Systems and methods for producing a lithium film

Abstract

A method, an apparatus, and a system for producing a lithium film are described. The apparatus / system may include a chamber having an inlet and an outlet, the chamber configured for intaking a fluid via the inlet and removing the fluid via the outlet; an anode; a holder configured to mount a substrate, the holder configured as a cathode; and a power source configured to supply a current across the anode and the cathode. In various embodiments, the inlet is oriented with respect to a surface of the substrate such that the fluid flowing through the inlet and arriving at the surface of the substrate is greater than 500 cm3 per minute or at a flow velocity greater than 900 cm per minute, and lithium ions contained within the fluid are electrochemically reduced and plated to form a lithium metal film on the surface of the substrate.

Description

FIELD OF INVENTION

[0001] The disclosure relates to electrochemical energy storage devices including lithium batteries, and more particularly related to methods and devices for producing a lithium film via electrodeposition. BACKGROUND

[0002] Lithium-based battery technologies have improved over time with advances culminating in battery cells with higher capacities, longer cycle lives, and superior charging and discharging rates. However, challenges remain with the scalability and production of certain critical battery components, such as, the lithium metal used in some battery systems. Among these challenges, forming thin lithium metal fdms for use as an anode in rechargeable batteries remains one of the top production issues.

[0003] Lithium metal coating process, in general, hinges on the ability to rapidly coat a thin film of lithium metal onto a conductive substrate. A thin lithium metal, for example, can be produced via electrodeposition, but may require the application of high currents during the coating process. With high current applied during electrodeposition, lithium metal films that are produced with this process can have poor morphology in the films, particularly due to the high current being applied during the film formation. It is well known that such high currents during lithium plating can result in lithium films with dendritic features with mossy lithium deposits throughout the film thickness that result in poor performance. Therefore, there remains a need for improved methodologies and processes, along with novel apparatuses and systems that can be used in electrodeposition for producing thin lithium metal films with superior electrochemical performances and better life cycles. BRIEF DESCRIPTION OF THE DRAWINGS

[0004] For a more complete understanding of the principles disclosed herein, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:

[0005] Figure 1 illustrates an embodiment of an apparatus for producing a lithium film, in accordance with various embodiments.

[0006] Figure 2 illustrates a method for producing a lithium film, in accordance with various embodiments.

[0007] Figure 3A illustrates a schematic of an electrodeposited lithium metal film on a copper electrode, showing a region of the electrode used to prepare a 1.2 cm-diameter lithium metal film for testing, in accordance with various embodiments.

[0008] Figure 3B illustrates an example configuration of a symmetric cell used to measure the lithium capacity of the electrodeposited lithium metal film prepared from the cutout shown in Figure 3A.

[0009] Figures 4A-4I show images of various electrodeposited lithium metal films fabricated under a constant current density of 20 mA / cm2 and a deposition time of 150 seconds at various fluid flow conditions, in accordance with various embodiments.

[0010] Figures 5A-5F show images of various electrodeposited lithium metal films fabricated under a constant flow of about 4300 cm per minute at various current densities, in accordance with various embodiments.

[0011] It is to be understood that the figures are not necessarily drawn to scale, nor are the objects in the figures necessarily drawn to scale in relationship to one another. The figures are depictions that are intended to bring clarity and understanding to various embodiments of apparatuses, systems, and methods disclosed herein. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. Moreover, it should be appreciated that the drawings are not intended to limit the scope of the present teachings in any way. DETAILED DESCRIPTION

[0012] The following shall be a detailed description of the drawings which are given for the purposes of illustrating the preferred embodiments of the present invention, and not for the purpose of limiting the same.

[0013] In accordance with one or more embodiments, the tools, apparatuses, systems, and methods disclosed herein can be used for producing thin lithium metal films with improved electrochemical performances and better life cycles. As described herein, unique chemical mixtures can be used as the electrolyte and can be introduced at a high velocity during electrodeposition to produce a thin lithium metal film with improved film morphology. In accordance with some embodiments, surface treatments can be applied to the substrates to improve the quality of thin lithium films deposited thereon. In some embodiments, additional parameters, such as a fluid pressure of the electrolyte and / or inert gas used in the electrodeposition chamber, can be modified, or adjusted, during production of the coatings to improve the film quality, e.g., texture and morphology. In addition to improving the quality of electrodeposited lithium metal films, the disclosed embodiments can offer lower-cost and lower-energy consumption processes suitable for producing films, which can offer a better resistance to the life cycle issues currently plaguing lithium films produced using existing apparatuses and processes.

