RECHARGEABLE METAL HALOGENIDE BATTERY

Abstract

Battery (10), comprising: an anode (12); an electrolyte (14), wherein the electrolyte (14) comprises: an oxidizing gas; an active cathode material comprising a metal halide; and a solvent containing a heterocyclic compound; and a current collector (16) in contact with the active cathode material, wherein the battery (10) does not have a dedicated cathode material.

Description

BACKGROUND

[0001] Rechargeable batteries are used as a power source in a wide range of applications, such as industrial units, medical units, electronic devices, electric vehicles, and grid energy storage systems. Battery technology is constantly being developed to enable higher energy density and efficiency, thereby expanding the use of batteries as power sources for even more applications.

[0002] The need for high specific capacities and energies led to the investigation of various metal-cell batteries. Lithium intercalation cathode materials, such as lithium nickel manganese cobalt oxide (NMC), lithium nickel cobalt aluminum oxide (NCA), lithium cobalt oxide (LCO), lithium iron phosphate (LFP), and the like, exhibit comparatively low energy densities and can be expensive. To find new and more effective cathode materials, conversion cathode materials, such as sulfur, oxygen, air, and others, were investigated.

[0003] Batteries made with lithium-oxygen, lithium-air, and lithium with other oxygen-containing gas mixtures exhibit excellent performance, at least in part due to the low atomic number, low density, and high reducing power of elemental lithium. Furthermore, a lithium-oxygen battery could potentially have a theoretical specific energy three to five times higher than that of conventional lithium-ion batteries.

[0004] Lithium metal has a high energy storage capacity and is used as a primary battery anode material. In some cases, lithium metal electrodes can form dendrites, which can cause short circuits during cell operation. Furthermore, it has proven difficult to find reasonably cost-effective cathode materials capable of absorbing the large quantity of lithium ions and electrons extracted from a lithium metal anode.

[0005] In this context, a published document already exists. Document WO 2018 / 225434A1 describes a non-aqueous electrolytic solution for lithium-air batteries, or a lithium-air battery itself. Specifically, the document describes a non-aqueous electrolyte for lithium-air batteries that comprises an organic solvent and a lithium salt. The lithium salt contains at least LiX (where X represents Br and / or I) and lithium nitrate. Furthermore, the document explicitly mentions lithium or a lithium alloy as the solid cathode material.

[0006] Despite the progress already made, there is still a need to further develop battery technologies, focusing on simplified manufacturing processes as well as a lower overall material usage while maintaining at least the same high or higher battery performance. SUMMARY

[0007] This problem is solved by the subject matter of the independent patent claims. Further embodiments are described by the dependent patent claims.

[0008] Some batteries containing sulfur, oxygen, air, or other active cathode materials exhibit poor cycle life, low power density, or both. For example, such batteries may be comparatively unstable and / or undergo parasitic reactions that can generate electrochemically irreversible carbonate byproducts, reducing the battery's cycle life and / or power density, for example, through electrolyte decomposition or carbon surface oxidation.

[0009] The present invention relates generally to a battery with an electrolyte comprising an oxidizing gas, a metal halide, and a solvent containing a heterocyclic compound. In various embodiments of the invention, the battery exhibits one or more advantages: a comparatively fast charging speed, high energy efficiency, high power density, and good cycle life. Furthermore, in some embodiments of the invention, the electrolyte can be more cost-effective and potentially less hazardous than some other battery electrolytes. The electrolyte can provide high power density in metal-based batteries by forming small and dense nuclei, which also have a comparatively uniform size and can effectively and naturally suppress undesirable dendrite growth on the anode. Furthermore, the electrolyte does not contain heavy metals, such as...Cobalt or nickel, and will therefore probably reduce the overall manufacturing costs of the battery.

[0010] In one embodiment, the present disclosure relates to a battery comprising: an anode; an electrolyte containing oxidizing gas; an active cathode material containing a metal halide; and a solvent containing a heterocyclic compound; and a current collector in contact with the active cathode material.

