Battery having an SEI protective layer on the surface of a metal anode and method for manufacturing the same

Abstract

The battery comprises a metal anode having a solid electrolyte interface (SEI) surface layer, a cathode having halogen species incorporated into a porous carbon material, an electrolyte having an organic solvent and salt in contact with the anode and cathode, and an oxidizing gas in contact with the electrolyte. The SEI layer has composition M α B β C γ N δ F ε X ζ O η The formula is such that M is a metal, B is boron, C is carbon, N is nitrogen, F is fluorine, X is a non-fluorine halogen species, O is oxygen, α is a number in the range of 0.2 to 0.4, β is a number in the range of 0.0 to 0.1, γ is a number in the range of 0.15 to 0.25, δ is a number in the range of 0.0 to 0.02, ε is a number in the range of 0.0 to 0.1, ζ is a number in the range of 0.005 to 0.02, and η is a number in the range of 0.40 to 0.60, and α, β, γ, δ, ε, ζ, and η are selected such that the sum of α + β + γ + δ + ε + ζ + η = 1. The SEI surface layer of the metal anode suppresses dendrite formation, promotes uniform lithium plating, limits electrolyte decomposition, and extends battery life.

Description

[Technical Field]

[0001] joint research agreement The subject matter of this disclosure describes activities commenced within the scope of a joint research agreement entered into prior to the effective filing date of this application. The parties to the joint research agreement are International Business Machines Corporation (Armonk, New York, USA) and Central Glass Co., Ltd. (Tokyo, Japan).

[0002] The present invention relates to a rechargeable battery in general, and more specifically, to a rechargeable battery having a solid electrolyte interface (SEI) protective layer on the surface of a metal anode that suppresses dendrite formation, promotes uniform lithium plating, limits electrolyte decomposition, and extends battery life. [Background technology]

[0003] Rechargeable batteries are in high demand for a wide range of applications, from small batteries for industrial and medical devices to larger batteries for electric vehicles (EVs) and grid energy storage systems, where each application requires a specific set of electrochemical performance characteristics. In many important and growing application species, such as EVs, battery performance is still considered a major limiting factor in meeting the high performance standards required to meet consumer needs.

[0004] Currently, two types of rechargeable batteries are being talked about in both industry and academia. The first is a battery that operates by the electrochemical intercalation / deintercalation behavior of active ions, and the second is a battery that operates by the conversion reaction of electrode / electrolyte active materials. Apart from the lead-acid battery used in internal combustion vehicles, the most widely used rechargeable battery is the lithium-ion battery (LIB). Currently available commercial LIBs have a metal oxide or metal phosphate-based lithium intercalation material as the positive electrode, a carbon graphite-based intercalation material as the negative electrode, and a liquid electrolyte. Here, when the battery is charged and discharged, lithium ions move through the liquid electrolyte between the two electrodes. Despite the rapid growth and success of LIBs, there are still several drawbacks that need to be overcome in order to meet the rapidly increasing demand for high-performance batteries in the market.

[0005] Lithium metal has attracted attention as an anode material due to its high theoretical specific capacity of 3860 mAh / g. This is more than 10 times higher than the specific capacity of graphite at 372 mAh / g. However, there are several problems that need to be overcome before lithium metal anodes can be incorporated into commercial batteries. First, current lithium metal anodes exhibit non-uniform lithium plating that leads to the formation of dendrites. As is well known in the art, dendrites can cause a short circuit in the battery cell, which can lead to cell ignition. Second, non-uniform lithium deposition can result in lithium flakes being detached from the anode and thus no longer contributing to the usable capacity of the device. Therefore, there is still a need in the art for improved lithium metal anodes for rechargeable batteries. SUMMARY OF THE INVENTION

[0006] The present invention overcomes the needs in the art by a rechargeable battery comprising a metal anode comprising a solid electrolyte interface (SEI) protective layer having a chemical composition that suppresses dendrite formation, promotes uniform lithium plating, limits electrolyte decomposition, and extends battery life.

[0007] In one embodiment, the present invention relates to a storage battery including a metal anode, a cathode, an electrolyte in contact with the anode and the cathode, and a solid electrolyte interface (SEI) layer on the surface of the metal anode. Here, the SEI layer has a composition according to formula (1). (1) M , , α , , , ε , γ , , β , , ,

[0008] , ζ , δ B β C γ N δ F ε X ζ O η Wherein, M is a metal, B is boron, C is carbon, N is nitrogen, F is fluorine, X is a non-fluorine halogen, O is oxygen, α is a number in the range of 0.2 to 0.4, β is a number in the range of 0.001 to 0.1, γ is a number in the range of 0.15 to 0.25, δ is a number in the range of 0.0 to 0.02, ε is a number in the range of 0.0 to 0.1, ζ is a number in the range of 0.005 to 0.02, η is a number in the range of 0.40 to 0.60, and α, β, γ, δ, ε, ζ, and η are selected such that the sum of α + β + γ + δ + ε + ζ + η = 1.

[0008] In another embodiment, the present invention assembles a battery stack in the presence of an oxidizing gas, where the battery stack includes a metal anode, a cathode with the surface of the metal anode facing the surface of the cathode, and an electrolyte containing an organic solvent and a salt, and here, the electrolyte is in contact with the opposing surfaces of the metal anode and the cathode. seals the battery stack in a battery cell case to form a storage battery, and introduces a current into the storage battery, where the first charge of the storage battery forms a solid electrolyte interface (SEI) layer on the surface of the metal anode facing the surface of the cathode. relates to a method for manufacturing a storage battery including Here, the SEI layer has a composition according to formula (1). (1) M α B β C γ N δ F ε X<​η In the formula, M is a metal, B is boron, C is carbon, N is nitrogen, F is fluorine, X is a nonfluorine halogen species, O is oxygen, α is a number in the range of 0.2 to 0.4, β is a number in the range of 0.001 to 0.1, γ is a number in the range of 0.15 to 0.25, δ is a number in the range of 0.0 to 0.02, ε is a number in the range of 0.0 to 0.1, ζ is a number in the range of 0.005 to 0.02, and η is a number in the range of 0.40 to 0.60. α, β, γ, δ, ε, ζ, and η are selected such that the sum of α + β + γ + δ + ε + ζ + η = 1.

[0009] In further embodiments, M is selected from the group consisting of lithium (Li), sodium (Na), potassium (K), calcium (Ca), zinc (Zn), aluminum (Al), vanadium (V), iron (Fe), and combinations thereof.

[0010] In another embodiment, X is selected from the group consisting of chlorine (Cl), bromine (Br), iodine (I), astatine (At), and combinations thereof.

