SYSTEMS AND METHODS OF LITHIUM ELECTRODEPOSITION GOVERNMENT SUPPORT CLAUSE [0001] This invention was made with government support under Contract No. DE-AC02- 06CH11357 awarded by the United States Department of Energy to UChicago Argonne, LLC, operator of Argonne National Laboratory. The government has certain rights in the invention. FIELD [0002] This disclosure relates generally to systems and methods for lithium electrodeposition. More specifically, this disclosure relates to systems and methods for continuous lithium electrodeposition on an electrode substrate when the width of the electrode substrate is oriented vertically. BACKGROUND [0003] Lithium has continued to play an increasingly large role in the energy needs of consumers as their demand has shifted heavily toward electricity and away from oil-based energy. In batteries, a lithium-based electrode can form the cathode or anode of a battery cell. Specifically, thin lithium anodes can enable high energy density rechargeable batteries that are desired for electric vehicles. A current method to form such thin lithium-based electrodes is to laminate or adhere a lithium foil to a substrate. This lamination process can include rolling a composite of lithium and substrate such that the lithium metal has a certain thickness on the substrate. However, lithium can be very ductile as well as highly reactive and tends to stick to rolls and itself throughout the lamination process. SUMMARY [0004] Described herein are lithium electrodeposition systems, devices, and methods. Specifically, the methods and systems disclosed herein can enable low-cost roll-to-roll production of thin lithium metal anodes from aqueous salt solutions at room temperature. The systems can include a catholyte chamber separated from at least one anolyte chamber by an ion-permeable membrane. In some embodiments, an electrode substrate can be oriented such that the width of the electrode substrate is substantially vertical or vertical as it moves through the catholyte chamber. By having the width of the electrode substrate oriented vertically (e.g., a width direction of the electrode substrate is substantially parallel
Attorney Docket No.: ESS-L2-8115 WO to a direction of gravity) as it moves through the catholyte chamber, the lithium ions to be deposited as lithium metal on the electrode substrate are not competing against gravity during the electrodeposition process. As such, Applicants discovered that orienting the width of the electrode substrate substantially vertically or vertically can increase uniform deposition on both sides of the electrode substrate. [0005] In addition, as lithium metal deposits on the electrode substrate, heat can be released. Furthermore, some water from the anolyte chamber may inevitably pass through the ion- permeable membrane from the anolyte to catholyte during the electrodeposition process. As such, the systems and methods disclosed herein can include a catholyte recirculation or recycle unit/system that can remove water and/or heat from the catholyte to be reused in the catholyte chamber. [0006] In some embodiments, a system for electrodeposition of lithium includes a catholyte chamber comprising a catholyte, wherein the catholyte chamber is configured to receive an electrode substrate such that a width direction of the electrode substrate is substantially parallel to a direction of gravity as it moves through the catholyte chamber; an anolyte chamber comprising an anolyte, wherein the catholyte chamber and the anolyte chamber are separated by at least an ion-permeable membrane; an electrode on a side of the anolyte chamber opposite the ion-permeable membrane, wherein the electrode is a counter electrode to the electrode substrate; wherein the system is configured to flow lithium ions from the anolyte chamber to the catholyte chamber through the ion-permeable membrane and deposit lithium metal on a side of the electrode substrate as it moves through the catholyte chamber. In some embodiments, the system includes a second anolyte chamber on a side of the catholyte chamber opposite the first anolyte chamber, wherein the catholyte chamber and the second anolyte chamber are separated by at least a second ion-permeable membrane; a second electrode on a side of the second anolyte chamber opposite the second ion-permeable membrane, wherein the second electrode is a counter electrode to the electrode substrate; and wherein the system is configured to flow lithium ions from the second anolyte chamber to the catholyte chamber through the second ion-permeable membrane and deposit lithium metal on a side of the electrode substrate opposite the first side as it moves through the catholyte chamber. In some embodiments, the system includes a catholyte recirculation unit comprising a catholyte reservoir, wherein the catholyte recirculation unit is configured to supply and remove catholyte from the catholyte chamber. In some embodiments, the catholyte recirculation unit comprises a dryer, wherein the dryer is configured to remove water from catholyte in the catholyte recirculation unit. In some embodiments, the catholyte
Attorney Docket No.: ESS-L2-8115 WO recirculation unit comprises a heat exchanger configured to remove heat from catholyte in the catholyte recirculation unit. In some embodiments, the system includes a washing chamber comprising a washing fluid, wherein the washing chamber is configured to receive and wash the lithium deposited electrode substrate. In some embodiments, the system includes a power source electrically connected to the electrode substrate and the electrode. In some embodiments, the ion-permeable membrane comprises polyacrylonitrile. In some embodiments, the catholyte comprises dimethoxyethane and lithium bis(fluorosulfonyl)imide. In some embodiments, the anolyte comprises lithium sulfate and water. In some embodiments, the electrode comprises titanium, platinum, stainless steel, or combinations thereof. In some embodiments, the electrode substrate comprises copper. [0007] In some embodiments, a method for electrodeposition of lithium includes moving an electrode substrate through a catholyte chamber comprising a catholyte such that a width direction of the electrode substrate is substantially parallel to a direction of gravity as it moves through the catholyte chamber; flowing lithium ions from an anolyte chamber to the catholyte chamber through an ion-permeable membrane; and depositing lithium metal on a side of the electrode substrate as it moves through the catholyte chamber. In some embodiments, the method includes flowing lithium ions from a second anolyte chamber to the catholyte chamber through a second ion-permeable membrane; and depositing lithium metal on a side of the electrode substrate opposite the first side as it moves through the catholyte chamber. In some embodiments, the method includes removing a portion of the catholyte from the catholyte chamber. In some embodiments, the method includes removing water from the catholyte removed from the catholyte chamber. In some embodiments, the method includes removing heat from the catholyte removed from the catholyte chamber. In some embodiments, the method includes supplying the catholyte removed from the catholyte chamber to the catholyte chamber. In some embodiments, the method includes washing the lithium deposited electrode substrate. In some embodiments, the method includes flowing electrons from an anode to the electrode substrate, wherein the anode is in contact with an anolyte of the anolyte chamber. [0008] It will be appreciated that any of the variations, aspects, features and options described in view of the electrodeposition systems or configurations apply equally to the systems, methods, other devices/configurations, and vice versa. It will also be clear that any one or more of the above variations, aspects, features and options can be combined.
Attorney Docket No.: ESS-L2-8115 WO [0009] Additional advantages will be readily apparent to those skilled in the art from the following detailed description. The aspects and descriptions herein are to be regarded as illustrative in nature and not restrictive. [0010] All publications, including patent documents, scientific articles and databases, referred to in this application are incorporated by reference in their entirety for all purposes to the same extent as if each individual publication were individually incorporated by reference. If a definition set forth herein is contrary to or otherwise inconsistent with a definition set forth in the patents, applications, published applications and other publications that are herein incorporated by reference, the definition set forth herein prevails over the definition that is incorporated herein by reference. BRIEF DESCRIPTION OF THE FIGURES [0011] The invention will now be described, by way of example only, with reference to the accompanying drawings, in which: [0012] FIG. 1 illustrates an example of a lithium electrodeposition two-chamber cell structure in accordance with some embodiments disclosed herein. [0013] FIG. 2 illustrates a system for the electrodeposition of lithium in accordance with some embodiments disclosed herein. [0014] FIG.3A illustrates an exemplary top view of a portion of an electrodeposition unit in accordance with some embodiments disclosed herein. [0015] FIG.3B illustrates an exemplary cross section view of the portion of the electrodeposition unit in FIG.3A along line A-A in accordance with some embodiments disclosed herein. [0016] FIG.4A illustrates an angle between the width of an electrode substrate and the direction of gravity in accordance with some embodiments disclosed herein. [0017] FIG.4B illustrates another angle between the width of an electrode substrate and the direction of gravity in accordance with some embodiments disclosed herein. [0018] FIG.5 illustrates an exemplary cross section view of a portion of an electrodeposition unit with a width of the electrode substrate substantially horizontal in accordance with some embodiments disclosed herein. [0019] FIG.6 illustrates an example of a catholyte recirculation unit in accordance with some embodiments disclosed herein.
