Vertically integrated production of pure lithium metal and lithium battery production

Abstract

The present invention provides a method for providing a pure lithium metal anode and a method for manufacturing a lithium metal battery. [Solution] A high-purity lithium metal electrode is fabricated from an aqueous lithium salt solution using electrolysis through a lithium-ion selective membrane, producing an electrode with a flow rate of approximately 10 mA / cm². 2 ~about 50mA / cm 2 A method is provided that is carried out at a constant current density, where the constant current is applied for a period of time from approximately 1 minute to approximately 60 minutes. The electrolysis is carried out under covering air, which is substantially free of lithium reactive components. The method is further provided to vertically integrate the electrolytic fabrication of high-purity lithium metal electrodes into the production of lithium metal batteries, where the fabrication of lithium electrodes and lithium metal batteries is carried out in a single facility.

Description

[Technical Field]

[0001] This invention relates to the production of high-purity lithium for use in lithium metal batteries and the integration of lithium metal production with the production of Li batteries. The resulting batteries are manufactured in a fully charged state and have an increased cycle life compared to conventional manufacturing methods. (Cross-reference of related applications)

[0002] This patent application claims the interests of U.S. Patent Application No. 17 / 006,073, filed on 28 August 2020, whose disclosure is incorporated herein by reference. A related application filed on 28 August 2020, titled “Lithium Metal Anode and Battery,” which assigns U.S. Patent Application No. 17 / 006,048, and which has the same inventors and assignees as this application is also incorporated herein by further reference. [Background technology]

[0003] Lithium-ion batteries (LIBs) dominate the lithium battery market. LIBs contain lithium that exists only in ionic form. Such batteries have good charge density and can function effectively through multiple charge / discharge cycles. Lithium metal batteries (LMBs), in contrast, use non-ionic lithium metal in the negative electrode. During discharge of an LMB, lithium ions are released from this electrode as electrons flow through the external circuit. As an LMB is recharged, lithium ions are reduced back to lithium metal as electrons flow back into the negative electrode. Because LMBs inherently have higher capacity than LIBs, they are a preferred technology for primary batteries. Furthermore, since LMBs can be manufactured in a fully charged state, they do not require the long formation process required for LIBs, which can take 20-30 days. However, the tendency to form lithium metal dendrites, which can lead to poor cycle life, volume expansion, and severe burning of LMBs, limits their practical use as rechargeable batteries.

[0004] The lithium anode in rechargeable lithium metal batteries (LMBs) is regarded as the "Holy Grail" of anode materials due to its extremely high theoretical specific capacity of 3,860 mAh / g and low reaction voltage. Lithium metal is the lightest metal on the periodic table, which is particularly desired for applications that require a low volume-to-weight ratio, such as electric vehicles. The most promising LMBs are lithium-sulfur (Li-S), lithium-air (Li-O₂), and solid-state or semi-solid LMBs. Primary batteries manufactured using lithium metal foils are widely commercialized, but numerous barriers to the commercialization of rechargeable LMBs include low Coulombic efficiency, poor cycle life, soft short circuits, volume expansion, and the growth of Li dendrites during plating, which can lead to thermal runaway and other sudden failures. Considerable efforts have been made to suppress dendrite formation, which includes providing additives in the electrolyte, varying the salt concentration, creating an artificial passivation layer on the lithium metal (which enables handling of the lithium metal in dry air for a short time but sacrifices higher impedance), and manipulating the electrode-electrolyte interface structure (which is extremely difficult when the foil is mechanically fused to a substrate to create a negative electrode, and that negative electrode is then mechanically fused to a solid-state electrolyte).

[0005] Other barriers include the quality and cost of available lithium metal raw materials, the handling of lithium metal, and the mechanical challenges of manufacturing lithium anodes. These barriers increase by several orders of magnitude when attempting to mechanically manufacture solid-state LMBs. Since 1976, researchers, including Nobel laureates, have attempted to solve all of these problems but to no avail. Unfortunately, as of 2020, despite all efforts in this field, there are still no commercially viable batteries for consumer applications.

[0006] ​Current commercially available supplies of lithium metal are produced by the molten salt electrolysis of lithium chloride. Lithium is poured into a mold and extruded into foils ranging in thickness from 100 μm to 750 μm. For environmental reasons, lithium metal foils are generally produced in China. Due to the classification of lithium as a flammable and potentially explosive material, these foils must then be shipped to battery manufacturers contained in mineral oil. This process results in impure foils that are essentially dendritic, with a non-uniform surface condition that can vary by + / - 50 μm under scanning electron micro-scope (SEM) imaging (U.S. Patent No. 10,177,366 (Patent Document 1), Figure 11A). The resulting impure product is sufficient for primary lithium batteries but not usable in rechargeable LMBs.

[0007] Shipping and handling, and the required immersion in mineral oil, compromise the integrity of the lithium metal. Prior to use in a battery, the mineral oil must be removed, which further compromises the lithium. Some battery developers manually rub the lithium from under the top layer for use and disperse it on copper or other substrates like peanut butter. Some battery developers employ lithium metal foils and vaporize them onto substrates. It is both expensive and energy intensive.

[0008] Impurities in this supply of lithium metal foil present an additional barrier to the commercialization of LMBs. As an alkali metal, lithium has one loosely held valence electron, which makes lithium inherently reactive. Notably, lithium is the only alkali metal that reacts with nitrogen in the air to form nitride Li3N. Due to undesirable side reactions, the introduction of impurities into lithium foil significantly limits the operation of working batteries. In particular, recent studies have found that such impurities can lead to the nucleation of subsurface dendritic structures (Harry et al., Nat. Mater. 13, 69-73 (2014)). The manufacturer of the lithium foil in this study (FMC Lithium) lists several elements other than lithium, the most abundant at a concentration of 300 ppm by weight being nitrogen, which is likely in the form of Li3N (US No. 4,781,756). Other common impurities include Na, Ca, K, Fe, Si, Cl, B, Ti, Mg, and C. This is not an exhaustive list, but the elements mentioned are the most common. Nitrogen in any form is undesirable, especially in rechargeable LMBs. Nitrogen creates voids and depressions within the lithium metal as the battery circulates, and these reactions consume lithium. The presence of impurities such as nitrogen leads to slow and uneven lithium deposition on the negative electrode during charging, affecting the overall current distribution within the battery and creating hot spots.

[0009] Non-uniformity on the lithium foil surface caused by nitrogen and other impurities is also a significant problem because it interferes with uniform contact between the electrodes and the substrate, leading to soft short circuits and, again, to an uneven distribution of current, which in turn can lead to dendrites and other undesirable effects.

[0010] A method is needed to provide pure lithium metal anodes, which would overcome the purity issues that conventionally limit the capacity and recyclability of LMBs. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] Strength Patent No. 10,177,366 [Overview of the Initiative] [Means for solving the problem]

[0012] The conventional approach is to suppress all the inherent problems in existing raw material supplies, an approach that has not been successful for 43 years. However, the inventors propose to address both material and manufacturing problems simultaneously by producing highly improved lithium metal products (perfect negative electrodes) and vertically integrating lithium metal production into battery manufacturing facilities.

[0013] According to one embodiment of the present invention, a method for manufacturing a lithium electrode is described, the method comprising (1) providing an electrolytic cell, the electrolytic cell is A first chamber containing a positive electrode and an aqueous lithium salt solution in contact with the positive electrode, A second chamber comprising a conductive substrate configured as a negative electrode, wherein the conductive substrate remains stationary within the chamber during lithium metal electrodeposition, a lithium ion selective film separates the first chamber from the second chamber, and a non-aqueous electrolyte is placed between the conductive substrate and the lithium ion selective film, and is in physical contact with both the conductive substrate and the lithium ion selective film. The electrolytic cell is configured to allow lithium ions to pass through a lithium ion selective membrane between the first and second chambers, while preventing the passage of other chemical species between the first and second chambers. (2) Covering the electrolytic cell with the surrounding air, wherein the surrounding air is substantially free of lithium reactive components, (3) A variable voltage is applied to maintain a constant current across the negative and positive electrodes, thereby causing lithium ions to move from the first chamber to the second chamber, across the lithium ion selective film and non-aqueous electrolyte, and electrodepositing a first layer of lithium onto a conductive substrate, thereby forming a lithium electrode, wherein the first layer of lithium has an inner surface and an outer surface, and the inner surface of the first layer of lithium is bonded to the conductive substrate. Includes, A constant current is approximately 10 mA / cm². 2 ~about 50mA / cm 2 The constant current is applied over a period of time ranging from approximately 1 minute to approximately 60 minutes.

[0014] In some embodiments, the surrounding atmosphere contains 10 ppm or less of lithium reaction components on a molar basis. In some embodiments, the surrounding atmosphere contains 10 ppm or less of nitrogen on a molar basis. In some embodiments, the surrounding atmosphere contains 5 ppm or less of nitrogen on a molar basis.

[0015] According to some embodiments, the conductive substrate comprises a plate having a first surface and a second surface, and the inner surface of a first layer of lithium metal is bonded to the first surface of the conductive substrate.

[0016] According to some embodiments, the aqueous lithium salt solution comprises a lithium salt selected from the group consisting of Li2SO4, Li2CO3, and combinations thereof. In a preferred embodiment, the aqueous lithium salt solution contains Li2SO4.

[0017] According to some embodiments, the conductive substrate is selected from the group consisting of copper, aluminum, graphite-coated copper, and nickel.

[0018] According to some embodiments, the lithium-ion selective film comprises a polymer matrix and a plurality of ion-conducting particles arranged within the polymer matrix. In this configuration, the lithium-ion selective film comprises a glass frit in which lithium-ion conductive particles are disposed. According to some embodiments, the covering atmosphere comprises argon with a purity exceeding 99.998 weight percent. According to some embodiments, the lithium electrode has lithium with a specific capacity greater than approximately 3,800 mAh per gram.

