al., “Sol-gel Synthesis and Electrical Properties of Li5La3Ta2O12 Lithium Ionic Conductors,” Solid State Ionics, vol. 181, Nos. 1-2, pp. 33-36 (2009).
  • Geiger et al., “Crystal Chemistry and Stability of‘Li7La3Zr2O12’ Garnet: A Fast Lithium-Ion Conductor,” Inorganic Chemistry, vol. 50, pp. 1089-1097 (2011).
  • Giordani et al., “A Molten Salt Lithium-Oxygen Battery,” Journal of the American Chemical Society, 26 pages (2016).
  • Glass et al., “Ionic Conductivity of Quenched Alkali Niobate and Tantalate Glasses,” Journal of Applied Physics, vol. 19, No. 9, pp. 4808-4811 (1978).
  • Goodenough et al., “Challenges for Rechargeable Li Batteries,” Chemistry of Materials, vol. 22, No. 3, pp. 587-603 (2010).
  • Hámáláinen et al., “Lithium Phosphate Thin Films Grown by Atomic Layer Deposition,” Journal of The Electrochemical Society, vol. 15 9, No. 3, pp. A259-A263 (2012).
  • Huggins, “Advanced Batteries: Materials Science Aspects,” Springer, Ed. 1, p. xvii-xxx and pp. 368-371 (2008).
  • Inaguma et al., “High Ionic Conductivity in Lithium Lanthanum Titanate,” Solid State Communications, vol. 86, No. 10, pp. 689-693 (1993).
  • Int'l Preliminary Examination Report on Patentability dated Jul. 5, 2018 in Int'l Application No. PCT/US2016/068105.
  • Int'l Preliminary Report on Patentability dated Feb. 14, 2013 in Int'l Application No. PCT/US2011/046289.
  • Int'l Preliminary Report on Patentability dated Apr. 23, 2015 in Int'l Application No. PCT/US2013/063160.
  • Int'l Preliminary Report on Patentability dated Sep. 2, 2014 in Int'l Application No. PCT/US2013/028672.
  • Int'l Preliminary Report on Patentability dated Sep. 12, 2014 in Int'l Application No. PCT/US2013/028633.
  • Extended European Search Report dated Dec. 16, 2021 in EP Application No. 21186896.3.
  • Office Action dated Feb. 9, 2022 in EP Application No. 16823507.5.
  • Office Action dated Jan. 22, 2016 in EP Application No. 13776685.3.
  • Office Action dated Jan. 24, 2012 in U.S. Appl. No. 12/198,421 by Johnson.
  • Office Action dated Jan. 25, 2018 in CN Application No. 201380052598.2.
  • Office Action dated Jan. 31, 2019 in U.S. Appl. No. 15/387,143, by Allie.
  • Office Action dated Feb. 7, 2018 in U.S. Appl. No. 14/382,194, by Thokchom.
  • Office Action dated Feb. 10, 2016 in U.S. Appl. No. 13/829,525 by Johnson.
  • Office Action dated Feb. 15, 2017 in CN Application No. 201380052598.2.
  • Office Action dated Feb. 20, 2017 in JP Application No. 2014-560097.
  • Office Action dated Feb. 21, 2020 in KR Application No. 1020187020835.
  • Office Action dated Mar. 2, 2016 in CN Application No. 201380023413.5.
  • Office Action dated Mar. 14, 2018 in U.S. Appl. No. 13/829,525, by Johnson.
  • Office Action dated Mar. 17, 2020 in U.S. Appl. No. 16/109,295, by Johnson.
  • Office Action dated Mar. 26, 2021 in CN Application No. 201680075318.3.
  • Office Action dated Mar. 30, 2018 in CN Application No. 201380023413.5.
  • Office Action dated Apr. 9, 2015 in U.S. Appl. No. 13/829,525 by Johnson.
  • Office Action dated Apr. 10, 2018 in EP Application No. 16202541.5.
  • Office Action dated Apr. 29, 2014 in U.S. Appl. No. 12/848,991 by Babic.
  • Office Action dated May 1, 2014 in U.S. Appl. No. 13/410,895, by Babic.
  • Office Action dated May 4, 2015 in U.S. Appl. No. 13/829,951 by Johnson.