[0011] In another embodiment, the present disclosure relates to a battery comprising: (a) an anode which, during charging, absorbs metal ions from an electrolyte and releases the ions to the electrolyte during discharging, wherein the electrolyte contains: (i) a solvent containing a heterocyclic compound, and (ii) a dissolved halide, wherein the halide acts as the cathode for the battery; (b) a solid electrolyte interphase layer (“solid-electrolyte interphase” layer, SEI layer) which is in contact with the anode, wherein the SEI layer contains an oxide of the metal; and (c) a current collector comprising an electrically conductive porous material, wherein the current collector is in contact with the dissolved halide.

[0012] In another embodiment, the present invention relates to a method for producing a battery, comprising: dissolving a metal halide in a solvent containing a heterocyclic compound to form a solution; impregnating a separator with the solution; stacking an anode, the separator impregnated with the solution, and a current collector, wherein the stacking comprises arranging the separator impregnated with the solution between the anode and the current collector; and introducing an oxidizing gas to the stacked anode, the separator impregnated with the solution, and the current collector to form the battery, wherein the battery comprises: an anode; an electrolyte containing an oxidizing gas; an active cathode material containing a metal halide; a solvent containing a heterocyclic compound; and a current collector in contact with the active cathode material.

[0013] The details of one or more examples of the invention are set forth in the accompanying drawings and the description below. Further features, tasks, and advantages of the invention will become apparent from the description, the drawings, and the claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. Figure 1 is a schematic representation depicting an example battery comprising an anode, an electrolyte, a current collector, and an optional separator. Fig. 2 is a schematic representation showing the example battery of Fig. 1 represents within a closed cell. Fig. Figure 3 is a flowchart that illustrates an example process for manufacturing a battery. Fig. 4A to Fig. Figure 4B shows plots of the galvanostatic discharge and charge cycle behavior of the first cycles and the area-specific discharge capacity based on the number of cycles of the cells with 1 M Lil-GBL in the presence of oxygen as described in Example 2. The cells were charged at a current density of 5 mA / cm². 2 operated. Fig. 5A to Fig. Figure 5B shows plots of the galvanostatic discharge and charge cycle behavior of the first cycles and the area-specific discharge capacity based on the number of cycles of the cells with 1 M Lil-ECL in the presence of oxygen as described in Example 3. The cells were charged at a current density of 5 mA / cm². 2 operated. Fig. 6A to Fig. Figure 6B shows plots of the galvanostatic discharge and charge cycle behavior of the first cycles and the area-specific discharge capacity based on the number of cycles of the cells with 1 M Lil-THF electrolyte in the presence of oxygen, as described in Example 4. The cells were charged at a current density of 5 mA / cm². 2 operated. Fig. Figure 7 is a plot of the galvanostatic discharge and charge cycle behavior of the first cycle using 1 M Lil-GBL in the absence of oxygen in the cell of comparison example 1. The cells were charged at a current density of 5 mA / cm². 2 operated. Fig. Figure 8 is a plot of the galvanostatic discharge and charge cycle behavior of the 50th cycle using 1 M Lil-TEGDME electrolyte in the presence of oxygen in the cell of comparison example 2. The cells were charged at a current density of 5 mA / cm². 2 operated.

[0014] Identical symbols in the figures represent identical elements. DETAILED DESCRIPTION

[0015] Fig. Figure 1 is a schematic representation of an example battery 10, which includes an anode 12, an electrolyte 14, a current collector 16, and an optional separator 18. The battery operates via reduction-oxidation (redox) reactions and uses different oxidation states and redox reactions of one or more components or elements for charging and discharging.

[0016] The anode 12 can be made of any metal, and suitable examples include, but are not limited to, lithium, magnesium, sodium, and mixtures and combinations thereof. In some examples, the anode 12 consists essentially of elemental lithium, magnesium, or sodium, or lithium, magnesium, or sodium alloyed with one or more additional elements. In some embodiments, the anode 12 consists of elemental lithium, magnesium, sodium, or lithium.