[0019] According to one embodiment of the present invention, a method for manufacturing a lithium electrode is described, the method being (1) to provide a gas-impermeable container, the container being The surrounding atmosphere, and the surrounding atmosphere is one that is substantially free of lithium reactive components, An electrolytic cell, wherein the electrolytic cell is completely covered by the surrounding atmosphere, A conductive substrate, which is stationary within the cell and configured as a negative electrode, Positive electrode and, An aqueous lithium salt solution inserted between the conductive substrate and the positive electrode, A lithium-ion selective membrane configured to function as a solid-state electrolyte, covering a conductive substrate and forming a barrier that separates the aqueous lithium salt solution from the conductive substrate. The electrolytic cell is configured to allow lithium ions to pass from a lithium salt solution through a lithium ion selective membrane onto the surface of a conductive substrate, while preventing the passage of other chemical species. To enclose, (2) In order to maintain a constant current across the negative and positive electrodes, a variable voltage is applied, thereby causing lithium ions to cross the lithium ion selective film from the lithium salt solution and electroplat a layer of lithium onto the conductive substrate, thereby forming a lithium electrode, wherein the lithium layer has an inner surface and an outer surface, the inner surface is bonded to the conductive substrate, and the outer surface is bonded to the lithium ion selective film. Includes, A constant current is approximately 10 mA / cm². 2 ~about 50mA / cm 2 A constant current is applied over a period of time ranging from approximately 1 minute to approximately 60 minutes.

[0020] According to one embodiment of the present invention, a method for manufacturing a lithium metal battery is described, comprising (1) manufacturing a lithium electrode according to the method of the present invention, (2) Assembling a casing containing a lithium electrode configured as an anode and other components necessary to form a lithium metal battery, (3) To seal the casing and isolate the contents of the casing from reactants present in the air, thereby providing a lithium metal battery, Includes.

[0021] In a preferred embodiment, the LIMB is manufactured in a single manufacturing facility. In some embodiments, all steps of battery manufacturing are carried out under an atmosphere that is substantially free of lithium reactive components.

[0022] In some embodiments, the lithium metal battery is fabricated using lithium metal electrodes having a layer of lithium metal bonded to a conductive substrate, wherein the lithium metal layer contains nonmetallic elements in a mass ratio of 5 ppm or less.

[0023] According to one embodiment of the present invention, a method for manufacturing a lithium metal battery is described, (1) providing an electrolytic cell, the electrolytic cell is A conductive substrate stationary in an electrolytic cell, wherein the conductive substrate comprises a plate having a first surface and a second surface, A first positive electrode and a first aqueous lithium salt solution in contact with the first positive electrode are included in the first Camba and, A second chamber comprising a first lithium-ion selective membrane and a first non-aqueous electrolyte disposed between a first surface of a conductive substrate and the first lithium-ion selective membrane, wherein the first lithium-ion selective membrane separates the first chamber from the second chamber, and the first non-aqueous electrolyte is in physical contact with both the first surface of the conductive substrate and the lithium-ion selective membrane. A third chamber comprising a second lithium-ion selective film and a non-aqueous electrolyte disposed between a second surface of a conductive substrate and the second lithium-ion selective film, wherein the non-aqueous electrolyte is in physical contact with both the second surface of the conductive substrate and the second lithium-ion selective film, A fourth chamber containing a second positive electrode and a second aqueous lithium salt solution in contact with the second positive electrode, A second lithium-ion selective membrane separates the third chamber from the fourth chamber, An electrolytic cell is configured to allow the passage of lithium ions through a first lithium-ion selective membrane between a first chamber and a second chamber, and to prevent the passage of other chemical species between the first chamber and the second chamber. The electrolytic cell is configured to allow lithium ions to pass through a second lithium-ion selective membrane between the fourth chamber and the third chamber, and to prevent the passage of other chemical species between the fourth chamber and the third chamber. (2) The electrolytic cell is completely covered with the surrounding air, and the surrounding air is inert to chemical reactions with lithium. (3) In order to maintain a constant current across the conductive substrate and the first positive electrode, a variable voltage is applied across the conductive substrate and the second positive electrode, thereby causing lithium ions to move from the first chamber to the second chamber, across the first lithium-ion selective film and the first non-aqueous electrolyte, electroplating a first layer of lithium onto the first surface of the conductive substrate; further causing lithium ions to move from the fourth chamber to the third chamber, across the second lithium-ion selective film and the second non-aqueous electrolyte, electroplating a second layer of lithium onto the second surface of the conductive substrate, thereby forming a lithium electrode, wherein the lithium electrode comprises a conductive substrate, a first layer of lithium, and a second layer of lithium, the first layer of lithium having an inner surface and an outer surface, the inner surface of which is bonded to the first surface of the conductive substrate, and the second layer having an inner surface and an outer surface, the inner surface of which is bonded to the second surface of the conductive substrate. Includes, A constant current is approximately 10 mA / cm². 2 ~about 50mA / cm 2 A constant current is applied over a period of time ranging from approximately 1 minute to approximately 60 minutes.

[0024] According to one embodiment of the present invention, a method for manufacturing a lithium metal battery is described, (1) providing an electrolytic cell, the electrolytic cell is A conductive substrate stationary within a cell, comprising a plate having a first surface and a second surface, a first surface covered with a first lithium-ion selective film, and a second surface covered with a second lithium-ion selective film, wherein the first and second lithium-ion selective films are configured to function as a solid-state electrolyte, A first chamber comprising a first positive electrode and a first aqueous lithium salt solution in contact with the first positive electrode and a first lithium ion selective membrane, A second positive electrode and a second chamber containing a second aqueous lithium salt solution in contact with the first positive electrode and the second lithium ion selective membrane, The electrolytic cell is configured to allow lithium ions to pass through a first lithium-ion selective film between the first chamber and the first surface of the conductive substrate, and to prevent the passage of other chemical species between the first chamber and the first surface of the conductive substrate. The electrolytic cell has a second lithium ion selection between the second chamber and the second surface of the conductive substrate. It is configured to allow the passage of lithium ions through the film, while preventing the passage of other chemical species between the second chamber and the second surface of the conductive substrate. (2) The electrolytic cell is completely covered with the surrounding air, and the surrounding air is inert to chemical reactions with lithium. (3) In order to maintain a constant current across the conductive substrate and the first positive electrode, a variable voltage is applied across the conductive substrate and the second positive electrode, thereby causing lithium ions to move from the first chamber across the first lithium-ion selective film and electroplat the first layer of lithium onto the first surface of the conductive substrate, and further causing lithium ions to move from the second chamber across the second lithium-ion selective film and electroplat the second layer of lithium onto the second surface of the conductive substrate, thereby lithium The invention relates to forming an electrode, wherein the lithium electrode comprises a conductive substrate, a first layer of lithium, and a second layer of lithium, the first layer of lithium having an inner surface and an outer surface, the inner surface of the first layer of lithium being bonded to the first surface of the conductive substrate, and the outer surface of the first layer of lithium being bonded to a first lithium-ion selective film, the second layer of lithium having an inner surface and an outer surface, the inner surface of the second layer of lithium being bonded to the second surface of the conductive substrate, and the outer surface of the second layer of lithium being bonded to a second lithium-ion selective film. Includes, A constant current is approximately 10 mA / cm². 2 ~about 50mA / cm 2 A constant current is applied over a period of time ranging from approximately 1 minute to approximately 60 minutes.

[0025] According to one embodiment of the present invention, a method for manufacturing a lithium metal electrode is described, wherein the lithium ion selective membrane is immobile in the electrolytic cell, and as a first layer of lithium is formed, the first layer of lithium displaces a non-aqueous electrolyte from the space between the conductive substrate and the lithium ion selective membrane, thereby bonding the inner surface of the first layer of lithium to the conductive substrate and the outer surface of the first layer of lithium to the ion selective membrane, thereby forming a lithium metal electrode comprising a conductive substrate and a first layer of lithium metal, with the inner surface of the first layer of lithium bonded to the conductive substrate and the outer surface of the first layer of lithium bonded to the lithium ion selective membrane, wherein the lithium ion selective membrane is configured to function as a solid-state electrolyte when the lithium metal electrode is incorporated into a galvanic cell.

[0026] According to one embodiment of the present invention, a method for manufacturing a lithium metal battery is described, wherein first and second lithium-ion selective films are immobile in the electrolytic cell, and as the first layer of lithium is formed, the first layer of lithium displaces the first non-aqueous electrolyte from the space between the first surface of the conductive substrate and the first lithium-ion selective film, thereby bonding the inner surface of the first layer of lithium to the first surface of the conductive substrate and the outer surface of the first layer of lithium to the first lithium-ion selective film, and as the second layer of lithium is formed, the second layer of lithium displaces the second non-aqueous electrolyte from the space between the second surface of the conductive substrate and the second lithium-ion selective film, thereby bonding the conductive substrate The inner surface of the second layer of lithium is bonded to the second surface, and the outer surface of the second layer of lithium is bonded to the second lithium-ion selective film, thereby forming a lithium metal electrode comprising a conductive substrate and first and second layers of lithium metal, further comprising the inner surface of the first layer of lithium bonded to the first surface of the conductive substrate, the outer surface of the first layer of lithium bonded to the first lithium-ion selective film, the inner surface of the second layer of lithium bonded to the second surface of the conductive substrate, and the outer surface of the second layer of lithium bonded to the second lithium-ion selective film. The first and second lithium-ion selective films are configured to function as a solid electrolyte when the lithium metal electrode is incorporated into a galvanic cell. [Brief explanation of the drawing]

[0027] The aforementioned features of the embodiment will be more readily understood by referring to the accompanying drawings and the following detailed description.

[0028] [Figure 1] Figure 1 shows the steps in manufacturing a lithium metal battery according to one embodiment of the present invention.

[0029] [Figure 2] Figure 2 shows an improved single-sided lithium metal electrode suitable for use as a working anode in a lithium metal battery according to one embodiment of the present invention.

[0030] [Figure 3] Figure 3 shows an electrolytic cell for manufacturing an improved single-sided lithium metal electrode suitable for use as a working anode in a lithium metal battery according to one embodiment of the present invention.

[0031] [Figure 4] Figure 4 shows an improved bifacial lithium electrode suitable for use as a working anode in a lithium metal battery according to one embodiment of the present invention.

[0032] [Figure 5] Figure 5 shows an electrolytic cell suitable for manufacturing a double-sided electrode suitable for use as a working anode in a lithium metal battery according to one embodiment of the present invention.