[0011] In a further embodiment, the present invention relates to a battery comprising a metal anode, a cathode, an electrolyte comprising an organic solvent and a salt in which the electrolyte is in contact with the surface of the metal anode and the surface of the cathode, an oxidizing gas in contact with the electrolyte, the metal anode, and the cathode, and a solid electrolyte interface (SEI) layer on the surface of the metal anode in contact with the electrolyte, wherein the SEI layer has a composition according to formula (2), (2) Li α B β C γ N δ F ε I ζ O η In the formula, Li is lithium, B is boron, C is carbon, N is nitrogen, F is fluorine, I is iodine, O is oxygen, α is a number in the range of 0.2 to 0.4, β is a number in the range of 0.001 to 0.1, γ is a number in the range of 0.15 to 0.25, δ is a number in the range of 0.0 to 0.02, ε is a number in the range of 0.0 to 0.1, ζ is a number in the range of 0.005 to 0.02, and η is a number in the range of 0.40 to 0.60. α, β, γ, δ, ε, ζ, and η are selected such that the sum of α + β + γ + δ + ε + ζ + η = 1.

[0012] In another embodiment, the metal anode includes a metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (B3), magnesium (Mg), calcium (Ca), aluminum (Al), and combinations thereof.

[0013] In further embodiments, the cathode comprises a halogen species selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), and combinations thereof.

[0014] In another embodiment, the halogen species of the cathode is in the form of a metal halide that dissociates into a cation and a halide ion upon solvation.

[0015] In a further embodiment, the present invention relates to a battery comprising a lithium anode, a cathode containing lithium iodide incorporated into a porous carbon material selected from the group consisting of carbon cloth, carbon paper, carbon felt, carbon nanotubes, carbon nanotube arrays, carbon fibers, activated carbon, carbon black, graphene, graphene oxide, reduced graphene oxide, 3D graphene skeleton, pyrolytic graphite, and combinations thereof, a liquid electrolyte containing an organic solvent and salts in contact with the surface of the lithium anode and the surface of the cathode, an oxidizing gas selected from the group consisting of air, oxygen, nitric oxide, nitrogen dioxide, and combinations thereof in contact with the electrolyte, metal anode, and cathode, and a solid electrolyte interface (SEI) layer on the surface of the metal anode in contact with the electrolyte, wherein the SEI has a composition according to formula (2), (2) Li α B β C γ N δ F ε I ζ O η In the formula, Li is lithium, B is boron, C is carbon, N is nitrogen, F is fluorine, I is iodine, O is oxygen, α is an integer in the range of 0.2 to 0.4, β is an integer in the range of 0.001 to 0.1, γ is an integer in the range of 0.15 to 0.25, δ is an integer in the range of 0.0 to 0.02, ε is an integer in the range of 0.0 to 0.1, ζ is an integer in the range of 0.005 to 0.02, and η is an integer in the range of 0.40 to 0.60. α, β, γ, δ, ε, ζ, and η are selected such that the sum of α + β + γ + δ + ε + ζ + η = 1.

[0016] In another embodiment, the present invention is A battery stack is assembled in the presence of an oxidizing gas, wherein the battery stack comprises a lithium anode, a cathode containing lithium iodide incorporated into a porous carbon material with the surface of the metal anode facing the surface of the cathode, and an electrolyte containing an organic solvent and a salt, wherein the electrolyte is in contact with the opposing surfaces of the metal anode and the cathode. The process of sealing a battery stack inside a battery cell case to form a rechargeable battery, and Current is introduced into the battery, and here, the initial charging of the battery involves forming a solid electrolyte interface (SEI) layer on the surface of the metal anode facing the cathode surface. Regarding a method for manufacturing a battery that includes, Here, the SEI layer has a composition according to equation (2), (2) Li α B β C γ N δ F ε I ζ O η In the formula, Li is lithium, B is boron, C is carbon, N is nitrogen, F is fluorine, I is iodine, O is oxygen, α is an integer in the range of 0.2 to 0.4, β is an integer in the range of 0.001 to 0.1, γ is an integer in the range of 0.15 to 0.25, δ is an integer in the range of 0.0 to 0.02, ε is an integer in the range of 0.0 to 0.1, ζ is an integer in the range of 0.005 to 0.02, and η is an integer in the range of 0.40 to 0.60. α, β, γ, δ, ε, ζ, and η are selected such that the sum of α + β + γ + δ + ε + ζ + η = 1.

[0017] In further embodiments, the electrolyte is a liquid electrolyte comprising at least one organic solvent and at least one salt.

[0018] In another embodiment, at least one organic solvent of the liquid electrolyte is selected from the group consisting of 1,2-dimethoxyethane (DME), tetraglyceride (G4), 1,3-dioxolane (DOL), tetrahydrofuran (THF), and combinations thereof.

[0019] In further embodiments, at least one salt of the liquid electrolyte is selected from the group consisting of bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3), lithium bis(oxalate) borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluorophosphate (LiPF6), and combinations thereof.

[0020] In a further embodiment, the battery further includes an oxidizing gas in contact with the electrolyte, where the oxidizing gas is selected from the group consisting of oxygen, air, zero air, carbon dioxide, nitric oxide, nitrogen dioxide, and combinations thereof.

[0021] Additional aspects and / or embodiments of the present invention are provided in the detailed description of the invention below, but are not limited to these. [Brief explanation of the drawing]