[0014] In accordance with one or more embodiments, a process for electrodeposition or electroplating lithium metal is described. The disclosed process can control the interaction of a lithium containing electrolyte and a (conductive) substrate such that a compact, electrochemically available lithium metal film can be formed under high applied currents, in accordance with one or more embodiments disclosed herein. Additionally, the embodiments disclosed herein demonstrate a production process with a high conversion efficiency of electrical energy into reduced lithium ions that facilitates formation of a compact thin lithium metal film, which is suitable for use as an anode in a lithium-ion battery. Tn one or more embodiments, this process directs a high velocity flow, exceeding, for example, a flow rate of 570 cm3 per minute and / or a fluid velocity of, or exceeding, 1700 cm per minute, of a lithium-ion containing electrolyte directly towards the surface of a conductive substrate such that the flow of electrolyte reaches a critical value to produce compact, electrochemically available films of lithium metal when an applied current ranging between 5 and 1000 mA / cm2 is applied to the electrodeposition system.

[0015] Figure 1 illustrates an embodiment of an apparatus 100 for producing a lithium film, in accordance with various embodiments. As illustrated in Figure 1, the apparatus 100 may include a chamber 110 configured for electrodeposition of lithium films. The apparatus 100 may have an inlet 230 and an outlet 130, for example, for introducing and removing, respectively, the electrolyte used in electrodeposition, in accordance with one or more embodiments. As shown in Figure 1, the chamber 110 is configured for intaking a fluid 140 (e.g., the electrolyte for electrodeposition) via the inlet 120 and removing the fluid 140 via the outlet 130. Tn various embodiments, the fluid 140 may include an electrolyte comprising a mixture of an organic solvent and a lithium salt. In various embodiments, the organic solvent may include solvents typical of lithium metal batteries, such as carbonates and / or glymes. In one or more embodiments, the lithium salt containing salts may include typical of lithium metal battery electrolytes, such as, for example, but not limited to, LiFSI, LiTFSI, LiPFe, and LiBOB.

[0016] Further illustrated in Figure 1, the apparatus 100 may include an anode 150 (also referred to herein as a counter-electrode) and a holder 160 for mounting a substrate 162. In some embodiments herein, the holder 160 with the substrate 162 mounted thereof, can be configured as a cathode 160 / 162 (also referred to herein as the electrode). In one or more embodiments, the substrate 162 is removably mounted on or in, or otherwise removably attached to, the holder 160 for electrodeposition. In various embodiments, the holder 160 and the anode 150 are spaced apart between 0.005 cm and 10 cm.

[0017] In various embodiments, the anode 150 may include a piece of lithium metal (e.g., a thin film or otherwise), or may be an electrode coating having one or more electrochemically active materials commonly employed as an anode or a cathode in a lithium-ion battery.

[0018] In various embodiments, the substrate 162 can include a planar or 3D copper sheet or any suitable sheet of a conductive material, such as, for example, but not limited to, conductive carbon, graphite, silicon, silver, gold, zinc, nickel, tin, brass.

[0019] The apparatus 100 may also include a power source (not shown) configured to supply a current 170 across the anode 150 and the cathode 160 / 162 during an electrodeposition operation. In various embodiments, the inlet 120 of the apparatus 100 is oriented with respect to a surface of the substrate 162 such that the fluid 140 flowing through the inlet 120 and arriving at the surface of the substrate is at least greater than 500 cm3 per minute (in some cases, greater than 570 cm3 per minute), and lithium ions contained within the fluid 140 are electrochemically reduced and plated to form a lithium metal film 180 on the surface of the substrate 162. In one or more embodiments, the fluid 140 may flow through the inlet 120 at a flow velocity greater than 900 cm per minute. In one or more embodiments, the fluid 140 may flow through the inlet 120 at a flow velocity between 860 cm per minute and 1500 cm per minute. In one or more embodiments, the fluid 140 may flow through the inlet 120 at a flow velocity greater than 1700 cm per minute. In one or more embodiments, the fluid 140 may flow through the inlet 120 at a lower fluid velocity at a lower applied current.

[0020] In various embodiments, the fluid 140 may include an abrasive material, in addition to electrolyte materials. The abrasive material may include a metal oxide, such as aluminum oxide, a non-metallic oxide, such as silica, or other common abrasive materials, such as diamond or boron carbide, in accordance with one or more embodiments.

[0021] In one or more embodiments, the abrasive material in the fluid 140 may contact the surface of the substrate 162 prior to the power supply supplying the current 170 across the anode 150 and the cathode 160 / 162. In one or more embodiments, the abrasive material in the fluid 140 may contact the surface of the substrate 162 while the power supply is supplying the current 170 across the anode 150 and the cathode 160 / 162. In one or more embodiments, the abrasive material in the fluid 140 may contact the surface of the substrate 162 after the power supply supplied the current 170 across the anode 150 and the cathode 160 / 162. In other words, the abrasive material in the fluid 140 may be used to clean the surface of the substrate 162 before electrodeposition begins, interact with the growing lithium film while lithium is being deposited during the electrodeposition, or after the lithium film has been deposited. During the growth of the lithium film 180, the abrasive material may be used to shear off dendritic portions of the lithium film or large polymeric portions of the solid-electrolyte-interphase (SEI) layer. After the film is formed, the abrasive material may assist in removing large surface features, such as abnormally thick SEI or mossy lithium.