[0033] [Figure 6] Figure 6 shows a battery having a single-sided lithium metal electrode as a working anode, with a layer of high-purity lithium metal sandwiched between a conductive substrate and a lithium-ion selective film, and the lithium-ion selective film is configured to function as a solid-state electrolyte.

[0034] [Figure 7] Figure 7 shows a suitable electrolytic cell for manufacturing a single-sided lithium metal electrode, as shown in Figure 6, prior to plating the lithium metal on the conductive substrate of the battery, with the conductive substrate coated with a lithium-ion selective film.

[0035] [Figure 8] Figure 8 shows the electrolytic cell of Figure 7, in which, after plating lithium metal onto a conductive substrate according to one embodiment of the present invention, the lithium metal is bonded to the conductive substrate on one side and to a solid electrolyte on the other side, and the electrodes are suitable for use as working anodes in lithium metal batteries.

[0036] [Figure 9]Figure 9 shows a battery according to one embodiment of the present invention, in which a bifacial lithium electrode serves as a working anode, with lithium metal sandwiched between a conductive substrate and a lithium-ion selective film, and the lithium-ion selective film is configured to function as a solid-state electrolyte.

[0037] [Figure 10] Figure 10 shows a suitable electrolytic cell for manufacturing a double-sided lithium metal electrode of the type embodied in Figure 9, prior to plating lithium metal on both sides of the conductive substrate of the battery, wherein the conductive substrate is covered with a lithium-ion selective film on both of its two sides.

[0038] [Figure 11] Figure 11 shows the electrolytic cell of Figure 10 according to one embodiment of the present invention, in which lithium metal is plated onto each of two surfaces of a conductive substrate, and with respect to each surface, the lithium metal is bonded to the conductive substrate on one side and to the solid electrolyte on the other side, and the electrodes are suitable for use as working anodes in lithium metal batteries.

[0039] [Figure 12] Figure 12 shows a lithium-ion battery manufacturing facility using conventional technology.

[0040] [Figure 13] Figure 13 shows a lithium metal battery manufacturing facility vertically integrated with the manufacturing process, as embodied in the method described herein.

[0041] [Figure 14] Figure 14 shows a battery case for a battery with a single-sided lithium anode according to an embodiment of the present invention.

[0042] [Figure 15] Figure 15 shows a battery case for a battery with a double-sided lithium anode according to an embodiment of the present invention. [Modes for carrying out the invention]

[0043] Definitions. As used in this specification and the appended claims, the following terms shall have the meanings indicated, unless the context requires otherwise.

[0044] "Cathode" is the electrode at which reduction occurs.

[0045] "Anode" is the electrode at which oxidation occurs.

[0046] "Working anode" is the anode in a galvanic cell.

[0047] "Positive electrode" is the anode in an electrolytic cell and the cathode in a galvanic cell.

[0048] "Negative electrode" is the cathode in an electrolytic cell and the anode in a galvanic cell. As a result, although a lithium metal electrode is the cathode in an electrolytic cell and the anode in a galvanic cell, it is always a "negative electrode".

[0049] In the context of this application, "lithium metal electrode" and "lithium electrode" are synonyms and each refers to a negative electrode comprising lithium metal.

[0050] "Lithium metal battery" (or "LMB") is a battery that utilizes a negative electrode comprising pure lithium metal (i.e., a lithium metal electrode). The positive electrode for such a battery is typically an intercalation compound such as Ti2S, which receives electrons from the anode through an external circuit during discharge and inserts Li + into its lattice structure.

[0051] "Lithium ion battery" is a rechargeable battery in which lithium ions shuttle between a negative electrode and an intercalation compound as the positive electrode.

[0052] The surrounding atmosphere is considered "substantially free" of lithium-reactive components when the atmosphere contains lithium-reactive components at a concentration of 10 ppm or less.

[0053] In the context of this disclosure, a “vertically integrated” lithium metal manufacturing facility is a facility in which lithium metal anodes are manufactured by electrodeposition within the facility and integrated into the battery manufacturing process.

[0054] Figure 1 shows the steps in the manufacture of a lithium metal battery (LMB) according to an embodiment of the present invention. In embodiments of Figures 2, 4, 6, 7, 9, and 10, etc., the electrolytic cell is covered with an ambient air, and the ambient air is substantially free of lithium reactive components, including nitrogen, oxygen, ozone, nitrogen oxides, sulfur and phosphorus, carbon dioxide, halogens, hydrogen halides, and water. In some embodiments, the ambient air contains lithium reactive components at a molar basis of 10 ppm or less. In some embodiments, the ambient air contains lithium reactive components at a molar basis of 5 ppm or less. In preferred embodiments, the ambient air contains nitrogen at a molar basis of 10 ppm or less. In preferred embodiments, the ambient air contains nitrogen at a molar basis of 5 ppm or less. In preferred embodiments, The atmosphere contains 1 ppm or less of nitrogen on a molar basis. In a preferred embodiment, the covering atmosphere is argon gas. In a preferred embodiment, the argon gas has a purity greater than 99.998 weight percent. The electrolytic cell operates at or near room temperature and uses an aqueous lithium salt solution as the anodelite, which provides lithium raw material for electrodeposition to form the negative electrode. In a preferred embodiment, the aqueous lithium salt solution contains lithium sulfate (Li2SO4) and / or lithium carbonate (Li2CO3). When the Li2SO4 solution is used as the raw material, the only byproduct is O2 gas, which is generated at the anode, exhausted from the anodelite, and does not come into contact with the inert cathodelite area. Li2SO4 is a very inexpensive lithium raw material in the process chain, and therefore the Li2SO4 solution provides an economical source of lithium ions for the method according to the present invention. When Li2CO3 is used as the raw material, the smallest amount of carbon dioxide generated can also be exhausted at the anode of the electrolytic cell. Typically, Li2CO3 is more expensive than Li2SO4. However, receiving lithium carbonate that does not meet quality control standards is not uncommon for battery manufacturers, and such lithium carbonate can easily be used for other purposes, such as lithium metal production. Aqueous lithium salt solutions do not need to be highly concentrated, as a flow cell can allow the depleted lithium ions to be replaced once they are depleted by electrodeposition.

[0055] The voltage across the electrolytic cell is adjusted to apply a constant current to cell 4. The applied voltage causes lithium ions to flow from the anode to the cathode 6 across a lithium-ion selective membrane, which is configured to allow the passage of lithium ions but prevent the passage of other chemical species. At the cathode, lithium ions are reduced to lithium metal, thereby plating onto a conductive substrate to form a lithium metal electrode 8. In some embodiments, the conductive substrate is selected from the group consisting of copper, aluminum, graphite-coated copper, and nickel. In a preferred embodiment, the conductive substrate is copper. The constant current is about 10 mA / cm². 2 ~about 50mA / cm 2 When applied within this range, lithium ions traverse the lithium ion selective film, and electrodeposition onto the conductive substrate does not produce nanorods or dendrites. Rather, currents within this range produce extremely high-density lithium metal deposits, allowing electrodeposition to proceed so that it is completed within 1 to 60 minutes. In a preferred embodiment, the constant current applied is about 10 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, the constant current applied is approximately 25 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, the constant current applied is approximately 40 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, the density of the deposited lithium metal is approximately 0.4 g / cm³. 3 ~0.543g / cm 3 In some preferred embodiments, the density of the deposited lithium metal is 0.45 g / cm³. 3 ~0.543g / cm 3 It reaches approximately 10mA / cm². 2 ~about 50mA / cm 2A constant current is higher than the operating current during the charge / discharge cycle that operates a battery manufactured using the lithium metal electrodes of the present invention. Lithium metal electrodes formed at a higher current density than those used in operating batteries improve the charge-discharge recycling capacity of such batteries. Although not constrained by theory, it is assumed that lithium metal electrodes formed at a higher current density than those used in operating batteries will not form dendrites during recycling, provided that no impurities are present anywhere in the battery. During the electrodeposition process, lithium continuously passes through a lithium-ion selective film and accumulates on the conductive substrate until the desired thickness is achieved (a 15 μm film can be fabricated in less than 5 minutes). Only lithium ions pass through from lithium ions containing aqueous electrolytes, allowing the use of inexpensive impure raw material solutions containing Li2SO4 and / or Li2CO3. The lithium electrodeposited on the negative electrode is never handled or exposed to air prior to entering the battery, and is therefore elementally pure and intact. Since electrodeposition occurs in an atmosphere that is substantially free of lithium reactive components (including nitrogen), the formation of impurities (particularly Li3N) is avoided.

[0056] In some embodiments, the lithium electrodeposited on the negative electrode coats all sides of the negative electrode. In some embodiments, the copper is in the form of a mesh. In some embodiments, the copper is in the form of a foam. In some embodiments, the conductive substrate comprises a plate with two faces, and the lithium metal coats at least one face of the plate. In some embodiments, the lithium metal coats both of the two faces of the plate.

[0057] In some embodiments, the lithium-ion selective film is a hybrid organic-inorganic film comprising a polymer matrix and a plurality of ion-conducting particles arranged within the polymer matrix. In some such embodiments, an inorganic coating is deposited on the polymer matrix, and the inorganic coating is a uniform layer with a thickness of 1 to 10,000 atoms. In some embodiments, the polymer may be a silica-based polyurethane, polyethylene oxide, polystyrene, or polyamide.

[0058] In some embodiments, the lithium-ion selective film comprises a glass frit in which lithium-ion conducting particles are disposed.

[0059] In some embodiments, the ion-conducting particles are LifePO4, LiCoO2, NASICON electrolyte, lithium lanthanite titanate (LLTO), garnet-type electrolyte, LISICON and Thio-LISICON electrolyte, Li7La3Zr3O 12 The phase is selected from the group consisting of (LLZO) and the cubic phase (c-LLZO).

[0060] Finally, the lithium metal electrodes thus formed are used in the production of LMB12. In a preferred embodiment, all steps in the manufacturing method are carried out in a single manufacturing facility. In some embodiments, the single manufacturing facility is located at 10 km 2 It is included within the following area. In some embodiments, the manufacturing facility is located at approximately 1 km². 2 It is contained within an area of ​​less than 100%. Since the lithium metal battery of the present invention is manufactured in a fully charged state, the present invention reduces the occupied area, cost, and time of rechargeable batteries compared to conventional LIBs, which are initially manufactured in an uncharged state and require time-consuming finishing steps to obtain a fully charged battery.