[0017] The anode 12 can absorb metal ions from the electrolyte 14 during charging and release the metal ions to the electrolyte 14 during discharging. In some embodiments, the anode 12 can be an intercalation host material capable of absorbing metal ions. In some examples, a solid electrolyte interphase (SEI) layer can be in contact with the anode 12. For example, the SEI layer can contain an oxide of a metal from the electrolyte 14.

[0018] The electrolyte 14, which may be aqueous or non-aqueous, contains a solvent containing a heterocyclic compound, a metal halide, and an oxidizing gas. In the present application, the term "heterocyclic compound" means an aromatic or non-aromatic cyclic compound having at least atoms of two different elements as ring elements. A cyclic compound (ring compound), as used in the present application, means a compound in which one or more rows of atoms in the compound are linked to form a ring. In various embodiments, suitable cyclic compounds for the electrolyte 14 include 5-membered rings, such as pyrrolidines, oxolanes, thiolanes, pyrroles, furans, and thiophenes; 6-membered rings, such as piperadines, oxanes, thianes, pyridines, pyrans, and thiopyrans; and 7-membered rings, such as azepanes, oxepans, thiepans, azepines, oxepines and thiepenes.Examples of suitable heterocyclic compounds include, but are not limited to, tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, oxathiolane, succinimide, oxazolidone, γ-butyrolactone, γ-caprolactone, ε-caprolactone, γ-valerolactone, pyrrolidine, imidazolidine, sulfolane, thiane, and mixtures and combinations thereof. In some embodiments, suitable heterocyclic compounds include, but are not limited to, cyclic ethers, cyclic esters, and mixtures and combinations thereof.

[0019] In some examples, the electrolyte 14 may contain one or more additional solvents. In some embodiments, the one or more additional solvents may be selected from non-aqueous organic solvents, such as an ether, a glymer, a carbonate, a nitrile, an amide, an amine, an organosulfur solvent, an organophosphorus solvent, an organosilicon solvent, a fluorinated solvent, adiponitrile (ADN), propylene carbonate (PC), dimethoxyethane (DME), and mixtures and combinations thereof. In some examples, the electrolyte 14 contains equal parts of the solvent containing the heterocyclic compound and of the one or more additional solvents. In some examples, the one or more additional solvents in the electrolyte 14 may be selected to further improve the electrochemical performance of the battery 10, such as...by increasing rechargeability, cycle life, or the like.

[0020] The electrolyte 14 contains an oxidizing gas. In some examples, the electrolyte 14 may be present in the presence of an oxidizing gas, and the term "contains an oxidizing gas" is intended to include such a configuration. In some examples, the oxidizing gas may be dissolved in the solvent containing the heterocyclic compound of the electrolyte 14. In some examples, which are not intended to be limiting, the oxidizing gas contains at least one of oxygen, air, nitric oxide, or nitrogen dioxide. The oxidizing gas helps to induce the redox reactions of the battery 10 as described above and helps to achieve highly reversible redox reactions, which can contribute to improved electrochemical performance of the battery 10. The oxidizing gas can help to induce such redox reactions but is neither consumed nor developed during the use of the battery 10 (e.g.,The oxidizing gas does not participate in the redox reactions of the battery (10). In some examples, an electrolyte containing a metal halide and a solvent containing a heterocyclic compound, but no oxidizing gas, may show little or no rechargeability.

[0021] Electrolyte 14 also contains a metal halide (e.g., MX, where M is a metal element and X is a halogen element). In some examples, the metal halide contains an electrolyte salt that dissociates into a corresponding halide ion and a corresponding metal ion. For example, the metal halide can dissolve in the solvent containing the heterocyclic compound and dissociate into the corresponding metal and halide ions. In some examples, the halide ion can contain an ion of at least one of I, Br, Cl, and F (e.g., XI, Br, Cl, or F), and the metal ion can contain an ion of at least one of Li, Mg, and Na (e.g., M, Li, Mg, or Na). In other examples, the metal halide can contain various elements of I, Br, Cl, F, Li, Mg, and / or Na. The metal halide can impart ionic conductivity to electrolyte 14.