Attorney Docket No.: ESS-L2-8115 WO [0020] FIG.7A illustrates a front view of an example of a container for housing at least some components of an electrodeposition system in accordance with some embodiments disclosed herein. [0021] FIG.7B illustrates a side view of an example of a container for housing at least some components of an electrodeposition system in accordance with some embodiments disclosed herein. [0022] FIG.8 illustrates an example of portions of electrodeposition unit and catholyte recirculation unit with respect to a container in accordance with some embodiments disclosed herein. [0023] FIG.9 illustrates an example of portions of washing chamber and washing fluid supply/recirculation unit with respect to a container in accordance with some embodiments disclosed herein. [0024] FIG.10 illustrates an example of catholyte dryer in accordance with some embodiments disclosed herein. [0025] In the Figures, like reference numbers correspond to like components of the systems unless otherwise stated. DETAILED DESCRIPTION [0026] Reference will now be made in detail to implementations and embodiments of various aspects and variations of electrodeposition devices, systems, and methods described herein. Although several exemplary variations of the devices, systems, and methods are described herein, other variations of the devices, systems, and methods may include aspects of the devices, systems, and methods described herein combined in any suitable manner having combinations of all or some of the aspects described. [0027] Described herein are electrodeposition systems and methods capable of applying a thin layer of lithium metal to a substrate. Electrodeposition can refer to the process of producing a metal coating on a substrate through the reduction of cations of that metal using an electric current. An exemplary method of electron transfer from the counter electrode to the electrode substrate for lithium metal deposition and lithium ions passing through the ion-permeable membrane is shown in FIG.1. The principles shown in FIG.1 can be applied to the various systems and methods disclosed herein. FIG. 1 illustrates an example of a lithium electrodeposition two chamber cell structure 50 and process. As shown in FIG. 1, the compartment cell can include a catholyte chamber 1 with a catholyte 1a, an anolyte chamber 2 with an anolyte 2a, and an ion-permeable membrane 3 separating the catholyte
Attorney Docket No.: ESS-L2-8115 WO chamber and the anolyte chamber. The electrodeposition compartment cell can also include an electrode substrate (i.e., a working electrode) 4 and at least one counter electrode 5 to the electrode substrate. Lithium metal can be electrodeposited onto the electrode substrate (i.e., working electrode) on the catholyte chamber side of the cell by applying a current (or potential) via power source 6 electrically connected to electrode substrate and/or the counter electrode. For example, when the electrode substrate is connected to a power supply, the electrode substrate can act as a cathode. When the current is applied, the anolyte can be oxidized at the counter electrode, thereby releasing electrons that flow to the electrode substrate (i.e., working electrode) as shown by the following equation (1): (1) H2O → ½O2 + e– [0028] The electrons can reduce lithium cations in the catholyte to lithium metal which can be deposited on a surface or side of the electrode substrate as shown by the following equation (2): (2) Li+ + e– → Li (deposit) [0029] As lithium ions are reduced at the catholyte to neutral lithium metal, lithium ions can flow from the anolyte through the ion-permeable membrane to maintain the charge balance. As such, the lithium metal depositing on the electrode substrate can be from lithium ions that originated in the catholyte or that migrated from the anolyte to the catholyte. [0030] FIG.2 illustrates system 100 for the electrodeposition of lithium in accordance with some embodiments disclosed herein. In some embodiments, system 100 can include an electrodeposition unit 101 configured to receive an electrode substrate 4 and deposit lithium metal on at least one side or surface of the electrode substrate. In some embodiments, the thickness of lithium metal on the electrode substrate after deposition can be at least about 1 micron, at least about 5 microns, at least about 10 microns, at least about 15 microns, at least about 20 microns, or at least about 25 microns. In some embodiments, the thickness of lithium metal on the electrode substrate after deposition can be at most about 50 microns, at most about 40 microns, at most about 30 microns, at most about 25 microns, at most about 20 microns, at most about 15 microns, or at most about 10 microns. In some embodiments, the thickness of lithium metal on the electrode substrate after deposition can be about 1-50 microns or about 5-20 microns. [0031] In some embodiments, the electrode substrate can be a current collector. In some embodiments, the electrode substrate can be a ribbon, foil, sheet, or foam. In some
Attorney Docket No.: ESS-L2-8115 WO embodiments, the electrode substrate can include a metal or metal alloy. In some embodiments, the metal can be aluminum, copper, nickel, iron, titanium, stainless steel, conductive metal, conductive mesh, conductive metal foams, or combinations thereof. In some embodiments, the electrode substrate can include a carbonaceous material. In some embodiments, the electrode substrate can be coated with carbon (e.g., carbon-coated metals such as graphite on copper). In some embodiments, the electrode substrate can be an oxide- coated substrate (e.g., Li2S or LiAlO2 on copper). [0032] In some embodiments, an electrode substrate source (not shown) can be a roll of an electrode substrate. In some embodiments, the electrode substrate can proceed along a roll pathway through the electrodeposition system or unit 101. In some embodiments, the systems disclosed herein can be a roll-to-roll based system. [0033] In some embodiments, the electrodeposition system or unit can include inlet 7 configured to receive an electrode substrate, as shown in FIG. 3A. In some embodiments, the inlet can be for a catholyte chamber 1 of the electrodeposition unit. In some embodiments, the electrode substrate can pass through the catholyte chamber at a line speed of at most 5 m/min, at most 3 m/min, at most 2 m/min, at most 1 m/min, at most 0.8 m/min, at most 0.6 m/min, or at most 0.5 m/min. In some embodiments, the electrode substrate can pass through the catholyte chamber at a line speed of at least about 0.1 m/min, at least about 0.3 m/min, at least about 0.5 m/min, at least about 0.6 m/min, at least about 1 m/min, or at least about 2 m/min. In some embodiments, the electrode substrate can pass through the catholyte chamber at a line speed (e.g., reel-to-reel speed) of about 1-30 cm/min. In some embodiments, the electrode substrate can pass through the catholyte chamber at an adjustable line speed. In some embodiments, the electrode substrate can pass through the washing chamber (explained in more detail below) at the same speeds listed above with respect to the catholyte chamber. In some embodiments, the electrodeposition unit and/or the washing chamber can be a reel-to-reel unit with a vertical train. [0034] In some embodiments, the catholyte chamber includes catholyte 1a. In some embodiments, the catholyte can serve as the electrolyte for the electrode substrate (i.e., the working electrode). In some embodiments, the catholyte can include at least one organic solvent and at least one lithium salt. In some embodiments, the catholyte can include more than one organic solvent and/or more than one lithium salt. In some embodiments, the organic solvent can be an ether-based solvent. In some embodiments, the organic solvent can include amyl ethyl ether, cyclopentyl methyl ether, diethyl ether, dimethoxyethane (“DME”) (e.g., 1,2 dimethoxyethane), dimethoxymethane (“DMM”), diisopropyl ether,