[0061] Figure 2 provides a single-sided lithium metal electrode 15 according to one embodiment of the present invention. The lithium electrode 15 includes a conductive substrate 10 in the form of a plate having two faces. In a preferred embodiment, the conductive substrate is selected from the group consisting of copper, aluminum, graphite-coated copper, and nickel. A layer of lithium metal 60 is bonded to one of the two faces of the conductive substrate, and the lithium metal contains nonmetallic elements at a mass ratio of 5 ppm or less. In a preferred embodiment, the lithium metal contains nonmetallic elements at a mass ratio of 1 ppm or less. In a preferred embodiment, the lithium metal contains nitrogen at a mass ratio of 1 ppm or less. In a preferred embodiment, the layer of lithium metal 60 has a thickness of about 1 micron to about 10 microns. The conductive substrate 10 and the layer of lithium metal 60 together constitute a single-sided lithium metal electrode 15 suitable for use as a fully charged working anode in an LMB. In a preferred embodiment, the lithium metal electrode 15 has lithium metal with a specific capacity greater than about 3,800 mAh per gram. In a preferred embodiment, the lithium metal layer 60 has a density of approximately 0.4 g / cm³. 3 ~Approx. 0.534g / cm 3 It has a density of approximately 0.45 g / cm³. In a preferred embodiment, the lithium metal layer 60 has a density of approximately 0.45 g / cm³. 3 ~Approx. 0.543g / cm 3 It has a density of .

[0062] In the method for manufacturing the single-sided lithium electrode 15 shown in Figure 2, the electrolytic cell 5 is used as shown in Figure 3. During the manufacturing process, the electrolytic cell 5 of this embodiment is covered by the atmosphere 24 The covering atmosphere is completely covered and substantially free of lithium reactive components. In a preferred embodiment, the covering atmosphere contains lithium reactive components at a molar basis of 10 ppm or less. In a preferred embodiment, the covering atmosphere contains lithium reactive components at a molar basis of 5 ppm or less. In a preferred embodiment, the covering atmosphere contains nitrogen at a molar basis of 10 ppm or less. In a preferred embodiment, the covering atmosphere contains nitrogen at a molar basis of 5 ppm or less. In a preferred embodiment, the covering atmosphere contains nitrogen at a molar basis of 1 ppm or less. In a preferred environment, the covering atmosphere contains argon with a purity greater than 99.998 weight percent. In the embodiment of Figure 3, the covering atmosphere 24 and the electrolytic cell 5 are sealed in a gas-impermeable container 500. The electrolytic cell 5 includes a first chamber 26 and a second chamber 28. The first chamber 26 includes a positive electrode 20 and an aqueous lithium salt solution 40 in contact with the positive electrode 20. The second chamber 28 includes a lithium metal electrode 15, a lithium ion selective membrane 50, and a non-aqueous electrolyte 30. The lithium ion selective membrane 50 has a first side and a second side, physically separating the first chamber 26 from the second chamber 28, and contacting the aqueous lithium salt solution 40 on the first side. In the second chamber 28, the non-aqueous electrolyte 30 is positioned between the lithium metal electrode 15 and the second side of the lithium ion selective membrane 50, and is in physical contact with both the lithium metal electrode 15 and the second side of the lithium ion selective membrane 50. The lithium metal electrode 15 includes a conductive substrate 10, which remains stationary during lithium metal electrodeposition in the second chamber and is electrodeposited with a layer of elemental lithium 60. The lithium ion selective membrane 50 allows lithium ions to pass between the first chamber 26 and the second chamber 28, but prevents the passage of other chemical species between the two chambers. In particular, the lithium-ion selective membrane does not allow water to pass from the first chamber 26 to the second chamber 28.

[0063] In manufacturing the single-sided lithium metal electrode 15 embodied in Figure 2, a variable voltage is applied across the positive electrode 20 of the electrolytic cell 5 and the conductive substrate 10 to maintain a constant current, thereby causing lithium ions to move through the aqueous lithium salt solution 40, across the lithium ion selective film 50 from the first chamber 26 to the second chamber 28, into the non-aqueous electrolyte, and proceed to the surface of the stationary conductive substrate 10, where each lithium ion acquires electrons, thereby causing a layer of elemental lithium 60 to be electrodeposited onto the conductive substrate 10, thereby forming the single-sided lithium metal electrode 15.

[0064] In some embodiments, the first chamber 26 of the electrolytic cell 5 in Figure 2 is a flow chamber with an inlet port 70 and an outlet port 80 that allows an aqueous lithium salt solution to enter the first chamber 26 and provide a renewable source of lithium ions for electrodeposition.

[0065] In a preferred embodiment, the constant current is approximately 10 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, the constant current applied is approximately 25 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, the constant current applied is approximately 40 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, a constant current is applied over a period of time from about 1 minute to about 60 minutes.

[0066] In a preferred embodiment, the aqueous lithium salt solution 40 is selected from the group consisting of Li2SO4, Li2CO3, and combinations thereof. In a preferred embodiment, the aqueous lithium salt solution 40 contains Li2SO4. In a preferred embodiment, the lithium ion selective membrane 50 comprises a polymer matrix and a plurality of ion-conducting particles disposed within the polymer matrix. In a preferred embodiment, the lithium ion selective membrane 50 contains glass frit in which the lithium ion-conducting particles are disposed.

[0067] Figure 4 provides a double-sided lithium metal electrode according to one embodiment of the present invention. The double-sided lithium metal electrode 115 includes a conductive substrate 110 in the form of a plate having a first surface and a second surface. In a preferred embodiment, the conductive substrate 115 is selected from the group consisting of copper, aluminum, graphite-coated copper, and nickel. The first and second surfaces of the conductive substrate 115 are coated with layers 160a and 160b of lithium metal, respectively, the lithium metal containing nonmetallic elements at a mass ratio of 5 ppm or less. In a preferred embodiment, the lithium metal contains nonmetallic elements at a mass ratio of 1 ppm or less. In a preferred embodiment, the lithium metal layers 160a and 160b have a thickness of about 1 micron to about 10 microns. The conductive substrate 110 and the lithium metal layers 160a and 160b together constitute the double-sided lithium metal electrode 115, which is suitable for use as a fully charged working anode in an LMB. In a preferred embodiment, the lithium metal electrode 115 has a lithium metal with a specific capacity greater than approximately 3,800 mAh per gram. In a preferred embodiment, each of the lithium metal layers 160a and 160b has a specific capacity of approximately 0.4 g / cm³ 3 ~Approx. 0.543g / cm 3 It has a density of approximately 0.45 g / cm³. In a preferred embodiment, each of the lithium metal layers 160a and 160b has a density of approximately 0.45 g / cm³. 3 ~Approx. 0.543g / cm 3 It has a density of .

[0068] In the method for manufacturing the double-sided lithium electrode 115 shown in Figure 4, the electrolytic cell 105 is used as shown in Figure 5. During the manufacturing process, the electrolytic cell 105 of this embodiment is covered with covering air 24, which is inert to chemical reactions with lithium. In a preferred embodiment, the covering air contains 10 ppm or less of lithium reactive components on a molar basis. In a preferred embodiment, the covering air contains 5 ppm or less of lithium reactive components on a molar basis. In a preferred embodiment, the covering air contains 10 ppm or less of nitrogen on a molar basis. In a preferred embodiment, the covering air contains 5 ppm or less of nitrogen on a molar basis. In a preferred embodiment, the covering air contains 1 ppm or less of nitrogen on a molar basis. In a preferred environment, the covering air contains argon with a purity greater than 99.998 weight percent. In the embodiment of Figure 5, the covering air 24 and the electrolytic cell 105 are sealed in a gas-impermeable container 500. The electrolytic cell 105 includes a first chamber 126a, a second chamber 128a, a third chamber 126b, and a fourth chamber 128b. The first chamber 126a includes a positive electrode 120a and an aqueous lithium salt solution 140a in contact with the positive electrode 120a, and the third chamber 126b includes a positive electrode 120b and an aqueous lithium salt solution 140b in contact with the positive electrode 120b. The second chamber 128a and the fourth chamber 128b share a double-sided lithium metal electrode 115, which connects the two chambers. The double-sided lithium metal electrode 115 includes a central conductive substrate 110 having a first surface and a second surface, the first and second surfaces being electrodeposited with lithium metal layers 160a and 160b, respectively, with lithium metal layer 160a extending into the second chamber 128a and lithium metal layer 160b extending into the fourth chamber. The second chamber 128a includes a lithium ion selective membrane 150a and a non-aqueous electrolyte 130a. The lithium ion selective membrane 150a has a first side and a second side, physically separating the first chamber 128a from the second chamber 128a and contacting an aqueous lithium salt solution 140a on the first side.In the second chamber 128a, a non-aqueous electrolyte 130a is located between the lithium metal layer 160a and the second side of the lithium ion selective membrane 150a. The fourth chamber includes a lithium ion selective membrane 150b and a non-aqueous electrolyte 130b. The lithium ion selective membrane 150b has a first side and a second side, physically separating the third chamber 126b from the fourth chamber 128b and contacting the aqueous lithium salt solution 140b on the first side. In the fourth chamber 128b, the non-aqueous electrolyte 130b is located between the lithium metal layer 160b and the second side of the lithium ion selective membrane 150b. The lithium ion selective membranes 150a and 150b allow lithium ions to pass between the first chamber 126a and the second chamber 128a, the third chamber 126b, and the fourth chamber 128a, respectively. This allows passage between b and b, but prevents the passage of other chemical species between the first chamber 126a and the second chamber 128a, and between the third chamber 126b and the fourth chamber 128b, respectively.