[0022] [Figure 1] Figure 1 is a graph showing the changes in the atomic percentages of lithium, carbon, and oxygen in the lithium metal surface layer during the first 30 cycles of a device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing bis(trifluoromethanesulfonyl)imide lithium (LiTFSI), lithium nitrate (LiNO3), 1,2-dimethoxyethane (DME), and 1,3-dioxolane (DOL). Here, the device was sealed in a clean dry air atmosphere (Comparative Example 1). [Figure 2] Figure 2 is a graph showing the changes in the atomic percentages of nitrogen, fluorine, and iodine in the lithium metal surface layer during the first 30 cycles of a device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LiTFSI, LiNO3, DME, and DOL. Here, the device was sealed in a clean dry air atmosphere (Comparative Example 1). [Figure 3]Figure 3 is a bar graph showing the surface composition of lithium, carbon, nitrogen, oxygen, fluorine, and iodine in the lithium metal surface layer after the first charge of a device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LiTFSI, LiNO3, DME, and DOL. Here, the device was sealed in a clean dry air atmosphere (Comparative Example 1). [Figure 4] Figure 4 is a bar graph showing the surface composition of lithium, carbon, nitrogen, oxygen, fluorine, and iodine in the lithium metal surface layer after 30 charges of a device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LiTFSI, LiNO3, DME, and DOL, sealed in a clean dry air atmosphere (Comparative Example 1). [Figure 5] Figure 5 is a graph showing the capacity retention rate after a 1-minute rest and a 24-hour rest at the open-circuit voltage for an a-time device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LiTFSI, LiNO3, DME, and DOL. Here, the device was sealed in a clean dry air atmosphere (Comparative Example 1). [Figure 6] Figure 6 is a graph showing the changes in the atomic percentages of lithium, carbon, and oxygen in the lithium metal surface layer during the first 30 cycles of a device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LiTFSI, LiNO3, DME, and DOL. Here, the device was cycled under positive pressure of pure O2 gas at an absolute pressure of approximately 1300 Torre (Comparative Example 2). [Figure 7] Figure 7 is a graph showing the changes in the atomic percentages of nitrogen, fluorine, and iodine in the lithium metal surface layer during the first 30 cycles of a device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LiTFSI, LiNO3, DME, and DOL. Here, the device was cycled under positive pressure of pure O2 gas at an absolute pressure of approximately 1300 Torre (Comparative Example 2). [Figure 8]Figure 8 is a bar graph showing the surface composition of lithium, carbon, nitrogen, oxygen, fluorine, and iodine in the lithium metal surface layer after the first charge of a device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LiTFSI, LiNO3, DME, and DOL. Here, the device was sealed in a pure oxygen atmosphere (Comparative Example 2). [Figure 9] Figure 9 is a bar graph showing the surface composition of lithium, carbon, nitrogen, oxygen, fluorine, and iodine in the lithium metal surface layer after 30 charges of a device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LiTFSI, LiNO3, DME, and DOL. Here, the device was sealed in a pure oxygen atmosphere (Comparative Example 2). [Figure 10] Figure 10 is a graph showing the changes in the atomic percentages of lithium, carbon, and oxygen in the lithium metal surface layer of a device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LiTFSI, LiNO3, LIBOB, DME, and DOL during the first 280 cycles. Here, the device was sealed in a clean dry air atmosphere (Example 1). [Figure 11] Figure 11 is a graph showing the changes in the atomic percentages of nitrogen, fluorine, iodine, and boron in the lithium metal surface layer during the first 280 cycles of a device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LiTFSI, LiNO3, LiBOB, DME, and DOL. Here, the device was sealed in a clean dry air atmosphere (Example 1). [Figure 12] Figure 12 is a bar graph showing the surface composition of lithium, boron, carbon, nitrogen, oxygen, fluorine, and iodine in the lithium metal surface layer after the first charge of a device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LiTFSI, LiNO3, LiBOB, DME, and DOL. Here, the device was sealed in a clean dry air atmosphere (Example 1). [Figure 13]Figure 13 is a bar graph showing the surface composition of lithium, boron, carbon, nitrogen, oxygen, fluorine, and iodine in the lithium metal surface layer after 280 charges of a device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LiTFSI, LiNO3, LiBOB, DME, and DOL. Here, the device was sealed in a clean dry air atmosphere (Example 1). [Figure 14] Figure 14 is a graph showing the capacity retention rate after a 1-minute rest and a 24-hour rest at open-circuit voltage for an a-time device having a lithium metal anode, a lithium iodide cathode, and a liquid electrolyte containing LITFSI, LiNO3, LiBOB, DME, and DOL. Here, the device was sealed in a clean dry air atmosphere (Example 1). [Figure 15] Figure 15 is a bar graph showing the surface composition of the lithium metal surface layer after pretreatment with a boric acid / dimethyl sulfoxide (BOH3 / DMSO) solution, cyclically treated in a clean dry air atmosphere (Example 2). [Figure 16] Figure 16 is a bar graph showing the surface composition of the boric acid-pretreated lithium metal surface layer after the 10th discharge of a device having a lithium metal anode, an iodine cathode, and a liquid electrolyte containing LITFSI, LiNO3, LiBOB, DME, and DOL, sealed in a clean dry air atmosphere (Example 2). [Modes for carrying out the invention]

[0023] Below is a description of what are currently considered to be preferred embodiments and / or features of the claimed invention. Any substitution or modification of any function, purpose, or structure is intended to be covered by the appended claims. Unless expressly otherwise in the context, the singular forms “a,” “an,” and “the” as used herein and in the appended claims include plural references. The terms “comprise,” “comprised,” “comprises,” and / or “comprising” as used herein and in the appended claims specify the presence of the expressly described components, elements, features, and / or steps, but do not preclude the presence or addition of one or more other components, elements, features, and / or steps.

[0024] As used herein, the term “battery” refers to an energy storage device that converts chemical energy into electrical energy. The components of a battery include an anode, cathode, and electrolyte, which are assembled to form a battery as a “stack” contained within a battery case for forming a battery cell. The batteries described herein are storage batteries, where the stack is sealed within a battery cell case. These may be button cells (e.g., 303 / 357, 11.6 mm diameter × 5.4 mm height), coin cells (e.g., CR2032, 20 mm diameter × 3.2 mm height), SWAGELOK® cells (Swagelok Corporation, Solon, Ohio, USA), cylindrical cells (e.g., 18650, 18 mm diameter × 65 mm height), prismatic cells (rectangular with a steel or aluminum casing), or pouch cells (typically rectangular with a flexible polymer aluminum casing). It should be understood that in some applications, such as electric vehicles (EVs), multiple battery cells may be required to produce enough energy to power the device. Therefore, as used herein, the term “battery cell” may be used to refer to a single battery unit, but the term “battery” more generally refers to all energy storage devices, including a single battery cell and energy storage devices that require multiple battery cells for operation.

[0025] As used herein, the term "intercalation" refers to a reaction in an electrode in which a host atom forms a static framework (e.g., lattice, layered, olivine, or spinel structure) and a (guest) mobile ion or molecule is reversibly incorporated into an empty position within the framework. Intercalation mechanisms minimize volume changes and mechanical strain during repeated insertion and deinsertion of alkaline ions, thus providing good cycle performance. Most commercially available lithium-ion batteries have intercalation electrodes. Intercalation in batteries occurs only during the charge-discharge process and not in idle state or when the battery is depleted. For example, in a Li-ion battery with a lattice-structured intercalation cathode, during discharge, electroactive species in the cathode material are reduced, and Li + The ions are intercalated at available positions within the host lattice. The driving force for intercalation during discharge is a spontaneous redox reaction at the electrode surface, where electrical neutrality is maintained by the flow of electrons from the anode to the positive cathode of the load charge via an external circuit. When the battery is recharged, the external load reverses the flow of ions and electrons back to the negative electrode.