Attorney Docket No.: ESS-L2-8115 WO dibutyl ether, di(propylene glycol) ether, 1,4-dioxane, ethyl butyl ether, methoxyethane, methyl butyl ether, 2-methyltetrahydrofuran, polyethylene glycol (“PEG”), propylene glycol methyl ether, tetrahydrofuran (“THF”), thtrahydrofufuryl alcohol, tetrahydropyran, 2,2,5,5,-tetramethyltetrahydrofuran, dimethyl sulfoxide (“DMSO”), N,N- dimethylformamide (“DMF”), or combinations thereof. In some embodiments, the catholyte can include at least about 50 wt.%, at least about 55 wt.%, at least about 60 wt.%, at least about 65 wt.%, at least about 70 wt.%, at least about 75 wt.%, at least about 77 wt.%, at least about 80 wt.%, or at least about 85 wt.% organic solvent(s). In some embodiments, the catholyte can include at most about 95 wt.%, at most about 90 wt.%, at most about 85 wt.%, at most about 80 wt.%, at most about 75 wt.%, or at most about 70 wt.% organic solvent(s). In some embodiments, the catholyte can include about 50-95 wt.%, about 60-90 wt.%, about 65-85 wt.%, about 70-85 wt.%, or about 75-80 wt.% organic (solvent). In some embodiments, the organic solvent in the catholyte includes DME. [0035] In some embodiments, the lithium salt can be lithium bis(fluorosulfonyl)imide (“LiFSI”), lithium bis(trifluoromethanesulfonyl)imide (“LiTFSI”), lithium bis(pentafluoroethanesulfonyl)imide (“LiBETI”), lithium hexafluorophosphate (“LiPF6”), lithium hexafluoroarsenate (“LiAsF6”), lithium perchlorate (“LiClO4”), lithium tetrafluoroborate (“LiBF4”), lithium bis(oxalate)borate (“LiBOB”), lithium difluoro(oxalate)borate (“LiDFOB”), lithium bis(fluoromalonato)borate (“LiBFMB”), lithium tetracyanoborate (“LiTCB”), lithium dicyanotriazolate (“LiDCTA”), lithium dicyano-trifluoromethyl-imidazole (“LiTDI”), and lithium dicyano-pentafluoroethyl- imidazole (“LiPDI”) or combinations thereof. In some embodiments, the catholyte can include at least about 5 wt.%, at least about 10 wt.%, at least about 15 wt.%, at least about 19 wt.%, at least about 20 wt.%, at least about 25 wt.%, or at least about 30 wt.% lithium salt(s). In some embodiments, the catholyte can include at most about 40 wt.%, at most about 35 wt.%, at most about 30 wt.%, at most about 25 wt.%, at most about 20 wt.%, at most about 15 wt.%, or at most about 10 wt.% lithium salt(s). In some embodiments, the catholyte can include about 5-30 wt.%, about 10-25 wt.%, or about 15-20 wt.% lithium salt(s). In some embodiments, the lithium salt in the catholyte includes LiFSI. [0036] In some embodiments, the catholyte can include one or more additives. As explained in US Publication No.2021/0381115, which is hereby incorporated by reference in its entirety, additives can: (1) produce a protective coating layer on the lithium metal in- situ and during the formation of the lithium metal; and/or (2) enable higher deposition current densities and thus shorter deposition times during the electrodeposition process. In
Attorney Docket No.: ESS-L2-8115 WO some embodiments, during the electrodeposition process, the additives can electrochemically break down and form a polymeric protective layer on top of the electrodeposited lithium metal. Additional additives can allow one of skill in the art to tune the exact atomic composition of the protective layer similarly. [0037] In some embodiments, the additives can be LiNO3, adiponitrile, fluoroethylene carbonate, vinylene carbonate, vinylethylene carbonate, phenylethylene carbonate, trifluoromethyl propylene carbonate, allyl methyl carbonate, chloroethylene carbonate, succinic anhydride, maleic anhydride, phthalic anhydride, methyl benzoate, bromobutyrolactone, methyl chloroformate, vinyl acetate, ethylene sulfite, propane sultone, propene sultone, butane sultone, propylene sulfite, butylene sulfite, dimethyl sulfite, diethyl sulfite, glycolide, dimethyl glycolide, tetramethyl glycolide, N-acetyl caprolactam, succinimide, 2-vinylpyridine, 2-cyanofuran, methyl cinnamate, vinyl ethylene sulfite, or combinations thereof. In some embodiments, the catholyte can include at least about 0.1 wt.%, at least about 0.5 wt.%, at least about 1 wt.%, at least about 2 wt.%, at least about 3 wt.%, at least about 4 wt.%, or at least about 5 wt.% additive(s). In some embodiments, the catholyte can include at most about 10 wt.%, at most about 7 wt.%, at most about 5 wt.%, at most about 4 wt.%, at most about 3 wt.%, at most about 2 wt.%, or at most about 1 wt.% additive(s). In some embodiments, the catholyte can include about 0.1-5 wt.%, about 0.5-4 wt.%, or about 1-3 wt.% additive(s). In some embodiments, the additive can include lithium nitrate and/or vinylene carbonate. In some embodiments, the catholyte includes about 0.1- 3 wt.% or about 0.5-1.5 wt.% lithium nitrate. In some embodiments, the catholyte includes about 0.5-4 wt.% or about 1-3 wt.% vinylene carbonate. In some embodiments, the catholyte has a density of about 0.5-1.5 g/cc, about 0.75-1.25 g/cc, about 0.9-1.1 g/cc, about 0.95-1.05 g/cc, about 1-1.05 g/cc, or about 1.02 g/cc. In some embodiments, the viscosity of the catholyte can be about 0.9-1.1 cP, about 0.95-1.05 cP, about 0.98-1.02 cP, or about 1 cP. [0038] In the catholyte chamber, the electrode substrate can be completely submerged or immersed in the catholyte as shown in FIG. 3B. The electrodeposition unit 101 can also include at least one anolyte chamber 2. In some embodiments, an anolyte chamber can include anolyte 2a. In some embodiments, the anolyte can serve as an electrolyte for an electrode that is a counter electrode to the electrode substrate (e.g., an anode). In some embodiments, the catholyte and anolyte can be the same or different. [0039] In some embodiments, the anolyte can include a lithium salt in a polar solvent. In some embodiments, the polar solvent can be water. In some embodiments, the lithium salt
Attorney Docket No.: ESS-L2-8115 WO can be Li2CO3, LiHCO3, Li2SO4, LiHSO4, or combinations thereof. In some embodiments, the concentration of the lithium salt or salts in the anolyte can be about 0.1-5 M, about 0.1- 3 M, about 0.1-2 M, or about 0.5-1 M. In some embodiments, the anolyte can be produced by reaction of a lithium salt with an acid. In some embodiments, the acid can be sulfuric acid, hydrochloric acid, or combinations thereof. For example, in some embodiments, the anolyte can be produced by the reaction of lithium carbonate with sulfuric acid (which can generate carbon dioxide). In some embodiments, the anolyte can include lithium carbonate and lithium sulfate (as shown in FIG.1). In some embodiments, the anolyte can have a pH of about 3-8, about 4-8, about 4-7, or about 6-8. In some embodiments, the pH of the anolyte can be adjusted by additions of lithium bases (e.g., lithium carbonate) or other bases (e.g., sodium hydroxide). In some embodiments, having a second lithium source (e.g., the anolyte) can provide lithium ions from a cheap anolyte to an expensive catholyte. [0040] In some embodiments, some components of electrodeposition system 100 can perform its functions or be under/in an inert and/or a controlled atmosphere. For example, the electrodeposition system can be inside of a container (e.g., fume hood, glovebox, or related structure) with an inert and/or controlled atmosphere. FIGS. 7A-7B illustrate container 70 that can house various components of electrodeposition system 100. In some embodiments, the container can house electrodeposition unit 101 and/or washing chamber 104. In some embodiments, container 70 can include trough 71. In some embodiments, the trough can accommodate various components of electrodeposition system 100 as shown in FIGS. 8 and 9. In some embodiments, trough 71 can accommodate electrodeposition unit 101 and/or washing chamber 104. [0041] In some embodiments, the inert and/or controlled atmosphere can include argon and/or helium. In some embodiments, the inert and/or controlled atmosphere of the electrodeposition system can have an oxygen content of at most about 5 ppm or at most about 2.5 ppm. In some embodiments, the inert and/or controlled atmosphere of the electrodeposition system can have a nitrogen content of at most about 10 ppm or at most about 5 ppm. In some embodiments, the inert and/or controlled atmosphere of the electrodeposition system can have a water content of at most about 2 ppm, at most about 1 ppm, at most about 0.5 ppm, or at most about 0.1 ppm. In some embodiments, the inert and/or controlled atmosphere of the electrodeposition system can be generated by a commercial inert gas (e.g., UHP argon with 1ppm oxygen and 5 ppm nitrogen) that can be dried (using a commercial gas dryer) such that the inert and/or controlled atmosphere has a water content of at most about 2 ppm, at most about 1 ppm, at most about 0.5 ppm, or at