[0069] When manufacturing the double-sided lithium metal electrode 115 embodied in Figure 4 using the electrolytic cell 105, a variable voltage is applied across the positive electrodes 120a, 120b and the conductive substrate 110 of the electrolytic cell 105 to maintain a constant current, thereby causing lithium ions to move through the aqueous lithium salt solutions 140a, 140b, respectively, across the first and third chambers 126a, 126b to the second and fourth chambers 128a, 128b, respectively, through the lithium ion selective films 150a, 150b, respectively, into the non-aqueous electrolytes 130a, 130b, respectively, and proceed to the first and second surfaces of the conductive substrate 110 where each lithium ion acquires electrons, thereby causing layers of elemental lithium 160a, 160b to be electrodeposited onto the first and second surfaces of the conductive substrate 110, respectively, thereby forming the double-sided lithium metal electrode 115. During the electrodeposition of lithium metal layers 160a and 160b onto the first and second surfaces of the conductive substrate 110, the conductive substrate 110 remains stationary.

[0070] In some embodiments, the first and third chambers 126a and 126b of the electrolytic cell 105 in Figure 4 are flow chambers, and the inlet ports 170a and 170b and outlet ports 180a and 180b allow aqueous lithium salt solutions 140a and 140b to enter the first chamber 126a and the third chamber 126b, providing a renewable supply of lithium ions for electrodeposition.

[0071] In a preferred embodiment, the constant current is approximately 10 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, the constant current applied is approximately 25 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, the constant current applied is approximately 40 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, a constant current is applied over a period of time from about 1 minute to about 60 minutes.

[0072] In preferred embodiments, the aqueous lithium salt solutions 140a and 140b are selected from the group consisting of Li2SO4, Li2CO3, and combinations thereof. In preferred embodiments, the aqueous lithium salt solutions 140a and 140b contain Li2SO4. In preferred embodiments, the lithium ion selective membranes 150a and 150b comprise a polymer matrix and a plurality of ion-conducting particles disposed within the polymer matrix. In preferred embodiments, the lithium ion selective membranes 150a and 150b contain a glass frit in which the lithium ion-conducting particles are disposed.

[0073] Figure 6 provides a galvanic cell 225 manufactured using a single-sided lithium metal electrode 215 configured to function as an anode. The lithium metal electrode 215 includes a conductive substrate 210 bonded to a lithium metal layer 260, the lithium metal containing nonmetallic elements at a mass ratio of 5 ppm or less. In a preferred embodiment, the lithium metal contains nonmetallic elements at a mass ratio of 1 ppm or less. In a preferred embodiment, the lithium metal contains nitrogen at a mass ratio of 1 ppm or less. The conductive substrate 210 and the lithium metal layer 260 together constitute the single-sided lithium metal electrode 215 of the galvanic cell 225. In a preferred embodiment, the lithium metal electrode 215 has a lithium metal specific capacity greater than about 3,800 mAh per gram. In a preferred embodiment, the lithium metal layer 60 is about 0.4 g / cm³ 3 ~Approx. 0.534g / cm 3 It has a density of approximately 0.45 g / cm³. In a preferred embodiment, the lithium metal layer 260 has a density of approximately 0.45 g / cm³. 3 ~Approx. 0.543g / cm 3 It has a density of . In a preferred embodiment, the conductive substrate is selected from the group consisting of copper, aluminum, graphite-coated copper, and nickel. The lithium metal layer 260 has a first surface and It has a second surface, bonded to the conductive substrate 210 on the first surface, and bonded to the lithium-ion selective film 250 on the second surface. The lithium-ion selective film 250 is configured to function as a solid-state electrolyte. The lithium-ion selective film 250 separates the lithium metal layer 260 from the cathode liquid 290. In a preferred embodiment, the cathode liquid 290 contains an ionic liquid forming salt. In a preferred embodiment, the cathode liquid 290 comprises an ionic liquid. The cathode liquid 290 then separates the lithium-ion selective film 250 from the cathode / cathode liquid interface 295, and the cathode / cathode liquid interface 295 covers the surface of the cathode 235, separating the cathode 235 from the cathode liquid 290. The electrical contacts of the anode 245 allow electrons to flow from the electrode 215 to the corresponding electrical contacts, the cathode 255, and then onto the cathode 235. In this configuration, the lithium-ion selective membrane 250 is configured to function as a solid-state electrolyte. During battery discharge, the pure lithium metal layer is oxidized to lithium ions, releasing electrons and lithium ions that flow from the single-sided electrode 215 to the cathode 235 through electrical contacts 245, 255. The lithium ions flow through the lithium-ion selective membrane 250 into the cathode 235, where electrons are taken up by the cathode 235. In various embodiments, the cathode 290 may comprise salts containing organic cations and inorganic ions that are capable of forming an ionic liquid. In embodiments, the cathode 290 comprises an ionic liquid. In embodiments, the cathode 290 comprises lithium salts of organic anions that are capable of forming an ionic liquid, where the organic anions are trifluoromethanesulfonyl-imide (TFSI), N-butyl-N-methylpyrrolidinium bromidobis(trifluoromethanesulfonyl)imide (Pyr 14The group is selected from the group consisting of TFSI, trifluoromethanesulfonyl-imide, bis(trifluoromethanesulfonyl)imide (LiTFSI), and 1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide (EMI-TFSI). In some embodiments, the cathode 290 comprises an ionic liquid forming salt dissolved in 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), or tetraethylene glycol dimethyl ether (TEGDME). In some embodiments, the cathode comprises (4.0-5.0 M) lithium bis(fluorosulfonyl)imide (LiFSI) concentrated in 1:1 DOL / DME.

[0074] Although not constrained by theory, it is thought that elementally pure lithium metal, chemically bonded to a substrate that is chemically bonded to a lithium-ion selective film configured to function as a solid-state electrolyte, would eliminate impedance fluctuations at the electrode / solid electrolyte separator interface, thereby minimizing dendrite formation.

[0075] In the method for manufacturing the galvanic cell 225 shown in Figure 6 by electrodeposition of the single-sided lithium electrode 215, an electrolytic cell 205 is used. Figure 7 shows the electrolytic cell 205 prior to electrodeposition, and Figure 8 shows the electrolytic cell following electrodeposition. According to the method, the electrolytic cell 205 is completely covered with covering air 24, which is inert to chemical reactions with lithium. In a preferred embodiment, the covering air contains 10 ppm or less of lithium reactive components on a molar basis. In a preferred embodiment, the covering air contains 5 ppm or less of lithium reactive components on a molar basis. In a preferred embodiment, the covering air contains 10 ppm or less of nitrogen on a molar basis. In a preferred embodiment, the covering air contains 5 ppm or less of nitrogen on a molar basis. In a preferred embodiment, the covering air contains 1 ppm or less of nitrogen on a molar basis. In a preferred environment, the covering air contains argon with a purity of 99.998 weight percent or higher. In the embodiments shown in Figures 7 and 8, the covering atmosphere 24 and the electrolytic cell 5 are sealed within a gas-impermeable container 500. During the electrodeposition process, the electrolytic cell 205 is trapped in the covering atmosphere 24.

[0076] The electrolytic cell 205 comprises a conductive substrate 210 configured as a negative electrode, and an ion-selective film 250. The solution comprises an aqueous lithium salt solution 240 and a positive electrode 220. The aqueous lithium salt solution 240 is inserted between the conductive substrate 210 and the positive electrode 220. Prior to electrodeposition, as shown in Figure 7, the lithium ion selective film 250 covers the conductive substrate 210, forming a barrier that separates the lithium salt solution 240 from the conductive substrate 210. Prior to electrodeposition, as shown in Figure 7, the conductive substrate 210 is physically coated with the lithium ion selective film 250, which is configured to function as a solid-state electrolyte. After electrodeposition, as shown in Figure 8, a layer of lithium metal 260 is electrodeposited between the conductive substrate 210 and the lithium ion selective film 250, bonding to both the conductive substrate 210 and the lithium ion selective film 250. During the electrodeposition process, the lithium ion selective film 250 separates the conductive substrate 210 and the electrodeposited lithium metal layer 260 from the lithium salt solution 240. The lithium-ion selective membrane 250 is configured to function as a solid-state electrolyte, allowing lithium ions to pass through from the aqueous salt solution 240 but preventing the passage of other chemical species, so that it can be electrodeposited onto the surface of the conductive substrate 210.

[0077] In manufacturing the single-sided lithium metal electrode 215 for the galvanic cell embodied in Figure 6, a variable voltage is applied across the conductive substrate 210 of the positive electrode 220 and electrolytic cell 205 to maintain a constant current, thereby causing lithium ions to move through the aqueous lithium salt solution 240 and the lithium ion selective film 250, with each lithium ion progressing to the surface of the conductive substrate 210 where it acquires electrons, thereby causing a layer of elemental lithium 260 to electrodeposit onto the conductive substrate 210. Thus, a layer of elemental lithium is formed, with the first side of the layer of elemental lithium 260 bonded to the conductive substrate and the second side of the layer of elemental lithium 260 bonded to the lithium ion selective film 250. In this way, as shown in Figures 7 and 8, the single-sided lithium metal electrode 215 is manufactured such that a sandwich of lithium metal layers 260 is formed between the conductive substrate 210 and the lithium ion selective film 250. During the electrodeposition process, the conductive substrate 210 remains stationary in the electrolytic cell.

[0078] In some embodiments, the electrolytic cell 205 in Figure 7 is a flow chamber, and the inlet port 270 and outlet port 280 allow the aqueous lithium salt solution 240 to enter the electrolytic cell 205 and provide a renewable supply of lithium ions for electrodeposition.

[0079] In a preferred embodiment, the constant current is approximately 10 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, the constant current applied is approximately 25 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, the constant current applied is approximately 40 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, a constant current is applied over a period of time from about 1 minute to about 60 minutes.

[0080] In a preferred embodiment, the aqueous lithium salt solution 240 is selected from the group consisting of Li2SO4, Li2CO3, and combinations thereof. In a preferred embodiment, the aqueous lithium salt solution 240 contains Li2SO4. In a preferred embodiment, the lithium ion selective membrane 250 comprises a polymer matrix and a plurality of ion-conducting particles disposed within the polymer matrix. In a preferred embodiment, the lithium ion selective membrane 250 contains glass frit in which the lithium ion-conducting particles are disposed.