[0022] In one or more embodiments, the power source is further configured to supply a pulsed current across the anode 150 and the cathode 160 / 162. The pulsed current may facilitate forming of a better lithium metal film 180 on the surface of the substrate 162. In one or more embodiments, the power source is further programmed via cyclic voltammetry to facilitate forming of the lithium metal film 180 on the surface of the substrate 162.

[0023] In one or more embodiments, the apparatus 100 may further include a replenishing source (not shown) for replenishing the fluid 140 with one or more lithium ion containing additive materials. In other words, the fluid 140 that is removed via the outlet 130 may be routed to a replenishing source (not shown) for replenishing the fluid 140 before recycling back into the inlet 120 for re-introducing the fluid 140 for electrodeposition, in accordance with one or more embodiments. This recycling / replenishing portion can help facilitate continuous electrodeposition using the apparatus 100, in accordance with one or more embodiments.

[0024] In one or more embodiments, the apparatus 100 may further include a filter (not shown) placed proximate to, or in-line with, the inlet 120 of the chamber 110. The filter can be configured to filter impurities, such as polymeric components of the SEI or pieces of mossy lithium sheared from the surface during film fabrication, from the fluid 140 prior to being introduced via the inlet 120 of the chamber 110, in accordance with one or more embodiments.

[0025] In one or more embodiments, the apparatus 100 may further include a pump (not shown) configured to pressurize the chamber 110 using an inert gas, such as argon or nitrogen above an ambient atmospheric condition. In one or more embodiments, the anode 150 is disposed in a portion or an area of the chamber 110 with little-to-no flow of the fluid 140. In other words, the anode 150 may not be in contact with the fluid 140 while the cathode 160 / 162 (the holder 160 and substrate 162) may be fully submersed in the fluid 140 during electrodeposition, in accordance with one or more embodiments. Although Figure 1 illustrates the anode 150 being submersed in the fluid 140, the anode 150 may be isolated from contacting the fluid 140 (illustration not shown), in accordance with one embodiment.

[0026] In one or more embodiments, the apparatus 100 may further include a nozzle 122 operationally coupled to the inlet 120 of the chamber 110 and positioned perpendicularly to the surface of the substrate 162. In one or more embodiments, the apparatus 100 may further include a nozzle 122 operationally coupled to the inlet 120 of the chamber 110 and positioned at an angle between 1 degree and 89 degrees off normal to the surface of the substrate 162. In one or more embodiments, the apparatus 100 may further include a nozzle 122 operationally coupled to the inlet 120 of the chamber 110 and positioned at a distance between 1 mm and 100 mm from the surface of the substrate 162. In one or more embodiments, the apparatus 100 may further include a nozzle 122 operationally coupled to the inlet 120 of the chamber 110 and positioned at a distance greater than or equal to 100 mm from the surface of the substrate 162. In other words, the nozzle 122, which is coupled to the inlet 120, can be swiveled, tilted, moved, or otherwise manipulatable such that the angle and the distance of the nozzle 122 with respect to the surface of the substrate 162 can be finely controlled or adjusted, in accordance with various embodiments. With the nozzle 122 being adjustable, the flow rate, flow capacity, flow volume, etc., of the fluid 140 and the angle of such fluid flow of the fluid 140 can be set as desired to provide electrodeposition conditions for depositing a high-quality lithium film on the substrate 162, in accordance with various embodiments. As illustrated in Figure 1, the nozzle 122 is configured to face the surface (i.e., the first surface) of the substrate 162 and the anode 150 (e.g., counter-electrode) faces the back surface (i.e., a second surface) of the substrate 162.

[0027] In one or more embodiments, a system for producing lithium films may include the apparatus 100 depicted and described with respect to Figure 1. Using the apparatus 100 of Figure 1, the system may also include one or more methods described as follows.

[0028] Now referring to Figure 2, Figure 2 illustrates a method S100 for producing a lithium film, in accordance with various embodiments. In one or more embodiments, the method SI00 for producing a lithium film is performed using the apparatus 100 illustrated in Figure 1.

[0029] As illustrated in Figure 2, the method S100 includes, at step SI 10, providing a chamber having a holder and a counter-electrode, the holder configured to hold a substrate, and the holder and the counter-electrode spaced apart between .005 cm and 10 cm; at step SI20, introducing a fluid via an inlet of the chamber such that the fluid introduced via the inlet contacts a surface of the substrate at a flow velocity greater than 900 cm per minute; and at step SI30, applying a current across the substrate and the counter-electrode such that lithium ions contained within the fluid are electrochemically reduced and plated to form a lithium metal film on the surface of the substrate. Various components, such as, the chamber, the holder, the counter-electrode, the substrate, the fluid, the inlet, the outlet, and various other components as described with respect to method S100 of Figure 2 refer to those with same or like-wise terms (e.g., the chamber 110, the holder 160, the counter-electrode / anode 150, the substrate 162, the fluid 140, the inlet 120, the outlet 130, etc.) that have been described above with respect to the apparatus 100 of Figure 1, unless otherwise noted herein.