Attorney Docket No.: ESS-L2-8115 WO most about 0.1 ppm and/or can have an oxygen content of at most about 5 ppm or at most about 2.5 ppm. In some embodiments, the inert and/or controlled atmosphere can be continuously recycled or ran through the inert gas drying system (as shown as 72 in FIG. 7B) to reach the desired water, oxygen, and/or nitrogen content of the inert and/or controlled atmosphere. The following Table 1 lists purity of a commercial helium gas (data from Praxiar) that can be used to generate the inert and/or controlled atmosphere of the electrodeposition system: Grade Purity N2 O2 H2O CO2 CO THC H2 Ar Research 6.0 6N 0.4 0.1 0.2 0.1 0.1 0.1 0.5 0.5 Chromatography 6N - 0.5 0.2 0.1 0.1 0.1 - - 6.0 Semiconductor 6.0 6N 0.5 0.2 0.2 0.1 0.1 0.1 0.1 - Trace Analytical 5.5N 2 1 2 0.5 0.5 0.1 - 1 5.5 Semiconductor 5.5 5.5N 2 0.5 0.5 0.5 0.5 - - - Laser Star 5.5 5.5N - 1 1 - - 0.1 - - UHP Plus 5.5 5.5N 3 1 1 0.5 0.5 0.5 - - Semiconductor 5 5N 6 2 3 1 1 1 - - UHP 5 5N 5 1 2 - - 0.5 - - Laser Star 5 5N - 1 2 - - 0.5 - - Laser Star 4.7 4.7N - 3 3 - - 1 - - Zero 4.8 4.8N - 4 3 - - 0.5 - - HP 4.8 4.8N - 5 5 - - - - - [0042] The following Table 2 lists purity of a commercial argon gas (data from Airgas) that can be used to generate the inert and/or controlled atmosphere of the electrodeposition system: Grade Purity N2 O2 H2O CO2 CO THC Research plus 6N 2 0.1 0.2 0.1 0.1 0.1 Research 5.7N 3 0.2 0.2 0.5 0.5 0.2 Ultra-pure carrier 5.3N 3 0.5 0.5 1 1 0.3 Semiconductor 5N 5 1 1 1 1 0.5 UHP 5.5N 5 1 1 0.5 0.5 - Laser Plus 4.8N 5 - 1 1 1 1 Zero Grade 4.8N - 4 3 - - 0.5 High purity/high 4.8N - 4 3 - - - pressure [0043] In some embodiments, at least some of the components of an electrodeposition system can be inside of a container (e.g., fume hood, glovebox, or related structure) with an inert and/or controlled atmosphere and the container can have at least one antechamber 73
Attorney Docket No.: ESS-L2-8115 WO (and/or at least one small antechamber 73a) for removing items from the container (e.g., the finished lithium-coated electrode substrate, anolyte samples, catholyte samples, etc.). [0044] In some embodiments, the method of producing a dry inert gas for the inert and/or controlled atmosphere of the electrodeposition system via inert gas drying system 72 can be a two-stage process. In the first stage, a molecular sieve can be used with the supply inert gas (e.g., UHP argon) to remove water. In a second stage, a heated metal (e.g., heated copper metal in the form of chips) can be used to remove oxygen and some of the nitrogen from the supply inert gas. In some embodiments, both the molecular sieve and the heated metal (e.g., the copper chips) can be regenerated. For example, copper can be regenerated by an argon-hydrogen mixture that can reduce a portion of the copper oxide formed in the oxygen removal process. In some embodiments, a further trap can be employed to remove nitrogen to very low levels using heated titanium chips. [0045] In some embodiments, the catholyte chamber can be open to the inert and/or controlled atmosphere of the electrodeposition system as shown in FIG. 3B. In some embodiments, the catholyte chamber can be closed or covered. In some embodiments, the catholyte can have significant vapor pressure, be moisture sensitive, and/or release toxic fumes. As such, a portion (e.g., the organic solvent) of the catholyte may evaporate into the inert and/or controlled atmosphere during the electrodeposition process. For example, dimethoxyethane can have a vapor pressure of about 50 torr at 25oC. The other components of the catholyte (e.g., lithium salt and additive(s)) may not be volatile. [0046] In some embodiments, when a current (or potential) is applied (via a power source) electrically connected to the electrode substrate and at least one counter electrode, the anolyte can generate a gas. In some embodiments, the gas can be oxygen (as shown in FIG. 1), carbon dioxide, or a combination thereof. In some embodiments, an anolyte chamber can be closed or sealed as shown in FIG.3B. In other words, the anolyte chamber may not be open to an atmosphere of the electrodeposition system (e.g., atmosphere of the container). In some embodiments, the anolyte chamber(s) can be sealed to prevent moisture and/or off gas generated from contacting the catholyte and/or washing fluid. In some embodiments, the anolyte chamber(s) can be sealed to prevent moisture and/or off gas (e.g., oxygen) from mixing with any components evaporated from the catholyte (e.g., solvent such as dimethoxyethane) and/or any components of the washing fluid (e.g., hexane, heptane, etc.) In some embodiments, the anolyte chamber can include a vent to vent out any gas generated in the anolyte. In some embodiments, any gas generated in the anolyte may not contact the
Attorney Docket No.: ESS-L2-8115 WO catholyte. In some embodiments, any gas generated in the anolyte of the anolyte chamber may be removed via vacuum. [0047] In some embodiments, the catholyte chamber and the at least one anolyte chamber are fluidically connected to one another. In some embodiments, the catholyte chamber and the at least one anolyte chamber are fluidically connected to each other through at least one ion-permeable membrane 3. In some embodiments, the catholyte chamber and the at least one anolyte chamber can be separated at least by an ion-permeable membrane. In some embodiments, the ion-permeable membrane can maintain physical separation of the anolytes and the catholytes in the system. In some embodiments, the ion-permeable membrane can be a lithium ion-permeable membrane. In some embodiments, the ion- permeable membrane can be a nonporous hybrid membrane that allows for asymmetric media (e.g., aqueous on one side e.g., anolyte side), organic on the other side e.g., catholyte side) while limiting transport to Li-ions by facilitated diffusion through the membrane. In some embodiments, the ion-permeable membrane can be inorganic, such as commercially available ceramic membranes. In some embodiments, the ion-permeable membrane can be a polymeric ion-permeable membrane. In some embodiments, the ion-permeable membrane can be an organic polymer or a hybrid organic polymer-inorganic composite. In some embodiments, the ion-permeable membrane may: (1) minimize the movement of water from the anolyte to the catholyte, since the lithium metal being deposited on the electrode substrate can react with water; (2) be ion-conducting, but not necessarily limited to Li-ions, as it is easier to pre-treat the Li-ion feedstock and control its impurities; (3) be stable against both aqueous (e.g., anolyte) and organic media (e.g., catholyte); and/or (4) have sufficient dielectric stability so as not to have its structure compromised during electrodeposition runs (e.g., voltages can approach 10 V). Examples of ion-permeable membranes include commercial membranes, such as the lithium-ion conducting glass by Ohara Corporation or lithium-ion conducting polymeric membrane by Ionic Materials, Inc., can be used, as well as any other composite membranes with lithium-ion conductors embedded in a non-porous matrix. In some embodiments, the ion-permeable membrane is a polymeric ion-permeable membrane (PAN:LiX, where X = ClO4, Br). [0048] In some embodiments, ion-permeable membrane can define at least a portion of the catholyte chamber. For example, as shown in FIGS. 3A-3B, ion-permeable membranes 3 can define at least a portion of opposite sides of catholyte chamber 1. In some embodiments, an ion-permeable membrane can define an entire side of a catholyte chamber. In some embodiments, an ion-permeable membrane can define at least a portion of an anolyte