[0081] In an alternative method for manufacturing the galvanic cell 225 in Figure 6 by electrodepositing the single-sided lithium electrode 215, the electrolytic cell 5 in Figure 3 is used. According to this method, both the lithium-ion selective film 50 and the conductive substrate 10 remain stationary in the electrolytic cell. A variable voltage is applied across the positive electrode 20 and conductive substrate 10 of the electrolytic cell 5 to maintain a constant current, thereby causing lithium ions to move through the aqueous lithium salt solution 40, across the lithium-ion selective film 50 from the first chamber 26 to the second chamber 28, and through the non-aqueous solution. Entering the electrolyte, each lithium ion is caused to propagate to the surface of the conductive substrate 10 where it gains electrons, thereby causing a layer of elemental lithium 60 to be electrodeposited onto the conductive substrate 10. As the layer of elemental lithium 60 increases, the layer of elemental lithium 60 displaces the non-aqueous electrolyte 30 from the second chamber 28 and eventually comes into contact with and bonds to the lithium-ion selective membrane 50, thereby forming a single-sided lithium metal electrode 215 in Figure 6 comprising the conductive substrate 10 and the layer of lithium 60, where the layer of lithium 60 is bonded to the conductive substrate 10 on one side and to the lithium-ion selective membrane 50 configured to function as a solid-state electrolyte on the other side.

[0082] Figure 9 provides a galvanic cell 325 manufactured using a double-sided lithium metal electrode 315 configured to function as an anode. The double-sided lithium metal electrode 315 includes a conductive substrate 310 in the form of a plate having a first surface and a second surface, the first and second surfaces being bonded to first and second lithium metal sheets 360a and 360b, respectively, and the lithium metal contains nonmetallic elements at a mass ratio of 5 ppm or less. In a preferred embodiment, the lithium metal contains nonmetallic elements at a mass ratio of 1 ppm or less. In a preferred embodiment, the lithium metal contains nitrogen at a mass ratio of 1 ppm or less. The conductive substrate 310 and each of the first and second layers 360a and 360b of lithium metal together constitute the double-sided lithium metal electrode 315 of the galvanic cell 325. In a preferred embodiment, the lithium metal electrode 315 has lithium metal with a specific capacity greater than about 3,800 mAh per gram. In a preferred embodiment, each of the first and second layers 360a and 360b of lithium metal contains approximately 0.4 g / cm³ 3 ~Approx. 0.534g / cm 3 It has a density of . In a preferred embodiment, each of the lithium metal layers 360a and 360b has a density of about 0.45 g / cm³. 3 ~Approx. 0.543g / cm 3It has a density of . In a preferred embodiment, the conductive substrate is selected from the group consisting of copper, aluminum, graphite-coated copper, and nickel. Each layer 360a, 360b of lithium metal has a first surface and a second surface, which are bonded to the conductive substrate 310 on the first surface and to the lithium-ion selective films 350a, 350b on the second surface. The lithium-ion selective films 350a, 350b are configured to function as solid-state electrolytes. The lithium-ion selective film 350a separates the lithium metal layer 360a from the cathode liquid 390a. In a preferred embodiment, the cathode liquid 390a contains an ionic liquid forming salt. In a preferred embodiment, the cathode liquid 390a comprises an ionic liquid. The cathode liquid 390a then separates the lithium ion selective membrane 350a from the cathode / cathode liquid interface 395a, and the cathode / cathode liquid interface 395a covers the surface of the cathode 335a, separating the cathode 335a from the ionic liquid 390a. The lithium ion selective membrane 350b separates the lithium metal layer 360b from the cathode liquid 390b. In a preferred embodiment, the cathode liquid 390b contains an ionic liquid forming salt. In a preferred embodiment, the cathode liquid 390b comprises an ionic liquid. The cathode liquid 390b then separates the lithium ion selective membrane 350b from the cathode / cathode liquid interface 395b, and the cathode / cathode liquid interface 395b covers the surface of the cathode 335b, separating the cathode 335b from the ionic liquid 390b.

[0083] The electrical contacts of anode 345 allow electrons to flow from electrode 315 to the corresponding electrical contacts of the two cathodes 355a and 355b, respectively, and then to cathodes 335a and 335b. During battery discharge, the layers of pure lithium metal 360a and 360b are oxidized to lithium ions, releasing electrons and lithium ions that flow from both electrodes 315 through electrical contacts 345, through electrical contacts 355a and 355b, to cathodes 335a and 335b. The lithium ions flow through lithium ion selective films 350a and 350b into the ionic liquids 390a and 390b, into cathodes 335a and 335b, where they are inserted into the cathodes 335a and 335b, and electrons are taken up at cathodes 335a and 335b. In various embodiments, the cathode liquid may comprise a salt containing organic cations and inorganic ions, capable of forming an ionic liquid. In this embodiment, the cathodelibrium 390a and 390b may comprise salts containing organic cations and inorganic ions, capable of forming an ionic liquid. In this embodiment, the cathodelibrium 390a and 390b comprise an ionic liquid. In this embodiment, the cathodelibrium 390a and 390b comprise a lithium salt of an organic anion capable of forming an ionic liquid, the organic anion being trifluoromethanesulfonyl-imide (TFSI), N-butyl-N-methylpyrrolidinium bromidobis(trifluoromethanesulfonyl)imide (Pyr 14 The following are selected from the group consisting of TFSI, trifluoromethanesulfonyl-imide, bis(trifluoromethanesulfonyl)imide (LiTFSI), and 1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide (EMI-TFSI). In some embodiments, the cathodes 390a, 390b comprise an ionic liquid forming salt dissolved in 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), or tetraethylene glycol dimethyl ether (TEGDME). In some embodiments, the cathodes 390a, 390b comprise (4.0-5.0 M) lithium bis(fluorosulfonyl)imide (LiFSI) concentrated in 1:1 DOL / DME.

[0084] Although not constrained by theory, it is thought that an elementally pure lithium metal chemically bonded to a substrate chemically bonded to a lithium-ion selective film configured to function as a solid-state electrolyte would eliminate impedance fluctuations at the electrode / solid electrolyte separator interface, thereby minimizing dendrite formation.

[0085] In the method for manufacturing the double-sided lithium electrodes 315 of the galvanic cell 325 shown in Figure 9 by electrodeposition, an electrolytic cell 305 is used. Figure 10 shows the electrolytic cell 305 prior to electrodeposition, and Figure 11 shows the electrolytic cell following electrodeposition. According to the method, the electrolytic cell 305 is completely covered with covering air 24, which is inert to chemical reactions with lithium. In a preferred embodiment, the covering air contains lithium reactive components at a molar basis of 10 ppm or less. In a preferred embodiment, the covering air contains lithium reactive components at a molar basis of 5 ppm or less. In a preferred embodiment, the covering air contains nitrogen at a molar basis of 10 ppm or less. In a preferred embodiment, the covering air contains nitrogen at a molar basis of 5 ppm or less. In a preferred embodiment, the covering air contains nitrogen at a molar basis of 1 ppm or less. In a preferred environment, the covering air contains argon with a purity of greater than 99.998 weight percent. In the embodiments shown in Figures 11 and 12, the covering atmosphere 24 and the electrolytic cell 5 are sealed within a gas-impermeable container 500. During the electrodeposition process, the electrolytic cell 305 is trapped in the covering atmosphere 24.

[0086] The electrolytic cell 305 includes a first chamber 326a and a second chamber 326b, the first chamber having a proximal and distal end, and the second chamber having a proximal and distal end. The conductive substrate 310 is continuous with respect to the first chamber 326a and separates it from the second chamber 326b, and the conductive substrate 310 has a first side facing the first chamber 326a and a second side facing the second chamber 326b. Prior to electrodeposition, as embodied in Figure 10, the first and second sides of the conductive substrate 310 are coated with a first lithium-ion selective film 350a configured to function as a solid-state electrolyte extending into the proximal end of the first chamber 326a and a second lithium-ion selective film 350b configured to function as a solid-state electrolyte extending into the proximal end of the second chamber 326b, respectively. At its distal end, the first chamber 326a and the second chamber 326b contain positive electrodes 320a and 320b, respectively. The positive electrode 320a and the first lithium-ion selective membrane 350a are separated by an aqueous salt solution 340a, which is in physical contact with both the positive electrode 320a and the lithium-ion selective membrane 350a. In a similar manner, the positive electrode 320b and the first lithium-ion selective membrane 350b are separated by an aqueous salt solution 340b, which is in physical contact with both the positive electrode 320a and the lithium-ion selective membrane 350a. Physical contact is made with both 20b and the lithium-ion selective film 350b.

[0087] After electrodeposition, as shown in Figure 11, lithium metal layers 320a and 320b are electrodeposited between the conductive substrate 310 and the lithium ion selective films 350a and 350b, respectively, and the lithium metal layers 320a and 320b are bonded to the conductive substrate 310 and the lithium ion selective films 350a and 350b, respectively.

[0088] During the electrodeposition process, the lithium-ion selective films 350a and 350b separate the conductive substrate 310 and the electrodeposited lithium metal layers 360a and 360b from the lithium salt solutions 340a and 340b, respectively.

[0089] The lithium-ion selective membranes 350a and 350b are configured to function as solid-state electrolytes, allowing lithium ions to pass between the aqueous lithium salt solutions 340a and 340b and the conductive substrate 310, while preventing the passage of other chemical species.

[0090] In manufacturing the double-sided lithium metal electrode 315 for the galvanic cell embodied in Figure 9, a variable voltage is applied across the positive electrodes 320a, 320b of the electrolytic cell 305 and the conductive substrate 310 to maintain a constant current, thereby causing lithium ions to move through aqueous lithium salt solutions 340a, 340b and lithium ion selective films 350a, 350b, respectively, and each lithium ion to advance to the surface of the conductive substrate 310 where it obtains electrons, thereby electrodepositing layers of elemental lithium 360a, 360b on the first and second sides of the conductive substrate 310, respectively, so that the layers of elemental lithium 360a, 360b bond to the conductive substrate 310 and to the lithium ion selective films 350a, 350b, respectively. Thus, as shown in Figures 10 and 11, the double-sided lithium metal electrode 315 is manufactured as a sandwich with a central conductive substrate 310 bounded on both sides by layers of elemental lithium 360, 360b, and the layers of elemental lithium 360a, 360b are then bounded by layers of lithium ion selective film 350a, 350b. During the electrodeposition process, the conductive substrate 310 remains stationary in the electrolytic cell.