[0026] As used herein, the term "conversion" refers to a reversible redox reaction that occurs in an electrode during a charge-discharge cycle. A conversion electrode is made of a material capable of accommodating the insertion and removal of ions or molecules during battery charging and discharging. The conversion reaction occurring within the electrode alters its chemical composition. For example, in a conversion cathode, during charging, ions flow from the anode (the electrode where oxidation occurs) towards the cathode. In the conversion cathode, these ions react with the cathode material, causing it to undergo a chemical transformation. Various mechanisms may be involved in the conversion reaction depending on the cathode material used. During charging, Li... +Ions move from the anode to the cathode. In the conversion cathode, the metal oxide undergoes a reduction reaction, where the metal atoms of the oxide material capture lithium ions and convert them into different compounds. The reaction is reversible in that it can occur during charging and discharging. During discharge, lithium ions are released from the cathode and move back to the anode, and the converted compound in the cathode is oxidized back to its original form. For example, in the case of cobalt oxide (CoO) (a known conversion cathode material), it is reduced to metallic cobalt (Co) during charging and oxidized back to CoO during discharging. Since the cathode material can accommodate a large number of ions or molecules, the conversion reaction enables high energy storage capacity.

[0027] As used herein, the term "anode" refers to the negative electrode of a battery cell. During discharge, it transfers electrons to the external circuit by oxidation, and during charging, it is reduced (i.e., gains electrons). In the context of the batteries described herein, the anode is a metallic anode containing a metal that may be selected from one or more metal groups of the periodic table, such as Group 1 alkali metals, Group 2 alkaline earth metals, Groups 3-12 transition metals, and Groups 13-15 post-transition metals. Examples of Group 1 alkali metals include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). Examples of Group 2 alkaline earth metals include beryllium (B3), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra). Examples of transition metals in groups 3-12 include, but are not limited to, titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and cadmium (Cd). Examples of post-transition metals in groups 13-15 include, but are not limited to, aluminum (Al), gallium (Ga), indium (In), and tin (Sn). Generally, metal anodes will mainly consist of metals selected from the alkali metals of group 1 and the alkaline earth metals of group 2.

[0028] As used herein, the term "cathode" refers to the positive electrode of a battery cell. During discharge, it receives electrons from the external circuit by reduction, and during charging, it is oxidized (i.e., loses electrons). In the context of the batteries described herein, the cathode includes halogen species incorporated into a suitable intercalation or conversion cathode material. Examples of intercalation cathode materials, but not limited to, include nickel-cobalt aluminum (NCA), nickel-manganese-cobalt (NMC), nickel-cobaltite (NiCo2O4 or NCO), lithium iron phosphate (LiFePO4 or LFP), lithium manganese oxide (LMO), lithium cobalt oxide (LiCoO2), lithium transition metal oxide (TMO), porous carbon materials, and combinations thereof. Examples of porous carbon materials that can constitute the cathode include, but are not limited to, carbon cloth, carbon paper, carbon felt, carbon nanotubes, carbon nanotube arrays, carbon fibers, activated carbon, carbon black, graphene, graphene oxide, reduced graphene oxide, 3D graphene skeletons, pyrolytic graphite, and combinations thereof. Examples of conversion cathode materials include, but are not limited to, metal oxides such as cobalt oxide (CoO), manganese oxide (MnO2), iron oxide (Fe2O3), and copper oxide (CuO), metal sulfides such as iron sulfide (FeS), copper sulfide (CuS), and molybdenum sulfide (MoS2), metal fluorides such as iron fluoride (FeF3) and copper fluoride (CuF2), transition metal compounds such as titanium nitride (TiN), vanadium phosphide (VP), and tungsten carbide (WC), and combinations thereof. The halogen species included in the cathode will be selected from Group 17 of the periodic table. This includes, but is not limited to, fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and astatine (At).

[0029] As used herein, the term "electrolyte" refers to a material that facilitates ion conductivity and cycling between the anode and cathode of a battery. During charging, the electrolyte facilitates the movement of ions from the cathode to the anode, and during discharging, the electrolyte facilitates the movement of ions from the anode to the cathode. Liquid electrolytes generally have at least two components: a solvent and a salt. Both of these together facilitate ion conductivity and transport.

[0030] As used herein, the term “solid electrolyte interface” or “SEI” refers to an ion-conductive passivation protective layer formed on the anode surface. The SEI layer is formed from the reduction of the electrolyte during the first battery cycle. The SEI layer enables metal ion transport and prevents further electrolyte decomposition, thus extending battery life.

[0031] As used herein, the term "oxidizing gas" refers to a gas that induces a redox reaction in a battery cell. Examples of oxidizing gases include, but are not limited to, oxygen, air, zero air (a mixture of pure oxygen and pure nitrogen), nitric oxide, nitrogen dioxide, carbon dioxide, and combinations thereof. As is well known to those skilled in the art, a redox reaction is a reaction in which electrons are transferred between a reducing agent that undergoes oxidation by (i) loss of electrons and an oxidizing agent that undergoes reduction by gaining electrons. The oxidizing gas is introduced into the battery within the confines of a sealed battery cell, where it should be understood that the battery uses the oxidizing gas to induce a redox reaction that drives the battery. When the oxidizing gas is air, the battery consumes oxygen from the air to carry out the redox reaction. In the context of the storage batteries described herein, the oxidizing gas works together with the electrolyte to form a stable SEI layer on the surface of the metal anode.

[0032] As used herein, the term "metal halide" refers to a compound having a metal and a halogen species. The metal in a metal halide may be a metal from any of Groups 1 through 16 of the periodic table, but is typically an alkali metal from Group 1 or an alkaline earth metal from Group 2. Examples of Group 1 alkali metals include, but are not limited to, lithium (Li), sodium (S), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). Examples of Group 2 alkaline earth metals include, but are not limited to, beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra). The halide in a metal halide may be a halogen species from any of Group 17 of the periodic table. This includes, but is not limited to, fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and astatine (At).

[0033] This specification describes a battery comprising a metal anode having a stable SEI surface layer that chemically protects the anode, a cathode, and a liquid electrolyte in contact with the metal anode and cathode. The SEI layer on the surface of the metal anode suppresses dendrite formation, promotes uniform lithium plating, limits electrolyte decomposition, and extends battery life. The SEI layer has a chemical composition according to formula (1), (1) M α B β C γ N δ F ε X ζ O η In the formula, M is a metal, B is boron, C is carbon, N is nitrogen, F is fluorine, X is a nonfluorine halogen species, O is oxygen, α is a number in the range of 0.2 to 0.4, β is a number in the range of 0.001 to 0.1, γ is a number in the range of 0.15 to 0.25, δ is a number in the range of 0.0 to 0.02, ε is a number in the range of 0.0 to 0.1, ζ is a number in the range of 0.005 to 0.02, and η is a number in the range of 0.40 to 0.60, and the sum of α + β + γ + δ + ε + ζ + η = 1.