[0022] In some embodiments, the electrolyte 14 contains an optional additional salt that dissociates into a corresponding metal ion and a corresponding counter-anion. In some examples, which are not intended to be limiting, the metal ion contains at least one of Li, Mg, and Na, and the counter-anion contains one or more of nitrate (NO3). - ), Hexafluorophosphate (PF6 - ) Tetrafluoroborate (BF4 - ), Bisoxalatoborate (BOB - ), Difluorooxalatoborate (DFOB) - ), Trifluoromethanesulfonate (TF - ) and trifluorosulfonylimide (TFSI - ).

[0023] Additionally or alternatively, the metal halide of the electrolyte 14 can act as an active cathode material. For example, the metal halide can absorb, store, and release metal ions during the charging and discharging of the battery 10. In this way, the battery 10 does not need to have a dedicated cathode material. Instead, the battery 10 can have the metal halide of the electrolyte 14 as its active cathode material and a current collector 16. Consequently, the battery 10 can be less expensive to manufacture, lighter, have a higher power density, or combinations thereof. In some cases, the high power density of the electrolyte containing the metal halide acting as the active cathode material can allow the battery 10 to charge significantly faster than some other batteries that do not contain the electrolyte described herein.In some examples, an electrolyte containing a solvent that includes a heterocyclic compound and an oxidizing gas, but not a metal halide, may exhibit reduced electrochemical performance (e.g., reversibility, rechargeability and / or cycleability), produce irreversible carbonate by-products, have reduced power density, or combinations thereof, compared to electrolyte 14.

[0024] The current collector 16 can contain a material with suitable electrical conductivity that collects electrons generated by a redox reaction during the discharge of the battery 10 and provides a conductive path to an external electrical circuit to which the battery 10 is connected. Similarly, during the recharging of the battery 10, the current collector 16 provides an electrical connection between an external voltage source and the electrolyte 14 to supply voltage for a further redox reaction to charge the battery 10. In some examples, the current collector 16 can contain electrically conductive powders, such as metal and / or carbon powders, woven or nonwoven metal fibers, metal foam, woven or nonwoven carbon fibers, or the like. Additionally or alternatively, the current collector 16 can contain a stainless steel mesh, an aluminum mesh (Al), nickel foam (Ni), and / or carbon paper.For example, in one embodiment, the current collector 16 can contain a stainless steel mesh with carbon nanoparticles deposited on it. As another example, the current collector can be a porous, electrically conductive material.

[0025] In other examples, the battery 10 can contain a dedicated cathode material in addition to the metal halide, which acts as the active cathode material and current collector 16. For example, the battery 10 can have a cathode that provides a conductive path to an external electrical circuit to which the battery 10 is connected. In some cases, the battery 10 can have a cathode that can be used in a lithium-ion battery. For example, the cathode can be at least one of lithium cobalt oxide (LCO, e.g., LiCoO2), nickel cobalt aluminum (NCA, e.g., Li-Ni), or other materials. x Co y Al z O2, LiNi 0,8 Co 0,15 Al0,05 O2), lithium ion manganese oxide (LMO, e.g. LiMn2O4), lithium nickel manganese cobalt oxide (NMC, e.g. LiNiMnCoO2), nickel cobalt manganese (NCM, e.g. Li-Ni x Co y Mn z O2, LiNi 0,33 Co 0,33 Mn 0,33 O2) or lithium iron phosphate (LFP, e.g., LiFePO4). In other examples, battery 10 may contain a different or an additional cathode material.