Attorney Docket No.: ESS-L2-8115 WO chamber. In some embodiments, an ion-permeable membrane can define an entire side of an anolyte chamber. For example, as shown in FIGS. 3A-3B, ion-permeable membranes 3 can define at least one side of anolyte chambers 2. In some embodiments, a counter electrode to the electrode substrate (i.e., working electrode) can be on a side of an anolyte chamber opposite the ion-permeable membrane. As such, a counter electrode can define at least a portion of an anolyte chamber. In some embodiments, the electrodeposition unit (or system) can be configured to flow lithium ions from the anolyte chamber to the catholyte chamber through an ion-permeable membrane and deposit lithium metal on a side of the electrode substrate as it moves through the catholyte chamber. In some embodiments, a counter electrode can define an entire side of an anolyte chamber. For example, as shown in FIGS. 3A-3B, counter electrodes 5 form a side of anolyte chamber 2 opposite their respective ion-permeable membranes 3. As such, in some embodiments, the electrodeposition unit can include a second anolyte chamber on a side of the catholyte chamber opposite the first anolyte chamber, wherein the catholyte chamber and the second anolyte chamber are separated by at least a second ion-permeable membrane. In addition, in some embodiments, a second counter electrode can be on a side of the second anolyte chamber opposite the second ion-permeable membrane. In some embodiments, the electrodeposition unit (or system) can be configured to flow lithium ions from the second anolyte chamber to the catholyte chamber through the second ion-permeable membrane and deposit lithium metal on a side of the electrode substrate opposite the first side as it moves through the catholyte chamber. In some embodiments, the first anolyte and the second anolyte can be the same or different. [0049] In some embodiments, a counter electrode can be an anode. In some embodiments, a counter electrode can include a metal or metal alloy. In some embodiments, the metal can be aluminum, copper, platinum, lithium, nickel, iron, titanium, stainless steel, conductive metal, conductive mesh, conductive foams, or combinations thereof. [0050] For generating the electrical potential difference for electrodeposition applications, a power source can be electrically connected to the electrode substrate and/or to the at least one counter electrode. For example, in some embodiments, a power source can be electrically connected to the electrode substrate (e.g., working electrode) and to at least one counter electrode. In some embodiments, a power source can be electrically connected via conductors (e.g., wires) extending from the power source to the electrode substrate and/or at least one counter electrode. In some embodiments, multiple conductors may connect the at least one counter electrode to the power source. In some embodiments, there may be
Attorney Docket No.: ESS-L2-8115 WO more than one power source electrically connected to the electrode substrate and/or at least one counter electrode. In some embodiments, the electrode substrate can be electrically connected to a first power source and the at least one counter electrode can be electrically connected to a second power source. In some embodiments, the power source can be configured to generate a current density (e.g., in the range of about 0.1-100 mA/cm2 or about 25-100 mA/cm2) on the electrode substrate. In other words, a deposition current density for the electrodeposition unit can be about 0.1-100 mA/cm2 or about 25-100 mA/cm2. In some embodiments, the power source can operate in a continuous or in a pulsed mode. [0051] As shown in FIGS.3A-3B, anolyte chambers 2 can be positioned opposite each other with an electrodeposition or electroplating region 8 defined in the deposition/plating path there between. As the electrode substrate moves through the catholyte chamber, lithium metal is deposited on at least one side of the electrode substrate. In some embodiments, a first anolyte chamber may be fluidically connected to a second anolyte chamber (not shown). For example, the anolyte chambers may still form an anolyte chamber on each side of the electrode substrate, but they may be fluidically connected below (or above) the electrode substrate. In such embodiments, the anolyte chambers may still be fluidically coupled to the catholyte chamber through the ion-permeable membrane on each side of the electrode substrate. In addition, lithium ions from at least one anolyte chamber can flow through at least one ion-permeable membrane to the catholyte chamber. The electrodeposition of lithium on the electrode substrate may occur in the electrodeposition region of the catholyte chamber. In some embodiments, the presence of an additive or additives in the catholyte can result in the formation of a protective coating directly on the lithium-coated electrode substrate during the electrodeposition/electroplating. In some embodiments, one-sided deposition of the electrode substrate is also possible when one of the anolyte chambers is not utilized or non-existent. [0052] In some embodiments, as an electrode substrate moves through a catholyte chamber in its length or machine direction M as shown in FIG. 3A (and coming out of the page towards the reader in FIG.3B), a width or width direction (w) of the electrode substrate can be substantially parallel to the direction of gravity (G). In other words, the electrode substrate can be moving through the catholyte chamber (and in the catholyte) such that the width of the electrode substrate is oriented substantially vertical or vertical. In some embodiments, a width of an electrode substrate can be about 1-100 cm, about 5-50 cm, about 10-30 cm, about 15-25 cm, or about 20 cm. In some embodiments, the length of the