[0030] In accordance one or more embodiments, the method SI00 may further include, optionally at step S140, removing the fluid via an outlet of the chamber; optionally at step SI50, replenishing the fluid with one or more lithium ion containing additive materials; and optionally at step SI 60, re-introducing the replenished fluid via the inlet of the chamber.

[0031] In various embodiments of the method SI00, the fluid introduced into the chamber can include an electrolyte comprising a mixture of an organic solvent and a lithium salt. In some embodiments, the fluid may also include an abrasive material. In various embodiments of the method S100, the method SI00 may further include abrasing the substrate prior to applying the current across the substrate and the counter-electrode, abrasing the substrate while the current is being applied across the substrate and the counter-electrode, and / or abrasing the substrate after applying the current across the substrate and the counterelectrode. In various embodiments of the method SI 00, the abrasive material may include a metal oxide, such as aluminum oxide, a non-metallic oxide, such as silica, or other common abrasive materials, such as diamond or boron carbide.

[0032] In various embodiments of the method SI00, the current applied across the substrate and the counter-electrode can be a pulsed current and the pulsed current may facilitate forming of the lithium metal film on the surface of the substrate. In various embodiments of the method SI00, the current applied across the substrate and the counter-electrode can be programmed via cyclic voltammetry that facilitates forming of the lithium metal film on the surface of the substrate.

[0033] In various embodiments of the method SI00, the fluid may make contact with the surface of the substrate via a nozzle operationally coupled to the inlet and positioned perpendicularly to the surface of the substrate. In various embodiments, the fluid may make contact with the surface of the substrate via a nozzle operationally coupled to the inlet and positioned at an angle between 1 degree and 89 degrees off normal to the surface of the substrate. In various embodiments, the fluid may make contact with the surface of the substrate via a nozzle operationally coupled to the inlet and positioned at a distance between 1 mm and 100 mm from the surface of the substrate. In various embodiments, the fluid may make contact with the surface of the substrate via a nozzle operationally coupled to the inlet and positioned at a distance greater than or equal to 100 mm from the surface of the substrate.

[0034] In various embodiments of the method SI00, the fluid can be introduced at a flow rate greater than 500 cm3 per minute. In various embodiments, the counter-electrode may include a lithium source, a 3 dimensional or a piece of thin-film lithium metal, a lithium metal alloy, such as, for example, but not limited to, Li-Sn or Li-Ag, or an electrode coating having an electrochemically active material, such as for example, but not limited to lithium alloys commonly employed as an anode or a cathode.

[0035] In various embodiments, the method SI00 may optionally include filtering the fluid via a filter placed proximate to, or in-line with, the inlet of the chamber. In various embodiments, the method S100 may optionally include pressurizing the chamber above an ambient atmospheric condition. In various embodiments, the chamber may be pressurized using an inert gas, such as argon or nitrogen.

[0036] In various embodiments of the method SI00, the counter-electrode may be disposed in a portion of the chamber with little-to-no fluid flow. In various embodiments of the method S100, the surface of the substrate is a first surface of the substrate, the counterelectrode faces a second surface of the substrate opposite the first surface of the substrate.

[0037] Various examples along with sample images are provided below to further illustrate the success of the disclosed apparatus, system, and method thereof in producing lithium films with superior electrochemical performances and better life cycles. EXAMPLES Example 1:

[0038] 200 ml of a conventional ether lithium metal electrolyte or an electrolyte comprising a mixture of an organic solvent and a lithium salt was added to the electrodeposition cell. The flow rate was adjusted to the values specified in table 1. A copper electrode was sandwiched between two pieces of polyethylene. The front piece of polyethylene contained a 1.5 cm circle hole to expose 1.5 cm of the copper surface to the electrolyte. The exposed portion of the copper electrode was placed directly in front of the electrolyte inlet, 2.0 cm from the inlet. The inlet was a tube with an internal diameter of 0.7 cm, thereby producing the velocity calculated in Table 1. A current density of 20 mA / cm2 was applied between the copper electrode and a bulk lithium metal counter electrode placed 2 cm behind the copper electrode and within the electrolyte bath. This configuration is described schematically in Figure 1. A total capacity of 0.83 mAh / cm2 was applied between the two electrodes, creating a film of metallic lithium on the copper electrode. After deposition, the lithium coating was removed from the system and the appearance was cataloged by a photograph.

[0039] This lithium film was then fabricated into a symmetric cell to measure the total lithium capacity. Figure 3A illustrates a schematic of an electrodeposited lithium metal film as-prepared over a copper electrode, highlighting the region of the electrode used to make the 1.2 cm-diameter lithium metal film. Figure 3B illustrates an example configuration of a symmetric cell used to measure the lithium capacity of the electrodeposited lithium metal film prepared from the cutout shown in Figure 3A.