[0034] In one embodiment, M in the SEI layer is a metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), calcium (Ca), zinc (Zn), aluminum (Al), vanadium (V), iron (Fe), and combinations thereof. In another embodiment, X in the SEI layer is a halogen species selected from the group consisting of chlorine (Cl), bromine (Br), iodine (I), astatine (At), and combinations thereof. In a further embodiment, according to formula (2), M in the SEI layer contains Li, and X in the SEI layer contains I. (2) Li α B β C γ N δ F ε I ζ O η In the formula, Li is lithium, B is boron, C is carbon, N is nitrogen, F is fluorine, I is iodine, O is oxygen, α is a number in the range of 0.2 to 0.4, β is a number in the range of 0.001 to 0.1, γ is a number in the range of 0.15 to 0.25, δ is a number in the range of 0.0 to 0.02, ε is a number in the range of 0.0 to 0.1, ζ is a number in the range of 0.005 to 0.02, and η is a number in the range of 0.40 to 0.60. α, β, γ, δ, ε, ζ, and η are selected such that the sum of α + β + γ + δ + ε + ζ + η = 1.

[0035] In another embodiment, the metal anode comprises a Group 1 alkali metal and / or a Group 2 alkaline earth metal. The Group 1 alkali metals that can be used for the metal anode are selected from the group consisting of Li, sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), and combinations thereof. The Group 2 alkaline earth metals that can be used for the metal anode are selected from the group consisting of beryllium (B3), magnesium (Mg), calcium (Ca), aluminum (Al), and combinations thereof.

[0036] In further embodiments, the cathode comprises at least one halogen species incorporated into the cathode material, where the halogen species is selected from the group consisting of F, Cl, Br, I, At, and combinations thereof. In another embodiment, the cathode comprises a molecule that dissociates into a cation and a halide ion by solvation. In further embodiments, the molecule is a metal halide as described herein, where the metal halide dissociates into a metal cation and a halide ion by solvation. In another embodiment, the metal halide is lithium iodide. In further embodiments, the cathode is an intercalation cathode comprising an intercalation material as described herein. In another embodiment, the cathode is a conversion cathode comprising a conversion material as described herein. In further embodiments, the cathode is an intercalation cathode comprising a porous carbon material having at least one halogen species incorporated therein. Porous carbon materials that can be used as cathodes are selected from the group consisting of carbon cloth, carbon paper, carbon felt, carbon nanotubes, carbon nanotube arrays, carbon fibers, activated carbon, carbon black, graphene, graphene oxide, reduced graphene oxide, 3D graphene skeletons, pyrolytic graphite, and combinations thereof.

[0037] In another embodiment, both the metal of the metal anode and M of the SEI layer are Li. In a further embodiment, both the halogen species of the cathode and X of the SEI layer are I. In another embodiment, M of the SEI layer and the metal of the metal anode are different. In a further embodiment, the halogen species of the cathode and X of the SEI layer are different.

[0038] In another embodiment, the battery comprises a liquid electrolyte having at least one polar aprotic organic solvent and at least one salt. Examples of polar aprotic organic solvents that may be used as the electrolyte include, but are not limited to, dichloromethane, 1,2-dimethoxyethane (DME), tetraglyceride (G4), 1,3-dioxolane (DOL), tetrahydrofuran (THF), ethyl acetate, acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, hexamethylphosphate triamide (HMPA), and combinations thereof. Examples of salts that may be used as the electrolyte include, but are not limited to, bis(trifluoromethanesulfonyl)imide lithium (LiTFSI), lithium nitrate (LiNO3), lithium bis(oxalate) borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluorophosphate (LiPF6), and combinations thereof.

[0039] In further embodiments, the battery includes an oxidizing gas sealed within the battery cell. Although not constrained by theory, it is conceivable that oxygen or another oxidizing gas may be injected into or incorporated into the cell during cell assembly and react with metal and electrolyte molecules at the anode in a dry air environment, resulting in the formation of the SEI passivation protective layer on the anode surface as described herein.

[0040] Comparative Example 1 describes the formation of an SEI layer on a Li anode incorporated into a battery cell having an electrolyte solution containing organic solvents DME and DOL and salts LiTFSI and LiNO3, which is sealed and cycled under clean dry air. Figure 1 shows the atomic ratios of Li, C, and O on the Li anode SEI layer during a 30-cycle process, and Figure 2 shows the atomic ratios of N, F, and I on the Li anode SEI layer during the same 30-cycle process. As shown therein, the atomic ratios of Li, C, O, N, F, and I in the SEI layer on the Li anode surface are Li α C γ N δ F ε I ζ O ηThe atoms are located within the space, where α=0.27~0.35, γ=0.16~0.22, δ=0.001~0.02, ε=0.004~0.09, ζ=0.0003~0.006, and η=0.43~0.48. Figure 3 shows the atomic ratios of Li, C, O, N, F, and I in the SEI layer after the first charge, and Figure 4 shows the atomic ratios of Li, C, O, N, F, and I in the SEI layer after the 30th charge. As shown therein, the overall percentages of Li, C, O, N, F, and I maintain the same general pattern from the first charge to the 30th charge. Figure 5 shows the capacity retention rate of the battery cell after a 1-minute rest and a 24-hour rest at the open-circuit voltage. As shown therein, the capacity retention rate of the battery cell decreases by approximately 20% from 1 minute to 24 hours.

[0041] Comparative Example 2 describes the formation of an SEI layer on a Li anode incorporated into a battery cell having an electrolyte solution containing organic solvents DME and DOL and salts LiTFSI and LiNO3, which is sealed under argon gas and cycled under pure O2. Figure 6 shows the atomic ratios of Li, C, and O on the Li anode SEI layer during a 30-cycle process, and Figure 7 shows the atomic ratios of N, F, and I on the Li anode SEI layer during the same 30-cycle process. As shown therein, the atomic ratios of Li, C, O, N, F, and I in the SEI layer on the Li anode surface are Li α C γ N δ F ε I ζ O η The atoms are located within the space, where α=0.27~0.35, γ=0.16~0.22, δ=0.001~0.02, ε=0.004~0.09, ζ=0.0003~0.006, and η=0.43~0.48. Figure 8 shows the atomic ratios of Li, C, O, N, F, and I after the first charge, and Figure 9 shows the atomic ratios of Li, C, O, N, F, and I after the 30th charge. The change from clean dry air in Comparative Example 1 to pure O2 in Comparative Example 2 produces an SEI layer with somewhat stable percentages of N, O, F, and I, but overall, the change from clean dry air to pure O2 does not significantly alter the overall SEI layer formation.