Attorney Docket No.: ESS-L2-8115 WO electrode substrate (e.g., typical copper foils used for plating) can be about 1-500 ft, about 10-250 ft, about 15-200 ft, about 20-150 feet, or about 25-100 ft. [0053] In some embodiments, the electrodeposition directions (ED1 and ED2) of lithium ions transferring from the ion-permeable membrane to a side of the electrode substrate can be substantially perpendicular or perpendicular to the direction of gravity (G). In some embodiments, the electrode substrate has a vertical train. In some embodiments, the thickness (T) of the electrode substrate is facing the top and bottom of the catholyte chamber. In some embodiments, there may not be an anolyte chamber (and an ion- permeable membrane) above or below the electrode substrate. [0054] As used herein, a width direction of the electrode substrate is substantially parallel to the direction of gravity if the absolute value of the angle between the width direction of the electrode substrate and the direction of gravity is less than 45 degrees. Examples of a width direction of the electrode substrate substantially parallel to a direction of gravity are shown in FIGS. 4A-4B. For example, in FIGS. 4A-4B, the absolute value of angle α between the width direction w of the electrode substrate and the direction of gravity G is less than 45 degrees. In some embodiments, the absolute value of the angle between the width direction of the electrode substrate and the direction of gravity is at most about 40 degrees, at most about 30 degrees, at most about 20 degrees, at most about 10 degrees, or at most about 5 degrees. In some embodiments, the absolute value of the angle between the width direction of the electrode substrate and the direction of gravity is about 0-1, degrees, 0-3 degrees, 0-5 degrees, about 0-10 degrees, or about 0-20 degrees. As used herein, the electrodeposition directions of lithium ions transferring from the ion-permeable membrane to a side of the electrode substrate is substantially perpendicular to the direction of gravity (G) if the absolute value of the angle between an electrodeposition direction of the electrode substrate and the direction of gravity is greater than 45 degrees. [0055] Applicants have discovered that by keeping the width of the electrode substrate substantially vertical or vertical (i.e., keeping the width direction (w) of the electrode substrate substantially parallel to the direction of gravity (G)), lithium can be deposited in a more uniform manner on both sides of the electrode substrate. In contrast, if the anolyte chamber were above and below the width of the electrode substrate as shown in FIG.5 (with the electrode substrate moving out of the page towards the reader) such that the width of the electrode substrate is substantially horizontal or that the width direction of the electrode substrate is substantially perpendicular to the direction of gravity (G), one side of the electrode substrate will have more lithium deposition than the other side. For example, in
Attorney Docket No.: ESS-L2-8115 WO FIG. 5, side 4a of the electrode substrate will have more lithium deposited during electrodeposition than side 4b of the electrode substrate because gravity is competing against or fighting against the electrodeposition direction ED1 of lithium ions on the bottom of electrode substrate 4. In other words, gravity is pulling the lithium ions down away from side 4b of the electrode substrate. [0056] Returning to FIG. 2, in some embodiments, electrodeposition system 100 can include a catholyte recirculation unit 102. In some embodiments, the catholyte recirculation unit is fluidically connected to the electrodeposition unit. In some embodiments, the catholyte recirculation unit is fluidically connected to the catholyte chamber of the electrodeposition unit. In some embodiments, the catholyte recirculation unit can supply and/or remove catholyte from the catholyte chamber. In some embodiments, the catholyte recirculation unit can supply fresh catholyte to the catholyte chamber. In some embodiments, catholyte can be removed from the catholyte chamber through a catholyte outlet. In some embodiments, the catholyte outlet can be on the bottom of the catholyte chamber such that gravity can be used to remove the catholyte. For example, FIG. 8 illustrates catholyte exiting catholyte chamber through a bottom of the catholyte chamber (and through the bottom of container 70 and trough 71 of container 70). In some embodiments, catholyte can be supplied to the catholyte chamber through a catholyte inlet. In some embodiments, the catholyte inlet may be on the top of the catholyte chamber (as shown in FIG.8). [0057] In some embodiments, catholyte recirculation unit can include a catholyte reservoir 9, a heat exchanger 10, and/or a catholyte dryer 11 as shown in FIG. 6. In some embodiments, the catholyte reservoir is configured to store catholyte. In some embodiments, the catholyte reservoir is configured to receive new catholyte from a catholyte source fluidically connected to the catholyte reservoir. In some embodiments, the catholyte chamber is fluidically connected with a catholyte reservoir, a catholyte heat exchanger, catholyte source, and/or a catholyte dryer. [0058] In some embodiments, lithium deposition on the electrode substrate can release heat which can be absorbed by the catholyte. As such, removing the catholyte from the catholyte chamber can also remove excess heat from the catholyte chamber. In some embodiments, catholyte recirculation unit can include a heat exchanger configured to remove heat from catholyte in the catholyte recirculation system. In some embodiments, the heat exchanger can be any heat exchanger known to those of ordinary skill in the art such as a liquid/liquid heat exchanger or an air/liquid heat exchanger. In some embodiments, the catholyte can be
Attorney Docket No.: ESS-L2-8115 WO cooled (i.e., heat can be removed) using water or a water/glycol mixture. In some embodiments, at least a portion of the catholyte heat exchanger can be integrated in the catholyte reservoir (as shown in FIG. 8) such that the heat exchanger can be configured to remove heat from catholyte in the catholyte reservoir or to control the temperature of the catholyte in the catholyte reservoir. In some embodiments, the heat exchanger can be a heat exchanger coil in the catholyte reservoir. In some embodiments, a catholyte removed from the catholyte chamber can first go through a heat exchanger to remove heat and reduce the temperature of the removed catholyte. In some embodiments, the catholyte recirculation system can include a temperature sensor configured to measure the temperature of the catholyte in the catholyte recirculation unit. In some embodiments, the catholyte recirculation system can include at least one controller configured to adjust the temperature of the catholyte in the catholyte recirculation unit to a desired temperature if the measured temperature is outside of a threshold temperature range. [0059] During the electrodeposition process, solvents (e.g., water) may inevitably flow from the anolyte chamber to the catholyte chamber. Unfortunately, water can react with lithium ions in the catholyte chamber such that the lithium ions can no longer be used for deposition purposes. As such, in some embodiments, water can be removed from the catholyte removed from the catholyte chamber. In some embodiments, the catholyte recirculation unit can include a dryer configured to remove water (and other unwanted solvents) from the catholyte in the catholyte recirculation unit. In some embodiments, the catholyte in the catholyte chamber may have a water concentration of at least about 350 ppm, at least about 400 ppm, at least about 500 ppm, at least about 1000 ppm, at least about 2000 ppm, at least about 3000 ppm, at least about 4000 ppm, or at least about 5000 ppm. In some embodiments, the dryer can remove water from the catholyte in the catholyte recirculation unit such that the catholyte after drying has a water concentration of at most 500 ppm, at most 450 ppm, at most 400 ppm, at most 350 ppm, or at most 330 ppm. In some embodiments, the dryer can remove water from the catholyte in the catholyte recirculation unit such that the catholyte after drying has a water concentration of at least about 100 ppm, at least about 200 ppm, at least about 300 ppm, or at least about 330 ppm. In some embodiments, the catholyte includes a small amount of water (e.g., about 100-500 ppm, about 200-400 ppm, about 300-350 ppm, or about 330 ppm) to produce quality lithium deposition. Controlling the water content of the catholyte can be important to achieving optimum lithium electrodeposition results.