[0091] In some embodiments, the first and second chambers 326a, 326b of the electrolytic cell 305 in Figures 10 and 11 are flow chambers, and the inlet ports 370a, 370b and outlet ports 380a, 380b allow aqueous lithium salt solutions 340a, 340b to enter the first chamber 326a and the second chamber 326b, providing a renewable supply of lithium ions for electrodeposition.

[0092] In a preferred embodiment, the constant current is approximately 10 mA / cm². 2 ~about 50mA / cm 2In a preferred embodiment, the constant current applied is approximately 25 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, the constant current applied is approximately 40 mA / cm². 2 ~about 50mA / cm 2 In a preferred embodiment, a constant current is applied over a period of time from about 1 minute to about 60 minutes.

[0093] In preferred embodiments, the aqueous lithium salt solutions 340a and 340b are selected from the group consisting of Li2SO4, Li2CO3, and combinations thereof. In preferred embodiments, the aqueous lithium salt solutions 340a and 340b contain Li2SO4. In preferred embodiments, the lithium ion selective membranes 350a and 350b comprise a polymer matrix and a plurality of ion-conducting particles disposed within the polymer matrix. In preferred embodiments, the lithium ion selective membranes 350a and 350b contain a glass frit in which the lithium ion-conducting particles are disposed.

[0094] In an alternative method for manufacturing the galvanic cell 325 in Figure 9 by electrodepositing the double-sided lithium electrodes 315, the electrolytic cell 105 in Figure 5 is used. According to the method, the lithium-ion selective films 150a, 150b and the conductive substrate 110 remain stationary in the electrolytic cell. A variable voltage is applied across the positive electrodes 120a, 120b and the conductive substrate 110 of the electrolytic cell 105 to maintain a constant current, thereby causing lithium ions to move through the aqueous lithium salt solutions 140a, 140b, respectively, across the first and fourth chambers 126a, 126b to the second and third chambers 128a, 128b, through the lithium ion selective films 150a, 150b, into the non-aqueous electrolytes 130a, 130b, and proceed to the first and second surfaces of the conductive substrate 110 where each lithium ion obtains electrons, thereby causing layers of elemental lithium 160a, 160b to be electrodeposited onto the conductive substrate 110. As the layers of elemental lithium 160a and 160b increase, the layers of elemental lithium 160a and 160b displace the non-aqueous electrolytes 130a and 130b from the second and third chambers 128a and 128b, respectively, and finally contact and bond to the lithium-ion selective films 150a and 150b, thereby forming the double-sided lithium metal electrode 315 of Figure 9, which comprises a conductive substrate 110 and lithium layers 160a and 160b, respectively. The lithium layers 160a and 160b are connected to the first and second surfaces of the conductive substrate 110 and bonded to the lithium-ion selective films 150a and 150b, which are configured to function as solid-state electrolytes.

[0095] In a preferred embodiment, the lithium metal electrodes described herein can be integrated into a battery, including, but not limited to, the battery embodied in Figures 6 and 9.

[0096] The method described above is highly suitable for vertically integrated battery production, thereby enabling supply chains in locally controlled LMB production in any region where lithium is mined (e.g., the United States). The development of such localized supply chains would significantly reduce costs and provide LMBs that are essentially cobalt-free.

[0097] A typical manufacturing setup for a lithium-ion battery using conventional technology is shown in Figure 12. The manufacturing process involves the fabrication of the anode 401 and cathode 403, battery assembly and battery finishing, and testing. The anode 401 and cathode 403 follow a parallel trajectory involving mixing (402) to form a slurry, coating (404) onto conductive foil, pressurizing (406) to bond the coating to the foil, and cutting (408) to form the desired electrode dimensions. Following roll forming 410, the battery is assembled (420), filled with electrolyte, and sealed (430). Since LIB batteries are manufactured in a fully discharged state, the final stage of the process involves a time-consuming battery finishing step which may include a charge and discharge (440) step, a degassing and final sealing (450) step, a further charge and discharge (460) step, and a final aging (480) step. Due to multiple time-consuming steps, the finishing process can take 20-30 days.

[0098] According to the embodiments described above, lithium metal electrodes can be fabricated in situ, thereby providing a lithium metal anode to the LMB in a fully charged state. According to the embodiment of Figure 13, the process described above for fabricating the lithium metal anode can be vertically integrated into a cost and energy efficient manufacturing method for the LMB. As embodied in Figure 13, the cathode 403 is still fabricated by a conventional method involving mixing (402), coating (404), and pressurization (406). However, the working anode is formed here by an electrolytic cell 405 according to a process embodied in Figure 1, the process of covering the electrolytic cell with an overhanging atmosphere 2, applying a constant current to the electrolytic cell 4, and applying Li across a lithium selective film 6. + Making it flow and Li Li + The process involves reducing the material and fabricating a Li metal battery 12, which is carried out by steps including pouch formation (412), battery assembly (420), battery filling and sealing (430), and finishing steps (490). Battery assembly 420 includes the steps of assembling a casing with contents including a working anode and other components for forming a lithium metal battery, and sealing the casing to isolate the contents from reactants present in the air.

[0099] As illustrated in Figure 13, the LMB manufacturing method according to the present invention is a vertically integrated process that replaces the anode fabrication process with an in-situ low-temperature electrodeposition process, utilizing an aqueous lithium salt solution as the raw material. The electrodeposition occurs through a lithium-ion selective film, producing a high-purity lithium metal anode resistant to dendrite formation. Since the lithium metal negative electrode is fabricated in a fully charged state, the long-term formation process required for lithium-ion batteries is not required.

[0100] The use of lithium-ion selective membranes and high current density allows relatively inexpensive impurity raw materials such as Li2SO4 to be used for electrodeposition, saving energy and reducing costs. Impurities in the lithium metal anode are further reduced by carrying out the electrodeposition entirely in an inert atmosphere that is substantially free of lithium reactive components (including nitrogen, oxygen, ozone, nitrogen oxides, sulfur and phosphorus, carbon dioxide, halogens, hydrogen halides, and water). In a preferred embodiment, the inert atmosphere is purified argon gas. In some embodiments, steps following electrodeposition, including battery assembly, electrolyte / battery filling, and sealing, are also carried out in the inert atmosphere. In other embodiments, only the lithium electrodeposition occurs under inert atmosphere, and the rest of the battery manufacturing process is carried out in "dry air," where dry air refers to air with less than 1% RH (relative humidity) (-45°C dew point). In a preferred embodiment, the temperature is maintained at about 20°C to about 30°C during LMB manufacturing. In a preferred embodiment, the temperature is maintained at about 23°C to about 27°C during LMB manufacturing.

[0101] It is understood that various different LMB battery configurations are encompassed by the invention described above. Figure 14 embodies a single-cell battery configuration 14, shown as being manufactured with a battery case, and shows the electrical contacts of the anode 245 and cathode 255. Figure 15 embodies a dual-cell battery configuration 16, such as being manufactured with a battery case, and shows a single electrical contact to the anode 245 and two electrical contacts 255a and 255b to the cathode.

[0102] The embodiments of the present invention described above are intended to be merely examples. Numerous variations and modifications will be obvious to those skilled in the art. All such changes and modifications are intended to be within the scope of the present invention as defined in any appended claims.

Claims

1. A method for manufacturing a lithium electrode, wherein the method is (1) To provide an electrolytic cell, the electrolytic cell is A first chamber containing a positive electrode and an aqueous lithium salt solution in contact with the positive electrode, A second chamber including a conductive substrate configured as a negative electrode and Includes, The conductive substrate remains stationary within the chamber during lithium metal electrodeposition, the lithium ion selective film separates the first chamber from the second chamber, and the non-aqueous electrolyte is positioned between the conductive substrate and the lithium ion selective film, and is in physical contact with both the conductive substrate and the lithium ion selective film. The electrolytic cell is configured to allow lithium ions to pass through the lithium ion selective membrane between the first chamber and the second chamber, and to prevent the passage of other chemical species between the first chamber and the second chamber. (2) Covering the electrolytic cell with the surrounding atmosphere, wherein the surrounding atmosphere is substantially free of lithium reaction components, (3) A variable voltage is applied to maintain a constant current across the negative electrode and the positive electrode, thereby causing lithium ions to move from the first chamber to the second chamber, across the lithium ion selective film and the non-aqueous electrolyte, and electrodeposit a first layer of lithium onto the conductive substrate. Includes, This forms the lithium electrode, the first layer of lithium having an inner surface and an outer surface, and the inner surface of the first layer of lithium being bonded to the conductive substrate. The aforementioned constant current is approximately 10 mA / cm². ２ ~Approx. 50mA / cm ２ The method involves applying the constant current over a period of time from approximately 1 minute to approximately 60 minutes.

2. The method according to claim 1, wherein the covering atmosphere contains 10 ppm or less of lithium reactive components on a molar basis.

3. The method according to claim 1, wherein the covering atmosphere contains 10 ppm or less of nitrogen on a molar basis.

4. The method according to claim 1, wherein the covering atmosphere contains 5 ppm or less of nitrogen on a molar basis.

5. The method according to claim 1, wherein the conductive substrate comprises a plate having a first surface and a second surface, and the inner surface of the first layer of lithium metal is bonded to the first surface of the conductive substrate.

6. The aqueous lithium salt solution contains Li ２ SO ４ Li ２ CO ３ The method according to claim 1, comprising a lithium salt selected from the group consisting of, and combinations thereof.

7. The aqueous lithium salt solution contains Li ２ SO ４ The method according to claim 1, including the method described in claim 1.

8. The method according to claim 1, wherein the conductive substrate is selected from the group consisting of copper, aluminum, graphite-coated copper, and nickel.

9. The method according to claim 1, wherein the lithium-ion selective membrane comprises a polymer matrix and a plurality of ion-conducting particles disposed within the polymer matrix.

10. The method according to claim 1, wherein the lithium ion selective film comprises glass frit, and lithium ion conductive particles are disposed within the glass frit.

11. The method according to claim 1, wherein the atmosphere comprises argon having a purity exceeding 99.998 weight percent.

12. The method according to claim 1, wherein the lithium electrode has lithium having a specific capacity greater than approximately 3,800 mAh per gram.