[0026] In some examples, the battery 10 includes an optional separator 18. The separator 18 can force electrons through an external electrical circuit to which the battery 10 is connected, preventing the electrons from migrating through the battery 10 (e.g., through the electrolyte 14 of the battery 10), while still allowing the metal ions to flow through the battery 10 during charging and discharging. In some examples, the separator 18 may be saturated with, contained within, or surrounded by electrolyte 14, or the like. The separator 18 may contain an electrically non-conductive material to prevent the movement of electrons through the battery 10, causing the electrons to move through the external circuit instead. For example, the separator 18 may contain glass, nonwoven fibers, polymer sheets, rubber, and the like.

[0027] In some examples, the battery 10 has a closed or substantially closed volume. For instance, the anode 12, the electrolyte 14, the current collector 16, and the separator 18 may be arranged within a closed or substantially closed cell or other enclosure. In this way, the oxidizing gas of the electrolyte 14 remains within the battery 10, so that the battery 10 exhibits a comparatively high charging rate, high energy efficiency, high power density, high reversibility, high cycle life, or combinations thereof, as described herein.

[0028] Battery 10 can be capable of undergoing numerous charge and discharge cycles even at comparatively high charge densities (e.g., exhibiting good rechargeability). In some examples, battery 10 is capable of at least 100 charge and discharge cycles at a current density of approximately 1 mA / cm² or higher. 2, approximately 5 mA / cm 2 , approximately 10 mA / cm 2 or about 20 mA / cm 2 To carry out this. For example, battery 10 may be capable of at least 1000 charge and discharge cycles at a current density of higher than or equal to approximately 1 mA / cm². 2 , approximately 5 mA / cm 2 , approximately 10 mA / cm 2 or about 20 mA / cm 2 to carry out.

[0029] Additionally or alternatively, battery 10 can exhibit a comparatively high energy efficiency. For example, battery 10 can have an energy efficiency of 90% or higher at a current density of approximately 1 mA / cm² or higher. 2 , approximately 5 mA / cm 2 , approximately 10 mA / cm 2 or about 20 mA / cm 2 exhibiting certain properties. In some examples, battery 10 can achieve an energy efficiency of 99% or higher at a current density of approximately 1 mA / cm² or higher. 2 , approximately 5 mA / cm 2 , approximately 10 mA / cm 2 or about 20 mA / cm2 exhibit.

[0030] Fig. Figure 2 is a schematic representation of the example battery 10 of Fig. 1 within a closed cell system 20. The closed cell system 20 may contain a cell that houses the battery 10 during operation of the battery 10, a cell used to manufacture the battery 10, or both. For example, the closed cell system 20 may contain a cell that is available from Swagelok, Solon, OH, under the trade name SWAGELOK, and may be used to manufacture the battery 10. In some examples, the closed cell system 20 may include an inlet tube 22 and / or an outlet tube 24. The inlet tube 22 and the outlet tube 24 may be used to introduce air or other gases, such as the oxidizing gas of the electrolyte 14, into and out of the closed cell.

[0031] Fig. 3 is a flowchart showing an example procedure for manufacturing battery 10. Fig. 1 represents the procedure of Fig. 3 is used for the closed cell system 20 of Fig. 2 described. In other examples, the procedure can be described by Fig. 3 but also with a different system than the closed cell system 20 of Fig. 2 can be used. The procedure of Fig. 3 is described for a closed cell system, Fig. However, in some examples, 3 can be used with a cell that is not completely closed (e.g., at least partially open).

[0032] The procedure of Fig. Figure 3 describes dissolving a metal halide in a solvent containing a heterocyclic compound to form a solution (30). To dissolve the metal halide in the solvent containing the heterocyclic compound, the metal halide can be added to the solvent containing the heterocyclic compound and stirred gently, e.g., stirred gently overnight. In some examples, the solution of the metal halide dissolved in the solvent containing the heterocyclic compound can have a concentration between about 0.1 M and about 20 M, about 0.5 M and about 10 M, or about 1 M and about 5 M.