[0040] As illustrated in Figure 3A and 3B, a 1.2 cm diameter punch was used to extract a circular electrode 382 of electrodeposited lithium 380 from the coating 300a to be used as a cathode 382 in the symmetric cell 300b. This circular electrode 382 of electrodeposited lithium was paired with a 1.5 cm diameter circular electrode 313 (of bare copper foil 313) and a separator 305 and liquid electrolyte in between (Figure 3B). The separator used was Celgard 2325 and the electrolyte comprised a conventional ether lithium metal electrolyte or an electrolyte comprising a mixture of an organic solvent and a lithium salt. A current of 0.1 mA was applied to the fabricated cell to strip lithium from the electrodeposited coating and plate it onto the bare electrode. The total capacity measured from the first charge of this configuration is the usable lithium capacity and is presented as a function of fluid velocity in Table 1. The efficiency values in Table 1 indicates the ratio between the total current applied to make the electrode coating and the measured electrochemically available lithium capacity measured in the half-cell coin cell. The efficiency in Table 1 can be calculated as follows: Total Lithium Capacity Measured (mAh') Efficiency (%) = ----------------------------------------------------* 100 Total Capacity Applied During Electrodeposition (mAh) Flow Rate (RPMs} Flow Rate |on3 / min) Fluid Velocity Applied Cuwent (mA / cm2) 11 Capacity {mAh} Efficiency (%} C G 0 20 0,07 7,80 250 143 £30 26 0 / W 11.76 500 235 861 20 0.05 5.40 1X0 571 1 / 21 20 6.20 243? 1503 856 2582 20 0.41 46.74 2300 1:42 3442 20 0.48 57.26 2500 1427 4303 20 0.56 66.57 3003 1713 5164 20 0.54 84.71 3509 1908 6324 20 6.52 81.32 Table 1. Compilation of the flow rates and resulting efficiencies from the formed lithium coating.

[0041] Figures 4A-4I show images of electrodeposited lithium metal films fabricated under a constant current density of 20 mA / cm2 and deposition time of 150 seconds at various fluid flow conditions. The fluid velocity is provided as an inset above each of the images 400a-400i illustrated in Figures 4A-4I. Example 2:

[0042] An identical configuration to Example 1 was used. The fluid flow was held constant at 1427 cm3 / min and a variable current ranging from 5 mA / cm2 to 100 mA / cm2 was applied for an amount of time that resulted in a fixed applied capacity of 0.83 mAh / cm2. The resulting measured lithium capacities and efficiencies are presented in Table 2 below. Appiied Current (mA / cm2) Input Capacity (mAh / cm2) Li Capacity (mAh) Efficiency (%) 5 0.83 0.55           58.7 ......................10...................... .....................0.83.................... ............0.57............ .........50 5......... 20 0.S3 0,55 59.4 40 0.83 0.43 45.1 80 0.33 0.40 43.2 ■00 0.83 0.33 35.2 Table 2. Compilation of applied currents and resulting efficiencies from the formed lithium coating.

[0043] Figures 5A-5F show images of electrodeposited lithium metal films fabricated under a constant flow of about 4300 cm per minute. The current density is provided as an inset above each of the images 500a-500f illustrated in Figures 5A-5F. RECITATION OF EMBODIMENTS

[0044] Embodiment 1. A method for producing a lithium film, comprising: providing a chamber having a holder and a counter-electrode, the holder configured to hold a substrate, and the holder and the counter-electrode spaced apart between 0.005 cm and 10 cm; introducing a fluid via an inlet of the chamber such that the fluid introduced via the inlet contacts a surface of the substrate at a flow velocity greater than 900 cm per minute; and applying a current across the substrate and the counter-electrode such that lithium ions contained within the fluid are electrochemically reduced and plated to form a lithium metal film on the surface of the substrate.

[0045] Embodiment 2. The method of Embodiment 1, further comprising: removing the fluid via an outlet of the chamber; replenishing the fluid with one or more lithium ion containing additive materials; and re-introducing the replenished fluid via the inlet of the chamber.

[0046] Embodiment 3. The method of Embodiments 1 or 2, wherein the fluid comprises an electrolyte comprising a mixture of an organic solvent and a lithium salt. In various embodiments, the organic solvent may include solvents typical of lithium metal batteries, such as carbonates and / or glymes. In one or more embodiments, the lithium salt containing salts may include typical of lithium metal battery electrolytes, such as, for example, but not limited to, LiFSI, LiTFSI, LiPFe, and LiBOB.

[0047] Embodiment 4. The method of any one of Embodiments 1-3, wherein the fluid comprises an abrasive material, the method further comprising: abrasing the substrate prior to applying the current across the substrate and the counter-electrode.

[0048] Embodiment 5. The method of any one of Embodiments 1-3, wherein the fluid comprises an abrasive material, the method further comprising: abrasing the substrate while the current is being applied across the substrate and the counter-electrode.

[0049] Embodiment 6. The method of any one of Embodiments 1-3, wherein the fluid comprises an abrasive material, the method further comprising: abrasing the substrate after applying the current across the substrate and the counter-electrode.

[0050] Embodiment 7. The method of any one of Embodiments 4-6, wherein the abrasive material comprises a metal oxide, such as aluminum oxide, a non-metallic oxide, such as silica, or other common abrasive materials, such as diamond or boron carbide.

[0051] Embodiment 8. The method of any one of Embodiments 1-7, wherein the current applied across the substrate and the counter-electrode is a pulsed current and the pulsed current facilitates forming of the lithium metal film on the surface of the substrate.

[0052] Embodiment 9. The method of any one of Embodiments 1-7, wherein the current applied across the substrate and the counter-electrode is programmed via cyclic voltammetry that facilitates forming of the lithium metal film on the surface of the substrate.

[0053] Embodiment 10. The method of any one of Embodiments 1-9, wherein the fluid is introduced at a flow rate greater than 500 cm3 per minute.

[0054] Embodiment 11. The method of any one of Embodiments 1-10, wherein the fluid contacts the surface of the substrate via a nozzle operationally coupled to the inlet and positioned perpendicularly to the surface of the substrate.

[0055] Embodiment 12. The method of any one of Embodiments 1-10, wherein the fluid contacts the surface of the substrate via a nozzle operationally coupled to the inlet and positioned at an angle between 1 degree and 89 degrees off normal to the surface of the substrate.

[0056] Embodiment 13. The method of any one of Embodiments 1-12, wherein the fluid contacts the surface of the substrate via a nozzle operationally coupled to the inlet and positioned at a distance between 1 mm and 100 mm from the surface of the substrate.

[0057] Embodiment 14. The method of any one of Embodiments 1-12, wherein the fluid contacts the surface of the substrate via a nozzle operationally coupled to the inlet and positioned at a distance greater than or equal to 100 mm from the surface of the substrate.

[0058] Embodiment 15. The method of any one of Embodiments 1-14, wherein the counterelectrode comprises a lithium source, a 3 dimensional or a piece of thin-film lithium metal, a lithium metal alloy, or an electrode coating comprising electrochemically active material commonly employed as an anode or a cathode.

[0059] Embodiment 16. The method of any one of Embodiments 1-15, further comprising: filtering the fluid via a filter placed proximate to, or in-line with, the inlet of the chamber.

[0060] Embodiment 17. The method of any one of Embodiments 1-16, further comprising: pressurizing the chamber above an ambient atmospheric condition.

[0061] Embodiment 18. The method of Embodiment 17, wherein the chamber is pressurized using an inert gas, such as argon or nitrogen.

[0062] Embodiment 19. The method of any one of Embodiments 1-18, wherein the counterelectrode is disposed in a portion of the chamber with little-to-no fluid flow.

[0063] Embodiment 20. The method of any one of Embodiments 1-19, wherein the surface of the substrate is a first surface of the substrate, the counter-electrode faces a second surface of the substrate opposite the first surface of the substrate.

[0064] Embodiment 21. An apparatus for producing a lithium film, comprising: a chamber having an inlet and an outlet, the chamber configured for intaking a fluid via the inlet and removing the fluid via the outlet; a lithium source configured as an anode; a holder configured to mount a substrate, the holder with the substrate mounted thereof configured as a cathode; and a power source configured to supply a current across the anode and the cathode, wherein the inlet is oriented with respect to a surface of the substrate such that: the fluid flowing through the inlet and arriving at the surface of the substrate is greater than 500 cm3 per minute, and lithium ions contained within the fluid are electrochemically reduced and plated to form a lithium metal film on the surface of the substrate.

[0065] Embodiment 22. The apparatus of Embodiment 21, wherein the fluid flowing through the inlet has a flow velocity greater than 900 cm per minute.

[0066] Embodiment 23. The apparatus of Embodiments 21 or 22, wherein the fluid comprises an electrolyte comprising a mixture of an organic solvent and a lithium salt.

[0067] Embodiment 24. The apparatus of any one of Embodiments 21-23, wherein the fluid comprises an abrasive material comprising a metal oxide, such as aluminum oxide, a non-metallic oxide, such as silica, or other common abrasive materials, such as diamond or boron carbide.

[0068] Embodiment 25. The apparatus of Embodiment 24, wherein the abrasive material in the fluid makes contact with the surface of the substrate prior to the power supply supplying the current across the anode and the cathode.

[0069] Embodiment 26. The apparatus of Embodiment 24, wherein the abrasive material in the fluid makes contact with the surface of the substrate while the power supply is supplying the current across the anode and the cathode.

[0070] Embodiment 27. The apparatus of Embodiment 24, wherein the abrasive material in the fluid makes contact with the surface of the substrate after the power supply supplied the current across the anode and the cathode.

[0071] Embodiment 28. The apparatus of any one of Embodiments 21-27, wherein the power source is further configured to supply a pulsed current across the anode and the cathode, and wherein the supplied pulsed current facilitates forming of the lithium metal film on the surface of the substrate.

[0072] Embodiment 29. The apparatus of any one of Embodiments 21-27, wherein the power source is further programmed via cyclic voltammetry to facilitate forming of the lithium metal film on the surface of the substrate.

[0073] Embodiment 30. The apparatus of any one of Embodiments 21-29, further comprising: a replenishing source for replenishing the fluid with one or more lithium ion containing additive materials.

[0074] Embodiment 31. The apparatus of any one of Embodiments 21-30, further comprising: a filter placed proximate to, or in-line with, the inlet of the chamber, the filter configured to filter impurities, such as mossy lithium or delaminated solid-electrolyte interphase (SEI) components, from the fluid prior to being introduced via the inlet of the chamber.

[0075] Embodiment 32. The apparatus of any one of Embodiments 21-31, wherein the holder and the anode are spaced apart between 0.005 cm and 10 cm.

[0076] Embodiment 33. The apparatus of any one of Embodiments 21-32, further comprising: a pump configured to pressurize the chamber using an inert gas, such as argon or nitrogen above an ambient atmospheric condition.

[0077] Embodiment 34. The apparatus of any one of Embodiments 21-33, wherein the anode is disposed in a portion of the chamber with little-to-no fluid flow.

[0078] Embodiment 35. The apparatus of any one of Embodiments 21-34, wherein the anode comprises a piece of lithium metal, or an electrode coating comprising electrochemically active material commonly employed as an anode or a cathode.

[0079] Embodiment 36. The apparatus of any one of Embodiments 21-35, further comprising: a nozzle operationally coupled to the inlet of the chamber and positioned perpendicularly to the surface of the substrate.

[0080] Embodiment 37. The apparatus of any one of Embodiments 21-35, further comprising: a nozzle operationally coupled to the inlet of the chamber and positioned at an angle between 1 degree and 89 degrees off normal to the surface of the substrate.

[0081] Embodiment 38. The apparatus of any one of Embodiments 21-37, further comprising: a nozzle operationally coupled to the inlet of the chamber and positioned at a distance between 1 mm and 100 mm from the surface of the substrate.

[0082] Embodiment 39. The apparatus of any one of Embodiments 21-37, further comprising: a nozzle operationally coupled to the inlet of the chamber and positioned at a distance greater than or equal to 100 mm from the surface of the substrate.

[0083] Embodiment 40. The apparatus of any one of Embodiments 21-39, wherein the surface of the substrate is a first surface of the substrate, the counter-electrode faces a second surface of the substrate opposite the first surface of the substrate.

[0084] Embodiment 41. A system for producing a lithium film comprising the apparatus of any one of Embodiments 21-40.

Claims

1. A method for producing a lithium film, comprising:providing a chamber having a holder and a counter-electrode, the holder configured to hold a substrate, and the holder and the counter-electrode spaced apart between 0.005 cm and 10 cm;introducing a fluid via an inlet of the chamber such that the fluid introduced via the inlet contacts a surface of the substrate at a flow velocity greater than 900 cm per minute; and applying a current across the substrate and the counter-electrode such that lithium ions contained within the fluid are electrochemically reduced and plated to form a lithium metal film on the surface of the substrate.

2. The method of claim 1, further comprising:removing the fluid via an outlet of the chamber;replenishing the fluid with one or more lithium ion containing additive materials; and re-introducing the replenished fluid via the inlet of the chamber.

3. The method of claims 1 or 2, wherein the fluid comprises an electrolyte comprising a mixture of an organic solvent and a lithium salt.

4. The method of any one of claims 1-3, wherein the fluid comprises an abrasive material, the method further comprising:abrasing the substrate prior to applying the current across the substrate and the counter-electrode.

5. The method of any one of claims 1-3, wherein the fluid comprises an abrasive material, the method further comprising:abrasing the substrate while the current is being applied across the substrate and the counter-electrode.

6. The method of any one of claims 1-3, wherein the fluid comprises an abrasive material, the method further comprising:abrasing the substrate after applying the current across the substrate and the counterelectrode.

7. The method of any one of claims 4-6, wherein the abrasive material comprises a metal oxide, such as aluminum oxide, a non-metallic oxide, such as silica, or other common abrasive materials, such as diamond or boron carbide.

8. The method of any one of claims 1-7, wherein the current applied across the substrate and the counter-electrode is a pulsed current and the pulsed current facilitates forming of the lithium metal film on the surface of the substrate.

9. The method of any one of claims 1-7, wherein the current applied across the substrate and the counter-electrode is programmed via cyclic voltammetry that facilitates forming of the lithium metal film on the surface of the substrate.

10. The method of any one of claims 1-9, wherein the fluid is introduced at a flow rate greater than 500 cm3 per minute.

11. The method of any one of claims 1-10, wherein the fluid contacts the surface of the substrate via a nozzle operationally coupled to the inlet and positioned perpendicularly to the surface of the substrate.

12. The method of any one of claims 1-10, wherein the fluid contacts the surface of the substrate via a nozzle operationally coupled to the inlet and positioned at an angle between 1 degree and 89 degrees off normal to the surface of the substrate.

13. The method of any one of claims 1-12, wherein the fluid contacts the surface of the substrate via a nozzle operationally coupled to the inlet and positioned at a distance between 1 mm and 100 mm from the surface of the substrate.