Attorney Docket No.: ESS-L2-8115 WO [0060] In some embodiments, the dryer 11 can be any dryer known by those of skill in the art capable of removing water from a catholyte. In some embodiments, the dryer can include dessicants to remove water from the catholyte. In some embodiments, the dessicants can be in a dryer column 111 as shown in FIG. 10. In some embodiments, the dessicants can include molecular sieves and alumina. In some embodiments, the dryer column can operate at less than or equal to 1 gpm and/or low operating pressures (e.g., 1-2 psi or lower). The dryer column can have a lifetime as in once the column is saturated it may no longer remove water (called breakthrough) and the column can be regenerated. In some embodiments, the column can include a heated dryer 112 to regenerate the desiccant. In some embodiments, any off gas from regeneration of the dryer column can be vented. In some embodiments, during draining of the dryer column, the majority of the organic solvent (e.g., DME) in the catholyte can be removed. However, some residual organic solvent might be present on the column and this material can be vented. In some embodiments, care should be taken to prevent air from entering the process. [0061] In some embodiments, a catholyte removed from the catholyte chamber can first go through a dryer to remove water from the catholyte removed from the catholyte chamber before going to the catholyte reservoir and/or heat exchanger. In such embodiments, the catholyte can go to catholyte dryer at point Y for example shown in FIG.8 before going to catholyte reservoir and/or catholyte heat exchanger. In some embodiments, the catholyte can go through the dryer prior to being supplied back to the catholyte chamber after going to the catholyte reservoir and/or heat exchanger. In such embodiments, the catholyte can go to catholyte dryer at point X for example shown in FIG. 8 before going to the catholyte chamber. In some embodiments, the catholyte recirculation system can include a water or moisture sensor configured to measure the water content or moisture of the catholyte in the catholyte recirculation unit. In some embodiments, the catholyte recirculation system can include at least one controller configured to adjust the water content or moisture of the catholyte in the catholyte recirculation unit to a desired water content or moisture if the measured water content or moisture is outside of a threshold water content or moisture. [0062] In some embodiments, any component of the catholyte recirculation unit (e.g., catholyte reservoir 9, a heat exchanger 10, and/or a dryer 11) can be outside the container (e.g., fume hood, glovebox, or related structure) with an inert and/or controlled atmosphere. For example, FIG.8 illustrates catholyte reservoir 9 and heat exchanger 10 outside container 70. In some embodiments, all components of the catholyte recirculation unit are within the container with the inert and/or controlled atmosphere.
Attorney Docket No.: ESS-L2-8115 WO [0063] In some embodiments, the lithium-coated electrode substrate 12 can exit the catholyte chamber at outlet 13 of the catholyte chamber. In some embodiments, the inlet and outlet for the electrode substrate of the catholyte chamber can be configured such that minimal catholyte can spill or leak from the catholyte chamber inlet and outlet. For example, the inlet and/or outlet for the electrode substrate of the catholyte chamber can include a wiper, squeegee, and/or seal such that the catholyte can remain in the catholyte chamber as the electrode substrate moves in and out of the catholyte chamber. [0064] In some embodiments, the electrodeposition system 100 can include a washing chamber 104 configured to receive and wash the lithium-coated or lithium-deposited electrode substrate. In some embodiments, before the washing chamber, a reel-to-reel system can include a polymer film un-leafer with a payout leaf reloaded after washing. In some embodiments, the washing chamber includes a washing fluid 14. In some embodiments, the washing fluid can include heptane, hexane, or combinations thereof. In some embodiments, the lithium-coated electrode substrate can be completely submerged or immersed in the washing fluid in the washing chamber similar to the electrode substrate in the catholyte chamber. As such, the washing chamber can be similar to the catholyte chamber in that it can include an inlet and outlet for the lithium-coated electrode substrate and that the inlet and outlet can be configured such that minimal washing fluid can spill or leak from the washing chamber inlet and outlet. In some embodiments, similar to the catholyte chamber, the washing chamber can be open to the inert and/or controlled atmosphere of the electrodeposition system. In some embodiments, the washing chamber can also include a drying chamber configured to dry or remove the washing fluid from the lithium-coated electrode substrate. In some embodiments, the washing fluid can quickly dry. [0065] In some embodiments, as a lithium-coated electrode substrate moves through a washing chamber in its length or machine direction M, a width or width direction (w) of the lithium-coated electrode substrate can be substantially parallel to the direction of gravity (G). In other words, the lithium-coated electrode substrate can also be moving through the washing chamber (and in the washing fluid) such that the width of the lithium-coated electrode substrate is oriented substantially vertical or vertical. [0066] As used herein, a width direction of the lithium-coated electrode substrate is substantially parallel to the direction of gravity if the absolute value of the angle between the width direction of the lithium-coated electrode substrate and the direction of gravity is less than 45 degrees. In some embodiments, the absolute value of the angle between the
Attorney Docket No.: ESS-L2-8115 WO width direction of the lithium-coated electrode substrate and the direction of gravity is at most about 40 degrees, at most about 30 degrees, at most about 20 degrees, at most about 10 degrees, or at most about 5 degrees. In some embodiments, the absolute value of the angle between the width direction of the lithium-coated electrode substrate and the direction of gravity is about 0-5 degrees, about 0-10 degrees, or about 0-20 degrees. [0067] In some embodiments, electrodeposition system 100 can include a washing fluid supply/recirculation unit 105. In some embodiments, the washing fluid supply/recirculation unit is fluidically connected to the washing chamber. In some embodiments, the washing fluid supply recirculation unit can include a washing fluid reservoir 90 fluidically connected to the washing chamber. In some embodiments, the washing fluid supply/recirculation unit can supply and/or remove washing fluid from the washing chamber. In some embodiments, after the washing fluid is loaded and no longer effective, it can be changed via the washing fluid supply/recirculation unit. In some embodiments, the washing fluid supply/recirculation unit can supply fresh washing fluid to the washing fluid chamber. In some embodiments, washing fluid can be removed from the washing chamber through a washing fluid outlet. In some embodiments, the washing fluid outlet can be on the bottom of the washing chamber such that gravity can be used to remove the washing fluid. For example, FIG.9 illustrates washing fluid exiting washing chamber through a bottom of the washing chamber (and through the bottom of container 70 and trough 71 of container 70). In some embodiments, washing fluid can be supplied to the washing chamber through a washing fluid inlet. In some embodiments, the washing fluid inlet may be on the top of the washing fluid chamber (as shown in FIG.9). [0068] In some embodiments, any component of the washing fluid supply/recirculation unit (e.g., washing fluid reservoir 90) can be outside the container (e.g., fume hood, glovebox, or related structure) with an inert and/or controlled atmosphere. For example, FIG. 9 illustrates washing fluid reservoir 90 outside container 70. In some embodiments, all components of the washing fluid supply/recirculation unit are within the container with the inert and/or controlled atmosphere. [0069] In some embodiments, electrodeposition system 100 can include an anolyte supply/recirculation unit 103. In some embodiments, the anolyte supply/recirculation unit is fluidically connected to the at least one anolyte chamber. In some embodiments, the anolyte supply/recirculation unit can include an anolyte reservoir fluidically connected to the at least one anolyte chamber. In some embodiments, the anolyte supply/recirculation unit can be similar to that of the washing fluid supply/recirculation unit. In other words, as