[0033] In some examples, the metal halide can be dried before dissolving it in the solvent containing the heterocyclic compound. The drying temperature and / or drying time can be selected according to the metal halide to be used in electrolyte 14, and in some non-restrictive examples, the metal halide can be dried on a hot plate in an argon-filled glovebox at about 120 °C for more than 12 hours.

[0034] In addition to or as an alternative to drying the metal halide, in some examples the solvent containing the heterocyclic compound can also be dried before dissolving the metal halide in it. For example, the solvent containing the heterocyclic compound can be stored overnight together with a molecular sieve.

[0035] The procedure of Fig. Figure 3 further describes impregnation of the optional separator 18 with the solution (32). Impregnation of the separator 18 with the solution may include immersion of the separator 18 in the solution, application of the solution to the separator 18, or any other method for impregnating the separator 18 with the solution. In some examples, impregnation of the separator 18 with the solution may involve an amount of approximately 1 µl / cm². 2 up to approximately 500 µl / cm² 2 , approximately 10 µl / cm² 2 up to approximately 250 µl / cm² 2 or approximately 50 µl / cm² 2 or approximately 100 µl / cm² 2 include.

[0036] Furthermore, the procedure of Fig. 3 stacking the anode 12, the optional solution-impregnated separator 18 and the current collector 16 within the closed cell system 20 on (34), e.g. as in Fig. Figure 2 shows. In some examples, the stacking may involve arranging the separator 18 between the anode 12 and the current collector 16. In some examples, one or more of the anode 12, the solution-impregnated separator 18, and the current collector 16 may be stacked before the separator 18 is impregnated with the solution. For example, the separator 18 may be stacked on top of the anode 12 and then impregnated with the solution. In some cases, the closed cell system 20 may be at least partially open during the stacking process, and after the anode 12, the solution-impregnated separator 18, and the current collector 16 have been stacked, the closed cell system 20 may be closed or substantially closed to form a closed or substantially closed volume around the anode 12, the solution-impregnated separator 18, and the current collector 16.

[0037] In other examples, the battery 10 may not have a separator 18. In such examples, the electrolyte 14 may be introduced into the battery 10 in a different way. For example, the battery 10 may contain an electrolyte 14 between the anode 12 and the current collector 16 without a separator 18. The electrolyte 14 may be introduced into the battery 10 in any suitable way so that the electrolyte 14 can function as described herein. In this way, the method of Fig. 3 stacks of the anode 12 and the current collector 16 within the closed cell system 20.

[0038] The procedure of Fig. Figure 3 also includes the introduction of an oxidizing gas into the closed cell system 20 to produce the electrolyte 14 and manufacture the battery 10 (36). In some examples, introducing the oxidizing gas into the closed cell system 20 to produce the electrolyte 14 and manufacture the battery 10 involves introducing the oxidizing gas into the closed cell 20 through an inlet tube 24. In some examples, the closed cell system 20 may contain or be in the presence of an inert gas, such as argon, before the oxidizing gas is introduced into the closed cell system 20. In some such examples, introducing the oxidizing gas may purge the inert gas contained within the closed cell system 20 and completely replace it with the oxidizing gas.For example, the oxidizing gas can be introduced into the closed cell 20 through the inlet tube 24, and the inert gas can be purged through the outlet tube 26. In some examples, the concentration of the oxidizing gas in the closed cell system 20 can be between approximately 5 wt% and approximately 100 wt%, approximately 50 wt% and approximately 100 wt%, or approximately 80 wt% and approximately 100 wt% of the total amount of gases within the closed cell system 20, such as the total amount of oxidizing gas and inert gas within the closed cell system 20.

[0039] The present invention will now be described with reference to the following non-limiting examples. EXAMPLES Example 1: Production of the electrolyte and the cell assembly

[0040] Lithium iodide (Lil) was placed in a vial and dried on a hot plate in an argon-filled glove box (< 0.1 ppm H₂O, O₂) for 1 hour at 120 °C. γ-Butyrolactone (GBL), ε-Caprolactone (ECL), and tetrahydrofuran (THF) were selected as suitable examples of heterocyclic compounds for the battery cell electrolyte and were purified overnight using a 3 Å molecular sieve. 1 M of dried Lil powder was added, dissolved in a solution containing the selected heterocyclic compound, and stirred gently overnight.

[0041] One M of lithium in the electrolyte solution containing the heterocyclic compound was used to saturate the separator positioned on top of the lithium metal anode, and a carbon-coated current collector was placed on the other side of the separator. Thus, the electrolyte-wetted separator was positioned between the anode and the cathode, in contact with both. Cell assembly was performed in an argon-filled glove box.

[0042] All cell components were arranged within a cell commercially available under the SWAGELOK brand from Swagelok, Inc., Solon, OH, which features inlet and outlet tubes for the flow of oxygen. Oxygen was then introduced through the inlet tube, purging and completely replacing the argon gas in the cell.

[0043] As shown below, cells with electrolytes containing GLB exhibited higher energy efficiency, while the use of ECL resulted in a longer cycle life. A mixture of these solvents would presumably provide the strengths of each and become an ideal electrolyte system for the rechargeable metal halide battery.

[0044] For comparison purposes, 1 M Lil-GBL was tested in an oxygen-free environment and 1 M Lil in tetraethylene glycol dimethyl ether (TEGDME) in an oxygen-containing environment with the same cell configuration. Example 2: Rechargeable lithium iodide battery with GBL electrolyte and oxygen

[0045] Fig. Figure 4A shows the first discharge and charge cycle of the cell from Example 1 with 1 M Lil-GBL electrolyte in the presence of ultrapure oxygen at a current density of 5 mA / cm². 2Lil was chosen as an example of the metal halide salt, GBL was chosen as an example of the heterocyclic compound, and oxygen was chosen as an example of the oxidizing gas.

[0046] As in Fig. As shown in Figure 4B, the cells maintained excellent energy efficiency (> 90 %) and generated a high output power (> 10 mW / cm²). 2 ) for over 500 cycles. The specific capacitance was normalized based on the electrode area. Example 3: Rechargeable lithium iodide battery with ECL electrolyte and oxygen

[0047] Fig. Figure 5A shows the first discharge and charge cycle of a cell from Example 1 with 1 M Lil-ECL electrolyte in the presence of ultrapure oxygen at a current density of 5 mA / cm². 2 Lil was chosen as an example of the metal halide salt, ECL was the heterocyclic compound, and oxygen was the oxidizing gas.

[0048] As in Fig. As shown in 5B, the cells maintained a high output power (> 10 mW / cm²). 2 ) for over 500 cycles. The specific capacitance was normalized based on the electrode area. Example 4: Rechargeable lithium iodide battery with THF electrolyte and oxygen

[0049] Fig. Figure 6A shows the first discharge and charge cycle of a cell from Example 1 with 1 M Lil-THF electrolyte in the presence of ultrapure oxygen at a current density of 5 mA / cm². 2 . Lil was chosen as the metal halide salt, THF was chosen as an example of the heterocyclic compound, and oxygen was chosen as the oxidizing gas.

[0050] As in Fig. As shown in 6B, the cells maintained a high output power (> 10 mW / cm²). 2 ) for over 100 cycles. The specific capacitance was normalized based on the electrode area. Comparison example 1: Lithium-iodide battery with GBL electrolyte without oxygen

[0051] Fig. Figure 7 shows the first discharge and charge cycle of a cell from Example 1 with 1 M Lil-GBL electrolyte in the absence of oxygen at a current density of 5 mA / cm². 2 Using the same electrolyte solution as in the cell of Example 2, the cell provided a negligible discharge capacity in the first cycle. The Coulomb efficiency was less than 10% in the first cycle and did not improve in subsequent cycles. The specific capacitance was normalized with respect to the electrode area. Comparison example 2: Lithium iodide battery with TEGDME electrolyte and oxygen

[0052] Fig. Figure 8 shows the 50th discharge and charge cycle of a cell from Example 1 with 1 M Lil-TEGDME electrolyte in the presence of ultrapure oxygen at a current density of 5 mA / cm². 2The cell provides a negligible discharge capacity in the 50th cycle under an oxygen environment. Although the cell's Coulomb efficiency was higher than 90% in the first cycle, it dropped significantly from the next cycle onward, finally falling below 10% in the 50th cycle. The specific capacity was normalized per unit area of ​​the electrode. A notable finding of this example is that battery performance decreases when the cyclic compound in the electrolyte lacks an ether group.

[0053] Several embodiments of the invention have been described. These and other embodiments of the invention are within the scope of the following claims.

Claims

[1] Battery (10), comprising: an anode (12); an electrolyte (14), wherein the electrolyte (14) comprises: an oxidizing gas; an active cathode material comprising a metal halide; and a solvent containing a heterocyclic compound; and a current collector (16) in contact with the active cathode material, wherein the battery (10) does not have a dedicated cathode material. [2] Battery (10) according to claim 1, wherein the solvent in the electrolyte (14) comprises a heterocyclic compound selected from the group consisting of cyclic ethers, cyclic esters and mixtures and combinations thereof. [3] Battery (10) according to claim 1, wherein the current collector (16) comprises a porous material which is electrically conductive. [4] Battery (10) according to claim 1, further comprising a separator (18) between the anode (12) and the current collector (16). [5] Battery(10) according to claim 1, wherein the anode (12) comprises at least one of Li, Mg and Na. [6] Battery (10) according to claim 1, wherein the oxidizing gas is selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide and mixtures and combinations thereof. [7] Battery (10) according to claim 1, wherein the solvent in the electrolyte (14) is selected from the group consisting of tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, oxathiolane, succinimide, oxazolidone, γ-butyrolactone, γ-caprolactone, ε-caprolactone, γ-valerolactone, pyrrolidine, imidazolidine, sulfolane, thiane and mixtures and combinations thereof. [8] Battery (10) according to claim 1, wherein the metal halide comprises an electrolyte salt which dissociates in the solvent into a corresponding halide ion and a corresponding metal ion, and wherein the halide ion comprises an ion of at least one of I, Br, Cl and F and the metal ion comprises an ion of at least one of Li, Mg and Na. [9] Battery (10) according to claim 1, further comprising an additional salt which dissociates into a corresponding metal ion and a corresponding counter-anion, wherein the metal ion is selected from the group consisting of Li, Mg and Na and mixtures and combinations thereof and the anion is selected from the group consisting of nitrate (NO3) - ), Hexafluorophosphate (PF6 - ), tetrafluoroborate (BF4), bisoxalatoborate (BOB - ) and difluorooxalatoborate (DFOB) - ), Trifluoromethanesulfonate (TF - ), Trifluorosulfonylimide (TFSI - ) and mixtures and combinations thereof. [10] Battery (10) according to claim 1, wherein the solvent further comprises an organic solvent selected from the group consisting of an ether, a glymer, a carbonate, a nitrile, an amide, an amine, an organosulfur solvent, an organophosphorus solvent, an organosilicon solvent, a fluorinated solvent and mixtures and combinations thereof. [11] Method for manufacturing a battery (10) comprising: Forming an electrolyte (14) comprising an oxidizing gas, a solvent comprising a heterocyclic compound, and an active anode material comprising a metal halide, which is dissolved in the solvent and thus forms a solution (30); Soaking (32) a separator (18) with the solution; Stacking (34) an anode (12), the solution-impregnated separator (18) and a current collector (16), wherein the stacking (34) is an arrangement between the anode (12) and the current collector (16) such that the current collector (16) contacts the active cathode material; and wherein the battery (10) does not have a dedicated cathode material.

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