[0042] Example 1 illustrates the formation of an SEI layer on a Li anode incorporated into a battery cell having an electrolyte solution containing organic solvents DME and DOL and salts LiTFSI, LiNO3, and LiBOB, which is sealed under argon gas and cycled under pure O2. Figure 10 shows the atomic percentages of Li, C, and O on the Li anode SEI layer during a 280-cycle process, and Figure 11 shows the atomic percentages of N, F, I, and B on the Li anode SEI layer during the same 280-cycle process. As shown therein, the atomic percentages of Li, C, O, N, F, I, and B in the SEI layer on the Li anode surface are Li α B β C γ N δ F ε I ζ O η The atoms are located within the space, where α=0.27~0.35, β=0.0144~0.0644, γ=0.16~0.22, δ=0.001~0.02, ε=0.004~0.09, ζ=0.0003~0.006, and η=0.43~0.48. Figure 12 shows the atomic percentages of Li, B, C, O, N, F, and I after the first charge, and Figure 13 shows the atomic percentages of Li, B, C, O, N, F, and I after the 280th charge. As shown therein, the addition of LiBOB to the electrolyte solution introduces several atomic percent of boron into the SEI layer. Figure 14 shows the capacity retention rate of the battery cell after a 1 minute rest and a 24-hour rest at the open-circuit voltage. In contrast to the battery capacity retention rate of the battery shown in Figure 5 (Comparative Example 1), which showed a decrease of approximately 20% after a 24-hour rest, the battery with LiBOB (Example 1) showed a nominal decrease of less than 10% after a 24-hour rest.

[0043] Example 2 illustrates the formation of an SEI layer on a Li anode after pre-immersion (also referred to herein as “pretreatment”) of the Li anode with a boric acid / dimethyl sulfoxide (BOH3 / DMSO) solution. After pre-immersion, the Li anode is incorporated into a battery cell that has an electrolyte solution containing organic solvents DME and DOL and salts LiTFSI and LiNO3, and is sealed and cycled under clean dry air. The battery cell was charged and discharged a total of 10 cycles. Figure 15 shows the atomic percentages of Li, B, C, O, N, F, and I on the lithium surface after pre-immersion, and Figure 16 shows the atomic percentages of Li, B, C, O, N, F, and I on the lithium surface after the 10th discharge. As shown therein, pre-immersion of the Li anode before the formation of the SEI layer results in a boron-rich SEI present after the 10th discharge.

[0044] In one embodiment, the SEI layer described herein may be formed in situ by incorporating additives into the electrolyte composition (as done in Example 1). Examples of additives that may be added to the electrolyte composition include, but are not limited to, lithium nitrate, bis(trifluoromethanesulfonyl)imidolithium, lithium bis(oxalate)borate, boric acid, iodic acid, and combinations thereof.

[0045] In another embodiment, the SEI layer may be formed indirectly by first exposing the metal anode to an oxidizing gas, and then treating the oxidized metal anode with an oxidizing acid anhydride dissolved in an aprotic solvent. Examples of oxidizing acids that may be used for anode treatment include, but are not limited to, nitric acid, hydrofluoric acid, iodic acid, boric acid, and combinations thereof. Examples of aprotic solvents that can dissolve oxidizing acids include, but are not limited to, dimethyl sulfoxide (DMSO), 1,2-dimethoxyethane (DME), acetonitrile, carbon disulfide, and combinations thereof. The treated electrode may be further rinsed and dried before use in a battery cell.

[0046] In further embodiments, the two methods of SEI layer formation described herein may be combined. For example, the two SEI layer formation processes may be combined in a single cell comprising a pre-treated metal electrode and an electrolyte composition containing additives.

[0047] The descriptions of various aspects and / or embodiments of the present invention are provided for illustrative purposes only and are not intended to be exhaustive or to limit the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope of the embodiments described. The terms used herein have been chosen to best describe the principles, practical applications, or technical improvements of the aspects and / or embodiments, or to enable those skilled in the art to understand the aspects and / or embodiments disclosed herein. [Examples]

[0048] The following examples are provided to give a complete disclosure of methods for manufacturing and using the embodiments and models of the present invention as shown herein to those skilled in the art. Efforts have been made to ensure accuracy with respect to variables such as quantities and temperatures, but experimental errors and deviations should be taken into consideration. Unless otherwise specified, percentages are by weight, temperatures are in degrees Celsius, and pressures are atmospheric pressure or near atmospheric pressure. Unless otherwise specified, all components were obtained commercially.

[0049] In the following example, all salts were dried at 150°C in an argon-filled glove box and stored at 100°C in an argon-filled glove box. All solvents were dried for at least 48 hours using a 3 Å molecular sieve before use. Comparative Example 1 SEI layer formation using LiTFSI, LiNO3, DOL, and DME electrolytes cyclically under a clean dry air atmosphere.

[0050] 0.5 mmol of LiTFSI and 0.02 mmol of LiNO3 were weighed out, and the salts were dissolved in 500 μL of DME. An electrolyte was then prepared by adding an additional 500 μL of DOL. The final solution was colorless and transparent, and no visible undissolved salts were present.

[0051] The battery stack was assembled in a clean, dry air atmosphere of 21% O2 and 79% N2. The lithium metal anode was mounted on a stainless steel current collector and brought into contact with the stainless steel cell casing. 30 μL of electrolyte was added to the lithium metal anode, and a polyethylene-polypropylene-polyethylene separator (CELGARD® 2325, Celgard, Charlotte, North Carolina, USA) was placed on top of it. Then, an additional 30 μL of electrolyte was added to the separator, and a pre-prepared cathode containing lithium iodide, carbon, and binder coated on a stainless steel substrate was placed cathode-side down on the assembled stack. After the completion of the battery stack, the stack was placed in a 2032 coin cell and the cell was sealed. The sealed cell was cycled several times and then disassembled, the anode was rinsed and dried, and the anode surface was chemically analyzed by X-ray photoelectron spectroscopy (XPS). Figure 1 shows the atomic percentages (%) of Li, C, and O on the Li anode surface during the first 30 cycles, and Figure 2 shows the atomic percentages (%) of N, F, and I on the Li anode surface layer during the same first 30 cycles. Figure 3 shows the surface composition of Li, C, N, O, F, and I after the first charge, and Figure 4 shows the surface composition of Li, C, N, O, F, and I after the 30th charge. Figure 5 shows the battery capacity retention rate after a 1-minute rest and a 24-hour rest at open-circuit voltage. Comparative Example 2 SEI layer formation using LiTFSI, LiNO3, DOL, and DME electrolytes cyclically under a pure O2 atmosphere.