13. A method for manufacturing a lithium electrode, wherein the method is (1) To provide a gas-impermeable container, the container is The surrounding atmosphere, wherein the surrounding atmosphere is substantially free of lithium reactive components, Electrolytic cell and Enclosed, The electrolytic cell is completely covered by the surrounding atmosphere, and the electrolytic cell is A conductive substrate, which is stationary within the electrolytic cell and configured as a negative electrode, Positive electrode and, An aqueous lithium salt solution inserted between the conductive substrate and the positive electrode, A lithium-ion selective membrane configured to function as a solid-state electrolyte and Includes, The lithium-ion selective film covers the conductive substrate and forms a barrier that separates the aqueous lithium salt solution from the conductive substrate. The electrolytic cell is configured to allow lithium ions to pass from the lithium salt solution through the lithium ion selective membrane to the surface of the conductive substrate, while preventing the passage of other chemical species. (2) A variable voltage is applied to maintain a constant current across the negative electrode and the positive electrode, thereby causing lithium ions to move from the lithium salt solution across the lithium ion selective film and electroplat the lithium layer onto the conductive substrate, thereby forming the lithium electrode. Includes, The lithium layer has an inner surface and an outer surface, the inner surface is bonded to the conductive substrate, and the outer surface is bonded to the lithium ion selective film. The constant current is about 10 mA / cm ２ to about 50 mA / cm ２ and the constant current is applied over a time period of about 1 minute to about 60 minutes, a method.

14. A method for manufacturing a lithium metal battery, wherein the method is A lithium electrode is manufactured according to the method of claim 1, Assembling a casing containing the lithium electrode configured as an anode and other components necessary to form the lithium metal battery, The casing is sealed, the contents of the casing are isolated from reactants present in the air, and thereby the lithium metal battery is provided. Methods that include...

15. The manufacturing method according to claim 14, wherein the method is carried out in a single manufacturing facility.

16. A method for manufacturing a lithium metal battery, wherein the method is A lithium electrode is manufactured according to the method of claim 13, The lithium-ion selective electrode configured as an anode, and the lithium metal battery Assembling a casing with contents including other components necessary to form it, The casing is sealed, the contents of the casing are isolated from reactants present in the air, and thereby the lithium metal battery is provided. Methods that include...

17. The manufacturing method according to claim 16, wherein the method is carried out in a single manufacturing facility.

18. The manufacturing method according to claim 17, wherein the method is carried out entirely under air that is inert to chemical reactions with lithium.

19. A method for manufacturing a lithium metal battery, wherein the method is The invention relates to the manufacture of a lithium metal electrode comprising a conductive substrate and a layer of lithium metal bonded to the conductive substrate, wherein the lithium metal layer contains a nonmetallic element in a mass ratio of 5 ppm or less. Assembling a casing containing the lithium metal electrode configured as an anode and other components necessary to form the lithium metal battery, The casing is sealed, the contents of the casing are isolated from reactants present in the air, and thereby the lithium metal battery is provided. Methods that include...

20. The manufacturing method according to claim 19, wherein the method is carried out in a single manufacturing facility.

21. The manufacturing method according to claim 20, wherein the method is carried out entirely under air that is inert to chemical reactions with lithium.

22. A method for manufacturing a lithium electrode, wherein the method is (1) To provide an electrolytic cell, the electrolytic cell is A conductive substrate stationary within the electrolytic cell, wherein the conductive substrate comprises a plate having a first surface and a second surface, A first chamber containing a first positive electrode and a first aqueous lithium salt solution in contact with the first positive electrode, A second chamber comprising a first lithium-ion selective membrane, wherein the first lithium-ion selective membrane separates the first chamber from the second chamber, and a first non-aqueous electrolyte disposed between the first surface of the conductive substrate and the first lithium-ion selective membrane is in physical contact with both the first surface of the conductive substrate and the first lithium-ion selective membrane. A third chamber comprising a second lithium-ion selective membrane and a non-aqueous electrolyte, wherein the non-aqueous electrolyte is positioned between the second surface of the conductive substrate and the second lithium-ion selective membrane, and is in physical contact with both the second surface of the conductive substrate and the second lithium-ion selective membrane, A fourth chamber containing a second positive electrode and a second aqueous lithium salt solution in contact with the second positive electrode. Includes, The second lithium-ion selective membrane separates the third chamber from the fourth chamber. The electrolytic cell is configured to allow lithium ions to pass through the first lithium-ion selective membrane between the first chamber and the second chamber, and to prevent the passage of other chemical species between the first chamber and the second chamber. The electrolytic cell is the second lithium between the fourth chamber and the third chamber. It is configured to allow lithium ions to pass through the ion-selective membrane and to prevent the passage of other chemical species between the fourth chamber and the third chamber, (2) The electrolytic cell is completely covered with the surrounding air, and the surrounding air is inert to chemical reactions with lithium. (3) In order to maintain a constant current across the conductive substrate and the first positive electrode, a variable voltage is applied across the conductive substrate and the second positive electrode, thereby causing lithium ions to travel from the first chamber to the second chamber, across the first lithium-ion selective film and the first non-aqueous electrolyte, electroplating a first layer of lithium onto the first surface of the conductive substrate; further causing lithium ions to travel from the fourth chamber to the third chamber, across the second lithium-ion selective film and the second non-aqueous electrolyte, electroplating a second layer of lithium onto the second surface of the conductive substrate, thereby forming the lithium electrode. Includes, The lithium electrode comprises the conductive substrate, the first layer of lithium, and the second layer of lithium, wherein the first layer of lithium has an inner surface and an outer surface, the inner surface being bonded to the first surface of the conductive substrate, and the second layer has an inner surface and an outer surface, the inner surface being bonded to the second surface of the conductive substrate. The aforementioned constant current is approximately 10 mA / cm². ２ ~Approx. 50mA / cm ２ The method involves applying the constant current over a period of time from approximately 1 minute to approximately 60 minutes.

23. A method for manufacturing a lithium electrode, wherein the method is (1) To provide an electrolytic cell, the electrolytic cell is A conductive substrate stationary within the cell, wherein the conductive substrate comprises a plate having a first surface and a second surface, the first surface being covered with a first lithium-ion selective film, the second surface being covered with a second lithium-ion selective film, and the first and second lithium-ion selective films being configured to function as a solid-state electrolyte, A first chamber comprising a first positive electrode and a first aqueous lithium salt solution in contact with the first positive electrode and the first lithium ion selective membrane, A second positive electrode and a second chamber containing a second aqueous lithium salt solution in contact with the first positive electrode and the second lithium ion selective membrane. Includes, The electrolytic cell is configured to allow lithium ions to pass through the first lithium ion selective film between the first chamber and the first surface of the conductive substrate, and to prevent the passage of other chemical species between the first chamber and the first surface of the conductive substrate. The electrolytic cell is configured to allow lithium ions to pass through the second lithium-ion selective film between the second chamber and the second surface of the conductive substrate, and to prevent the passage of other chemical species between the second chamber and the second surface of the conductive substrate. (2) The electrolytic cell is completely covered with the surrounding air, and the surrounding air is inert to chemical reactions with lithium. (3) In order to maintain a constant current across the conductive substrate and the first positive electrode, a variable voltage is applied across the conductive substrate and the second positive electrode, thereby causing lithium ions to cross the first lithium ion selective film from the first chamber and electroplat the first layer of lithium onto the first surface of the conductive substrate, and further causing lithium ions to cross the second lithium ion selective film from the second chamber and electroplat the second layer of lithium onto the second surface of the conductive substrate, thereby forming the lithium electrode. Includes, The lithium electrode comprises the conductive substrate, the first layer of lithium, and the lithium The lithium first layer comprises a second layer, the lithium first layer having an inner surface and an outer surface, the inner surface of the lithium first layer being bonded to the first surface of the conductive substrate, the outer surface of the lithium first layer being bonded to the first lithium ion selective film, the lithium second layer having an inner surface and an outer surface, the inner surface of the lithium second layer being bonded to the second surface of the conductive substrate, the outer surface of the lithium second layer being bonded to the second lithium ion selective film, The aforementioned constant current is approximately 10 mA / cm². ２ ~Approx. 50mA / cm ２ The method involves applying the constant current over a period of time from approximately 1 minute to approximately 60 minutes.

24. The method according to claim 1, wherein the lithium-ion selective membrane is stationary in the electrolytic cell, and as the first layer of lithium is formed, the first layer of lithium displaces a non-aqueous electrolyte from the space between the conductive substrate and the lithium-ion selective membrane, thereby bonding the inner surface of the first layer of lithium to the conductive substrate and bonding the outer surface of the first layer of lithium to the ion selective membrane, thereby forming a lithium metal electrode comprising the conductive substrate and the first layer of lithium metal, the inner surface of the first layer of lithium being bonded to the conductive substrate and the outer surface of the first layer of lithium being bonded to the lithium-ion selective membrane, and the lithium-ion selective membrane is configured to function as a solid-state electrolyte when the lithium metal electrode is incorporated into a galvanic cell.

25. The first and second lithium-ion selective films are immobile in the electrolytic cell, and as the first lithium layer is formed, the first lithium layer displaces the first non-aqueous electrolyte from the space between the first surface of the conductive substrate and the first lithium-ion selective film, thereby bonding the inner surface of the first lithium layer to the first surface of the conductive substrate and the outer surface of the first lithium layer to the first lithium-ion selective film. As the second lithium layer is formed, the second lithium layer displaces the second non-aqueous electrolyte from the space between the second surface of the conductive substrate and the second lithium-ion selective film, thereby bonding the inner surface of the second lithium layer to the second surface of the conductive substrate. The method according to claim 24, wherein the outer surface of the second lithium layer is bonded to the second lithium-ion selective film, thereby forming a lithium metal electrode comprising the conductive substrate and the first and second layers of lithium metal, the inner surface of the first lithium layer is bonded to the first surface of the conductive substrate, the outer surface of the first lithium layer is bonded to the first lithium-ion selective film, the inner surface of the second lithium layer is bonded to the second surface of the conductive substrate, the outer surface of the second lithium layer is bonded to the second lithium-ion selective film, and the first and second lithium-ion selective films are configured to function as a solid electrolyte when the lithium metal electrode is incorporated into a galvanic cell.

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