14. The method of any one of claims 1-12, wherein the fluid contacts the surface of the substrate via a nozzle operationally coupled to the inlet and positioned at a distance greater than or equal to 100 mm from the surface of the substrate.

15. The method of any one of claims 1-14, wherein the counter-electrode comprises a lithium source, a 3 dimensional or a piece of thin-film lithium metal, a lithium metal alloy, oran electrode coating comprising electrochemically active material commonly employed as an anode or a cathode.

16. The method of any one of claims 1-15, further comprising:filtering the fluid via a filter placed proximate to, or in-line with, the inlet of the chamber.

17. The method of any one of claims 1-16, further comprising:pressurizing the chamber above an ambient atmospheric condition.

18. The method of claim 17, wherein the chamber is pressurized using an inert gas, such as argon or nitrogen.

19. The method of any one of claims 1-18, wherein the counter-electrode is disposed in a portion of the chamber with little-to-no fluid flow.

20. The method of any one of claims 1-19, wherein the surface of the substrate is a first surface of the substrate, the counter-electrode faces a second surface of the substrate opposite the first surface of the substrate.

21. An apparatus for producing a lithium film, comprising:a chamber having an inlet and an outlet, the chamber configured for intaking a fluid via the inlet and removing the fluid via the outlet;a lithium source configured as an anode;a holder configured to mount a substrate, the holder with the substrate mounted thereof configured as a cathode; anda power source configured to supply a current across the anode and the cathode, wherein the inlet is oriented with respect to a surface of the substrate such that: the fluid flowing through the inlet and arriving at the surface of the substrate is greater than 500 cm3 per minute, andlithium ions contained within the fluid are electrochemically reduced and plated to form a lithium metal film on the surface of the substrate.

22. The apparatus of claim 21, wherein the fluid flowing through the inlet has a flow velocity greater than 900 cm per minute.

23. The apparatus of claims 21 or 22, wherein the fluid comprises an electrolyte comprising a mixture of an organic solvent and a lithium salt.

24. The apparatus of any one of claims 21-23, wherein the fluid comprises an abrasive material comprising a metal oxide, such as aluminum oxide, a non-metallic oxide, such as silica, or other common abrasive materials, such as diamond or boron carbide.

25. The apparatus of claim 24, wherein the abrasive material in the fluid makes contact with the surface of the substrate prior to the power supply supplying the current across the anode and the cathode.

26. The apparatus of claim 24, wherein the abrasive material in the fluid makes contact with the surface of the substrate while the power supply is supplying the current across the anode and the cathode.

27. The apparatus of claim 24, wherein the abrasive material in the fluid makes contact with the surface of the substrate after the power supply supplied the current across the anode and the cathode.

28. The apparatus of any one of claims 21-27, wherein the power source is further configured to supply a pulsed current across the anode and the cathode, and wherein the supplied pulsed current facilitates forming of the lithium metal film on the surface of the substrate.

29. The apparatus of any one of claims 21-27, wherein the power source is further programmed via cyclic voltammetry to facilitate forming of the lithium metal film on the surface of the substrate.

30. The apparatus of any one of claims 21-29, further comprising:a replenishing source for replenishing the fluid with one or more lithium ion containing additive materials.

31. The apparatus of any one of claims 21-30, further comprising:a filter placed proximate to, or in-line with, the inlet of the chamber, the filter configured to filter impurities from the fluid prior to being introduced via the inlet of the chamber.

32. The apparatus of any one of claims 21-31, wherein the holder and the anode are spaced apart between 0.005 cm and 10 cm.

33. The apparatus of any one of claims 21-32, further comprising:a pump configured to pressurize the chamber using an inert gas, such as argon or nitrogen above an ambient atmospheric condition.

34. The apparatus of any one of claims 21-33, wherein the anode is disposed in a portion of the chamber with little-to-no fluid flow.

35. The apparatus of any one of claims 21-34, wherein the anode comprises a piece of lithium metal, or an electrode coating comprising electrochemically active material commonly employed as an anode or a cathode.

36. The apparatus of any one of claims 21-35, further comprising:a nozzle operationally coupled to the inlet of the chamber and positioned perpendicularly to the surface of the substrate.

37. The apparatus of any one of claims 21-35, further comprising:a nozzle operationally coupled to the inlet of the chamber and positioned at an angle between 1 degree and 89 degrees off normal to the surface of the substrate.

38. The apparatus of any one of claims 21-37, further comprising:a nozzle operationally coupled to the inlet of the chamber and positioned at a distance between 1 mm and 100 mm from the surface of the substrate.

39. The apparatus of any one of claims 21-37, further comprising:a nozzle operationally coupled to the inlet of the chamber and positioned at a distance greater than or equal to 100 mm from the surface of the substrate.

40. The apparatus of any one of claims 21-39, wherein the surface of the substrate is a first surface of the substrate, the counter-electrode faces a second surface of the substrate opposite the first surface of the substrate.

41. A system for producing a lithium film comprising the apparatus of any one of claims 21-40.

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