[0052] The electrolyte and battery stack were prepared in the same manner as in Example 1. The only difference was that the battery stack was assembled in an argon atmosphere instead of a clean dry air atmosphere. The sealed cells were disassembled after being cycled multiple times under continuous positive pressure of pure O2 gas at an absolute pressure of approximately 1300 Torr. The anodes were rinsed and dried, and the anode surface was chemically analyzed by XPS. Figure 6 shows the atomic percentages (%) of Li, C, and O on the Li anode surface during the first 30 cycles, and Figure 7 shows the atomic percentages (%) of N, F, and I on the Li anode surface layer during the same first 30 cycles. Figure 8 shows the surface composition of Li, C, N, O, F, and I after the first charge, and Figure 9 shows the surface composition of Li, C, N, O, F, and I after the 30th charge. Example 1 SEI layer formation using LiTFSI, LiNO3, DOL, DME, and LiBOB electrolytes cyclically under a clean dry air atmosphere.

[0053] The electrolyte and battery stack were prepared in the same manner as in Comparative Example 1. The only difference was the addition of LiBOB to the electrolyte composition. As in Comparative Example 1, the sealed battery stack was cycled multiple times under clean dry air, then disassembled, the anode was rinsed and dried, and the anode surface was chemically analyzed by XPS. Figure 10 shows the atomic percentages (%) of Li, C, and O on the Li anode surface during the first 280 cycles, and Figure 11 shows the atomic percentages (%) of N, F, I, and B on the Li anode surface layer during the same first 280 cycles. Figure 12 shows the surface composition of Li, B, C, N, O, F, and I after the first charge, and Figure 13 shows the surface composition of Li, B, C, N, O, F, and I after the 280th charge. Figure 14 shows the capacity retention rate of the battery after a 1-minute rest and a 24-hour rest at open-circuit voltage. Example 2 SEI layer formation after boric acid / DMSO pretreatment

[0054] A lithium metal anode was mounted on a stainless steel current collector in an argon-filled glove box (O2 < 0.1 ppm, H2O < 0.1 ppm). The lithium anode was polished with a nylon brush to remove the original surface layer, and then left at approximately 790 Torr for 5 hours under clean dry air (a gas environment of nitrogen, oxygen, or carbon dioxide may also be used) to form a new surface film on the lithium. The lithium anode was then transferred to an argon-filled glove box and pre-immersed in a 50 mM boric acid (BOH3) solution in dimethyl sulfoxide (DMSO) for 10 minutes. After this, the lithium anode was vacuum-dried for at least 3 hours. After drying the lithium anode, an SEI layer was formed on the lithium anode as described in Example 1. After the completion of the battery stack, the cells were sealed and disassembled after being cycled several times under clean dry air, the anodes were rinsed and dried, and the anode surfaces were chemically analyzed by XPS. Figure 15 shows the surface composition of Li, B, C, N, O, F, and I after pretreatment, and Figure 16 shows the surface composition of Li, C, N, O, F, and I after the 10th discharge.

Claims

1. It is a storage battery, Metal anode, Cathode, The electrolyte in contact with the anode and the cathode, and Solid electrolyte interface (SEI) layer on the surface of the metal anode Includes, Here, the SEI layer has a composition according to formula (1), (1) M α B β C γ N δ F ε X ζ O η During the ceremony, M is a metal, B is boron, C is carbon, N is nitrogen, F is fluorine, X is a non-fluorine halogen, and O is oxygen. α is a number in the range of 0.2 to 0.

4. β is a number in the range of 0.001 to 0.

1. γ is a number in the range of 0.15 to 0.

25. δ is a number in the range of 0.0 to 0.

02. ε is a number in the range of 0.0 to 0.

1. ζ is a number in the range of 0.005 to 0.

02. η is a number in the range of 0.40 to 0.

60. α, β, γ, δ, ε, ζ, and η are selected such that the sum of α + β + γ + δ + ε + ζ + η = 1. Battery storage.

2. The storage battery according to claim 1, wherein M is selected from the group consisting of lithium (Li), sodium (Na), potassium (K), calcium (Ca), zinc (Zn), aluminum (Al), vanadium (V), iron (Fe), and combinations thereof.

3. The storage battery according to claim 1, wherein X is selected from the group consisting of chlorine (Cl), bromine (Br), iodine (I), astatine (At), and combinations thereof.

4. The storage battery according to claim 1, wherein the metal anode comprises a metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (B3), magnesium (Mg), calcium (Ca), aluminum (Al), and combinations thereof.

5. The storage battery according to claim 1, wherein the cathode contains a halogen species selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), and combinations thereof.

6. The battery according to claim 1, wherein the halogen species of the cathode is in the form of a metal halide that dissociates into a cation and a halide ion by solvation.

7. The battery according to claim 1, wherein the electrolyte is a liquid electrolyte comprising at least one organic solvent and at least one salt.

8. The storage battery according to claim 1, wherein the organic solvent is selected from the group consisting of 1,2-dimethoxyethane (DME), tetraglyceride (G4), 1,3-dioxolane (DOL), tetrahydrofuran (THF), and combinations thereof.

9. The salt is selected from the group consisting of bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO ３ ), lithium bis(oxalato)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluorophosphate (LiPF ６ ), and combinations thereof, the storage battery according to claim 1.

10. The battery according to claim 1, further comprising an oxidizing gas in contact with the electrolyte, wherein the oxidizing gas is selected from the group consisting of oxygen, air, zero air, carbon dioxide, nitric oxide, nitrogen dioxide, and combinations thereof.

11. It is a storage battery, Metal anode, Cathode, An electrolyte comprising an organic solvent and a salt, wherein the electrolyte is in contact with the surface of the metal anode and the surface of the cathode. The electrolyte, the metal anode, and the oxidizing gas in contact with the cathode, A solid electrolyte interface (SEI) layer on the surface of the metal anode in contact with the electrolyte, Includes, Here, the SEI layer has a composition according to formula (2), (2) Li α B β C γ N δ F ε I ζ O η During the ceremony, Li is lithium, B is boron, C is carbon, N is nitrogen, F is fluorine, I is iodine, and O is oxygen. α is a number in the range of 0.2 to 0.

4. β is a number in the range of 0.001 to 0.

1. γ is a number in the range of 0.15 to 0.

25. δ is a number in the range of 0.0 to 0.

02. ε is a number in the range of 0.0 to 0.

1. ζ is a number in the range of 0.005 to 0.