  • Office Action dated May 4, 2016 in KR Application No. 10-2014-7027734.
  • Office Action dated May 19, 2017 in U.S. Appl. No. 12/198,421, by Johnson.
  • Office Action dated May 30, 2017 in JP Application No. 2015-535772.
  • Office Action dated Jun. 2, 2016 in CN Application No. 201380052598.2.
  • Office Action dated Jun. 5, 2019 in CN Application No. 201380052598.2.
  • Office Action dated Jun. 12, 2017 in U.S. Appl. No. 14/382,194, by Thokchom.
  • Office Action dated Jun. 13, 2017 in JP Application No. 2015-535773.
  • Office Action dated Jun. 15, 2017 in U.S. Appl. No. 14/382,191, by Thokchom.
  • Office Action dated Jun. 17, 2019 in U.S. Appl. No. 15/387,143, by Allie.
  • Office Action dated Jun. 19, 2014 in U.S. Appl. No. 13/829,951, by Johnson.
  • Office Action dated Jun. 24, 2019 in JP Application No. 2018551909.
  • Office Action datedJun. 26, 2015 in U.S. Appl. No. 14/530,171 by Babic.
  • Office Action dated Jun. 29, 2018 in U.S. Appl. No. 14/382,194, by Thokchom.
  • Office Action dated Jul. 1, 2015 in U.S. Appl. No. 13/829,525 by Johnson.
  • Office Action dated Jul. 5, 2016 in CN Application No. 201380052635.X.
  • Office Action dated Jul. 13, 2011 in U.S. Appl. No. 12/163,044, by Johnson.
  • Office Action dated Jul. 15, 2016 in KR Application No. 10-2014-7027734.
  • Office Action dated Jul. 20, 2017 in CN Application No. 201380052635.X.
  • Office Action dated Jul. 21, 2016 in U.S. Appl. No. 13/829,951, by Johnson.
  • Office Action dated Jul. 27, 2016 in U.S. Appl. No. 13/829,525, by Johnson.
  • Office Action dated Aug. 3, 2020 in CN Application No. 201680075318.3.
  • Office Action dated Aug. 7, 2017 in U.S. Appl. No. 13/829,525, by Johnson.
  • Office Action dated Aug. 7, 2019 in U.S. Appl. No. 12/198,421, by Johnson.
  • Office Action dated Aug. 9, 2021 in U.S. Appl. No. 12/198,421, by Johnson.
  • Office Action dated Aug. 11, 2017 in CN Application No. 2013800234135.
  • Office Action dated Aug. 21, 2020 in U.S. Appl. No. 12/198,421, by Johnson.
  • Office Action dated Aug. 22, 2016 in JP Application No. 2014-560097.
  • Office Action dated Aug. 30, 2021 in JP Application No. 2020114023.
  • Office Action dated Aug. 31, 2015 in KR Application No. 10-2014-7027734.
  • Office Action dated Sep. 3, 2018 in CN Application No. 201380052598.2.
  • Office Action dated Sep. 4, 2015 in EP Application No. 13776685.3.
  • Office Action dated Sep. 7, 2015 in JP Application No. 2014-560097, translation only.
  • Office Action dated Sep. 8, 2015 in U.S. Appl. No. 12/198,421 by Johnson.
  • Office Action dated Sep. 10, 2021 in CN Application No. 201910697285.1 (with English Translation of Search Report).
  • Office Action dated Sep. 14, 2016 in U.S. Appl. No. 12/198,421, by Johnson.
  • Office Action dated Sep. 28, 2020 in JP Application No. 2019173287.
  • Office Action dated Nov. 2, 2018 in U.S. Appl. No. 12/198,421, by Johnson.
  • Office Action dated Nov. 16, 2021 in CN Application No. 201680075318.3.
  • Office Action dated Nov. 18, 2016 in CN Application No. 201380023413.5.
  • Office Action dated Nov. 18, 2016 in U.S. Appl. No. 13/829,951, by Johnson.
  • Office Action dated Dec. 6, 2013 in U.S. Appl. No. 12/848,991 by Babic.
  • Office Action dated Dec. 13, 2018 in CN Application No. 2013800234135.
  • Oh et al., “Ionomer Binders Can Improve Discharge Rate Capability in Lithium-Ion Battery Cathodes,” Journal of The Electrochemical Society, vol. 158, No. 2, pp A207-A213 (2011).
  • Ohta et al., “All-solid-state lithium ion battery using garnet-type oxide and Li3BO3 solid electrolytes fabricated by screen-printing,” Journal of Power Sources (2013).
  • Okumura et al., “All-Solid-State Lithium-Ion Battery Using Li2.2C0.8B0.8B0.2O3 Electrolyte”, Solid State Ionic, vol. 288, pp. 248-252 (2016).
  • Owen, “Rechargeable Lithium Batteries,” Chemical Society Reviews, vol. 26, pp. 259-267 (1997).
  • Peters et al., “Ionic Conductivity and Activation Energy for Oxygen Ion Transport in Superlattices - The Multilayer System CSZ (ZrO2 + CaO) / AI203,” Solid State Ionics, vol. 178, Nos. 1-2, pp. 67-76 (2007).
  • Pham et al., “Synthesis and Characterization of Nanostructured Fast Ionic Conductor Li0.30La0.56TiO3,” Chemistry ol Materials, vol. 18, No. 18, pp. 4385-4392 (2006).
  • Popovici et al., “Sol-gel Preparation and Characterization of Perovskite Lanthanum Lithium Titanate,” Journal of Materials Science, vol. 42, pp. 3373-3377 (2007).
  • Ramzy et al., “Tailor-Made Development of Fast Li Ion Conducting Garnet-Like Solid Electrolytes,” Applied Materials & Interfaces, vol. 2, No. 2, pp. 385-390 (2010).
  • Raskovalov et al., “Structure and transport properties of Li7La3Zr2-0.75xAlxO2 superionic solid electrolytes,” Journal of Power Sources (2013).
  • Rowsell et al., “A new class of materials for lithium-ion batteries: iron(III) borates,” Journal of Power Sources, vol. 98-98, pp. 254-257 (2001).
  • Sakamoto, “Lithium Batteries,” Michigan State University (2011).
  • Sanchez et al., “Chemical Modification of Alkoxide Precursors,” Journal of Non-Crystalline Solids, vol. 100, pp. 65-76 (1988).
  • Scanlon, “Lithium Polymer Battery, Final Report for Dec. 8, 1994-Dec. 30, 2002,” Energy Storage and Thermal Sciences Branch, Air Force Research Laboratory (2003).
  • Shannon et al., “New Li Solid Electrolytes”, Electro, vol. 22, No. 7, pp. 783-796 (Jul. 1977).
  • Singhal et al., “High Temperature Solid Oxide Fuel Cells: Fundamentals, Design and Applications,” Elsevier Advanced Technology, 430 pages (2003).
  • Song et al., “Review of Gel-Type Polymer Electrolytes for Lithium-ion Batteries,” Journal of Power Sources, vol. 77, pp. 183-197 (1999).
  • Stramare et al., “Lithium Lanthanum Titanates: A Review,” Chemistry of Materials, vol. 15, pp. 3974-3990 (2003).
  • Sulaiman, “Fabrication and Characterization of LiN03-AI203 Composite Solid Electrolytes,” 2013 3rd International Conference on Chemistry and Chemical Engineering, vol. 38, pp. 1-5 (2012).
  • Sun et al., “High-Strength All-Solid Lithium Ion Electrodes Based on Li4Ti5012,” Journal of Power Sources, vol. 196, pp. 6507-11 (2011).
  • Tadnaga et al., “Low temperature synthesis of highly ion conductive Li7La3Zr2O12-Li3B03 composites,” Electrochemistry Communications (Apr. 3, 2013).
  • Tan et al., “Fabrication and Characterization of Li7La3Zr2012 Thin Films for Lithium Ion Battery,” ECS Solid State Letters, vol. 1, No. 6, pp. 057-060 (2012).
  • Tan et al., “Garnet-type Li7La3Zr2O12 Electrolyte Prepared by a Solution-Based Technique for Lithium ion battery,” Water. Res. Soc. Symp. Proc, vol. 1440, 6 pages (2012).
  • Fan et al., “Synthesis of Cubic Phase Li7La3Zr2O12 Electrolyte for Solid-State Lithium-Ion Batteries,” Electrochemical and Solid-State Letters, vol. 15, No. 3, pp. A37-A39 (2012).
  • Tan, “Materials for energy storage in Lithium-Ion batteries,” Dissertation submitted to the University of Utah (Dec. 2012).
  • Thangadurai et al., “Investigations on Electrical Conductivity and Chemical Compatibility Between Fast Llithium Ion Conducting Garnet-Life Li6BaLa2Ta2O12 and Lithium Battery Cathodes,” Journal of Power Sources, vol. 142, pp. 339-344 (2005).
  • Vijayakumar et al., “Synthesis of Fine Powders of Li3xLa2/3-xTiO3 Perovskite by a Polymerizable Precursor Method,” Chemistry of Materials, vol. 16, No. 14, pp. 2719-2724 (2004).
  • Wang et al., “lonic/Electronic Conducting Characteristics of LiFePO4 Cathode Materials,” Electrochemical and Solid-State Letters, vol. 10, No. 3, pp. A65-A69 (2007).
  • West, “Basic Solid State Chemistry,” John Wiley & Sons Ltd., Ed. 2, pp. vii-xv, 346-351 (1999).
  • Wohrle et al., “Sol-Gel Synthesis of the Lithium-Ion Conducting Perovskite La0.57Li0.3TiO3 Effect of Synthesis and Thermal Treatments on the Structure and Conducting Properties,” Ionics, vol. 2, pp. 442-445 (1996).
  • Wolfenstine, “Grain Boundary Conductivity in Crystalline LiTi2(PO4)3,” Army Research Laboratory (Apr. 2008).
  • Written Opinion dated Sep. 22, 2014 in Int'l Application No. PCT/US2013/063161.
  • Wu et al., “Sol-gel preparation and characterization of Li1.3AI0.3Ti1 7(PO4)3 sintered with flux of LiBO2,” Rare Metals, vol. 29, No. 5, p. 515(2010).
  • Xiong et al., “Effects of Annealing Temperature on Structure and Opt-Electric Properties of Ion-Conducting LLTO Thin Films Prepared by RF Magnetron Sputtering,” Journal of Alloys and Compounds, vol. 509, pp. 1910-1914 (2011).
  • Xu et al., “Structures of Orthoborate Anions and Physical Properties of Their Lithium Salt Nonaqueous Solutions,” Journal of The Electrochemical Society, vol. 150, No. 1, pp. E74-E80 (2003).
  • Xu, “Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries,” Chemical Reviews, vol. 104, pp. 1303-4417 (2004).
  • Yang et al., “Ionic to Mixed lonic/Electronic Conduction Transition of Chemically Lithiated Li0.33La0.56TiO3 at Room Temperature: Lithium-ion-Motion Dependent Electron Hopping,” Applied Physics Letters, vol. 89, pp. 1-3 (2006).
  • Yu et al., “A Stable Thin-Film Lithium Electrolyte: Lithium Phosphorus Oxynitride,” J. Electrochem. Soc., vol. 144, No. 2, pp. 524-532 (1997).
  • Zallen, “The Physics of Amorphous Solids,” Wiley-VCH, Ed. 1, pp. ix-xi (1983).
  • Zhang et al., “Effect of lithium borate addition on the physical and electrochemical properties of the lithium ion conductor Li3.4Si0.4P0.6O4,” Solid State Ionics, vol. 231, pp. 109-115 (2013).
  • Int'l Preliminary Report on Patentability dated Dec. 22, 2014 in Int'l Application No. PCT/US2013/063161.
  • Int'l Search Report and Written Opinion dated Jan. 6, 2012 in Int'l Application No. PCT/US2011/046289.
  • Int'l Search Report and Written Opinion dated Mar. 25, 2014 in Int'l Application No. PCT/US2013/063160.
  • Int'l Search Report and Written Opinion dated Apr. 23, 2014 in Int'l Application No. PCT/US2013/063161.
  • Int'l Search Report and Written Opinion dated Aug. 15, 2013 in Int'l Application No. PCT/US2013/028672.
  • Int'l Search Report and Written Opinion dated Aug. 22, 2013 in Int'l Application No. PCT/US2013/028633.
  • Int'l Search Report and Written Opinion dated Aug. 25, 2020 in Int'l Application No. PCT/US2020/026334.
  • Int'l Search Report dated Feb. 17, 2017 in Int'l Application No. PCT/US2016/068105 (Partial).
  • Int'l Search Report dated Apr. 12, 2017 in Int'l Application No. PCT/US2016/068105 (Complete).
  • Jena et al., “Studies on the Ionic Transport and Structural Investigations of La0.5Li0.5TiO3 Perovskite Synthesized by Wet Chemical Methods and the Effect of Ce, Zr Substitution at Ti site,” Journal of Materials Science, vol. 40, pp. 4737-4748 (2005).
  • Jin et al., “Al-doped Li7La3Zr2O12 synthesized by a polymerized complex method,” Journal of Power Sources, vol. 196, pp. 8683-8687 (2011).
  • Jin et al., “All-Solid-State Rechargeable Lithium Ion Battery Fabrication with Al-Doped Li7La3Zr2O12 Solid Electrolyte,” Retrieved from <http://intemational.dep.anl.gov/Postdocs/Symposium/Program/Presentations/32.pdf>, Download date: Oct. 8, 2012, original posting date: unknown, 1 page.
  • Jin et al., “Bulk solid state rechargeable lithium ion battery fabrication with Al-doped Li7La3Zr2O12 electrolyte and Cu0.1V2O5 cathode,” Electrochimica Acta, vol. 89, pp. 407-412 (2013).
  • Jin, “Processing and characterization of secondary solid-state Li-Ion batteries,” Dissertation submitted to the University of Notre Dame, 128 pages (Apr. 2013).
  • Jinlian et al., “Enhanced high temperature performance of LiMn2O4 coated with Li3BO3 solid electrolyte,” Bull. Mater. Sci., vol. 36, No. 4, pp. 687-691 (2013).
  • Kanamura et al., “Three Dimensionally ordered composite solid materials for all solid-state rechargeable lithium batteries” Journal of Power Sources, 146, pp. 86-89, 2005.
  • Khatun et al., Impact of Lithium Composition on Structural, Electronic and Optical Properties of Lithium Cobaltite Prepared by Solid-state Reaction Journal of Scientific Research, vol. 6, No. 2, pp. 217-231 (2014).
  • Kim et al., “Characterization of the Interface Between LiCoO2 and Li7La3Zr2O12 in an All-Solid-State Rechargeable Lithium Battery,” Journal of Power Sources, vol. 196, pp. 764-767 (2011).
  • Kishida et al., “Microstructure of the LiCoO2 (cathode)/La2/3-xLi3xTiO3 (electrolyte) Interface and its Influences on the Electrochemical Properties,” Acta Materialia, vol. 55, No. 14, pp. 4713-4722 (2007).
  • Kitaoka et al., “Preparation of La0.5Li0.5TiO3 Perovskite Thin Films by the Sol-Gel Method,” Journal of Materials Science, vol. 32, pp. 2063-2070 (1997).
  • Kobayashi et al., “All-Solid-State Lithium Secondary Battery with Ceramic/Polymer Composite Electrolyte,” Solid State Ionics, vol. 152-153, pp. 137-142 (2002).
  • Kokal et al., “Sol-gel Synthesis and Lithium Ion Conductivity of Li7La3Zr2O12 with a Garnet-Related Type Structure,” Solid State Ionics, vol. 185, pp. 42-46 (2011).
  • Kotobuki et al., “Fabrication of All-Solid-State lithium battery using novel garnet type electrolyte,” ECS Meeting Abstracts (2010).
  • Kotobuki et al., “Fabrication of Three-Dimensional Battery Using Ceramic Electrolyte with Honeycomb Structure by Sol-Gel Process,” Journal of The Electrochemical Society, vol. 157, No. 4, pp. A493-A498 (2010).
  • Kreiter et al., “Sol-gel Routes for Microporous Zirconia and Titania Membranes,” J. Sol-Gel Sci. Technol., vol. 48, pp. 203-211 (2008).
  • Laughlin et al., “Using Sol-Gel Chemistry to Synthesize a Material with Properties Suited for Chemical Sensing,” Journal of Chemical Education, vol. 77, No. 1, pp. 77-78 (2000).
  • Lee et al., “The Production of LiCoO2 Cathode Thick Films for an All-Solid-State Microbattery,” Journal of Ceramic Processing Research, vol. 8, No. 2, pp. 106-109 (2007).
  • Li et al., “Developments of electrolyte systems for lithium-sulfur batteries: a review,” Frontiers in Energy Research, vol. 3, No. 5, pp. 1-12 (2015).
  • Li et al., “Physical and Electrochemical Characterization of Amorphous Lithium Lanthanum Titanate Solid Electrolyte Fhin-Film Fabricated by e-beam Evaportation,” Thin Solid Films, vol. 515, pp. 1886-1892 (2006).
  • Li et al., “Synthesis and Characterization of Li ion Conducting La2/3-xLi3xTiO3 by a Polymerizable Complex Method,” Ceramics International, vol. 33, pp. 1591-1595 (2007).
  • Liu et al., “Enhanced high temperature performance of LiMn204 coated with Li3B03 solid electrolyte,” Bull. Mater. Sci., vol. 36, No. 4, pp. 687-691 (2013).
  • Ma, Ying, “Ceria-based Nanostructured Materials for Low-Temperature Solid Oxide Fuel Cells,” School of Information and Communication Technology, Functional Materials Division, Royal Institute of Technology, 52 pages (2012).
  • Machida et al., “All-Solid-State Lithium Battery with LiCo0.3Ni0.7O2 Fine Powder as Cathode Materials with an Amorphous Sulfide Electrolyte,” Journal of The Electrochemical Society, vol. 149, No. 6, pp. A688-A693 (2002).
  • Maqueda et al., “Structural, Microstructural and Transport Properties Study of Lanthanum Lithium Titanium Perovskite Thin Films Grown by Pulsed Laser Deposition,” Thin Solid Films, vol. 516, pp. 1651-1655 (2008).
  • Masset et al., “Thermal activated (thermal) battery technology Part II Molten salt electrolytes,” Journal of Power Sources, vol. 164, pp. 397-414 (2007).
  • Mateishina et al., “Solid-State Electrochemical Lithium Cells with Oxide Electrodes and Composite Solid Electrolyte,” Russian Journal of Electrochemistry, vol. 43, No. 5, pp. 606-608 (2007).
  • Meda et al., “Lipon Thin Films Grown by Plasma-Enhanced Metalorganic Chemical Vapor Deposition in a N2-H2-Ar Gas Mixture,” Thin Solid Films, vol. 520, pp. 1799-1803 (2012).
  • Mei et al., “Role of amorphous boundary layer in enhancing ionic conductivity of lithium-lanthanum-titanate electrolyte,” Electrochimica Acta, vol. 55, pp. 2958-2963 (2010).
  • Munshi, “Handbook of Solid State Batteries & Capacitors,” World Scientific, Chapters 10-12 (1995).
  • Murugan et al., “Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12,” Angewandte Chemie International Edition, vol. 46, pp. 7778-7781 (2007).
  • Nagata et al., “All Solid Battery with Phosphate Compounds Made Through Sintering Process,” Journal of Power Sources, vol. 174, pp. 832-837 (2007).
  • Nimisha et al., “Chemical and Microstructural Modifications in LiPON Thin Films Exposed to Atmospheric Humidity,” Solid State Ionics, vol. 185, pp. 47-51 (2011).
  • Office Action and Search Report dated Jan. 20, 2021 in TW Application No. 109111527 (with Brief Summary of Relevanl Portions of Office Action).
  • Office Action dated Jan. 2, 2015 in U.S. Appl. No. 12/198,421 by Johnson.
  • Office Action dated Jan. 7, 2013 in U.S. Appl. No. 12/198,421 by Johnson.
  • Office Action dated Jan. 12, 2022 in U.S. Appl. No. 16/592,562, by Allie.
  • Office Action dated Jan. 15, 2015 in U.S. Appl. No. 13/829,951 by Johnson.
  • Office Action dated Jan. 16, 2018 in JP Application No. 2015-535773.
  • Office Action dated Jan. 17, 2017 in CN Application No. 201380052635.
  • Office Action dated Jan. 18, 2017 in U.S. Appl. No. 13/829,525, by Johnson.
  • Zhang et al., “Study on Synthesis and Evolution of Sodium Potassium Niobate Ceramic Powders by an Oxalic Acid-Based Sol-Gel Method,” Journal of Sol-Gel Science and Technology, vol. 57, pp. 31-35 (2011).
  • International Search Report dated May 3, 2022 in International Application No. PCT/US2022/011012.
  • Office Action dated May 16, 2022 in U.S. Appl. No. 16/838,706, by Johnson.
  • Office Action dated Jun. 20, 2022 in U.S. Appl. No. 16/918,647, by Johnson.
  • Obrovac et al, “Reversible Cycling of Crystalline Silicon Powder,” Journal of the Electrochemical Society, vol. 154, No. 2, pp. A103-A108 (2007).
  • Limthongkul et al, “Electrochemically-Driven Solid State Amorphization in Lithium-Silicon Alloys and Implications for Lithium Storage,” Acta Materialia, vol. 51, pp. 1103-1113 (2003).
  • Datta et al, “Silicon and Carbon Based Composite Anodes for Lithium Ion Batteries,” Journal of Power Sources, vol. 158, pp. 557-563 (2006).
  • Read et al, “Characterization of the Lithium/Oxygen Organic Electrolyte Battery,” Journal of the Electrochemical Society, vol. 149, No. 9, pp. A1190-A1195 (2002).
  • Abraham et al, “A Polymer Electrolyte-Based Rechargeable Lithium/Oxygen Battery,” Journal of the Electrochemical Society, vol. 143, No. 1, pp. 1-5 (1996).
  • Miles et al, “Cation Effects on the Electrode Reduction of Molten Nitrates,” Journal of the Electrochemical Society, vol. 127, pp. 1761-1766 (1980).
  • Briant et al, “Ionic Conductivity in Lithium and Lithium-Sodium Beta Alumina,” Journal of the Electrochemical Society, vol. 128, No. 9, pp. 1830-1834 (1981).
  • Wang et al, “Ionic Conductivities and Structure of Lithium Phosporus Oxynitride Glasses,” Journal of Non-Crystalline Solids, vol. 183, pp. 297-306 (1995).
  • Kotobuki et al, “Fabrication of All-Solid-State Lithium Battery with Lithium Metal Anode Using Al2O3-Added Li7La3Zr2O12 Solid Electrolyte,” Journal of Power Sources, vol. 196, pp. 7750-7754 (2011).
  • Kotobuki et al, “Compatibility of Li7La3Zr2O12 Solid Electrolyte to All-Solid-State Battery Using Li Metal Anode,” Journal of the Electrochemical Society, vol. 157, No. 10, pp. A1076-A1079 (2010).
  • Miles, Melvin H., “Lithium Batteries Using Molten Nitrate Electrolytes,” Battery Conference on Applications and Advances. The Fourteenth Annual, pp. 39-42 (1999).
  • Int'l Search Report and Written Opinion dated Mar. 16, 2017 in Int'l Application No. PCT/US2017/014035.
  • International Preliminary Report on Patentability dated Aug. 2, 2018 in International Application No. PCT/US2017/014035.
Patent History
Patent number: RE49205
Type: Grant
Filed: Jun 11, 2019
Date of Patent: Sep 6, 2022
Assignee: JOHNSON IP HOLDING, LLC (Atlanta, GA)
Inventors: Lonnie G. Johnson (Atlanta, GA), Tedric D. Campbell (Lithia Springs, GA)
Primary Examiner: Sean E Vincent
Application Number: 16/437,141
Classifications
Current U.S. Class: With Specified Electrode Structure Or Material (429/405)
International Classification: H01M 12/08 (20060101); H01M 8/04276 (20160101); H01M 12/02 (20060101); H01M 10/652 (20140101); H01M 10/617 (20140101); H01M 10/654 (20140101); H01M 4/86 (20060101); H01M 10/615 (20140101); H01M 4/38 (20060101); H01M 10/655 (20140101); H01M 10/0569 (20100101); H01M 10/48 (20060101); H01M 50/431 (20210101); H01M 50/434 (20210101); H01M 50/437 (20210101); H01M 10/6551 (20140101); H01M 10/6571 (20140101); H01M 10/39 (20060101); H01M 10/0562 (20100101); H01M 4/134 (20100101); H01M 10/63 (20140101); H01M 10/0563 (20100101); H01M 4/02 (20060101);