Johnson lithium oxygen electrochemical engine
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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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 INVENTIONThe 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.
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
A need remains for a lithium air cell which overcomes problems associated with those of the prior art.
BRIEF SUMMARY OF THE INVENTIONA 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.
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:
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.
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.
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.
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.
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.
In an exemplary cell shown in
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
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
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
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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
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);