02. η is a number in the range of 0.40 to 0.

60. α, β, γ, δ, ε, ζ, and η are selected such that the sum of α + β + γ + δ + ε + ζ + η = 1. Battery storage.

12. The storage battery according to claim 11, wherein the metal anode comprises a metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (B3), magnesium (Mg), calcium (Ca), aluminum (Al), and combinations thereof.

13. The storage battery according to claim 11, wherein the halogen species of the cathode is selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), and combinations thereof.

14. The battery according to claim 1, wherein the halogen species of the cathode is in the form of a metal halide that dissociates into a cation and a halide ion by solvation.

15. The battery according to claim 11, wherein the oxidizing gas is selected from the group consisting of air, oxygen, nitric oxide, nitrogen dioxide, and combinations thereof.

16. The battery according to claim 11, wherein the electrolyte is a liquid electrolyte containing an organic solvent and a salt.

17. The storage battery according to claim 16, wherein the organic solvent is selected from the group consisting of 1,2-dimethoxyethane (DME), tetraglyceride (G4), 1,3-dioxolane (DOL), tetrahydrofuran (THF), and combinations thereof.

18. The salts mentioned above include bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium nitrate (LiNO). ３ ), lithium bis(oxalate) borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluorophosphate (LiPF) ６ A battery according to claim 16, selected from the group consisting of ), and combinations thereof.

19. It is a storage battery, Lithium anode, A cathode containing lithium iodide incorporated into a porous carbon material selected from the group consisting of carbon cloth, carbon paper, carbon felt, carbon nanotubes, carbon nanotube arrays, carbon fibers, activated carbon, carbon black, graphene, graphene oxide, reduced graphene oxide, 3D graphene skeleton, pyrolysis graphite, and combinations thereof. A liquid electrolyte comprising an organic solvent and a salt, wherein the electrolyte is in contact with the surface of the lithium anode and the surface of the cathode. An oxidizing gas in contact with the electrolyte, the metal anode, and the cathode, wherein the oxidizing gas is selected from the group consisting of air, oxygen, nitric oxide, nitrogen dioxide, and combinations thereof, and A solid electrolyte interface (SEI) layer on the surface of the metal anode in contact with the electrolyte, Includes, Here, the SEI has a composition according to formula (2), (2) Li α B β C γ N δ F ε I ζ O η During the ceremony, Li is lithium, B is boron, C is carbon, N is nitrogen, F is fluorine, I is iodine, and O is oxygen. α is an integer in the range of 0.2 to 0.

4. β is an integer in the range of 0.001 to 0.

1. γ is an integer in the range of 0.15 to 0.

25. δ is an integer in the range of 0.0 to 0.

02. ε is an integer in the range of 0.0 to 0.

1. ζ is an integer in the range of 0.005 to 0.

02. η is an integer in the range of 0.40 to 0.

60. α, β, γ, δ, ε, ζ, and η are selected such that the sum of α + β + γ + δ + ε + ζ + η = 1. Battery storage.

20. The storage battery according to claim 19, wherein the organic solvent is selected from the group consisting of 1,2-dimethoxyethane (DME), tetraglyceride (G4), 1,3-dioxolane (DOL), tetrahydrofuran (THF), and combinations thereof.

21. The salts mentioned above include bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium nitrate (LiNO). ３ ), lithium bis(oxalate) borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluorophosphate (LiPF) ６ A battery according to claim 19, selected from the group consisting of ), and combinations thereof.

22. A method for manufacturing a storage battery, The battery stack is assembled in the presence of an oxidizing gas, where the battery stack is: Metal anode, Cathode, where the surface of the metal anode faces the surface of the cathode, An electrolyte comprising an organic solvent and a salt, wherein the electrolyte is in contact with the opposing surfaces of the metal anode and the cathode. Including, The battery stack is sealed inside a battery cell case to form the storage battery, and Current is introduced into the battery, and here, the initial charging of the battery involves forming a solid electrolyte interface (SEI) layer on the surface of the metal anode facing the surface of the cathode. Includes, Here, the SEI layer has a composition according to formula (1), (1) M α B β C γ N δ F ε X ζ O η During the ceremony, M is a metal, B is boron, C is carbon, N is nitrogen, F is fluorine, X is a non-fluorine halogen species, and O is oxygen. α is a number in the range of 0.2 to 0.

4. β is a number in the range of 0.001 to 0.

1. γ is a number in the range of 0.15 to 0.

25. δ is a number in the range of 0.0 to 0.

02. ε is a number in the range of 0.0 to 0.

1. ζ is a number in the range of 0.005 to 0.

02. η is a number in the range of 0.40 to 0.

60. α, β, γ, δ, ε, ζ, and η are selected such that the sum of α + β + γ + δ + ε + ζ + η = 1. A method for manufacturing storage batteries.

23. The storage battery according to claim 19, wherein the organic solvent is selected from the group consisting of 1,2-dimethoxyethane (DME), tetraglyceride (G4), 1,3-dioxolane (DOL), tetrahydrofuran (THF), and combinations thereof.

24. The salts mentioned above include bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium nitrate (LiNO). ３ ), lithium bis(oxalate) borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluorophosphate (LiPF) ６ A battery according to claim 19, selected from the group consisting of ), and combinations thereof.

25. A method for manufacturing a storage battery, The battery stack is assembled in the presence of an oxidizing gas, where the battery stack is: Lithium anode, A cathode containing lithium iodide incorporated into a porous carbon material, wherein the surface of the metal anode faces the surface of the cathode, and An electrolyte comprising an organic solvent and a salt, wherein the electrolyte is in contact with the opposing surfaces of the metal anode and the cathode. Including, The battery stack is sealed inside a battery cell case to form the storage battery, and Current is introduced into the battery, and here, the initial charging of the battery involves forming a solid electrolyte interface (SEI) layer on the surface of the metal anode facing the surface of the cathode. Includes, Here, the SEI layer has a composition according to formula (2), (2) Li α B β C γ N δ F ε I ζ O η During the ceremony, Li is lithium, B is boron, C is carbon, N is nitrogen, F is fluorine, I is iodine, and O is oxygen. α is an integer in the range of 0.2 to 0.

4. β is an integer in the range of 0.001 to 0.

1. γ is an integer in the range of 0.15 to 0.

25. δ is an integer in the range of 0.0 to 0.

02. ε is an integer in the range of 0.0 to 0.

1. ζ is an integer in the range of 0.005 to 0.

02. η is an integer in the range of 0.40 to 0.

60. α, β, γ, δ, ε, ζ, and η are selected such that the sum of α + β + γ + δ + ε + ζ + η = 1. A method for manufacturing storage batteries.

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