Attorney Docket No.: ESS-L2-8115 WO shown in FIG. 9, you can replace washing chamber 104 with at least one anolyte chamber 2 and wedding fluid reservoir 90 with the anolyte reservoir. In some embodiments, the anolyte supply/recirculation unit can supply and/or remove anolyte from the at least one anolyte chamber. In some embodiments, the anolyte chamber can include a sensor to determine lithium ion concentration in the anolyte. In some embodiments, the anolyte can be adjusted to keep the lithium ion concentration in the desired operating range. In some embodiments, the anolyte supply/recirculation unit can supply fresh anolyte to the at least one anolyte chamber. In some embodiments, anolyte can be removed from the at least one anolyte chamber through at least one anolyte outlet. In some embodiments, each anolyte chamber can have at least one anolyte outlet. In some embodiments, the at least one anolyte outlet can be on the bottom of the at least one anolyte chamber such that gravity can be used to remove the anolyte. In some embodiments, anolyte can be supplied to the at least one anolyte chamber through an anolyte inlet. In some embodiments, the anolyte inlet may be on the top of the at least one anolyte chamber. In some embodiments, any component of the anolyte supply/recirculation unit (e.g., anolyte fluid reservoir) can be outside the container (e.g., fume hood, glovebox, or related structure) with an inert and/or controlled atmosphere. In some embodiments, all components of the anolyte supply/recirculation unit are within the container with the inert and/or controlled atmosphere. [0070] In some embodiments, an interleaf material, such as a non-conductive polymer film, can be applied to one or both sides of the lithium-coated, washed electrode substrate 15. The interleaf can be used at a rewinder to keep the lithium-coated electrode substrate separated from itself. For example, the interleaf material can be co-rolled with the lithium- coated electrode substrate. In some embodiments, mechanical roll-roll components, such as routing or movement rollers can be utilized to move the electrode substrate throughout the electrodeposition system and process. In some embodiments, once the washed, lithium- coated electrode substrate is rewound on a roll/reel, it can be placed in a container and then removed from the container (e.g., fume hood, glove box, etc.) comprising the electrodeposition system. In some embodiments, the container is a custom glove box. [0071] In some embodiments, the systems and methods described herein can take place at room temperature. In some embodiments, the systems and methods described herein (including the temperature in the container) can take at about 15-80oC, about 15-50oC, about 15-30oC, about 15-25oC, or about 20-25oC. In some embodiments, the systems and methods described herein can take place under atmospheric pressure. In some embodiments, the systems and methods described herein (including the pressure in the container) can take
Attorney Docket No.: ESS-L2-8115 WO place under about 0.1-5 atm, about 0.5-3 atm, about 0.5-2 atm, about 0.5-1.5 atm, about 0.9- 1.1 atm, or about 1 atm. [0072] For the purpose of clarity and a concise description, features are described herein as part of the same or separate embodiments; however, it will be appreciated that the scope of the disclosure includes embodiments having combinations of all or some of the features described. EXAMPLES [0073] Heat Balance: Estimated temperature increase of copper foil before entering the catholyte. This is based on resistance heating of the foil. No losses are estimated from free and forces convection, even though the foil moves at about 1 ft/min. This estimate should be the highest that the copper will achieve before platting. [0074] Given: [0075] Cathode current density 10 mA/cm2, double side [0076] Plating area, 30 in x 20 cm (1524 cm2) [0077] Current estimate: (2)1525(10mA)/1000 =60 A [0078] Copper foil thickness, 7^m [0079] Width 20 cm [0080] Cross sectional area, (20)7x10-4 = 0.014 cm2 [0081] Density of section 8,96 g/cm3 [0082] Mass of foil – 20(.014)(8.96) = 2.5 g, 0.0025 kg. [0083] Electrical resistance: 1.724 x 10-8 ohm-m [0084] Length of foil before entering catholyte: 20 cm [0085] Estimated resistance: 1.724x10-8(0.2)/(.014/1002) = 0.0025 ohms [0086] Heat generated: [0087] Q = I2R , (.0025)(60)2 = 23 J [0088] Heat capacity of copper, 392 J/kg K [0089] 57.76 J = 0.0025(392.6(^T)) [0090] ^T = 23/(0.9815) = 23 °C. [0091] Mass Balance: A mass balance/ voltage drop calculator has been developed for the process. This estimates the current density as function of lithium foil thickness, reel to reel speed. It calculates the cell operating voltage drops and estimates the heat generated. A typical output is shown below in the Table: Goals Anode-membrane Li foil thickness 10 ^m gap 5 cm Cathode/ Feed Rate 0.1 ft/min membrane gap 7 cm Plating chamber Width of copper foil 20 cm length 30 in
Attorney Docket No.: ESS-L2-8115 WO Thickness of copper foil 8 ^m Washing chamber 24 in cm Membrane 7 onside Membrane panel count 20 Membrane area 980 cm2 Current yield 98% Current density 5 mA/cm2 Given Washing length 5 inch Lithium Sulfate pH Anolyte 1 mol/liter 3.5 6.8 k S/m Catholyte 1 mol/liter LIiFSI in DME Catholyte conductivity 3 S/m Membrane Thickness 200 ^m Conductivity 2.00E- membrane 05 S/cm Recirculation rate Process Results chiller GPL Voltage drop Catholyte 1.15 V Catholyte 0.2 gpm 187 LiTFSI Voltage drop Anolyte 0.36 V Anolyte 0.3 gpm 109.6 Li2SO4 Voltage drop Membrane 7.64 V Voltage drop contacts 0.05 V Make up sulfate total volts 9 V solution 0.00 gpm Load, A 15 A Resistance anode 0.05 ^ Resistance Cathode 0.15 ^ Evaporation rate Replacement Resistance 4E- membrane 1.02 ^ DME 05 g/sec/cm2 150 g/hr Resistance one side 1.22 ^ Drag out 3 ml/m2 1 g/hr Evaporation rate 1E- Total Resistance 0.61 ^ Heptane 04 g/sec/cm2 45 g/hr Heat Input 137 W Heat Catholyte 17 W Gas flow (anodes) Heat membrane & anolyte 120 W Flow rate CFM 0.01 scfm wet oxygen Power supply kW 0.14 kW DC 0.06 kW AC Total power 0.20 kW
Attorney Docket No.: ESS-L2-8115 WO Residence time catholyte 34 seconds Anolyte 25 seconds Catholyte volume 23 gallon Flow rate 10 gpm Anolyte volume 13 gallons Flow rate 10 gpm DEFINITIONS [0092] Unless defined otherwise, all terms of art, notations and other technical and scientific terms or terminology used herein are intended to have the same meaning as is commonly understood by one of ordinary skill in the art to which the claimed subject matter pertains. In some cases, terms with commonly understood meanings are defined herein for clarity and/or for ready reference, and the inclusion of such definitions herein should not necessarily be construed to represent a substantial difference over what is generally understood in the art. [0093] Reference to “about” a value or parameter herein includes (and describes) variations that are directed to that value or parameter per se. For example, description referring to “about X” includes description of “X”. In addition, reference to phrases “less than”, “greater than”, “at most”, “at least”, “less than or equal to”, “greater than or equal to”, or other similar phrases followed by a string of values or parameters is meant to apply the phrase to each value or parameter in the string of values or parameters. [0094] As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It is also to be understood that the term “and/or” as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items. It is further to be understood that the terms “includes, “including,” “comprises,” and/or “comprising,” when used herein, specify the presence of stated features, integers, steps, operations, elements, components, and/or units but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, units, and/or groups thereof. [0095] This application discloses several numerical ranges in the text and figures. The numerical ranges disclosed inherently support any range or value within the disclosed numerical ranges, including the endpoints, even though a precise range limitation is not stated verbatim in the specification because this disclosure can be practiced throughout the disclosed numerical ranges.
Attorney Docket No.: ESS-L2-8115 WO [0096] The above description is presented to enable a person skilled in the art to make and use the disclosure, and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the disclosure. Thus, this disclosure is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein.